WO2012133721A1 - Sheet-elongatable organic base material - Google Patents

Sheet-elongatable organic base material Download PDF

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Publication number
WO2012133721A1
WO2012133721A1 PCT/JP2012/058496 JP2012058496W WO2012133721A1 WO 2012133721 A1 WO2012133721 A1 WO 2012133721A1 JP 2012058496 W JP2012058496 W JP 2012058496W WO 2012133721 A1 WO2012133721 A1 WO 2012133721A1
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WO
WIPO (PCT)
Prior art keywords
polymer
base material
extensible
sheet
cylindrical
Prior art date
Application number
PCT/JP2012/058496
Other languages
French (fr)
Japanese (ja)
Inventor
達也 北原
内藤　友也
国夫 長崎
亮 志村
凡子 村山
仁嗣 平野
Original Assignee
日東電工株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2012015392A external-priority patent/JP5956171B2/en
Priority claimed from JP2012015385A external-priority patent/JP5876307B2/en
Priority claimed from JP2012015388A external-priority patent/JP5876309B2/en
Priority claimed from JP2012015387A external-priority patent/JP5876308B2/en
Priority claimed from JP2012015384A external-priority patent/JP5876306B2/en
Priority claimed from JP2012015393A external-priority patent/JP2013155121A/en
Priority claimed from JP2012015389A external-priority patent/JP2013155241A/en
Priority claimed from JP2012015386A external-priority patent/JP2012214015A/en
Priority claimed from JP2012030137A external-priority patent/JP2013166280A/en
Priority claimed from JP2012030088A external-priority patent/JP2013166279A/en
Priority claimed from JP2012030086A external-priority patent/JP2013166278A/en
Priority claimed from JP2012030041A external-priority patent/JP2013166276A/en
Priority claimed from JP2012030087A external-priority patent/JP2013166836A/en
Priority claimed from JP2012030138A external-priority patent/JP2013166281A/en
Priority claimed from JP2012030089A external-priority patent/JP2013166837A/en
Priority claimed from JP2012030040A external-priority patent/JP2013168258A/en
Priority claimed from JP2012030090A external-priority patent/JP2013166838A/en
Priority claimed from JP2012030039A external-priority patent/JP2013166275A/en
Priority claimed from JP2012030042A external-priority patent/JP2013166277A/en
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Publication of WO2012133721A1 publication Critical patent/WO2012133721A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
    • B29C41/12—Spreading-out the material on a substrate, e.g. on the surface of a liquid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets

Definitions

  • the present invention relates to a sheet-like extensible organic base material, more specifically, an easily extensible polymer base material and a cylindrical hard-extensible polymer portion whose surface shape or projection shape onto the base material surface is an annular shape. It is related with the sheet-like extensible organic base material (especially elastic organic base material) currently formed.
  • the sheet-like extensible organic base material can be used as, for example, a band member, a binding member, a sanitary article, a clothing part, a base cloth for a poultice, etc. by utilizing its extensibility and stretchability.
  • this sheet-like extensible organic base material when this sheet-like extensible organic base material is extended in the surface direction, the whole base material is extended, but the cylindrical difficult-to-extend polymer part is not extended, but its shape is maintained. Designs such as characters can be applied to the difficult-to-extend polymer part, and other members can be held and fixed. Furthermore, since the region corresponding to the cylindrical cavity of the cylindrical difficult-to-extend polymer part is made of an easily-extensible polymer material, it can be extended in the thickness direction, so it is easy to follow the shape of the object to be attached. Excellent. Therefore, this sheet-like extensible organic base material can be used for, for example, an electronics member, an optical member, an optoelectronic member, a car electronics member, a household appliance member, a housing equipment member, a building material, and the like.
  • the organic members having stretchability and stretchability are widely used for band members, binding members, sanitary goods, clothing items, base materials for poultices, and the like.
  • the extensible member is usually composed of a composition having uniform extensibility (Patent Document 1). However, when such an extensible member is extended, every part of the extensible member is extended. Further, in a member having not only extensibility but also elasticity, when this is expanded and contracted, all parts expand and contract. Therefore, even if a design is applied to a certain place, the design is distorted when the extensible member is extended. Moreover, when fixing another member to an extensible member, since every part of an extensible member expand
  • An object of the present invention is to provide a sheet-like extensible substrate having a possible easily stretchable portion.
  • Another object of the present invention is to have a stretchable portion in the surface direction and a hard stretchable portion whose shape hardly changes even when stretched in the plane direction, and further stretches in the thickness direction inside the hard stretchable portion.
  • An object of the present invention is to provide a sheet-like extensible substrate having an easily stretchable part.
  • the present inventors have found that a tubular (hollow columnar) hardly stretchable polymer having a predetermined thickness and extending in the sheet thickness direction in an easily stretchable polymer base material.
  • the present invention has been completed by finding that the above object can be achieved by integrally forming the portions.
  • a cylindrical stretchable polymer portion A having a ring-shaped projection when the surface shape or the sheet-like stretchable organic substrate surface is a projection surface is partially included in the easily stretchable polymer base material.
  • a sheet-like extensible organic substrate formed integrally and integrally.
  • the outer peripheral shape of the annular zone in the surface shape or projected shape of the cylindrical hardly extensible polymer portion A may be any of a substantially circular shape, a substantially polygonal shape, an amorphous shape, or a shape representing a character, a symbol, or a number.
  • the outer peripheral shape of the annular zone in the surface shape or the projected shape of the cylindrical difficult-to-extend polymer part A is a substantially polygon, and the inner angle of the substantially polygon is an angle of 90 degrees or less or more than 90 degrees. May be.
  • a plurality of cylindrical difficult-to-extend polymer parts A may be formed in a regular pattern.
  • the distance between adjacent cylindrical difficult-to-extend polymer parts A is, for example, 0.05 mm to 50 cm. Further, the distance between the centers of adjacent cylindrical hardly extensible polymer portions A is, for example, 5 mm to 80 cm.
  • the projection shape when the surface shape or the sheet-like extensible organic base material surface is the projection surface You may have 1 or 2 or more or less the difficulty extensible polymer part B which is a substantially circular shape, a substantially polygonal shape, an amorphous shape, the shape showing a character, a symbol, or a number, a ring shape, or linear.
  • the thickness of the sheet-like extensible organic base material is, for example, 0.01 mm to 1 cm.
  • the length of the cylindrical hardly extensible polymer portion A in the thickness direction is at least 1/50 of the thickness of the sheet-like extensible organic base material.
  • the cylindrical difficulty extensible polymer part A may be continuously formed from one surface of the sheet-like extensible organic base material to the other surface.
  • the elongation characteristics may have a gradation.
  • the sheet-like extensible organic base material may further have stretchability.
  • a cylindrical hardly stretchable polymer portion A having a projection shape when the surface shape or the sheet-like organic base material surface is a projection surface is partially and It has an adhesive layer on at least one surface of an integrally formed sheet-like organic substrate having extensibility, and the adhesive strength of the adhesive layer (temperature 23 ° C., humidity 65% RH, tensile speed)
  • a multifunctional sheet-like extensible organic base material having an adhesiveness of 300 mm / min, peeling angle of 180 °, and SUS304) of 0.1 N / 20 mm or more.
  • a cylindrical hardly stretchable polymer portion A having a projection shape when the surface shape or the sheet-like organic base material surface is a projection surface is partially and
  • the adhesive strength (temperature 23 ° C., humidity 65% RH, tensile speed 300 mm / min, peel angle 180 °, vs. SUS304) of at least one surface of the integrally formed sheet-like organic substrate having extensibility is 0.
  • a multifunctional sheet-like extensible organic base material having adhesiveness of 1 N / 20 mm or more.
  • a cylindrical hardly stretchable polymer portion A having a projection shape when the surface shape or the sheet-like organic base material surface is a projection surface is partially and A multi-functional sheet-like extensible organic base material which is an integrally formed sheet-like organic base material having extensibility, wherein the easily extensible polymer base material contains a weathering agent.
  • the cylindrical hardly stretchable polymer portion A whose projection shape when the surface shape or the surface of the sheet-like organic base material is a projection surface is an annular shape is partially and Multi-functional sheet-like extensibility, which is an integrally formed sheet-like organic base material having extensibility, in which an easily extensible polymer base material and / or a cylindrical hardly extensible polymer portion contains a fragrance Organic base material.
  • a cylindrical hardly stretchable polymer portion A having a projection shape when the surface shape or the surface of the sheet-like organic substrate is a projection surface is partially and A multifunctional sheet-like extensible organic base material having a deodorizing layer on at least one surface of an integrally formed sheet-like organic base material having extensibility.
  • the cylindrical hardly stretchable polymer portion A having a projection shape when the surface shape or the sheet-like organic base material surface is the projection surface is partially and Monomer generated when a sheet-like extensible organic base material including a sheet-like organic base material having extensibility formed integrally is heated at 150 ° C. for 3 minutes.
  • a cylindrical hardly stretchable polymer portion A having a projection shape when the surface shape or the sheet-like organic base material surface is a projection surface is partially and A sheet-like organic base material having extensibility formed integrally, wherein the easily extensible polymer base material and / or the cylindrical hardly extensible polymer portion A contains a dye or a pigment Stretchable organic base material.
  • the cylindrical hardly stretchable polymer portion A having a projection shape when the surface shape or the sheet-like organic substrate surface is the projection surface is partially and A multifunctional sheet-like extensible organic substrate having a colored layer on at least one surface of an integrally formed sheet-like organic substrate having extensibility.
  • the cylindrical hardly stretchable polymer portion A having a projection shape when the surface shape or the sheet-like organic base material surface is the projection surface is partially and A multifunctional sheet-like extensible organic base material having a printing layer on at least one surface of an integrally formed sheet-like organic base material having extensibility.
  • the cylindrical hardly stretchable polymer portion A having a projection shape when the surface shape or the sheet-like organic base material surface is the projection surface is partially and An integrally formed sheet-like organic base material having extensibility, wherein the sheet-like organic base material contains a flame retardant, and / or flame retardant on at least one side of the sheet-like organic base material A multifunctional sheet-like extensible organic base material having a flame retardancy having a layer.
  • the cylindrical hardly stretchable polymer portion A having a ring shape when the surface shape or the sheet-like organic base material surface is the projection surface is partially and A sheet-like organic substrate having extensibility formed integrally, the sheet-like organic substrate containing a heat conductive substance, and / or on at least one surface of the sheet-like organic substrate A multifunctional sheet-like extensible organic base material having thermal conductivity having a thermal conductive layer.
  • thermoelectric layer is a layer containing a metal, a metal compound, a boron compound, graphite, or a heat conductive carbon fiber.
  • Multifunctional sheet-like extensible organic base material having properties.
  • the cylindrical hardly stretchable polymer portion A having a projection shape when the surface shape or the sheet-like organic base material surface is the projection surface is partially and A sheet-like organic substrate having extensibility formed integrally, wherein the sheet-like organic substrate contains a heat-insulating agent, and / or on at least one side of the sheet-like organic substrate.
  • a multifunctional sheet-like extensible organic base material having a heat insulating property having a heat insulating layer having a heat insulating layer.
  • [7-2] A multifunctional sheet-like extensible organic base material having heat insulating properties according to [7-1], wherein the heat insulating property imparting agent is hollow particles.
  • [7-3] Multifunctional having heat insulating properties according to [7-1] or [7-2], wherein the heat insulating layer is a layer containing hollow particles and / or a layer formed of foamed plastic. Sheet-like extensible organic base material.
  • the cylindrical hardly stretchable polymer portion A whose projection shape when the surface shape or the surface of the sheet-like organic base material is a projection surface is an annular shape is partially and A sheet-like organic base material having extensibility formed integrally, wherein the easily extensible polymer base material contains an impact resistance imparting agent.
  • the cylindrical hardly stretchable polymer portion A having a projection shape when the surface shape or the surface of the sheet-like organic base material is a projection surface is partially and A multifunctional sheet-like extensible organic base material having an impact absorbing layer on at least one surface of an integrally formed sheet-like organic base material having extensibility.
  • the impact absorbing layer is an impact resistance-containing agent-containing layer containing at least one selected from the group consisting of inorganic hollow particles and foamed plastic particles, or a foamed layer formed from a plastic foam.
  • the impact absorbing layer is an impact resistance-containing agent-containing layer containing at least one selected from the group consisting of inorganic hollow particles and foamed plastic particles, or a foamed layer formed from a plastic foam.
  • Multifunctional sheet-like extensible organic base material is an impact resistance-containing agent-containing layer containing at least one selected from the group consisting of inorganic hollow particles and foamed plastic particles, or a foamed layer formed from a plastic foam.
  • the cylindrical hardly stretchable polymer portion A having a projection shape when the surface shape or the sheet-like organic substrate surface is a projection surface is partially and A multifunctional sheet having a gas barrier layer on at least one surface of an integrally formed sheet-like organic substrate having extensibility and satisfying one or both of the following [i] and [ii] Stretchable organic base material.
  • the oxygen permeability corresponding to a thickness of 100 ⁇ m measured under the conditions of 20 ° C. and 70% RH according to JIS K7126-2 method is 10 mL / m 2 /0.1 MPa / day or less.
  • JIS K7129B method The water vapor permeability corresponding to a thickness of 100 ⁇ m measured under the conditions of 40 ° C. and 90% RH is 10 g / m 2 /0.1 MPa / day or less
  • the oxygen permeability corresponding to a thickness of 100 ⁇ m measured under the conditions of 20 ° C. and 70% RH according to JIS K7126-2 method is 10 mL / m 2 /0.1 MPa / day or less.
  • JIS K7129B method The water vapor permeability corresponding to a thickness of 100 ⁇ m measured under the conditions of 40 ° C. and 90% RH is 10 g / m 2 /0.1 MPa / day or less
  • the cylindrical hardly stretchable polymer portion A whose projection shape when the surface shape or the sheet-like organic base material surface is the projection surface is an annular shape is partially and It is an integrally formed sheet-like organic base material having extensibility, and has a water vapor transmission rate corresponding to a thickness of 40 ⁇ m measured at 40 ° C. and 90% RH in accordance with JIS K7129A method of 100 g / m 2.
  • Multifunctional sheet-like extensible organic base material that is at least 0.1 MPa / day.
  • the cylindrical hardly stretchable polymer portion A having a projection shape when the surface shape or the surface of the sheet-like organic base material is a projection surface is partially and A sheet-like organic substrate having extensibility formed integrally, wherein the sheet-like organic substrate contains a conductive substance, and / or is conductive on at least one surface of the sheet-like organic substrate.
  • Conductive multifunctional sheet-like extensible organic base material having a conductive layer is not limited to, the cylindrical hardly stretchable polymer portion A having a projection shape when the surface shape or the surface of the sheet-like organic base material is a projection surface.
  • the conductive substance is at least one selected from a carbon-based conductive filler, a metal-based conductive filler, a conductive polymer, a surfactant, a hydrophilic compound, a hydrophilic polymer, and an ionic liquid.
  • the multifunctional sheet-like extensible organic base material having conductivity according to [11-1].
  • the conductive layer contains at least one selected from a carbon-based conductive filler, a metal-based conductive filler, a conductive polymer, a surfactant, a hydrophilic compound, a hydrophilic polymer, and an ionic liquid.
  • the multifunctional sheet-like extensible organic base material having conductivity according to [11-1] or [11-2], which is a layer to be used.
  • the cylindrical hardly stretchable polymer portion A whose projection shape when the surface shape or the sheet-like organic base material surface is the projection surface is an annular shape is partially and A multifunctional sheet-like extensible organic base material having a surface layer, which has a surface layer made of a fluorine-based compound on at least one surface of the integrally formed sheet-like organic base material having extensibility.
  • the surface layer is formed of at least one composition selected from the group consisting of a composition containing a fluoroethylene vinyl ether copolymer and a composition containing a hybrid material containing a fluorine group.
  • a composition containing a fluoroethylene vinyl ether copolymer and a composition containing a hybrid material containing a fluorine group.
  • a multifunctional sheet-like extensible organic base material having the surface layer described in [12-1].
  • the cylindrical hardly stretchable polymer portion A having a ring shape when the surface shape or the sheet-like organic base material surface is the projection surface is partially and An anti-reflective multifunctional sheet-like extensible organic base material having an anti-reflection layer on at least one surface of an integrally formed sheet-like organic base material having extensibility.
  • the tubular hardly stretchable polymer portion A is partially formed in a state where it is exposed on at least one surface of the sheet-like organic base material or not exposed.
  • the multifunctional sheet-like extensible organic substrate according to any one of [13-2].
  • the projection shape when the surface shape of the cylindrical hardly extensible polymer part A or the surface of the sheet-like organic base material of the cylindrical hardly extensible polymer part A is a substantially circular or substantially polygonal shape
  • the multi-functional sheet-like extensible organic base material according to [14-1] which is amorphous, or has a shape representing a character, symbol or number, an annular shape, or a linear shape.
  • [14-6] The above [1-1] to [1-2], [2-1] to [2-2], [3-1] to [3-3] having a thickness of 0.01 mm to 1 cm. [4-1] to [4-3], [5-1] to [5-3], [6-1] to [6-3], [7-1] to [7-3], [ 8-1] to [8-4], [9-1] to [9-2], [10-1] to [10-2], [11-1] to [11-3], [12- 1] to [12-2], [13-1] to [13-2], and [14-1] to [14-5].
  • the shape of the cylindrical hardly extensible polymer portion hardly changes. While having this function, a desired design can be applied to the shape invariant portion, and other members can be held and fixed using appropriate fixing means. Moreover, since the area
  • the shape of the cylindrical difficult-to-extend polymer part hardly changes even when the base is stretched, so that it has a function as a stretchable member.
  • region which hits the cylindrical cavity part of a cylindrical difficulty extensible polymer part can be expand
  • FIG. 6 is a cross-sectional view taken along a plane perpendicular to the direction in which the annular zone extends, which is the projected shape of FIG. It is the schematic (sectional drawing) which shows an example of the manufacturing method of the sheet-like extensible organic base material of this invention.
  • FIG. 4 is a schematic view showing a pattern shape of a cylindrical hardly extensible polymer portion A on the surface of the sheet-like extensible organic base material obtained in Examples 1 to 4.
  • FIG. 6 is a schematic view showing a pattern shape of a cylindrical hardly extensible polymer portion A on the surface of the sheet-like extensible organic base material obtained in Examples 5 to 8.
  • FIG. 4 is a schematic view showing a pattern shape of a cylindrical hardly extensible polymer portion A on the surface of the sheet-like extensible organic base material obtained in Examples 1 to 4.
  • FIG. 6 is a schematic view showing a pattern shape of a cylindrical hardly extensible polymer portion A on the surface of the sheet-like extensible organic base material obtained in Examples 5 to 8.
  • FIG. 3 is a schematic view showing a pattern shape of a cylindrical hardly extensible polymer portion A on the surface of a sheet-like extensible organic base material obtained in Examples 9 to 12.
  • FIG. 6 is a schematic view showing a pattern shape of a cylindrical hardly extensible polymer portion A on the surface of a sheet-like extensible organic base material obtained in Examples 13 to 16.
  • FIG. 3 is a schematic view showing a pattern shape of a cylindrical hardly extensible polymer portion A on the surface of a sheet-like extensible organic base material obtained in Examples 17 to 20.
  • FIG. 2 is a schematic view showing a pattern shape of a cylindrical hardly extensible polymer portion A on the surface of a sheet-like extensible organic base material obtained in Examples 21 to 24.
  • FIG. 3 is a schematic view showing the shape of a cylindrical hardly extensible polymer portion A on the surface of a sheet-like extensible organic base material obtained in Examples 25 to 28.
  • FIG. 3 is a schematic view showing the shape of a cylindrical hardly extensible polymer portion A on the surface of a sheet-like extensible organic base material obtained in Examples 29-30.
  • 6 is a schematic view showing the shape of a cylindrical hardly extensible polymer portion A on the surface of a sheet-like extensible organic base material obtained in Example 31.
  • FIG. It is the schematic which shows the shape of the cylindrical difficulty extensible polymer part A in the surface of the sheet-like extensible organic base material obtained in Example 32.
  • It is a schematic sectional drawing which shows the other example (multifunctional sheet-like extensible organic base material) of the sheet-like extensible organic base material of this invention.
  • a cylindrical hardly extensible polymer portion A is partially and integrally formed in an easily extensible polymer base material.
  • the material surface projection shape is sometimes referred to as “ring surface shape”.
  • the tubular hardly extensible polymer portion A a design whose shape is desired not to change, and to fix and hold other members.
  • region which hits the cylindrical cavity part of the cylindrical difficulty extensible polymer part A is comprised with an easily extensible polymer material, it can expand
  • FIG. 1 is a schematic perspective view showing an example of a sheet-like extensible organic substrate of the present invention.
  • FIG. 2 is a schematic perspective view showing a II-II section of the sheet-like extensible organic base material of FIG. 1 and 2, a sheet-like extensible organic base material 1 is formed integrally with an easily extensible polymer base material 2 (easily extensible polymer base material portion) and the easily extensible polymer base material 2. It is comprised with the cylindrical difficulty extensible polymer part A3.
  • 3a is a region (part) corresponding to the cylindrical hollow portion of the cylindrical hardly extensible polymer portion A3, and is made of an easily extensible polymer material.
  • This easily extensible polymer material may be the same as or different from the material constituting the easily extensible polymer base material portion 2.
  • the cylindrical difficult-to-extend polymer part A3 only needs to be formed integrally in the easily-extensible polymer base material 2, for example, it may be formed only at one place, and is discontinuously scattered at a plurality of places. Or it may be scattered.
  • the surface shape or base material surface projection shape of the cylindrical hardly extensible polymer portion A3 is a ring-like shape and has an annular shape having a predetermined width.
  • the shape of the annular zone (outer peripheral shape and / or inner peripheral shape, particularly outer peripheral shape) is not particularly limited and can be appropriately selected according to the purpose.
  • a substantially circular shape perfect circle, ellipse, etc.
  • a substantially polygonal shape substantially Any of a triangle, a substantially rectangular shape, a substantially pentagonal shape, a substantially hexagonal shape, etc.
  • an amorphous shape indefinite shape
  • the inner angle may be 90 degrees or less, or may be an angle exceeding 90 degrees.
  • the surface shape of the cylindrical difficult-to-extend polymer part A3 or the projected surface shape of the base material is substantially circular or substantially rectangular. Is preferred.
  • the length (for example, the diameter) of the long axis (the longest part of the shape forming the outer periphery) of the cylindrical difficult-to-extend polymer part A3 is, for example, 0.05 mm to 10 cm.
  • this length is too small, the utility value of the cylindrical difficult-to-extend polymer part A becomes small, and when it is too large, it becomes difficult to manufacture.
  • the cylindrical shape If the length of the long axis in the surface direction of the hardly extensible polymer part A3 (the longest part of the shape forming the outer periphery) is less than 0.05 mm, the shape is obtained even when the entire sheet-like extensible organic substrate 1 is extended in one direction. The technical significance of having an invariant site is reduced. Moreover, when this length exceeds 10 cm, not only manufacture becomes difficult, but the said technical significance tends to become small.
  • the length of the long axis in the surface direction of the cylindrical hardly extensible polymer portion A3 (the longest portion of the shape forming the outer periphery) is preferably 0.1 mm or more, more preferably 0.5 mm or more, and even more preferably 1 mm or more, particularly Preferably it is 2 mm or more, and especially 5 mm or more is preferable.
  • the upper limit of the length of the long axis in the surface direction of the cylindrical hardly extensible polymer portion A3 (the longest portion of the shape forming the outer periphery) is preferably 8 cm, and particularly preferably 5 cm.
  • the width of the annular zone (that is, the distance between the outer peripheral surface and the inner peripheral surface of the cylindrical hardly extensible polymer portion A3; the thickness) which is the surface shape of the cylindrical hardly extensible polymer portion A3 or the projected surface shape of the base material is Although it can be appropriately selected depending on the purpose, it is usually 1 to 40% of the length of the long axis (longest part of the shape forming the outer periphery) in the surface direction of the cylindrical hardly extensible polymer part A3.
  • the lower limit of the width of the annular zone (thickness of the cylindrical hardly extensible polymer portion A3) is relative to the length of the long axis in the surface direction of the cylindrical hardly extensible polymer portion A3 (the longest part of the shape forming the outer periphery). Therefore, it is preferably 2%, more preferably 5%.
  • the upper limit of the width of the annular zone (thickness of the cylindrical hardly extensible polymer portion A3) is the length of the long axis (the longest part of the shape forming the outer periphery) in the surface direction of the cylindrical hardly extensible polymer portion A3. On the other hand, it is preferably 30%, more preferably 20%.
  • the width of the annular zone is more specifically 0.01 mm to 4 cm, for example, and the lower limit thereof is preferably 0.02 mm, more preferably It is 0.1 mm, more preferably 0.2 mm, particularly preferably 0.4 mm, especially 1 mm, and the upper limit is preferably 3 cm, more preferably 2 cm.
  • the sheet-like extensible organic base material 1 having such gradation (for example, gradation about the elongation rate described later) in the vicinity of the interface between the cylindrical hardly extensible polymer portion A3 and the easily extensible polymer base portion 2 is, for example, When the sheet-like extensible organic base material 1 is extended, the sheet-like extensible organic base material 1 has a characteristic that it is difficult to cut at the interface between the cylindrical hardly extensible polymer portion A3 and the easily extensible polymer base material portion 2.
  • the cylindrical hardly extensible polymer part A3 and the easily extensible polymer base part 2 may be exhibited over many parts or the whole.
  • the boundary between the cylindrical hardly extensible polymer part A3 and the easily extensible polymer base part 2 is the hardness of the non-gradient part of the easily extensible polymer base part 2
  • the hardness of the lowest hardness portion and the hardness of the non-gradient portion of the tubular hardly extensible polymer portion A3 tubular difficult stretchability
  • the gradation can be determined by a line connecting the average values of the hardness of the highest hardness portion.
  • the cylindrical hardly extensible polymer part A3 may be formed in any part of the easily extensible polymer base material 2.
  • the cylindrical difficult-to-extend polymer part A3 may be formed in a state of being exposed on at least one surface of the sheet-like extensible organic base material 1 or exposed on the surface of the sheet-like extensible organic base material 1 It may be formed in a state where it is not.
  • the surface shape of the cylindrical hardly extensible polymer part A3 and the substrate surface projection shape May be different in shape and size (such as when there is a bulge inside).
  • the sheet extensible organic substrate of the cylindrical hardly extensible polymer portion A3 is used.
  • the projected shape (shape viewed from the surface side of the sheet-like extensible organic base material 1) when the surface of 1 (at least one surface) is used as a projection surface is a ring-shaped shape.
  • the cylindrical hardly extensible polymer portion A3 is formed in a state of being exposed on at least one surface of the sheet-like extensible organic base material 1.
  • the cylindrical hardly extensible polymer portion A ⁇ b> 3 is formed at a place other than the end portion in the surface direction of the easily extensible polymer base material 2. It is preferable. That is, it is preferable that the cylindrical hardly extensible polymer portion A3 is formed in a state of being included in the easily extensible polymer base material 2 (excluding both surfaces).
  • the cylindrical hardly stretchable polymer portion 3 may be formed at the end portion.
  • the plurality of cylindrical hardly extensible polymer portions A3 may be randomly formed, and a regular pattern May be formed.
  • the distance between the adjacent cylindrical difficult-to-extend polymer parts A3 is, for example, 0.05 mm to 50 cm,
  • the upper limit of the distance is preferably 30 cm, more preferably 20 cm, still more preferably 15 cm, and particularly preferably 10 cm.
  • the lower limit of the distance is preferably 0.1 mm, more preferably 1 mm, still more preferably 3 mm, and particularly preferably 5 mm.
  • the distance between the centers (centers of gravity) of adjacent cylindrical difficult-to-extend polymer parts A3 is, for example, 5 mm to 80 cm.
  • the upper limit of the distance is preferably 50 cm, more preferably 30 cm, still more preferably 20 cm, and particularly preferably 12 cm.
  • the lower limit of the distance is preferably 10 mm, more preferably 15 mm, still more preferably 20 mm, and particularly preferably 25 mm.
  • the cylindrical difficult-to-extend polymer part A3 is formed in a regular pattern in advance, a large number of sheet-like extensible organic base materials 1 can be efficiently manufactured by cutting.
  • size of several cylindrical difficulty extensible polymer part A3 may be the same, or may differ.
  • the plurality of cylindrical hardly extensible polymer portions A3 have the same shape and size, a sheet-like extensible organic base material having the same shape and size can be produced with high production efficiency.
  • the region 3a corresponding to the cylindrical cavity of the cylindrical hardly extensible polymer portion A3 is made of an easily extensible polymer material.
  • the projection shape (substrate surface projection shape) when the surface shape or the sheet-like extensible organic substrate surface is the projection surface is (i) a substantially circular shape, 1 or 2 or more of the hardly extensible polymer part B which is substantially polygonal, amorphous, or a shape representing a character, a symbol or a number, (ii) an annular shape, or (iii) a linear shape may be formed.
  • the region corresponding to the cylindrical cavity is cylindrical.
  • the region corresponding to the cylindrical cavity of the hardly extensible polymer portion A it is made of an easily extensible polymer material.
  • the thickness of the sheet-like extensible organic substrate 1 of the present invention is, for example, 0.01 mm or more, preferably 0.03 mm or more, and more preferably 0.05 mm or more.
  • the upper limit of the thickness of the sheet-like extensible organic substrate 1 is, for example, 1 cm, preferably 5 mm, and more preferably 2 mm.
  • the cylindrical difficult-to-extend polymer part A3 may be continuously formed from one surface of the sheet-like extensible organic substrate 1, and from one surface of the sheet-like extensible organic substrate 1 to the other surface It may be formed continuously up to. Moreover, the said cylindrical difficulty extensible polymer part A3 may be embedded and formed in the inside of the sheet-like extensible organic base material 1.
  • the length (thickness) in the thickness direction of the cylindrical difficult-to-extend polymer part A3 is preferably at least 1/50 of the thickness of the sheet-like extensible organic base material 1 in any of the above cases. More preferably at least 1/20, even more preferably at least 1/10, particularly preferably at least 1/4.
  • the length (thickness) in the thickness direction of the cylindrical hardly extensible polymer portion A3 is further at least 1/3, especially at least 1/2 (especially at least 2/3) of the thickness of the sheet-like extensible organic base material 1. It is desirable that
  • FIG. 3 are cross-sectional views showing examples of the sheet-like extensible organic base material of the present invention (the surface shape of the cylindrical hardly extensible polymer portion or the cylindrical hardly extensible polymer portion). Sectional view when cut along a plane perpendicular to the direction in which the annular zone extends, which is a projected shape when the surface of the sheet-like extensible organic base material is a projection plane) (only the cross section on one side of the cylinder is shown) .
  • the cross-sectional shape (cross-section of the cylinder wall) of the cylindrical hardly extensible polymer portion 3 has various shapes such as a rectangle, a hoof, an arc, a semicircle, a circle, an ellipse, and a dumbbell. obtain.
  • the cross-sectional shape of the cylindrical hardly extensible polymer part A3 is the kind, composition, viscosity of the easily extensible polymer base material forming material and the cylindrical hardly extensible polymer part forming material; for forming the cylindrical hardly extensible polymer part.
  • Application method e.g., dropping, pouring, etc.
  • material layer for forming easily stretchable polymer base material application location, application amount; conditions for forming easily stretchable polymer base material and cylindrical hardly stretchable polymer part, etc.
  • the coating liquid for forming the cylindrically difficult-to-extend polymer part to the material layer for forming the easily-extensible polymer base material, and to form the cylindrically-extensible polymer part by curing, etc.
  • the coating solution diffuses in the lateral direction, and a dumbbell-shaped cylindrical hardly extensible polymer portion as shown in (7) of FIG. 3 is formed.
  • the elongation (breaking elongation) of the sheet-like extensible organic base material of the present invention in a tensile test is preferably 50% or more. More preferably, it is 70% or more, more preferably 120% or more, and the strength (breaking stress) is preferably 1.0 MPa or more, more preferably 2.0 MPa or more, and further preferably 3.0 MPa or more. The higher the strength, the better, but the upper limit is, for example, 100 MPa, and usually 50 MPa or less.
  • FIG. 7 shows an example of a sheet-like extensible organic base material sample used for a tensile test using a tensile tester.
  • the easily extensible polymer base material 2 is excellent in extensibility, but the cylindrical hardly extensible polymer portion A3 has low extensibility.
  • the sheet-like extensible organic substrate of the present invention is 1.5 times (150% of the original length) of the sheet-like extensible organic substrate in an elongation test (temperature 25 ° C.) using a tensile tester.
  • the elongation rate S 1 (%) of the cylindrical difficult-to-extend polymer part A3 is preferably 49% or less, more preferably It is 40% or less, more preferably 25% or less, and particularly preferably 10% or less.
  • the sheet-like extensible organic substrate of the present invention is 1.5 times (150% of the original length) of the sheet-like extensible organic substrate in an elongation test (temperature 25 ° C.) using a tensile tester.
  • a sheet-like organic base material that does not extend up to 1.5 times when it is extended up to 1.25 times, and for a sheet-like organic base material that does not extend up to 1.25 times
  • the elongation rate S 2 (%) of the stretchable polymer base material part 2 the ratio of the stretched length to the original length
  • the cylindrical stretchable polymer part It is preferable that the ratio [S 2 (%) / S 1 (%)] of the elongation rate S 1 (%) is larger than 1.
  • the cylindrical hardly-extensible polymer part A3 is difficult to extend. Since the shape hardly changes, it is possible to give a desired design to the cylindrical difficult-to-extend polymer part A3 or to fix and hold a desired member.
  • the ratio [S 2 (%) / S 1 (%)] is more preferably 2 or more, and further preferably 5 or more (particularly 10 or more).
  • the sheet-like extensible organic substrate of the present invention is 1.5 times (150% of the original length) of the sheet-like extensible organic substrate in an elongation test (temperature 25 ° C.) using a tensile tester.
  • the difference in the elongation S 2 easily stretched polymer matrix section 2 (%) and the elongation rate S 1 of the tubular flame stretch polymer unit A3 (%) [S 2 (%)-S 1 (%)] is preferably 20% or more, and more preferably 40% or more.
  • the extensibility of the sheet-like extensible organic base material is preferably isotropic.
  • the ratio [S 2 (1) / S 2 (2)] [where S 2 (1) ⁇ S 2 (2)] is preferably 1 to 1.3. ⁇ 1.2 is more preferable, and 1 to 1.1 is particularly preferable.
  • the sheet-like extensible organic base material of the present invention may further have stretchability.
  • the sheet-like extensible organic base material has stretchability, it can be suitably used in fields where stretchability is required such as band members.
  • stretchability can be imparted to the sheet-like stretchable organic substrate 1.
  • a hysteresis test at 50% elongation using a tensile tester Is preferably 10% or more, more preferably 30% or more, still more preferably 50% or more (particularly preferably 70% or more).
  • the easily extensible polymer base material 2 is usually soft, and the cylindrical hardly extensible polymer portion A3 is hard.
  • a hardness test using a rubber hardness tester (10-sheet laminate product of the sheet-like extensible organic substrate 1 having a test piece of 30 mm ⁇ 30 mm, after 10 seconds of pushing in the needle hardness of the ratio of the hardness H 1 and hardness of H 2 easily extensible polymer matrix 2 of the tubular flame stretch polymer unit A3 as determined by the temperature of 25 °C) (H 1 / H 2) is from 1 It is preferably large, more preferably 1.01 or more, further preferably 1.10 or more, and particularly preferably 1.20 or more.
  • a tensile elasticity modulus can also be used as a scale of the hardness of the easily extensible polymer base material 2 and the cylindrical hardly extensible polymer part A3.
  • a solid viscoelasticity measuring device (sample size: length 25 mm ⁇ width 3 mm, distance between chucks: 5 mm, mode: time dispersion, temperature: 27 ° C., frequency: 1 Hz, initial stage
  • the elastic modulus E ′ 2 (Pa) ratio (E ′ 1 / E ′ 2 ) is preferably greater than 1, more preferably 5 or more, still more preferably 10 or more, and particularly preferably 100 or more.
  • the load in the nanoindentation measurement can also be used as a measure of the hardness of the easily extensible polymer base material 2 and the cylindrical hardly extensible polymer portion A3.
  • the load P 1 of the cylindrical hardly extensible polymer portion A3 and the easy extensibility in nanoindentation measurement (indentation depth 4 ⁇ m, indentation speed 1.5 ⁇ m / second, temperature 25 ° C.).
  • the ratio of the polymer base material 2 to the load P 2 (P 1 / P 2 ) is preferably greater than 1, more preferably 1.01 or more, further preferably 1.10 or more, and particularly preferably 1.50 or more. is there.
  • the surface roughness Ra of the surface (at least one surface) of the easily extensible polymer base material portion 2 and the surface (at least one surface) of the formation site of the cylindrical hardly extensible polymer portion A3 is 100 nm or less, respectively. Preferably, 50 nm or less is more preferable, and 30 nm or less is more preferable. In particular, when precise members and parts are mounted on each surface, the smaller the surface roughness, the more accurately the members and parts can be installed, and the functions and performances of the members and parts are reliably exhibited. Can be made. Ra can be measured by an AFM (atomic force microscope).
  • the easily extensible polymer base material 2 can be composed of a polymer having extensibility (or further stretchability).
  • stretchable (or even stretchable) polymers include polyurethane polymers, polyurea polymers, polyurethane urea polymers, polyolefin polymers (particularly polydiene polymers), silicone polymers, polyester polymers, and polyethers.
  • These polymers can be used alone or in combination of two or more.
  • the proportion of these polymers in the polymer constituting the easily stretchable polymer matrix is preferably 30% by weight or more, more preferably 50% by weight or more, still more preferably 70% by weight or more, and particularly preferably 90% by weight or more. It is.
  • polyurethane polymers polyurethane polymers, polyurea polymers, polyurethane urea polymers, polyolefin polymers (particularly polydiene polymers), silicone polymers, polystyrene polymers (for example, styrene-isoprene-styrene block copolymers, styrene- Styrenic thermoplastic elastomers such as butadiene-styrene block copolymers are particularly preferred.
  • Commercially available products polymer alone, polymer aqueous dispersion, polymer organic solvent solution, etc.
  • the polymer having extensibility or further stretchability.
  • the easily stretchable polymer base material part 2 is formed by, for example, coating a liquid precursor of a polymer constituting the easily stretchable polymer base material on a support to form a material layer for easily stretchable polymer base material, After the forming material of the cylindrical hardly extensible polymer portion is arranged at a predetermined portion of the easily extensible polymer base material forming material layer, the liquid precursor in the easily extensible polymer base material forming material layer is changed to the target polymer. It can be formed by conversion.
  • the liquid precursor examples include a monomer that can be derived from the polymer (such as an energy ray-curable monomer), a partially polymerized product of the monomer, and a polymer that is precured or crosslinked that can be induced to the polymer by curing or crosslinking.
  • the conversion of the liquid precursor into a target polymer can be performed by, for example, polymerization (energy ray or heat polymerization), curing, cross-linking reaction, or the like.
  • the easily stretchable polymer base material part 2 is formed, for example, by applying a solution or dispersion containing a polymer constituting the easily stretchable polymer base material onto the support to form the easily stretchable polymer base material forming material layer.
  • the solvent in the easily-extensible polymer base material forming material layer is dried and removed It can also be formed.
  • the solvent used in the solution containing the polymer may be any solvent that can dissolve the polymer.
  • esters such as ethyl acetate; hydrocarbons such as aromatic hydrocarbons such as toluene; ketones such as acetone; methylene chloride and the like. Halocarbons; lactones; amides; lactams; water; and mixed solvents thereof.
  • dispersion containing the polymer include an aqueous dispersion (such as a reaction liquid after emulsion polymerization).
  • the easily extensible polymer base material part 2 forms an easily extensible polymer base material forming material layer from a single polymer constituting the easily extensible polymer base material on a support, for example, It can also be formed by performing a melting / cooling process (hot melt process) after disposing a forming material for the cylindrical difficult-to-extend polymer part at a predetermined portion of the material forming material layer.
  • the easily stretchable polymer base material forming material layer can be formed by subjecting the polymer alone to a general film molding method (extrusion molding, injection molding, compression molding, hot melt treatment, etc.).
  • the easily stretchable polymer base material forming material layer and the easily stretchable polymer base material are often composed of substantially the same material composition.
  • the melting / cooling treatment means cooling after melting.
  • the easily extensible polymer base material part 2 includes, for example, a polyurethane chain, a polyurea chain, a polyurethane urea chain, a polyolefin chain (particularly, a polydiene chain), a silicone chain, a polyester chain, a polyether chain, a polyamide chain, and a polystyrene series.
  • the curable polymer P and the mixture of the curable polymer P and the curable monomer M having the energy ray curable group A 2 are precursors of the polymer.
  • Examples of energy rays include ionizing radiation such as ⁇ rays, ⁇ rays, ⁇ rays, neutron rays, and electron rays, ultraviolet rays, and visible rays. Among these, ultraviolet rays and electron beams are preferable, and ultraviolet rays are particularly preferable.
  • Examples of the energy ray-curable groups A 1 and A 2 include a group containing a carbon-carbon unsaturated bond (a group containing a radical polymerizable group) such as a (meth) acryloyl group or a vinyl group, an epoxy group, And cationically polymerizable groups such as oxetanyl group.
  • a group containing a carbon-carbon unsaturated bond such as a (meth) acryloyl group or a vinyl group, an epoxy group
  • cationically polymerizable groups such as oxetanyl group.
  • the energy ray-curable groups A 1 in the curable polymer P having an energy ray-curable groups A 1 is a group containing a radically polymerizable group in the main chain or side chain, having an energy ray-curable groups A 2
  • the energy ray curable group A 2 in the curable monomer M is also preferably a group containing a radical polymerizable group, and the energy ray curable property in the curable polymer P having the energy ray curable group A 1 in the main chain or side chain.
  • the group A 1 is a cationic polymerizable group
  • the energy ray curable group A 2 in the curable monomer M having the energy ray curable group A 2 is also preferably a cationic polymerizable group.
  • the curable polymer P includes a compound having an energy ray curable group A 1 and a reactive functional group R 1 , and a reactive functional group R 2 having reactivity to the reactive functional group R 1 in the molecule. And at least one selected from the group consisting of a polyurethane chain, a polyurea chain, a polyurethane urea chain, a polyolefin chain (particularly a polydiene chain), a silicone chain, a polyester chain, a polyether chain, a polyamide chain, and a polyacryl chain. It can be obtained by reacting with a polymer having a polymer chain.
  • Examples of the combination (regardless of order) of the reactive functional group R 1 and the reactive functional group R 2 include a combination of a hydroxyl group and an isocyanate group, a combination of a hydroxyl group and an epoxy group, a carboxyl group, or an acid anhydride.
  • a combination with a group having a heavy bond is exemplified.
  • a polymer having a reactive functional group R 2 and a polyurethane chain is prepared by combining a polyisocyanate compound, a long-chain polyol compound, and a chain extender and other isocyanate-reactive compounds used as necessary. It can obtain by making it react.
  • polyisocyanate compound examples include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; alicyclic diisocyanates such as isophorone diisocyanate, dicyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, norbornene diisocyanate, and norbornane diisocyanate; naphthalene diisocyanate, Aromatic diisocyanates such as phenylene diisocyanate, tolylene diisocyanate, diphenyl diisocyanate, diphenylmethane diisocyanate, diphenyl ether diisocyanate, diphenylpropane diisocyanate; araliphatic diisocyanates such as xylylene diisocyanate and tetramethylene xylylene diisocyanate DOO; and dimer acid diisocyanate.
  • long-chain polyol compound examples include polyether polyol, polyester polyol, polycarbonate polyol, polyolefin polyol, and polyacryl polyol.
  • the number average molecular weight of the long-chain polyol is usually 500 or more, preferably 500 to 10,000, more preferably 550 to 4000.
  • Long chain polyols can be used alone or in combination of two or more.
  • polyether polyol examples include polyalkylene ether glycols such as polyethylene ether glycol, polypropylene ether glycol, polytetramethylene ether glycol (PTMG), and a plurality of alkylene oxides as monomer components such as an ethylene oxide-propylene oxide copolymer. (Alkylene oxide-other alkylene oxide) copolymer containing etc. are mentioned.
  • polyester polyol examples include a condensation polymer of a polyhydric alcohol and a polyvalent carboxylic acid; a ring-opening polymer of a cyclic ester (lactone); a reaction by three kinds of components: a polyhydric alcohol, a polyvalent carboxylic acid, and a cyclic ester. Things can be used.
  • examples of polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 2-methyl-1 , 3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, glycerin, trimethylolpropane, trimethylolethane, cyclohexanediol (Such as 1,4-cyclohexanediol), cyclohexanedimethanols (such as 1,4-cyclohexanedimethanol), bisphenols (such as bisphenol A), sugar alcohols (such as xylitol and sorbitol), etc.
  • examples of the polyvalent carboxylic acid include aliphatic dicarboxylic acids such as malonic acid, maleic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid; 1,4-cyclohexanedicarboxylic acid, etc.
  • aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid and trimellitic acid.
  • examples of the cyclic ester include propiolactone, ⁇ -methyl- ⁇ -valerolactone, and ⁇ -caprolactone.
  • examples of the reaction product of the three types of components those exemplified above can be used as the polyhydric alcohol, polycarboxylic acid, and cyclic ester.
  • polycarbonate polyol examples include a reaction product of a polyhydric alcohol and phosgene, chloroformate, dialkyl carbonate or diaryl carbonate; a ring-opening polymer of a cyclic carbonate (such as alkylene carbonate).
  • the polyhydric alcohol includes the polyhydric alcohols exemplified above (for example, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol). , Neopentyl glycol, 1,6-hexanediol, etc.) can be used.
  • examples of the alkylene carbonate include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, hexamethylene carbonate, and the like.
  • the polycarbonate polyol should just be a compound which has a carbonate bond in a molecule
  • polycarbonate polyols include polyhexamethylene carbonate diol, diol obtained by ring-opening addition polymerization of lactone to polyhexamethylene carbonate diol, and co-condensate of polyhexamethylene carbonate diol with polyester diol or polyether diol. Etc.
  • the polyolefin polyol is a polyol having an olefin as a component of the skeleton (or main chain) of the polymer or copolymer and having at least two hydroxyl groups in the molecule (particularly at the terminal).
  • the olefin may be an olefin having a carbon-carbon double bond at the terminal (for example, an ⁇ -olefin such as ethylene or propylene), or an olefin having a carbon-carbon double bond at a position other than the terminal.
  • isobutene and the like and diene (for example, butadiene, isoprene and the like) may be used.
  • polyolefin polyols include butadiene homopolymers, isoprene homopolymers, butadiene-styrene copolymers, butadiene-isoprene copolymers, butadiene-isoprene copolymers such as butadiene-modified polymers modified with hydroxyl groups at the ends. .
  • the polyacrylic polyol is a polyol having (meth) acrylate as a component of the polymer (or copolymer) skeleton (or main chain) and having at least two hydroxyl groups in the molecule (particularly at the terminal).
  • (meth) acrylate (meth) acrylic acid alkyl ester [for example, (meth) acrylic acid C 1-20 alkyl ester, etc.] is preferably used.
  • chain extender a chain extender usually used in the production of thermoplastic polyurethane can be used, and the kind thereof is not particularly limited, but a low molecular weight polyol, polyamine or the like can be used.
  • the molecular weight of the chain extender is usually less than 500, preferably 300 or less.
  • a chain extender can be used individually or in combination of 2 or more types.
  • chain extenders include, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, Polyols (especially diols) such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol; hexamethylenediamine, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 4,4'-methylenebis- Examples include polyamines (particularly diamines) such as 2-chloroaniline.
  • Examples of the polymer having a polyurethane chain include a polyisocyanate compound, a long-chain polyol compound, and, if necessary, a chain extender and another isocyanate-reactive compound, the number of moles of isocyanate groups of the polyisocyanate, and a long-chain polyol.
  • the ratio (NCO / isocyanate reactive group) to the number of moles of isocyanate reactive groups (hydroxyl group, amino group, etc.) of the chain extender and the like is 0.8 to 2.0, particularly 0.95 to 1.5. What was obtained by making it react in the range which becomes is preferable.
  • a catalyst such as a tertiary amine, an organometallic compound, or a tin compound may be used in the above reaction as necessary.
  • a polymer having a polyurethane chain is an isocyanate group
  • the isocyanate group as a reactive functional group R 2.
  • hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, etc. can be used as the compound having the energy ray curable group A 1 and the reactive functional group R 1 .
  • the end of the polymer having a polyurethane chain is a hydroxyl group, it can be used the hydroxyl groups as reactive functional groups R 2.
  • the compound having the energy ray-curable groups A 1 and reactive functional groups R 1, or the like can be used (meth) acryloyloxyethyl isocyanate.
  • Polymer having reactive functional group R 2 and having polyurea chain polymer having reactive functional group R 2 and having polyurethane urea chain, polyolefin having reactive functional group R 2 and polyolefin chain (particularly polydiene chain) ), A reactive functional group R 2 and a silicone chain, a reactive functional group R 2 and a polyester chain, a reactive functional group R 2 and a polyether chain , A polymer having a reactive functional group R 2 and a polyamide chain, and a polymer having a reactive functional group R 2 and a polyacryl chain can also be obtained by known or conventional methods.
  • the polymer and having a specific polymer chains having these reactive functional groups R 2 depending on the type of reactive functional group R 2 having the said polymer, said energy ray-curable groups A 1 and reactive by reacting a compound having a functional group R 1, it may produce a curable polymer P having an energy ray-curable groups a 1 in the main chain or side chain.
  • the curable monomers M having said energy ray-curable groups A 2 (meth) acryloyl group, carbon atoms such as a vinyl group - a compound having a group containing a carbon-carbon unsaturated bond (radical polymerizable group);
  • examples thereof include compounds having a cationically polymerizable group such as an epoxy group and an oxetanyl group.
  • a compound containing a radical polymerizable group is preferable.
  • curable monomers M having an energy ray-curable groups A 2 may be used in combination of at least one kind alone, or two or.
  • a compound energy ray-curable groups and A 2 is a radical polymerizable group, e.g., methyl (meth) acrylate, (meth) acrylate, ( Meth) propyl acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, (meth) Pentyl acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, (meth ) Nonyl acrylate, isononon
  • Oxygen-containing heterocycle-containing monomers amino group-containing monomers such as aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, and t-butylaminoethyl (meth) acrylate; cyano such as acrylonitrile and methacrylonitrile Group-containing monomers; Imido group-containing monomers such as cyclohexylmaleimide and isopropylmaleimide; Isocyanate group-containing monomers such as 2-methacryloyloxyethyl isocyanate; Styrene such as styrene, ⁇ -methylstyrene and vinyltoluene Olefin monomers such as ethylene, propylene, isoprene, butadiene, and isobutylene; vinyl ester monomers such as vinyl acetate and vinyl propionate; vinyl ether monomers such as vinyl alkyl ether; vinyl chloride; vinylidene chlor
  • a compound energy ray-curable groups and A 2 is a radical polymerizable group
  • a compound energy ray-curable groups and A 2 is a cationic polymerizable group, an epoxy group, a known compound having a cationically polymerizable group such as oxetanyl group Can be used.
  • curable monomers M having said energy ray-curable groups A 2 curable monomer having a radical polymerizable group is preferred.
  • curable monomer having a radical polymerizable group is preferred.
  • the same kind of monomer as the polymer constituting the cylindrical hardly extensible polymer portion as the curable monomer M is used. It is also preferable to use a monomer (particularly the same monomer).
  • the proportion of (meth) acrylic acid C 1-20 alkyl ester in the entire curable monomer is, for example, 40% by weight or more (40 ⁇ 100% by weight), preferably 50% by weight or more (50 to 100% by weight), and more preferably 60% by weight or more (60 to 100% by weight).
  • a carboxyl group such as (meth) acrylic acid or an acid anhydride group-containing monomer, or a hydroxyl group such as 2-hydroxyethyl (meth) acrylate Containing monomers may be used.
  • the amount of the carboxyl group- or acid anhydride group-containing monomer and the hydroxyl group-containing monomer is, for example, in the range of 0 to 50% by weight (about 0.1 to 50% by weight), respectively, with respect to the entire curable monomer. From about 1 to 45% by weight may be used.
  • the easily extensible polymer base material 2 can be formed by irradiating an energy ray to the curable polymer P or a mixture of the curable polymer P and the curable monomer M and curing it. At this time, a photopolymerization initiator is usually used.
  • examples of the photopolymerization initiator include a benzoin ether photopolymerization initiator, an acetophenone photopolymerization initiator, and an ⁇ -ketol photopolymerization initiator.
  • Agent aromatic sulfonyl chloride photopolymerization initiator, photoactive oxime photopolymerization initiator, benzoin photopolymerization initiator, benzyl photopolymerization initiator, benzophenone photopolymerization initiator, ketal photopolymerization initiator, thioxanthone A photopolymerization initiator or the like is used.
  • benzoin ether photopolymerization initiator examples include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethane-1-one, Anisole methyl ether etc. are mentioned.
  • acetophenone photopolymerization initiator examples include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 4-phenoxydichloroacetophenone, and 4- (t-butyl). ) Dichloroacetophenone and the like.
  • Examples of the ⁇ -ketol photopolymerization initiator include 2-methyl-2-hydroxypropiophenone and 1- [4- (2-hydroxyethyl) phenyl] -2-methylpropan-1-one. It is done.
  • Examples of the aromatic sulfonyl chloride photopolymerization initiator include 2-naphthalenesulfonyl chloride.
  • Examples of the photoactive oxime photopolymerization initiator include 1-phenyl-1,1-propanedione-2- (o-ethoxycarbonyl) -oxime.
  • Examples of the benzoin photopolymerization initiator include benzoin.
  • Examples of the benzyl photopolymerization initiator include benzyl.
  • benzophenone photopolymerization initiator examples include benzophenone, benzoylbenzoic acid, 3,3′-dimethyl-4-methoxybenzophenone, polyvinyl benzophenone, ⁇ -hydroxycyclohexyl phenyl ketone, and the like.
  • ketal photopolymerization initiator examples include benzyl dimethyl ketal.
  • thioxanthone photopolymerization initiator examples include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, dodecylthioxanthone, and the like.
  • the energy beam curable groups A 1 and A 2 are cationic polymerizable groups
  • a known or conventional cationic curing catalyst can be used as a photopolymerization initiator.
  • the amount of the photopolymerization initiator used is not particularly limited, but for example 0.01 to 3 parts by weight with respect to 100 parts by weight of the total amount of the curable compound, and the upper limit is preferably 1 part by weight, more preferably The lower limit is preferably 0.02 parts by weight, more preferably 0.05 parts by weight.
  • polyurethane chain in the polymer having stretchability (or further stretchability) constituting the easily stretchable polymer matrix 2, polyurethane chain, polyurea chain, polyurethaneurea chain, polyolefin chain (particularly polydiene chain), silicone chain, polyester
  • the proportion of the at least one polymer chain portion in the whole polymer is 20% by weight or more (for example, 20 to 100% by weight) is preferable, more preferably 25% by weight or more (for example, 25 to 90% by weight), and still more preferably about 30% by weight or more (for example, 30 to 75% by weight). If this ratio is too small, the extensibility tends to decrease.
  • the polymer having stretchability (or further stretchability) constituting the stretchable polymer base material 2 is an acrylic polymer having a low glass transition temperature (Tg) (Tg is, for example, less than 5 ° C., preferably 0 ° C. or less. In the case of an acrylic polymer having a temperature of ⁇ 5 ° C. or lower), the ratio of the polyacryl chain in the whole polymer may be 100% by weight.
  • Tg glass transition temperature
  • a crosslinking agent for example, an isocyanate crosslinking agent, an epoxy crosslinking agent, a melamine crosslinking agent, a peroxide crosslinking agent, a urea crosslinking agent, Metal alkoxide crosslinking agent, metal chelate crosslinking agent, metal salt crosslinking agent, carbodiimide crosslinking agent, oxazoline crosslinking agent, aziridine crosslinking agent, amine crosslinking agent, etc.), crosslinking accelerator, silane coupling agent, adhesive Giving resins (rosin derivatives, polyterpene resins, petroleum resins, oil-soluble phenols, etc.), anti-aging agents, fillers, colorants (pigments and dyes, etc.), UV absorbers, antioxidants, plasticizers, softeners, surface activity Additives such as an agent and an antistatic agent may be included as long as the characteristics of the present invention are not impaired.
  • a crosslinking agent for example, an isocyanate crosslinking agent, an epoxy crosslinking agent
  • the material constituting the cylindrical hardly extensible polymer part A3 is usually a polymer material containing at least a polymer, and this polymer material may contain a filler (inorganic filler, organic filler). .
  • the polymer in the polymer material may be a single type or a mixture of two or more types.
  • Examples of the cylindrical difficult-to-extend polymer part A include (i) a monomer having a Tg of a homopolymer of 5 ° C. or higher (more preferably 15 ° C. or higher, more preferably 50 ° C. or higher) [particularly, (meth) acrylic Monomer] is a polymer containing 50% by weight or more (more preferably 60% by weight or more, and still more preferably 80% by weight or more) with respect to all the structural units of the polymer [for example, Tg is 5 ° C. or more, Preferably derived from a polymer material containing a polymer (especially an acrylic polymer) at 15 ° C.
  • a polyfunctional monomer having two or more curable groups (radical polymerizable groups, cationic polymerizable groups) in the molecule A polymer containing 50% by weight or more (more preferably 60% by weight or more, more preferably 80% by weight or more) based on the total structural units of the polymer.
  • the structural unit derived from a polyfunctional monomer having 2 or more radical polymerizable groups in the molecule is 50% by weight or more (more preferably Polymer material containing], (iii) filler-containing polymer material, and (iv) tensile elastic modulus of 0.1 MPa or more (more preferably 0.5 MPa or more), More preferably, it can be composed of a polymer material of 1 MPa or more, particularly preferably 5 MPa or more.
  • the cylindrical hard-extensible polymer portion A of a polymer containing 50% by weight or more of a structural unit derived from a monomer having a Tg of 5 ° C. or higher with respect to the total structural unit of the homopolymer is formed.
  • the proportion of the polymer material in the entire polymer material is, for example, 5% by weight or more, preferably 10% by weight or more, more preferably 15% by weight or more, and may be 50% by weight or more (for example, 90% by weight or more).
  • the proportion of the polymer material constituting the total is, for example, 5% by weight or more, preferably 10% by weight or more, more preferably 15% by weight or more, and may be 50% by weight or more (for example, 90% by weight or more).
  • examples of the monomer having a Tg of homopolymer of 5 ° C. or higher include alicyclic rings such as isobornyl acrylate (homopolymer Tg: 97 ° C.) and cyclohexyl acrylate (homopolymer Tg: 15 ° C.).
  • (Meth) acrylic acid ester having a formula group (meth) acrylic acid tertiary alkyl ester such as t-butyl acrylate (homopolymer Tg: 41 ° C.); methyl methacrylate (homopolymer Tg: 105 ° C.); Methacrylic acid C 1-4 alkyl esters such as ethyl methacrylate (Tg of homopolymer: 65 ° C.), butyl methacrylate (Tg of homopolymer: 20 ° C.), isobutyl methacrylate (Tg of homopolymer: 67 ° C.); styrene Styrenic monomers such as (Tg of homopolymer: 100 ° C.); acrylonite Ril (homopolymer Tg: 100 ° C.) and the like.
  • acrylic acid tertiary alkyl ester such as t-butyl acrylate (homopolymer Tg: 41 °
  • examples of the polyfunctional monomer include 1,6-hexanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly ) Propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate , Trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, trimethylolpropane EO-added tri (meth) acrylate, glycerin PO-added tri (meth) acrylate,
  • examples of the filler include inorganic oxides such as silica, alumina, titanium oxide, zirconium oxide, iron oxide, copper oxide, zinc oxide and tin oxide; nitrides such as boron nitride and aluminum nitride; Carbonates such as calcium and magnesium carbonate; clay minerals such as mica, smectite, kaolinite, montmorillonite, vermiculite; metals such as gold, silver, copper, iron, nickel, zinc, aluminum, tin (including metal alloys); glass And inorganic fillers; organic fillers and the like.
  • the filler may have a core / shell structure that is surface-treated and coated with an appropriate component.
  • the filler may have a hollow structure such as a glass balloon, a ceramic balloon, a fly ash balloon, or hollow silica.
  • a filler can be used individually by 1 type or in combination of 2 or more types. By using the filler, not only can the stretchability and hardness be imparted to the tubular hardly stretchable polymer part A3, but various functions such as conductivity and thermal conductivity can be imparted depending on the type of filler.
  • the shape of the filler is not particularly limited, and may be any of a bulk shape, a spherical shape, a needle shape, a plate shape, and the like.
  • the average particle diameter of the filler (in the case of needles, the average diameter of the major axis) is, for example, 0.001 to 100 ⁇ m.
  • the upper limit of the average particle diameter of the filler (in the case of needles, the average diameter of the major axis) is preferably 50 ⁇ m, more preferably 20 ⁇ m, and the lower limit is preferably 0.005 ⁇ m, more preferably 0.008 ⁇ m.
  • the “polymer” in the filler-containing polymer material is not particularly limited, and the polymer exemplified as the polymer constituting the easily stretchable polymer base material, the polymer exemplified as the polymer constituting the cylindrical hardly stretchable polymer portion A (i )
  • the polymer may be an energy ray curable polymer.
  • the polymer having a tensile modulus of elasticity of 0.1 MPa or more is not particularly limited as long as the polymer has a tensile modulus of elasticity of 0.1 MPa or more (a mixture of one or two or more polymers).
  • the tensile modulus of the polymer mixture may be 0.1 MPa or more.
  • a polymer having a tensile modulus of elasticity of 0.1 MPa or more for example, a polyurethane-based polymer having a Tg of 5 ° C. or more (more preferably 20 ° C. or more); a styrene-butadiene-styrene block copolymer (SBS) Polystyrene polymers such as hydrogenated product (SEBS) and hydrogenated product (SEPS) of styrene-isoprene-styrene block copolymer (SIS); and acrylic polymers such as polymethyl methacrylate.
  • SEBS hydrogenated product
  • SEPS hydrogenated product
  • SIS styrene-isoprene-styrene block copolymer
  • acrylic polymers such as polymethyl methacrylate.
  • a polymer material having a tensile modulus of elasticity of 0.1 MPa or more it is preferable to contain these polymers, for example, 50% by weight or more,
  • the cylindrical difficult-to-extend polymer part A is a polymer part formed by converting a polymer material precursor constituting the cylindrical difficult-to-extend polymer part A to the polymer material, a solution or dispersion containing the polymer material Any of a polymer part formed by drying and removing the solvent therein, a polymer part formed by melting and cooling the polymer material, and the like may be used.
  • a polymer material comprising a cylindrical hard-extensible polymer part A, the polymer comprising (i) 50% by weight or more of a structural unit derived from a monomer having a Tg of a homopolymer of 5 ° C. or higher based on the total structural unit of the polymer
  • a monomer component containing 50% by weight or more of the monomer having a Tg of 5 ° C. or higher of the homopolymer at a predetermined portion of the easily stretchable polymer base material forming material layer.
  • It can be formed by irradiating with energy rays and curing (polymerization).
  • a monomer exemplified as the curable monomer M having the energy ray curable group A 2 can be appropriately selected and used.
  • the cylindrical difficult-to-extend polymer part A contains (ii) a polymer containing 50% by weight or more of a structural unit derived from a polyfunctional monomer having two or more curable groups in the molecule based on the total structural unit of the polymer.
  • a polymer material for example, a monomer component containing 50% by weight or more of the polyfunctional monomer in the whole monomer is disposed at a predetermined portion of the easily stretchable polymer base material forming material layer, and then irradiated with energy rays. It can be formed by curing (polymerization).
  • examples of monomer other than the polyfunctional monomer examples of monomer other than the polyfunctional monomer, a monofunctional monomer of the monomers exemplified as the curable monomer M having said energy ray-curable groups A 2 appropriately selected and can be used.
  • a photopolymerization initiator is usually used to cure the curable group. It does not specifically limit as a photoinitiator, The photoinitiator similar to the case where the said easily extensible polymer base material 2 is formed can be used.
  • the amount of the photopolymerization initiator used is not particularly limited, but for example 0.01 to 3 parts by weight with respect to 100 parts by weight of the total amount of the curable compound, and the upper limit is preferably 1 part by weight, more preferably The lower limit is preferably 0.02 parts by weight, more preferably 0.05 parts by weight.
  • the cylindrical hardly extensible polymer part A is composed of the (iii) filler-containing polymer, a dispersion containing a filler (an aqueous dispersion, a predetermined portion of the easily extensible polymer base material forming material layer) After disposing the organic solvent dispersion or the like, the cylindrical hardly extensible polymer portion A can be formed by drying and removing the solvent in the dispersion.
  • the cylindrical hardly extensible polymer portion A is composed of the filler and the same polymer as the polymer constituting the easily extensible polymer base material 2.
  • the material layer for forming an easily stretchable polymer base material is formed from an organic solvent solution of a polymer constituting the layer, it is preferable to use an organic solvent dispersion of a filler.
  • the forming material layer is formed with an aqueous dispersion of the polymer constituting the layer, it is preferable to use an aqueous dispersion of filler.
  • the said cylindrical difficulty extensible polymer part A can be formed by superposing
  • the cylindrical difficult-to-extend polymer part A can be formed by crosslinking the pre-crosslinking polymer.
  • the easily stretchable polymer matrix forming material layer is converted into an easily stretchable polymer matrix. Thereby, the cylindrical difficult-to-extend polymer part A can be formed simultaneously.
  • the cylindrical hardly extensible polymer part A is composed of the filler and the same polymer as the polymer constituting the easily extensible polymer base material.
  • the usage-amount of a filler can be suitably adjusted with the magnitude
  • the content of the filler in the cylindrical difficult-to-extend polymer part A is, for example, about 0.1 to 99% by weight, and the upper limit thereof is preferably 95% by weight, more preferably 90% by weight, particularly preferably.
  • the lower limit is preferably 1% by weight, more preferably 5% by weight, and particularly preferably 10% by weight.
  • the cylindrical difficult-to-extend polymer part A is composed of (iv) a polymer material having a tensile modulus of elasticity of 0.1 MPa or more, a monomer (such as an energy ray-curable monomer) that can be derived from the polymer or a partial polymerization thereof
  • a monomer such as an energy ray-curable monomer
  • the cylindrical difficult-to-extend polymer part A can be formed by polymerizing a product, or curing or crosslinking a polymer before curing or crosslinking that can be induced by curing or crosslinking.
  • a crosslinking agent for example, an isocyanate-based crosslinking agent, an epoxy-based crosslinking agent, a melamine-based crosslinking agent, a peroxide-based crosslinking agent, a urea-based crosslinking agent, Metal alkoxide crosslinking agent, metal chelate crosslinking agent, metal salt crosslinking agent, carbodiimide crosslinking agent, oxazoline crosslinking agent, aziridine crosslinking agent, amine crosslinking agent, etc.), crosslinking accelerator, silane coupling agent, adhesive Giving resins (rosin derivatives, polyterpene resins, petroleum resins, oil-soluble phenols, etc.), anti-aging agents, fillers, colorants (pigments and dyes, etc.), UV absorbers, antioxidants, plasticizers, softeners, surface activity Additives such as an agent and an antistatic agent may be included as long as the characteristics of the present invention are not impaired.
  • a crosslinking agent for example, an isocyanate-
  • an easily extensible polymer base material is used as the polymer.
  • a polymer having the same type of polymer chain as the polymer constituting the polymer or a polymer chain (main chain or side chain) of the polymer constituting the easily extensible polymer matrix in the main chain or side chain is preferable.
  • a combination of polyurethane polymers, a combination of polyurea polymers, polyurethane urea Combinations of polymers, combinations of polyolefin polymers, combinations of silicone polymers, combinations of polyester polymers, combinations of polyether polymers, combinations of polyamide polymers, combinations of polystyrene polymers, acrylic A combination of the base polymers may be mentioned.
  • a combination of a polystyrene polymer and an acrylic polymer is also preferable.
  • a combination of polymers having a polyurethane chain a combination of polymers having a polyurea chain, a combination of polymers having a polyurethane urea chain, a combination of polymers having a polyolefin chain, and a polymer having a silicone chain Combination of polymers having a polyester chain, combination of polymers having a polyether chain, combination of polymers having a polyamide chain, combination of polymers having a polystyrene-based polymer chain, between polymers having a polyacryl chain Combinations are mentioned.
  • a combination of polyurethane polymers, a combination of polymers having a polyurethane chain, a polystyrene series A combination of polymers, a combination of polymers having a polystyrene polymer chain, a combination of acrylic polymers, a combination of polymers having a polyacryl chain, and a combination of a polystyrene polymer and an acrylic polymer are particularly preferable.
  • the sheet-like extensible organic base material of this invention can be manufactured by passing through the following process A, process B, and process C, for example.
  • Step A A polymer (a) liquid precursor constituting the easily stretchable polymer matrix, a solution or dispersion containing the polymer (a), or the polymer (a) alone, on the support.
  • Step B Forming a Base Material Forming Material Layer
  • Step B Placing a Cylindrical Difficulty Polymer Part Forming Material at a Predetermined Part of the Easy-Extensible Polymer Base Material Forming Material Layer
  • Step C Cylindrical Difficulty Stretching
  • the easily stretchable polymer base material forming material layer in which the polymer material forming material is disposed at a predetermined site is subjected to at least one treatment selected from a reaction, a solvent dry removal treatment, and a melting / cooling treatment.
  • step A the polymer (a) liquid precursor constituting the easily stretchable polymer matrix, the solution or dispersion containing the polymer (a), or the polymer (a) alone is easily formed on the support.
  • An extensible polymer base material forming material layer is formed.
  • the support is not particularly limited, and for example, a separator can be used.
  • the separator is not particularly limited, and a conventional release paper, a separator having a release treatment layer, a low adhesive substrate made of a fluoropolymer, a low adhesive substrate made of a nonpolar polymer, and the like can be used.
  • the separator having the release treatment layer include a plastic film or paper surface-treated with a release treatment agent such as silicone-based, long-chain alkyl-based, fluorine-based, or molybdenum sulfide.
  • fluorine-based polymer in the low-adhesive substrate made of the above-described fluoropolymer examples include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, chloro Examples include fluoroethylene-vinylidene fluoride copolymer.
  • nonpolar polymer olefin resin (for example, polyethylene, a polypropylene, etc.) etc. are mentioned, for example.
  • the separator can be manufactured by a known or conventional method. Further, the thickness of the separator is not particularly limited.
  • liquid precursor of the polymer (a) constituting the easily stretchable polymer matrix examples include monomers that can be derived into the polymer (a) (energy ray curable monomers, etc.), partial polymers of the monomers, polymers by curing or crosslinking ( Examples thereof include a polymer that can be derived into a), a polymer before curing or crosslinking. A mixture thereof may be used.
  • the solution or dispersion containing the polymer (a) include an aqueous solution or an organic solvent solution of the polymer (a), an aqueous dispersion of the polymer (a), and an organic solvent dispersion. As the solvent, those exemplified in the above section [Easily stretchable polymer matrix] can be used.
  • the viscosity of the coating liquid is, for example, 0.1 to 50 Pa ⁇ s at a coating temperature (for example, a predetermined temperature within a range of 10 to 40 ° C., particularly 25 ° C.) from the viewpoint of workability and the like.
  • the upper limit is preferably 30 Pa ⁇ s, more preferably 20 Pa ⁇ s, and the lower limit is preferably 0.5 Pa ⁇ s, more preferably 1 Pa ⁇ s. If the viscosity is too low, the shape tends to be difficult to maintain. Conversely, if the viscosity is too high, the coating workability tends to decrease.
  • the coating method is not particularly limited, and for example, a coater such as a Meyer bar, a blade coater, an air knife coater, a roll coater or a die coater, an extruder or a printing machine can be used.
  • a coater such as a Meyer bar, a blade coater, an air knife coater, a roll coater or a die coater, an extruder or a printing machine can be used.
  • the easily stretchable polymer base material forming material layer is formed of the polymer (a) alone, for example, a predetermined amount of the polymer (a) is placed on the support, and a support (separator) is further provided thereon. Etc.), and this is pressed under heating (at a temperature equal to or higher than the melting temperature of the polymer) to form an easily stretchable polymer base material forming material layer.
  • the easily extensible polymer base material forming material layer can be formed on the support by extruding the polymer (a).
  • a layer that becomes a material layer for forming an easily stretchable polymer base material is separately prepared by an appropriate molding method, and the layer is transferred onto a support to thereby easily stretch the polymer base material.
  • a material forming material layer can also be formed.
  • formation of the material layer for easily stretchable polymer base material formation can also be performed using a suitable type
  • the viscosity of the forming material may be lower than the above range.
  • the thickness of the easily stretchable polymer base material forming material layer is, for example, 0.01 mm to 1 cm.
  • the upper limit is preferably 5 mm, more preferably 2 mm, and the lower limit is preferably 0.03 mm. Preferably it is 0.05 mm.
  • Step B a cylindrical difficult-to-extend polymer part forming material is disposed on a predetermined portion of the easily-extensible polymer base material forming material layer.
  • the material for forming the cylindrical difficult-to-extend polymer part may be any of solid, liquid, gas, solution, dispersion and the like.
  • a precursor for example, an energy beam curable composition
  • the material (polymer material) (b) itself constituting the conductive polymer part A, or a solution or dispersion containing the material (polymer material) (b) constituting the cylindrical difficult-to-extend polymer part A can be used.
  • the cylindrical difficult-to-extend polymer part A is a structural unit derived from a monomer whose Tg of the homopolymer is 5 ° C. or higher.
  • a monomer component containing 50% by weight or more of the monomer having a Tg of 5 ° C. or more of the homopolymer, or its A curable composition (such as an energy beam curable composition) containing a partial polymer can be used.
  • This curable composition usually contains a polymerization initiator.
  • the cylindrical difficult-to-extend polymer part A contains (ii) a polymer containing 50% by weight or more of a structural unit derived from a polyfunctional monomer having two or more curable groups in the molecule based on the total structural unit of the polymer.
  • the curable composition energy beam curable composition etc.
  • This curable composition usually contains a polymerization initiator.
  • cylindrical difficult-to-extend polymer part A is composed of the above-mentioned (iii) filler-containing polymer material
  • a dispersion liquid an aqueous dispersion or an organic solvent
  • a filler is used as the cylindrical difficult-to-extend polymer part forming material.
  • a curable composition containing the filler a monomer (energy ray curable monomer, etc.) or a partial polymer thereof that can be derived into a polymer that constitutes the cylindrical hardly extensible polymer part, a filler, and a cylinder
  • a pre-curing or cross-linking polymer that can be induced by curing or cross-linking and a cross-linking agent or the like, or a filler alone (powder) can be used.
  • the cylindrical hardly extensible polymer part A is composed of the polymer material having (iv) a tensile elastic modulus of 0.1 MPa or more, the tensile elastic modulus of 0.
  • a curable composition (such as an energy beam curable composition) containing a monomer (such as an energy beam curable monomer) that can be derived into a polymer of 1 MPa or more or a partial polymer thereof can be used.
  • the method (means) for arranging the cylindrically difficult-to-extend polymer part forming material at a predetermined site of the easily-extensible polymer base material-forming material layer For example, (1) cylindrically difficult-to-extend The surface shape of the cylindrical hardly extensible polymer portion A or the projected surface shape of the base material becomes a desired shape from above, at a predetermined position of the easily stretchable polymer base material forming material layer. Coating, dripping, placing, driving or printing, and (2) cylindrical hard-to-extend polymer part forming material in a liquid form at a predetermined position of the easily-extensible polymer base material forming material layer.
  • a material for forming the cylindrical difficult-to-extend polymer part on a support different from Coating, dripping, mounting or printing is performed so that the surface shape of the cylindrical hardly extensible polymer portion A or the projected shape of the substrate surface is a desired shape, and this is used as the material layer for forming the easily extensible polymer base material. Examples include a method of transferring up.
  • the viscosity of the liquid is the temperature at the time of coating, dripping, etc. from the viewpoint of workability and the like (for example, within a range of 10 to 40 ° C.
  • the upper limit is preferably 30000 mPa ⁇ s, more preferably 20000 mPa ⁇ s
  • the lower limit is preferably 20 mPa ⁇ s, more preferably 30 mPa ⁇ s. If this viscosity is too low, it will be difficult to obtain a cylindrical difficult-to-extend polymer part A having a desired shape, and conversely if too high, the coating workability will tend to be reduced.
  • Coating, dripping, placing, driving, printing, pouring, and transfer are not particularly limited, and can be performed by a known or common method.
  • an appropriate dropping device can be used for dropping, and a syringe or the like can be used for injection.
  • Examples of printing include screen printing.
  • the cylindrical difficult-to-extend polymer part forming material By selecting and adjusting the kind, amount of use, viscosity, etc. of the cylindrical difficult-to-extend polymer part forming material disposed in a predetermined portion of the easily-extensible polymer base material-forming material layer, the cylindrical difficult-to-extend polymer part The size of A (the size and height in the surface direction) can be controlled. In the case of forming a plurality of cylindrical difficult-to-extend polymer parts A, a cylindrical hard-to-extend polymer part forming material is applied at an appropriate interval. In addition, the shape of the cylindrical difficult-to-extend polymer part A can be controlled by using a means for regulating dropping and injection of the cylindrical hard-to-extend polymer part forming material.
  • the drop method is often used when the size of the cylindrical difficult-to-extend polymer part A is relatively large, and the injection method is often used when the size of the cylindrical hardly-extensible polymer part A is relatively small.
  • the tip of the dropping device does not come into contact with the material for forming an easily stretchable polymer base material, so that it does not get dirty.
  • the cylindrical hardly extensible polymer part forming material is less likely to diffuse into the easily extensible polymer base material forming material layer than the dropping method.
  • the energy ray curable composition which is a precursor of the material (b) which comprises the cylindrical difficulty extensible polymer part A as a material for cylindrical difficulty extensible polymer part formation
  • this energy ray hardening When disposing an adhesive composition (coating liquid) on a predetermined part of an easily stretchable polymer base material forming material layer, a peripheral portion of the energy ray curable composition (coating liquid) (easy stretchable polymer base material forming material layer) ) Is preferably contained in the energy ray-curable composition.
  • the coating liquid diffuses to the peripheral part (bleeds) with the passage of time at the place where the coating liquid is initially disposed, and cures in that state to have a desired shape and size.
  • the cylindrical difficult-to-extend polymer part A may not be obtained, or the outline of the cylindrical difficult-to-extend polymer part A may not be clear.
  • the energy beam curable composition (coating liquid) if a polymer is contained in the energy beam curable composition (coating liquid), the monomer and the like contained in the coating liquid are in the periphery (material layer for forming an easily extensible polymer base material). ) Can be suppressed, and even when a large number of cylindrically difficult-to-extend polymer parts A are formed, it is possible to form a cylindrically-extensible polymer part A having a uniform shape and size with a clear outline. it can.
  • This method provides a great diffusion suppressing effect particularly when the energy beam curable composition (coating liquid) is disposed by dropping at a plurality of predetermined sites of the easily stretchable polymer base material forming material layer.
  • the weight average molecular weight of the polymer blended in the energy beam curable composition is not particularly limited, but is, for example, 1000 or more, preferably 2000 or more, and more preferably 3000 or more. If the weight average molecular weight of the polymer is too low, the diffusion suppressing effect tends to be small. On the other hand, if the weight average molecular weight of the polymer is too large, the viscosity of the composition (coating solution) becomes too high, and the coating workability may be reduced. From this viewpoint, the upper limit of the weight average molecular weight of the polymer is, for example, 5000000, preferably 1000000, and more preferably 100,000.
  • the polymer content in the energy ray-curable composition (coating liquid) is, for example, 5% by weight or more, preferably 10% by weight or more, and more preferably 20% by weight or more.
  • the polymer content is less than 5% by weight, the diffusion suppressing effect is small.
  • the viscosity of an energy-beam curable composition (coating liquid) will become high too much, and coating workability
  • the upper limit of the content of the polymer in the energy beam curable composition (coating liquid) is, for example, 95% by weight, preferably 90% by weight, and more preferably 85% by weight.
  • the polymer blended in the energy ray-curable composition is not particularly limited as long as it does not impair the physical properties (characteristics) required for the cylindrical difficult-to-extend polymer part A, and the easily-extensible polymer base material.
  • the polymer exemplified as the polymer constituting the polymer, the polymer exemplified as the polymer constituting the cylindrical hardly extensible polymer part A, etc. may be used, but the easily extensible polymer base material and the cylindrical hardly extensible polymer part From the viewpoint of the integrity, adhesion, etc.
  • a polymer having the same type of polymer chain in the main chain or side chain is preferred.
  • the easy-extensible polymer matrix 60 seconds after dropping the coating liquid onto the material layer for forming an easily extensible polymer matrix (drop amount 0.03 ⁇ L).
  • the diameter of the coating liquid on the material forming material layer is preferably 1.2 times or less, more preferably 1.15 times or less than the diameter of the coating liquid immediately after dropping.
  • the diameter of the coating liquid on the easily stretchable polymer base material forming material layer 120 seconds after dropping the coating liquid on the easily stretchable polymer base material forming material layer is Those that are 1.4 times or less the diameter of the coating solution immediately after dropping are preferred, and those that are 1.3 times or less are more preferred.
  • a pattern sheet [easily stretchable polymer base material]
  • a sheet-like extensible organic base material in which a large number of cylindrical hardly extensible polymer portions A are formed may not be obtained.
  • the material for forming a cylindrically-extensible polymer part is an easily extensible polymer base. It is allowed to stand until it penetrates, moves and settles to a predetermined depth of the material forming material layer.
  • step C the reaction, the solvent drying and removal treatment, and the melting / cooling treatment are performed on the easily stretchable polymer base material forming material layer in which the cylindrical hardly stretchable polymer portion forming material is arranged at a predetermined site.
  • reaction examples include polymerization reaction by energy rays and heat, curing or cross-linking reaction.
  • the solvent is removed by drying at an appropriate temperature according to the type of the solvent.
  • the solvent may be removed by drying at normal pressure or under reduced pressure.
  • the melting is preferably performed at a temperature at which both the easily stretchable polymer base material forming material layer and the cylindrical hardly stretchable polymer portion forming material are melted.
  • the combination of the form of the easily stretchable polymer base material forming material used in step A and the form of the cylindrical hardly stretchable polymer part forming material used in step B is not particularly limited, and may be arbitrarily combined. Can do.
  • an energy ray curable material liquid precursor of polymer (a) (syrup or the like)
  • a solvent-based material solution containing polymer (a)] is used.
  • the form of the easily stretchable polymer base material forming material and the cylindrical hardly stretchable polymer part forming material is a combination of energy ray curable materials (energy ray curable syrup, etc.), solvent Combinations of system materials (solutions), combinations of dispersion materials (emulsions, etc.), combinations of hot-melt materials, and combinations of solvent materials (solutions) and dispersion materials (emulsions, etc.) (In no particular order), a combination of a hot-melt material and a solvent-based material (solution) (no order), a combination of a hot-melt material and a dispersion-based material (emulsion, etc.) (in no particular order), a solvent-based material (solution) And a filler (powder), a dispersion material (emulsion, etc.) and a filler (powder), a hot-melt material and a filler (powder), etc. .
  • step C a sheet-like stretchable organic material in which the cylindrical
  • the sheet-like extensible organic base material having a gradation regarding the composition and / or physical properties (elongation characteristics, hardness, etc.)
  • materials that are common or similar to each other solvent, monomer, etc.
  • materials that are compatible with each other solvent, monomer
  • Etc. can be used as the material for forming the easily stretchable polymer base material and the material for forming the cylindrical difficult stretchable polymer part.
  • the easily stretchable polymer base material forming material and the cylindrical hardly stretchable polymer part forming material with materials containing acrylic monomers (polymer liquid precursors, etc.),
  • the above gradation can be obtained.
  • Such gradation is formed by diffusion and migration of monomer components, solvents, and the like, and subsequent curing, solvent removal, and the like. Therefore, the gradation part of the sheet-like extensible organic base material having the gradation is different from the composition assumed from the material for forming each part [tubular hardly extensible polymer part A, easily extensible polymer base part]. It becomes.
  • variety) of gradation can be adjusted with the kind and quantity of the easily extensible polymer base material forming material and the cylindrical difficulty extensible polymer part forming material (solvent, monomer, etc.).
  • the type of the polymer when the polymer is blended in the energy beam curable composition, the type of the polymer
  • the degree of gradation (width) can be adjusted by the amount, weight average molecular weight, and the like.
  • region which consists of an easily extensible polymer material which hits the cylindrical cavity part of the cylindrical hardly extensible polymer part A surface shape or projection shape when using a sheet-like extensible organic base material surface as a projection surface
  • the part B can be formed in the same manner as in the case of forming the cylindrical difficult-to-extend polymer part A.
  • the following modes (I) to (III) are preferable from the viewpoint of efficiently producing a sheet-like extensible organic substrate.
  • step A an easily extensible polymer base material-forming material layer is formed on the support using an energy ray-curable composition that is a liquid precursor of the polymer (a).
  • An energy ray-curable composition that is a precursor of the material (b) constituting the cylindrical difficult-to-extend polymer part A is disposed at a predetermined portion of the extensible polymer base material forming material layer.
  • the energy beam curable composition that is the precursor of (b) is irradiated with energy rays on the easily stretchable polymer base material forming material layer arranged at a predetermined site, and the two energy beam curable compositions are cured.
  • step A an easily stretchable polymer base material forming material layer is formed on the support using a solution or dispersion containing the polymer (a), and in step B, the easily stretchable polymer base material is formed.
  • the material (b) [for example, polymer, filler (powder), etc.] constituting the cylindrical difficult-to-extend polymer part or a solution or dispersion containing the material (b) is disposed at a predetermined portion of the material layer for use.
  • the material (b) constituting the cylindrical hardly extensible polymer part A or the easily extensible polymer base material forming material layer in which the solution or dispersion containing the material (b) is disposed at a predetermined site A method for obtaining a sheet-like extensible organic base material in which a cylindrical hardly extensible polymer portion A is partially and integrally formed in an easily extensible polymer base material by subjecting the solvent to dry removal treatment.
  • step A an easily stretchable polymer base material forming material layer is formed on the support by the polymer (a) alone, and in step B, the easily stretchable polymer base material forming material layer is predetermined.
  • the material (b) [for example, polymer, filler (powder), etc.] constituting the cylindrical hardly extensible polymer part A is arranged at the site, and the material constituting the cylindrical hardly extensible polymer part A in Step C
  • the material layer for forming an easily stretchable polymer base material (b) arranged at a predetermined site is subjected to a melting / cooling process (hot melt process) to form a cylindrical difficult stretch in the easily stretchable polymer base material (A).
  • a melting / cooling process hot melt process
  • the sheet-like extensible organic substrate of the present invention can be produced, for example, through the following steps.
  • Step A1 Step of forming an easily extensible polymer matrix-forming energy beam curable composition layer on a support
  • Step B1 In a predetermined part of the easily extensible polymer matrix-forming energy beam curable composition layer, The step of arranging (containing) the energy ray-curable composition for forming a cylindrical difficult-to-extend polymer part so that the surface shape of the cylindrical difficult-to-extend polymer part A or the projected shape of the substrate surface becomes a desired shape.
  • the energy ray curable composition for forming a polymer part and the energy ray curable composition layer for forming an easily extensible polymer matrix are cured, and the cylindrical hardly extensible polymer part A is partially in the easily extensible polymer matrix. And Obtaining a sheet-shaped organic substrate having a body-formed extensibility
  • FIG. 4 is a schematic explanatory view (sectional view).
  • (a) is a process A1
  • (b) is a process B1
  • (c) is a process B1
  • (d) is a process B1
  • (c) is a process B1
  • (d) is a process B1
  • (c) is a process B1
  • (d) is a process B1
  • (c) is a process B1
  • (c) (d), (e), (f) [or (d '), (e'), (f)]
  • step A1 the energy ray-curable composition layer 20 for forming an easily extensible polymer base material is formed on the support 4.
  • the support 4 those described above can be used.
  • the energy-extensible curable composition layer 20 for forming an easily stretchable polymer base material includes, for example, the polyurethane chain, polyurea chain, polyurethane urea chain, polyolefin chain (particularly, polydiene chain), silicone chain, polyester chain, and polyether.
  • a solvent may be added as necessary, but it is preferable not to use a solvent because a step of removing the solvent later increases. Moreover, in order to prevent the superposition
  • the curable composition is preferably syrup-like.
  • the viscosity of the curable composition and the coating method are the same as described above.
  • formation of the energy-beam curable composition layer 20 for easily extensible polymer base material formation can also be performed using a suitable type
  • the thickness of the energy-beam curable composition layer 20 for forming the easily stretchable polymer base material is the same as described above.
  • Step B1 the energy ray-curable composition 30 for forming a cylindrical difficult-to-extend polymer part is disposed (included) in the energy-ray-curable composition layer 20 for forming an easily extensible polymer base material.
  • a monomer particularly, a (meth) acrylic monomer having a Tg of the homopolymer of 5 ° C. or higher (more preferably 15 ° C. or higher, more preferably 50 ° C.
  • An energy ray-curable composition containing a monomer component and a photopolymerization initiator is added to a predetermined portion of the easily extensible polymer base material forming energy ray-curable composition layer 20 from above. (Dropping) or by injecting into a predetermined location in the energy-beam curable composition layer 20 for forming the easily stretchable polymer base material. Kill.
  • the energy ray-curable composition 30 for forming a cylindrical difficult-to-extend polymer part is in a syrup shape.
  • the viscosity of the energy ray-curable composition 30 for forming a cylindrical difficult-to-extend polymer part is the temperature at the time of coating (for example, a predetermined temperature within a range of 10 to 40 ° C., particularly 25 ° C.) from the viewpoint of workability and the like.
  • the upper limit is preferably 30000 mPa ⁇ s, more preferably 20000 mPa ⁇ s, and the lower limit is preferably 20 mPa ⁇ s, more preferably 30 mPa ⁇ s. If the viscosity is too low, it is difficult to obtain a desired shape.
  • the addition and injection method of the energy ray-curable composition 30 for forming a cylindrical difficult-to-extend polymer part is not particularly limited, and for example, a syringe, an appropriate dropping device, or the like can be used.
  • the transfer method of the energy ray-curable composition 30 for forming a cylindrical hardly extensible polymer part is not particularly limited.
  • coated and dripped the energy-beam curable composition 30 and the method of bonding the energy-beam curable composition layer 20 for extensible polymer base material formation etc. can be used.
  • the size (size and height in the plane direction) of the cylindrical hardly extensible polymer part A3 after curing is adjusted.
  • the energy ray curable composition 30 for forming a cylindrical hardly extensible polymer portion is applied at an appropriate interval.
  • step C1 the energy ray-curable composition layer 20 for forming an easily extensible polymer base material containing the energy ray-curable composition 30 for forming a cylindrical hardly extensible polymer portion is irradiated with energy rays,
  • the energy ray curable composition 30 for forming a cylindrical hardly extensible polymer part and the energy ray curable composition layer 20 for forming an easily extensible polymer base material are cured, and the cylindrical difficult extension in the easily extensible polymer base material 2 is cured.
  • the sheet-like organic base material which has the extensibility in which the property polymer part A3 was partially and integrally formed is obtained.
  • UV ultraviolet rays
  • ionizing radiation such as ⁇ rays, ⁇ rays, ⁇ rays, neutron rays, electron rays, or visible rays may be used.
  • the irradiation energy, irradiation time, irradiation method and the like of the energy beam are not particularly limited as long as the photopolymerization initiator can be activated to cause the monomer component to react.
  • the energy beam irradiation device a conventional device can be used.
  • a mercury lamp, a fluorescent lamp, a sodium lamp, a metal halide lamp, a xenon lamp, a neon tube, a neon lamp, a high-intensity discharge lamp, or the like can be used.
  • the cover film 5 may be laminated on the surface of the base material forming energy beam curable composition layer 20.
  • the same separator as the support 4 can be used.
  • stacking of the cover film 5 can be performed using a hand roller etc., for example.
  • Energy beam irradiation may be performed in several stages. For example, when irradiated with ultraviolet rays, as shown in FIG. 4 (c), advance high illuminance (e.g., 50 ⁇ 1000mW / cm 2) irradiation briefly at (e.g., integrated radiation, 10 ⁇ 1000mJ / cm 2) After that, as shown in FIG. 4 (d), the cover film 5 is laminated, and then, as shown in FIG. 4 (e), it is long with a low illuminance (for example, 1 to 40 mW / cm 2 ). Time irradiation (for example, an integrated dose of 500 to 10,000 mJ / cm 2 ) may be performed.
  • advance high illuminance e.g., 50 ⁇ 1000mW / cm 2
  • irradiation briefly at e.g., integrated radiation, 10 ⁇ 1000mJ / cm 2
  • the cover film 5 is laminated, and then, as shown in FIG. 4 (e), it is long with
  • 200 is a partially cured energy ray-curable composition layer for forming an easily extensible polymer base material
  • 300 is a partially cured energy ray curable composition for forming a cylindrical hardly extensible polymer portion.
  • the cover film 5 may be laminated on the surface of the energy ray-curable composition layer 20 for forming an easily stretchable polymer base material, and irradiated with ultraviolet rays as shown in FIG.
  • the illuminance of ultraviolet rays is, for example, 1 to 40 mW / cm 2
  • the integrated irradiation amount is, for example, 500 to 10000 mJ / cm 2 .
  • the cover film 5 and the support 4 are peeled off as necessary, cut into an appropriate size as necessary, and used as the sheet-like extensible organic substrate 1.
  • the cutting operation may be performed before the cover film 5 or the support 4 is peeled off.
  • the sheet-like extensible organic base material of the present invention can be more specifically manufactured through the following steps.
  • Step A2 A step of coating a solution or dispersion containing polymer a constituting the easily stretchable polymer matrix on the support to form a material layer for easily stretchable polymer matrix formation
  • Step B2 The easy stretch A solution or dispersion containing a polymer constituting the cylindrical hardly extensible polymer part or a filler (powder) constituting the cylindrical hardly extensible polymer part A at a predetermined portion of the material layer for forming the porous polymer base material
  • Step C2 A material for forming an easily stretchable polymer base material provided with a solution or dispersion containing a polymer constituting the cylindrical hardly extensible polymer part A or a filler (powder
  • FIG. 5 is a schematic explanatory view (cross-sectional view) thereof.
  • (g) corresponds to step A2
  • (h) corresponds to step B2
  • (i) and (j) correspond to step C2.
  • Reference numeral 21 denotes a layer (material layer for forming an easily extensible polymer base material) made of a solution or dispersion containing a polymer constituting the easily extensible polymer matrix
  • reference numeral 31 denotes a polymer constituting the cylindrical hardly extensible polymer portion.
  • the filler (powder) which comprises the solution or dispersion liquid to contain or a cylindrical difficulty extensible polymer part is shown.
  • Reference numerals 1, 2, 3, and 4 are the same as described above.
  • the sheet-like extensible organic base material of the present invention can be more specifically manufactured through the following steps.
  • Step A3 Step of forming a material layer for forming an easily stretchable polymer base material by forming the polymer a constituting the easily stretchable polymer base material on a support by sheeting by hot pressing, extrusion molding or the like
  • Step B3 The polymer or filler (powder) constituting the cylindrical difficult-to-extend polymer part A is applied to a predetermined portion of the extensible polymer base material forming material layer, and the surface shape of the cylindrical difficult-to-extend polymer part A or the projected surface of the base material Is placed (added) by placing or dropping (melt) or the like so as to have a desired shape.
  • Step C3 A polymer or filler (powder) constituting the cylindrical difficult-to-extend polymer part is placed. After the material layer for forming an easily stretchable polymer base material is heated and melted, it is cooled, and the stretchability in which the cylindrical difficult stretchable polymer portion A is partially and integrally formed in the easily stretchable polymer base material is obtained. Obtain a sheet-like organic base material A process
  • FIG. 6 is a schematic explanatory view (cross-sectional view) thereof.
  • 6K corresponds to the step A3
  • (l) corresponds to the step B3
  • (m) and (n) correspond to the step C3.
  • Reference numeral 22 denotes a sheet (material layer for forming an easily extensible polymer base material) made of a polymer constituting the easily extensible polymer matrix
  • reference numeral 32 denotes a polymer or filler (powder) constituting the cylindrical hardly extensible polymer portion A.
  • Reference numerals 1, 2, 3, and 4 are the same as described above.
  • the sheet-like extensible organic base material 1 obtained in this way is an electronic product (transistor, integrated circuit, capacitor, sensor, actuator, etc.) as an extensible member having a shape-invariant portion (or an elastic member having a shape-invariant portion).
  • the cylindrical difficult-to-extend polymer part is continuously formed (penetrated) from one surface of the sheet-like extensible organic base to the other surface, and the cylindrical difficult-to-extend polymer part is electrically conductive.
  • a conductive filler it can be used as, for example, an anisotropic conductive sheet, a dicing tape capable of conducting an on-chip conduction test, or a base material thereof.
  • the cylindrical difficult-to-extend polymer part is continuously formed (penetrated) from one surface of the sheet-like extensible organic base material to the other surface, and the cylindrical difficult-to-extend polymer part is heated.
  • a conductive filler it can be used as, for example, a heat transfer sheet that can be stretched or stretched.
  • the sheet-like extensible organic substrate may further have other characteristics and functions other than extensibility or stretchability.
  • the sheet-like extensible organic base material of the present invention includes such a multi-functional and multi-functional sheet-like extensible organic base material (multi-functional sheet-like extensible organic base material).
  • multi-functional sheet-like extensible organic base material hereinafter, the multifunctional sheet-like extensible organic base material will be described.
  • the multifunctional sheet-like extensible organic substrate basically conforms to the method for producing the sheet-like extensible organic substrate of the present invention or the production of the sheet-like extensible organic substrate of the present invention. It can be manufactured by using the method.
  • the multifunctional sheet-like extensible organic base A shown in (1) of FIG. 18 has a cylindrical hardly extensible polymer portion A3 partially and integrally formed in the easily extensible polymer base material 2. It is an example which has the functional layer 6 on one surface of the sheet-like organic base material (sheet-like extensible organic base material) 1 having extensibility.
  • the multifunctional sheet-like extensible organic base material A shown in (2) of FIG. 18 has a cylindrical hardly extensible polymer portion A3 partially and integrally formed in the easily extensible polymer base material 2.
  • the cylindrical hardly extensible polymer portion A3 is partially and integrally formed in the easily extensible polymer base material 2.
  • the extensible sheet-like organic base material (sheet-like extensible organic base material) 1 itself has functions and characteristics other than extensibility or stretchability.
  • Adhesive sheet-like extensible organic substrate As a sheet-like extensible organic base material having adhesiveness, (i) a sheet-like form having extensibility in which a cylindrical hardly extensible polymer portion A is partially and integrally formed in an easily extensible polymer matrix. It has an adhesive layer on at least one surface of the organic substrate, and the adhesive strength of the adhesive layer (temperature 23 ° C., humidity 65% RH, tensile speed 300 mm / min, peel angle 180 °, vs.
  • a sheet-like extensible organic base material having a thickness of 0.1 N / 20 mm or more, and (ii) an extensibility in which a cylindrical hardly extensible polymer portion A is partially and integrally formed in an easily extensible polymer base material.
  • a sheet-like organic base material having an adhesive strength (temperature 23 ° C., humidity 65% RH, tensile speed 300 mm / min, peeling angle 180 °, vs. SUS 304) on at least one side of the sheet-like organic base material .1N / 20mm or more A toroidal organic base material.
  • the sheet-like extensible organic base material of (ii) is a sheet-like organic group having extensibility in which a cylindrical hardly extensible polymer portion A is partially and integrally formed in an easily extensible polymer base material.
  • the functional layer 6 is an adhesive layer.
  • the functional layer 6 is an adhesive layer, and the multifunctional sheet-like stretchability shown in (3) of FIG.
  • the organic base material A include those in which the sheet-like organic base material 1 itself having extensibility has adhesiveness.
  • the stretchable polymer base material 2 is a polymer having a low glass transition temperature (Tg) (a polymer having a Tg of, for example, less than 5 ° C., preferably 0 ° C. or less, more preferably ⁇ 5 ° C. or less; Acrylic polymer having a polyacrylic chain) can be used to impart tackiness.
  • Tg glass transition temperature
  • the adhesive strength temperature 23 ° C., humidity 65% RH, tensile speed 300 mm / min, peel angle 180 °, vs.
  • SUS304 of at least one surface of the sheet-like organic base material is 0.1 N / 20 mm or more.
  • the adhesive strength is preferably 0.2 N / 20 mm or more, and may be 0.5 N / 20 mm or more, or 1.0 N / 20 mm or more depending on the application.
  • the sheet-like extensible organic base material having adhesiveness according to the present invention has extensibility in which a cylindrical hardly extensible polymer portion A is partially and integrally formed in an easily extensible polymer base material.
  • the adhesive strength of the adhesive layer (temperature 23 ° C., humidity 65% RH, tensile speed 300 mm / min, peeling The angle is 180 ° and SUS304 is 0.1 N / 20 mm or more.
  • the adhesive strength is preferably 0.2 N / 20 mm or more, and may be 0.5 N / 20 mm or more, or 1.0 N / 20 mm or more (particularly 2.0 N / 20 mm or more) depending on the application.
  • the thickness of the adhesive sheet-like extensible organic substrate A is, for example, 0.01 mm or more, preferably 0.03 mm or more, and more preferably 0.05 mm or more.
  • the upper limit of the thickness of the adhesive sheet-like extensible organic substrate is, for example, 1 cm, preferably 5 mm, and more preferably 2 mm.
  • an adhesive which comprises the adhesive layer 6 (adhesion layer)
  • a rubber adhesive an acrylic adhesive, a vinyl alkyl ether adhesive, a silicone adhesive, a polyester adhesive
  • Known adhesives such as polyamide-based adhesives, urethane-based adhesives, styrene-diene block copolymer-based adhesives, and adhesives with improved creep characteristics in which a hot-melt resin having a melting point of about 200 ° C. or less is blended with these adhesives
  • An agent can be used 1 type or in combination of 2 or more types.
  • the pressure-sensitive adhesive may be any known pressure-sensitive adhesive such as a solvent type, an emulsion type, a hot-melt type, an energy ray curable pressure-sensitive adhesive, and a heat release type, and an appropriate one can be selected depending on the application. Further, the pressure-sensitive adhesive may be any of a weak pressure-sensitive adhesive type, a strong pressure-sensitive adhesive type, a re-peeling type, and the like, and can be appropriately selected according to the application.
  • the pressure-sensitive adhesive a rubber-based pressure-sensitive adhesive using natural rubber or various synthetic rubbers as a base polymer; an acrylic polymer using one or more (meth) acrylic acid alkyl esters as monomer components
  • An acrylic pressure-sensitive adhesive having a base polymer (homopolymer or copolymer) is used.
  • an acrylic adhesive having an acrylic polymer as a base polymer is particularly preferably used.
  • Examples of the (meth) acrylic acid alkyl ester used as the monomer component of the acrylic polymer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and (meth) acrylic acid.
  • the acrylic polymer may contain other monomer components (copolymerizable) that can be copolymerized with the (meth) acrylic acid alkyl ester as necessary.
  • a structural unit derived from a monomer component) may be included. Examples of such monomer components include aliphatic groups such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, bornyl (meth) acrylate, and isobornyl (meth) acrylate.
  • Hydroxyl group-containing monomer styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (meth) acrylamide propane sulfonic acid, sulfopropyl (meth) acrylate, (meth) acryloyloxynaphthalene sulfonic acid Sulfonic acid group-containing monomers such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-butyl (meth) acrylamide, N-methylol (meth) acrylamide, -(N-substituted) amide group-containing monomers such as methylolpropane (meth) acrylamide; aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate
  • copolymerizable monomer components can be used alone or in combination of two or more.
  • copolymerizable monomer components in particular, carboxyl group-containing monomers, acid anhydride group-containing monomers, hydroxyl group-containing monomers, (N-substituted) amide group-containing monomers, (meth) acrylic acid aminoalkyl monomers , (Meth) acrylic acid alkoxyalkyl monomers, maleimide monomers, polyfunctional monomers and the like are preferable.
  • the proportion of the structural unit derived from the (meth) acrylic acid C 1-20 alkyl ester is, for example, 50% by weight or more, preferably 60% by weight or more, based on all the structural units of the polymer. Preferably it is 80 weight% or more, Most preferably, it is 85 weight% or more. The upper limit is 100% by weight, preferably 99% by weight, more preferably 98% by weight.
  • the proportion of structural units derived from (meth) acrylic acid C 4-12 alkyl ester is 60% by weight or more based on the total structural units of the polymer. It is preferable that it is 80% by weight or more.
  • the upper limit is 100% by weight, preferably 99% by weight, more preferably 98% by weight.
  • the proportion of the structural unit derived from the copolymerizable monomer component is, for example, 0.1 to 50% by weight with respect to all the structural units of the polymer, and the lower limit is The upper limit is preferably 1% by weight, more preferably 2% by weight, and the upper limit is preferably 40% by weight, more preferably 20% by weight.
  • the proportion of the structural unit derived from the monomer component is preferably 0.1 to 40% by weight with respect to the total structural unit of the polymer, and the lower limit thereof is more preferably 0.5% by weight, particularly preferably 1% by weight. %, The upper limit thereof is more preferably 30% by weight, particularly preferably 20% by weight.
  • the acrylic polymer can be produced by a known radical polymerization method such as solution polymerization, bulk polymerization, and emulsion polymerization.
  • the acrylic polymer may be any of a random copolymer, a block copolymer, a graft polymer, and the like.
  • a commonly used polymerization initiator or chain transfer agent can be used.
  • the weight average molecular weight of the base polymer constituting the pressure-sensitive adhesive is, for example, 10,000 to 2,000,000, preferably 300,000 to 1,500,000.
  • the weight average molecular weight of the base polymer is too low, although excellent in the followability with the adherend, for example, when peeling by heating, contamination such as adhesive residue tends to occur on the adherend.
  • the weight average molecular weight of the base polymer is too high, the followability to the adherend tends to decrease.
  • crosslinking agents epoxy crosslinking agents, isocyanate crosslinking agents, melamine crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, metal chelate compounds, etc.
  • crosslinking Accelerator crosslinking catalyst
  • tackifier for example, rosin derivative resin, polyterpene resin, petroleum resin, oil-soluble phenol resin, etc.
  • thickener plasticizer
  • filler foaming agent
  • an anti-aging agent antioxidant
  • an appropriate additive such as an ultraviolet absorber, an antistatic agent, a surfactant, a leveling agent, a colorant, a flame retardant, and a silane coupling agent.
  • the formation of the pressure-sensitive adhesive layer 6 can be performed by a known or common method. For example, a method of applying a pressure-sensitive adhesive composition onto a sheet-like organic substrate 1 having extensibility (or an intermediate layer when an intermediate layer is present on the sheet-like extensible organic substrate), a pressure-sensitive adhesive composition Is applied onto a suitable separator to form a pressure-sensitive adhesive layer, and then the pressure-sensitive adhesive layer is formed into a sheet-like organic substrate 1 having extensibility (if an intermediate layer is present on the sheet-like extensible organic substrate) And a method of transferring (transferring) onto the intermediate layer).
  • the coating can be performed by a coater, an extruder, a printing machine or the like generally used for forming the pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive layer 6 may be provided on the entire surface of the sheet-like organic substrate 1 having extensibility, and depending on the application, the adhesive layer 6 is only part of the surface of the sheet-like organic substrate 1 having extensibility. May be provided.
  • the thickness of the pressure-sensitive adhesive layer 6 can be appropriately selected depending on the application and the like, and is, for example, 5 to 3000 ⁇ m, the lower limit is preferably 10 ⁇ m, and the upper limit is preferably 500 ⁇ m.
  • the sheet-like organic base material 1 having extensibility and the pressure-sensitive adhesive layer 6 may be provided as necessary as long as extensibility and the like are not impaired.
  • a separator for protecting the pressure-sensitive adhesive layer 6 may be provided on the pressure-sensitive adhesive layer 6 until the adhesive sheet-like extensible organic base material A is used.
  • An adhesive sheet-like extensible organic base material has an adhesive property and an extensible member having a shape-invariable portion (or an elastic member having an adhesive shape and a shape-invariable portion) as an electronic product ( Transistors, integrated circuits, capacitors, sensors, actuators, etc.) members, optical products (displays, lighting, optical waveguide circuits, etc.) members, optoelectronics products (light emitting diodes, photodiodes, solar cells, etc.), car electronics products It can be used as a member for home appliances, a member for home appliances, a member for housing equipment, a building material, a band member, a member for binding, a sanitary article, a clothing part, a base cloth for a poultice.
  • Sheet-like extensible organic base material having weather resistance As a sheet-like extensible organic base material having weather resistance, a sheet-like extension in which a cylindrical hardly extensible polymer portion A is partially and integrally formed in an easily extensible polymer base material containing a weathering agent An organic base material.
  • the sheet-like organic base material 1 itself having extensibility corresponds to that having weather resistance.
  • the easily extensible polymer base material 2 contains a weathering agent. It does not specifically limit as a weathering agent, A well-known weathering agent can be used.
  • the weathering agent is preferably at least one selected from ultraviolet absorbers and antioxidants.
  • a weathering agent can be used individually by 1 type or in combination of 2 or more types.
  • Examples of the ultraviolet absorber as the weathering agent include at least one selected from benzotriazole compounds, hydroxyphenyltriazine compounds, salicylic acid ester compounds, benzophenone compounds, oxybenzophenone compounds, and cyanoacrylate compounds. . Only 1 type may be used for the ultraviolet absorber as a weathering agent, and it may use 2 or more types together.
  • benzotriazole compounds examples include 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole (TINUVIN PS, manufactured by BASF), benzenepropanoic acid and 3- (2H-benzotriazole-2).
  • hydroxyphenyl triazine compound examples include 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hydroxyphenyl and [(C 10- Reaction product with C 16 (mainly C 12 -C 13 ) alkyloxy) methyl] oxirane (TINUVIN 400, manufactured by BASF; 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5 -Triazin-2-yl] -5- [3- (dodecyloxy) -2-hydroxypropoxy] phenol), 2- (2,4-dihydroxyphenyl) -4,6-bis- (2,4-dimethylphenyl) ) -1,3,5-triazine and (2-ethylhexyl) -glycidic acid ester reaction product (TINUVIN405, manufactured by BASF), 2,4-bis " -Hydroxy-4-butoxyphenyl "-6- (2,4-bis
  • benzophenone compounds and oxybenzophenone compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid (anhydrous and trihydrate), 2-hydroxy-4-octyloxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy Examples include -4,4'-dimethoxybenzophenone.
  • salicylic acid ester compounds include phenyl-2-acryloyloxybenzoate, phenyl-2-acryloyloxy-3-methylbenzoate, phenyl-2-acryloyloxy-4-methylbenzoate, and phenyl-2-acryloyloxy-5.
  • cyanoacrylate compound examples include alkyl-2-cyanoacrylate, cycloalkyl-2-cyanoacrylate, alkoxyalkyl-2-cyanoacrylate, alkenyl-2-cyanoacrylate, alkynyl-2-cyanoacrylate, and the like.
  • antioxidant examples include at least one selected from a phenol stabilizer, a phosphorus stabilizer, a thioether stabilizer, and an amine stabilizer.
  • Antioxidants as weathering agents are also called light stabilizers. Only one type of antioxidant (light stabilizer) as a weathering agent may be used, or two or more types may be used in combination.
  • phenol-based stabilizer examples include 2,6-di-tert-butyl-4-methylphenol, 4-hydroxymethyl-2,6-di-tert-butylphenol, and 2,6-di-tertiary.
  • Examples of the phosphorus stabilizer include trisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris [2-tertiary butyl-4- (3-tertiary butyl).
  • phosphite tridecyl phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, di (tridecyl) pentaerythritol diphosphite, di Stearyl pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl) -4-methylphenyl) pentaerythritol diphosphite, bis 2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite, tetra (tridecyl
  • thioether-based stabilizer examples include dialkylthiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl, and distearyl; ⁇ -alkyl mercaptopropionate of polyols such as tetrakis [methylene (3-dodecylthio) propionate] methane Compound; and the like.
  • amine stabilizers include dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol polymer (TINUVIN 622, manufactured by BASF), dimethyl succinate and 4-hydroxy.
  • the content (total amount) of the weathering agent in the easily stretchable polymer base material is, for example, 0.001 to 10% by weight with respect to the entire easily stretchable polymer base material.
  • the lower limit of the content (total amount) of the weathering agent is preferably 0.01% by weight, more preferably 0.1% by weight, still more preferably 0.3% by weight, and the upper limit is preferably 8% by weight. Preferably it is 6 weight%, More preferably, it is 5 weight%.
  • an ultraviolet absorber is used as the weathering agent, the amount thereof is, for example, 0.001 to 10% by weight with respect to the whole stretchable polymer base material 2 and the lower limit is preferably 0.01% by weight.
  • the upper limit is preferably 5% by weight, more preferably 3% by weight, still more preferably 2% by weight.
  • the amount thereof is, for example, 0.001 to 10% by weight with respect to the entire stretchable polymer base material 2, and the lower limit is preferably 0.01% by weight.
  • the upper limit is preferably 5% by weight, more preferably 4% by weight, and still more preferably 3% by weight.
  • the weathering agent only one of the ultraviolet absorber and the antioxidant (light stabilizer) can be used, or both can be used in combination. Preferably, both are used together. Thereby, weather resistance can be remarkably improved.
  • the easily stretchable polymer base material can be formed according to the method for forming the polymer base material (A).
  • the easily stretchable polymer base material may be formed by, for example, applying a composition obtained by adding a weathering agent to a liquid precursor of a polymer constituting the easily stretchable polymer base material on a support. After forming the forming material layer and arranging the forming material of the cylindrical difficult-to-extend polymer part A at a predetermined portion of the easily-extensible polymer base material forming material layer, the easily-extensible polymer base material forming material layer It can be formed by converting the liquid precursor therein to the target polymer.
  • the easily stretchable polymer base material part is, for example, for forming an easily stretchable polymer base material by applying a solution or dispersion containing a polymer constituting the easily stretchable polymer base material and a weather resistance agent on a support. After forming the material layer and arranging the forming material of the cylindrical hardly extensible polymer portion A at a predetermined portion of the easily extensible polymer base material forming material layer, in the easily extensible polymer base material forming material layer It can also be formed by removing the solvent by drying.
  • the easily stretchable polymer base material part forms, on the support, for example, an easily stretchable polymer base material forming material layer by a mixture of a single polymer constituting the easily stretchable polymer base material and a weathering agent, It can also be formed by performing a melting / cooling process (hot melt process) after arranging the forming material of the cylindrical difficult-to-extend polymer part A at a predetermined portion of the easily stretchable polymer base material forming material layer.
  • a melting / cooling process hot melt process
  • the material constituting the cylindrical difficult-to-extend polymer part A3 is usually a polymer material containing at least a polymer.
  • this polymer material the same materials as those described in the explanation of the structure part (B) can be used.
  • the cylindrical difficult-to-extend polymer part A3 may contain a weathering agent in the same manner as the easily-extensible polymer base part 2.
  • a weathering agent also to the cylindrical hardly extensible polymer part A (hardly extensible part)
  • deterioration of the sheet-like extensible organic base material outdoors can be suppressed more remarkably.
  • the same weathering agent as described above can be used.
  • the content (total amount) of the weathering agent in the cylindrical difficult-to-extend polymer part A3 is, for example, 0.001 to 10% by weight with respect to the entire cylindrical difficult-to-extend polymer part A (hard extension part) 3.
  • the lower limit of the content (total amount) of the weathering agent is preferably 0.01% by weight, more preferably 0.1% by weight, still more preferably 0.3% by weight, and the upper limit is preferably 8% by weight. Preferably it is 6 weight%, More preferably, it is 5 weight%.
  • the amount thereof is, for example, 0.001 to 10% by weight with respect to the entire tubular hardly extensible polymer part A (hardly stretchable part) 3, and the lower limit is Preferably it is 0.01 wt%, more preferably 0.1 wt%, still more preferably 0.3 wt%, and the upper limit is preferably 5 wt%, more preferably 3 wt%, even more preferably 2 wt%. It is.
  • the amount thereof is, for example, 0.001 to 10% by weight with respect to the entire tubular difficult-to-extend polymer part A (hardly-extensible part) 3, and the lower limit is preferably 0.01% by weight, more preferably 0.2% by weight, still more preferably 0.5% by weight, and the upper limit is preferably 5% by weight, more preferably 4% by weight, still more preferably 3% by weight. .
  • Only one of the ultraviolet absorber and the antioxidant (light stabilizer) can be used as the weathering agent in the cylindrical hardly extensible polymer part A3, or both can be used in combination. Preferably, both are used together. Thereby, weather resistance can be remarkably improved.
  • the sheet-like extensible organic base material having weather resistance is, for example, a method similar to the method for producing the sheet-like extensible organic base material of the present invention, in which a weathering agent is blended in an easily extensible polymer base material forming material. Can be manufactured.
  • a sheet-like stretchable organic base material having weather resistance is an electronic product (a transistor, an integrated circuit, a capacitor, a sensor, an actuator, etc.) as an extensible member having a shape-invariant portion (or an elastic member having a shape-invariant portion).
  • Materials, optical products (displays, lighting, optical waveguide circuits, etc.), optoelectronics products (light emitting diodes, photodiodes, solar cells, etc.), car electronics products, home appliances, housing equipment It can be used as building materials, band members, binding members, sanitary products, clothing parts, base fabrics for poultices, and the like.
  • a cylindrical hardly extensible polymer portion A is partially and integrally in an easily extensible polymer matrix.
  • a sheet-like organic base material having extensibility that is formed, and is a sheet-like extensible organic base material (“ (Ii) the cylindrical stretchable polymer portion A is partially and integrally formed in the stretchable polymer base material (sometimes referred to as the “sheet-like stretchable organic substrate of the first aspect”).
  • a sheet-like extensible organic substrate having a deodorizing layer on at least one surface of the extensible sheet-like organic substrate (sometimes referred to as “sheet-like extensible organic substrate of the second aspect"), (Iii) Cylindrical difficult-to-extend polymer part A in the easily-extensible polymer base material
  • a sheet-like extensible organic substrate comprising a sheet-like organic substrate having extensibility that is partially and integrally formed, when the sheet-like extensible organic substrate is heated at 150 ° C. for 3 minutes
  • a sheet-like extensible organic substrate (sometimes referred to as “the sheet-like extensible organic substrate of the third embodiment”) in which the amount of monomer generated in the above is 300 ppm or less.
  • the functional layer 6 is a deodorizing layer in the multifunctional sheet-like extensible organic base material A shown in (1) of FIG.
  • the functional layer 6 is a deodorizing layer, and the multifunctional sheet-like shape shown in (3) of FIG.
  • Examples of the extensible organic base material A include those in which the generation of an unpleasant odor is suppressed in the extensible sheet-like organic base material 1 itself.
  • the sheet-like extensible organic base material of the first aspect includes an easily extensible polymer base material and / or a cylindrical hardly extensible polymer portion A (any of the easily extensible polymer base material and the cylindrical hardly extensible polymer portion A).
  • One or both) contains a fragrance.
  • flavor all can be used if it has fragrance
  • the fragrance is preferably one that does not inhibit the formation of an easily stretchable polymer matrix (for example, one that does not inhibit the polymerization reaction), is a liquid at room temperature, and has a boiling point of 150 ° C. or higher under normal pressure. Is particularly preferred.
  • flavor may be used individually by 1 type and may be used in combination of 2 or more type.
  • the improvement of a handleability can be aimed at by mixing and melt
  • the perfume include (1) alcohols, aldehydes and ketones which are organic low-molecular-weight compounds; (2) alcohols, aldehydes, ketones and esters which are alicyclic compounds. (3) Alcohols that are terpene compounds, aldehydes, ketones, esters, ethers; (4) Alcohols that are aromatic compounds, aldehydes, ketones, ethers, etc. And the like classified into
  • Examples of the fragrance classified as (1) include alcohols having 6 to 12 carbon atoms [for example, cis-3-hexenol, 3,3,5-trimethylhexanol, etc.], aldehydes having 6 to 16 carbon atoms [for example, 2,6,10-trimethyl-9-undecene-1-al, etc.], ketones having 6 to 12 carbon atoms [for example, methyl amyl ketone, etc.] and the like.
  • flavor can also be used individually by 1 type, and can also be used in combination of 2 or more type.
  • fragrance classified as (2) examples include pt-butylcyclohexanol, ot-butylcyclohexanol, synthetic sandals, 4- (tricyclo [5,2,1,02,6]- Decylidene-8) -butanal, 2,4-dimethylcyclohex-3-ene-3-carbaldehyde, pt-butylcyclohexyl acetate, ot-butylcyclohexyl acetate, tricyclo [5,2,1,0 2 , 6 ] -dec-3-en-8 (or 9) -yl acetate, 4-acetoxy-3-pentyltetrahydropyran, ethylene brushate, ot-butylcyclohexanone, pt-amylcyclohexanone, 2- Examples include ethyl hexanal ethylene glycol acetal.
  • flavor can also be used individually by 1 type
  • fragrance classified as (3) examples include linalool, terpineol, citronellol, geraniol, borneol, cedrol, lavandulol, 2,6-dimethyl-heptan-2-ol, citral, citronellal, methoxycitronellal.
  • the terpene compound 4-
  • fragrance classified into the above (4) examples include phenylethyl alcohol, anis alcohol, phenylethyldimethylcarbinol, eugenol, iso-eugenol, cinnamic alcohol, hexyl cinnamaldehyde, p-tert-butyl-2- Methylhydrocinnamic aldehyde, anisaldehyde, cuminaldehyde, phenoxyacetaldehyde, heliotropin, vanillin, p-ethyl-2,2-dimethylhydrocinnamic aldehyde, benzophenone, p-methoxyacetophenone, ⁇ -methylnaphthyl ketone, auran All, phenylacetaldehyde, dimethylacetal, nitromusks, coumarins, isocoumarone musks, methylanthranilates, iso-butylquinoline,
  • the content (total amount) of the fragrance in the easily stretchable polymer matrix is not particularly limited.
  • the amount is 1.0 ⁇ 10 ⁇ 5 to 1.0 ⁇ 10 ⁇ 1 parts by weight with respect to 100 parts by weight of the polymer constituting the (extensible polymer base material).
  • the lower limit of the content (total amount) of the fragrance is preferably 5.0 ⁇ 10 ⁇ 5 parts by weight, more preferably 1.0 ⁇ 10 ⁇ 4 parts by weight.
  • the upper limit is preferably 5.0 ⁇ 10 ⁇ 2 parts by weight, more preferably 1.0 ⁇ 10 ⁇ 2 parts by weight. If the content of the fragrance is less than 1.0 ⁇ 10 ⁇ 5 parts by weight, the mask of unpleasant odor may be insufficient, and if the content exceeds 1.0 ⁇ 10 ⁇ 1 parts by weight, Odor may be felt uncomfortable.
  • the content (total amount) of the fragrance in the difficultly stretched part is not particularly limited, but the difficultly stretched part (tubular hardly stretchable polymer)
  • the lower limit of the content (total amount) of the fragrance is preferably 5.0 ⁇ 10 ⁇ 5 parts by weight, more preferably 1.0 ⁇ 10 ⁇ 4 parts by weight.
  • the upper limit is preferably 5.0 ⁇ 10 ⁇ 2 parts by weight, more preferably 1.0 ⁇ 10 ⁇ 2 parts by weight. If the content of the fragrance is less than 1.0 ⁇ 10 ⁇ 5 parts by weight, the mask of unpleasant odor may be insufficient, and if the content exceeds 1.0 ⁇ 10 ⁇ 1 parts by weight, Odor may be felt uncomfortable.
  • the easily extensible polymer base material and / or the cylindrical hardly extensible polymer portion A contains a fragrance, thereby reducing the occurrence of an unpleasant odor due to the fragrance of the fragrance.
  • the sheet-like extensible organic base material of the first aspect is the same as the sheet-like extensible organic base material of the third aspect when the sheet-like extensible organic base material is heated at 150 ° C. for 3 minutes.
  • the amount of monomer generated in may be 300 ppm or less. That is, the sheet-like extensible organic substrate of the first aspect can also be the sheet-like extensible organic substrate of the third aspect.
  • the sheet-like extensible organic base material of the second aspect is a sheet-like organic material having extensibility in which a cylindrical hardly extensible polymer portion A is partially and integrally formed in an easily extensible polymer base material. It is a sheet-like extensible organic base material having a deodorizing layer on at least one side (one side or both sides) of the base.
  • the deodorant layer is not particularly limited, and any layer having a deodorizing effect can be adopted.
  • Specific examples of the deodorant layer include a layer containing a deodorant.
  • the content (content ratio) of the deodorant in the deodorant layer is not particularly limited, but is, for example, 0.01 to 20% by weight.
  • the lower limit of the deodorant content is preferably 0.1% by weight, more preferably 0.5% by weight, while the upper limit is preferably 15% by weight, more preferably 10% by weight.
  • the deodorizing layer exhibits a very excellent deodorizing property, and as a result, generation of unpleasant odor from the sheet-like extensible organic base material is effective. Tend to be suppressed or deterred.
  • a deodorizer can also be used individually by 1 type, and can also be used in combination of 2 or more type.
  • the deodorant a known or conventional deodorant can be used, and it is not particularly limited, but in particular, an inorganic powder carrying a metal component can be preferably used.
  • the supported amount of the metal component in the deodorant is, for example, 0.1 to 30% by weight as the content in the deodorant.
  • the lower limit of the metal component loading is preferably 0.5 wt%, more preferably 1 wt%, while the upper limit is preferably 20 wt%.
  • inorganic powder in the deodorant inorganic powder carrying a metal component
  • known or commonly used inorganic powder can be used, and is not particularly limited.
  • zeolite, silica gel, titanium oxide, aluminum oxide, And at least one inorganic powder selected from the group consisting of activated carbon can be preferably used.
  • An inorganic powder can also be used individually by 1 type, and can also be used in combination of 2 or more type.
  • metal component in the deodorant inorganic powder carrying the metal component
  • a known or commonly used metal component metal
  • metal component silver, copper, zinc, tin
  • At least one metal component selected from the group consisting of lead, bismuth, cadmium, chromium, and mercury can be preferably used.
  • a metal component can also be used individually by 1 type and can also be used in combination of 2 or more type.
  • Examples of the deodorant include trade names “Kesmon NS-10”, “Kesmon NS-20”, “Kesmon NS-10C”, “Kesmon NS-10N”, “Kesmon NS-70”, “Kesmon NS-”.
  • Commercial products such as “Shoe Cleanse KD-311”, “Shoe Cleanse KD-411” (manufactured by Lhasa Kogyo Co., Ltd.), and trade name “FINEX-25LP” (manufactured by Sakai Chemical Industry Co., Ltd.) can also be used. .
  • the deodorizing layer may contain a resin (polymer).
  • the resin may be a known or commonly used resin, and is not particularly limited. For example, phenol resin, urea resin, melamine resin, alkyd resin, diallyl phthalate resin, epoxy resin, polyurethane Thermosetting resins such as silicon resins and silicon resins; polyvinyl chloride resins, polyvinylidene chloride resins, fluorine resins, polyvinyl fluoride resins, polyvinylidene fluoride resins, polyvinyl acetate resins, polyvinyl alcohol resins Resin, polyvinyl formal resin, saturated polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, ABS resin, acrylic resin, polyamide resin, polyacetal resin, chlorinated polyether resin, polycarbonate resin, Polyarylate resin Resins such as cellulose, cellulose acetate and cellulose nitrate; natural rubber, isoprene rubber, acrylonitrile rubber
  • the deodorizing layer may contain any other additive depending on the purpose.
  • the additive include a photopolymerization initiator, a silane coupling agent, a mold release agent, a curing agent, a curing accelerator, a diluent, an anti-aging agent, a modifier, a surfactant, a dye, a pigment, and a discoloration preventing agent. UV absorbers, softeners, stabilizers, plasticizers, antifoaming agents and the like.
  • the kind of additive which can be contained in a deodorizing layer, the number, and quantity can be suitably set according to the objective.
  • the deodorizing layer may have a single-layer form or a multi-layer (laminated) form.
  • the said deodorizing layer is a sheet-like organic base material (sheet-like extensible organic base material) 1 having extensibility (if the below-described intermediate layer is present on the sheet-like extensible organic base material, Layer) may be provided on the entire surface (entire surface), and depending on the application, it may be partially applied only to necessary portions of the surface of the sheet-like organic base material (sheet-like extensible organic base material) 1 having extensibility. It may be provided.
  • the thickness of the deodorant layer is not particularly limited, but is, for example, 0.1 to 100 ⁇ m.
  • the lower limit of the thickness is preferably 1 ⁇ m.
  • the deodorizing layer can be formed by a known or commonly used method.
  • a deodorant layer material for example, a resin composition containing a deodorant and a resin
  • an extensible sheet-like organic base material described later on the sheet-like extensible organic base material.
  • a method of vapor-depositing for example, vacuum vapor deposition
  • a sheet-like organic substrate having extensible deodorizing layer on the sheet-like extensible organic substrate
  • a method of laminating on the intermediate layer after forming a deodorizing layer on a suitable support, a sheet-like extensible organic substrate (the sheet-like extensible organic group)
  • a method of transferring onto the intermediate layer may be mentioned.
  • sheet-like organic base material 1 having extensibility and the deodorizing layer 6 may be provided as necessary as long as extensibility and the like are not impaired.
  • the sheet-like extensible organic base material of the said 2nd aspect is an easily extensible polymer base material and / or a cylindrical difficulty extensible polymer part A similarly to the sheet-like extensible organic base material of a 1st aspect.
  • the easily extensible polymer base material and the cylindrical hardly extensible polymer portion A may contain a fragrance.
  • the kind and content of the fragrance are exemplified by those similar to those in the sheet-like extensible organic substrate of the first aspect.
  • the sheet-like extensible organic substrate of the second aspect is similar to the sheet-like extensible organic substrate of the third aspect when the sheet-like extensible organic substrate is heated at 150 ° C. for 3 minutes.
  • the amount of monomer generated in may be 300 ppm or less. That is, the sheet-like extensible organic substrate of the second aspect may be the sheet-like extensible organic substrate of the third aspect.
  • the sheet-like extensible organic base material according to the third aspect is a sheet-like organic material having extensibility in which a cylindrical hardly extensible polymer portion A is partially and integrally formed in an easily extensible polymer base material.
  • a sheet-like extensible organic substrate containing a substrate, and the amount of monomer generated when the sheet-like extensible organic substrate is heated at 150 ° C. for 3 minutes is 300 ppm or less.
  • the sheet-like extensible organic base material of the third aspect only needs to include the extensible sheet-like organic base material, and may be, for example, the extensible sheet-like organic base material.
  • the sheet-like extensible organic base material which has a deodorizing layer in the at least one surface of the said sheet-like organic base material which has the extendibility may be sufficient.
  • the monomer generated when the sheet-like extensible organic base material of the third aspect is heated at 150 ° C. for 3 minutes mainly has the extensibility constituting the easily extensible polymer matrix (extensible polymer matrix). It originates in the residual monomer (residual monomer) contained in the polymer which has, and the residual monomer (residual monomer) contained in the polymer (polymer material) which comprises the cylindrical difficulty extensible polymer part A. Moreover, when it has a deodorizing layer and an intermediate
  • the compound having the energy ray curable group A1 and the reactive functional group R1 the curable monomer M having the energy ray curable group A2, and the Tg of the homopolymer are as follows.
  • Examples thereof include a monomer having a temperature of 5 ° C. or more, a polyfunctional monomer, and a monomer constituting a polymer material having a tensile modulus of elasticity of 0.1 MPa or more.
  • the sheet-like extensible organic base material of the third aspect is a monomer amount generated when the sheet-like extensible organic base material is heated at 150 ° C. for 3 minutes (monomer generation amount; sheet-like extensible organic base material).
  • the amount (weight) [ ⁇ g / g]) of the monomer (generated monomer) with respect to the weight is not particularly limited as long as it is 300 ppm or less, but is preferably 250 ppm or less and may be 200 ppm or less depending on the application.
  • the lower limit is not particularly limited, but 0 ppm is most preferable.
  • the monomer generation amount can be measured using a known or conventional method, for example, gas chromatography or the like, and more specifically can be measured according to the method described in ⁇ Method for measuring monomer generation amount> described later.
  • the means for controlling the amount of monomer generated in the sheet-like extensible organic substrate of the third aspect to 300 ppm or less is not particularly limited.
  • the implementation time of the drying step is not particularly limited, and may be incorporated and implemented during the production process of the sheet-like extensible organic substrate (for example, the production process of the sheet-like extensible organic substrate) Or after step C), and after the production of the sheet-like extensible organic substrate, it may be carried out at a stage before shipment.
  • the heating temperature in the drying step is, for example, 50 to 200 ° C., and the lower limit thereof is preferably 70 ° C., more preferably 80 ° C., further preferably 90 ° C., while the upper limit thereof is preferably 180 ° C., more preferably. It is 160 degreeC, More preferably, it is 140 degreeC.
  • the heating temperature in the drying process may always be constant in the process, or may be changed in stages.
  • the heating time in the drying step is, for example, 1 minute to 3 hours, and the lower limit thereof is preferably 1.5 minutes, more preferably 2 minutes, further preferably 3 minutes, while the upper limit is 2 hours. It is preferably 1 hour, more preferably 30 minutes.
  • the heat treatment in the drying step can be carried out using a known or conventional apparatus (for example, various types of ovens).
  • the heat treatment in the drying step can be performed under normal pressure, reduced pressure, or increased pressure.
  • Means for controlling the amount of monomer generated in the sheet-like extensible organic substrate of the third aspect to 300 ppm or less include, for example, monomer (energy rays) in addition to subjecting the sheet-like extensible organic substrate to the drying step.
  • Curable monomers, etc.) and conditions for polymerizing the partially polymerized monomers for example, energy ray irradiation conditions, heating conditions, etc.
  • monomer reaction rate polymerization rate
  • the sheet-like extensible organic base material of the third aspect generation of unpleasant odor (particularly, unpleasant odor derived from monomer (monomer odor)) is reduced by controlling the amount of monomer generated to 300 ppm or less.
  • the sheet-like extensible organic base material of the said 3rd aspect is an easily extensible polymer base material and / or a cylindrical difficulty extensible polymer part A similarly to the sheet-like extensible organic base material of a 1st aspect. May contain a fragrance. That is, the sheet-like extensible organic substrate of the third aspect can also be the sheet-like extensible organic substrate of the first aspect.
  • the kind and content of the fragrance are exemplified by those similar to those in the sheet-like extensible organic substrate of the first aspect.
  • the sheet-like extensible organic substrate of the third aspect may have a deodorizing layer on at least one surface of the sheet-like extensible organic substrate. That is, the sheet-like extensible organic substrate of the third aspect may be the sheet-like extensible organic substrate of the second aspect.
  • the deodorizing layer include those similar to those exemplified in the sheet-like extensible organic substrate of the second aspect.
  • the thickness of the sheet-like extensible organic base material having an unpleasant odor preventing property is, for example, 0.01 mm or more, preferably 0.03 mm or more, and more preferably 0.05 mm or more.
  • the upper limit of the thickness of the sheet-like extensible organic base material having an unpleasant odor preventing property is, for example, 1 cm, preferably 5 mm, and more preferably 2 mm.
  • the sheet-like extensible organic base material is used as an extensible member that suppresses generation of unpleasant odor and has a shape-invariable portion (or an elastic member that suppresses generation of unpleasant odor and has a shape-invariable portion).
  • Products transistors, integrated circuits, capacitors, sensors, actuators, etc.
  • optical products displays, lighting, optical waveguide circuits, etc.
  • optoelectronics products light emitting diodes, photodiodes, solar cells, etc.
  • cars It can be used as a member for electronics products, a member for home appliances, a member for household equipment, a building material, a band member, a binding member, a sanitary article, a clothing part, a base material for a poultice.
  • the sheet-like extensible organic base material having coloring printability includes a sheet-like extensible organic base material imparted with designability and a sheet-like extensible organic base material that is easily imparted with designability.
  • a sheet-like extensible organic base material having colored printability (i) a sheet having extensibility in which a cylindrical hardly extensible polymer portion A is partially and integrally formed in an easily extensible polymer base material
  • the organic base material is an easily extensible polymer base material and / or a cylindrical hardly extensible polymer portion A (one or both of the easily extensible polymer base material and the cylindrical hard extensible polymer portion A) are dyes.
  • the sheet-like extensible organic base material containing a pigment (ii) It has the extensibility by which the cylindrical difficulty extensible polymer part A is partially and integrally formed in the easily extensible polymer base material.
  • the functional layer 6 is a colored layer or a printed layer.
  • the functional layer 6 is a colored layer or a printing layer (one of the two functional layers is a colored layer)
  • the other sheet-like organic substrate 1 itself (easily extensible) Examples thereof include those in which the polymer base material 2 and / or the cylindrical hardly extensible polymer portion A3) are colored.
  • the easily extensible polymer base material 2 may contain a dye or a pigment.
  • the easily extensible polymer base material 2 may contain both a dye and a pigment. Thereby, an easily extensible polymer base material is colored and the design property excellent in the sheet-like extensible organic base material of this invention is provided.
  • the dye and pigment known or commonly used dyes can be used.
  • the dye may be a known or commonly used dye, and is not particularly limited.
  • a dye can be used individually by 1 type or in combination of 2 or more types.
  • a commercial item can also be used.
  • the dye can also be used in the form of a solution or a dispersion.
  • the content (total amount) of the dye in the stretchable polymer base material 2 is, for example, 0.001 to 50% by weight with respect to the whole stretchable polymer base material 2.
  • the lower limit of the dye content (total amount) is preferably 0.01% by weight, more preferably 0.1% by weight, still more preferably 0.3% by weight, and the upper limit is preferably 45% by weight, more preferably. Is 40% by weight, more preferably 35% by weight. If the content is less than 0.001% by weight, the design may be insufficient depending on the application. On the other hand, if the content exceeds 50% by weight, the mechanical strength of the easily extensible polymer base material may be lowered depending on the application.
  • pigments known or commonly used pigments can be used, and are not particularly limited.
  • a pigment can be used individually by 1 type or in combination of 2 or more types.
  • a commercial item can also be used as a pigment.
  • the pigment can also be used in the form of a solution or a dispersion.
  • the content (total amount) of the pigment in the stretchable polymer base material 2 is, for example, 0.001 to 50% by weight with respect to the whole stretchable polymer base material 2.
  • the lower limit of the pigment content (total amount) is preferably 0.01% by weight, more preferably 0.1% by weight, still more preferably 0.3% by weight, and the upper limit is preferably 45% by weight, more preferably. Is 40% by weight, more preferably 35% by weight. If the content is less than 0.001% by weight, the design may be insufficient depending on the application. On the other hand, if the content exceeds 50% by weight, the mechanical strength of the easily extensible polymer base material may be lowered depending on the application.
  • the cylindrical difficult-to-extend polymer part A3 may contain a dye or a pigment, like the easily-extensible polymer base part 2.
  • the cylindrical difficult-to-extend polymer part A may contain both a dye and a pigment.
  • the cylindrical difficulty extensible polymer part A is colored, and excellent designability is imparted to the sheet-like extensible organic base material of the present invention.
  • the easily extensible polymer base material portion and the cylindrical hardly extensible polymer portion A may be the same color, for example, the easily extensible polymer base material portion and the cylindrical hardly extensible polymer portion A have different colors. It is also possible to impart more excellent design properties by coloring or coloring the plurality of cylindrical difficult-to-extend polymer parts A to different colors.
  • the dye and pigment known or commonly used ones can be used, and specifically, the same ones as described above can be used.
  • the content (total amount) of the dye in the cylindrical difficult-to-extend polymer part A3 is, for example, 0.001 to 50% by weight with respect to the entire cylindrical difficult-to-extend polymer part A3.
  • the lower limit of the dye content (total amount) is preferably 0.01% by weight, more preferably 0.1% by weight, still more preferably 0.3% by weight, and the upper limit is preferably 45% by weight, more preferably. Is 40% by weight, more preferably 35% by weight. If the content is less than 0.001% by weight, the design may be insufficient depending on the application. On the other hand, if the content exceeds 50% by weight, the mechanical strength of the easily extensible polymer base material may be lowered depending on the application.
  • the content (total amount) of the pigment in the cylindrical difficult-to-extend polymer part A3 is, for example, 0.001 to 50% by weight with respect to the entire cylindrical difficult-to-extend polymer part A3.
  • the lower limit of the pigment content (total amount) is preferably 0.01% by weight, more preferably 0.1% by weight, still more preferably 0.3% by weight, and the upper limit is preferably 45% by weight, more preferably. Is 40% by weight, more preferably 35% by weight. If the content is less than 0.001% by weight, the design may be insufficient depending on the application. On the other hand, if the content exceeds 50% by weight, the mechanical strength of the easily extensible polymer base material may be lowered depending on the application.
  • the sheet-like extensible organic base material to which the design property is imparted has the aspect (i) or (ii).
  • the easily extensible polymer base material and / or the cylindrical hardly extensible polymer portion A contains a dye or a pigment. Examples of such dyes and pigments and their contents are as described above.
  • the sheet-like extensible organic base material of the aspect of said (i) may have a below-mentioned printing layer in the at least one surface of the sheet-like organic base material which has the extensibility, for example.
  • the sheet-like extensible organic base material of the aspect of (ii) is a sheet-like form having extensibility in which a cylindrical hardly extensible polymer portion A is partially and integrally formed in an easily extensible polymer base material. It is a sheet-like extensible organic base material having a colored layer on at least one surface (one side or both sides) of the organic base.
  • the color layer is not particularly limited, and a layer colored in an arbitrary color can be employed.
  • Specific examples of the colored layer include a layer containing a dye and / or a pigment.
  • the dye and pigment in the colored layer those exemplified above can be used.
  • the content (content ratio) of the dye in the colored layer is not particularly limited, and is, for example, 0.01 to 50% by weight.
  • the lower limit of the dye content is preferably 0.1% by weight, more preferably 0.5% by weight, while the upper limit is preferably 40% by weight, more preferably 30% by weight.
  • the content (content ratio) of the pigment in the colored layer is not particularly limited, and is, for example, 0.01 to 50% by weight.
  • the lower limit of the pigment content is preferably 0.1% by weight, more preferably 0.5% by weight, while the upper limit is preferably 40% by weight, more preferably 30% by weight.
  • the pigment can be used individually by 1 type in the said colored layer, and can also be used in combination of 2 or more type.
  • the colored layer may contain a resin (polymer).
  • the resin may be a known or commonly used resin, and is not particularly limited. For example, phenol resin, urea resin, melamine resin, alkyd resin, diallyl phthalate resin, epoxy resin, polyurethane Thermosetting resins such as silicon resins and silicon resins; polyvinyl chloride resins, polyvinylidene chloride resins, fluorine resins, polyvinyl fluoride resins, polyvinylidene fluoride resins, polyvinyl acetate resins, polyvinyl alcohol resins Resin, polyvinyl formal resin, saturated polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, ABS resin, acrylic resin, polyamide resin, polyacetal resin, chlorinated polyether resin, polycarbonate resin, Polyarylate resin Resins such as cellulose, cellulose acetate and cellulose nitrate; natural rubber, isoprene rubber, acrylonitrile rubber, acrylic
  • the colored layer may contain any other additive depending on the purpose.
  • the additive include a photopolymerization initiator, a silane coupling agent, a release agent, a curing agent, a curing accelerator, a diluent, an anti-aging agent, a modifier, a surfactant, a discoloration preventing agent, and an ultraviolet absorber. , Softeners, stabilizers, plasticizers, antifoaming agents and the like.
  • the kind of additive which can be contained in a colored layer, the number, and quantity can be suitably set according to the objective.
  • the colored layer may have a single layer form or a multi-layer form.
  • the colored layer is formed on the entire surface (entire surface) of the sheet-like organic substrate 1 having extensibility (if the intermediate layer described later is present on the sheet-like extensible organic substrate, the intermediate layer). Depending on the application, it may be partially provided only on a necessary portion of the surface of the sheet-like organic substrate 1 having extensibility. Moreover, the colored layer of a several different color can also be provided in one surface of a sheet-like extensible organic base material (or intermediate
  • the thickness of the colored layer is not particularly limited, but is, for example, 0.1 to 100 ⁇ m.
  • the lower limit of the thickness is preferably 1 ⁇ m, more preferably 5 ⁇ m, and the upper limit thereof is preferably 90 ⁇ m, more preferably 80 ⁇ m.
  • the colored layer can be formed by a known or commonly used method. Specifically, for example, a sheet-like organic substrate having an extensible property (such as a resin composition containing a dye and / or a pigment and a resin) or a dispersion containing a coloring layer material (the sheet-like elongation) A method of coating on the intermediate layer when the intermediate layer is present on the extensible organic substrate; a sheet-like organic substrate (or intermediate) having a stretchable material (for example, dye and / or pigment) of the colored layer A method of depositing (for example, vacuum deposition) on the layer); a method of laminating the colored layer on the sheet-like organic substrate (or intermediate layer) having extensibility; and after forming the colored layer on an appropriate support, Examples thereof include a method of transferring onto a sheet-like extensible organic substrate (or intermediate layer) through an adhesive layer or the like as necessary.
  • the sheet-like extensible organic base material to which designability is imparted is provided as needed between the sheet-like organic base material 1 having extensibility and the colored layer 6 as long as extensibility is not impaired. (Intermediate layer) may be included.
  • the sheet-like extensible organic base material of the aspect of (ii) has a designability by having a colored layer.
  • the sheet-like extensible organic base material of the aspect of (ii) is an easily extensible polymer base material and / or a cylindrical difficulty extensible similarly to the sheet-like extensible organic base material of the aspect of (i).
  • the polymer part A may contain a dye or a pigment. Examples of the types and contents of the dyes and pigments are the same as those in the sheet-like extensible organic substrate of the aspect (i).
  • the sheet-like extensible organic base material of the aspect (ii) is, for example, printed on a surface opposite to the colored layer of the extensible sheet-like organic base material or the surface of the colored layer, which will be described later. It may have a layer.
  • the thickness of the sheet-like extensible organic base material to which designability is imparted is, for example, 0.01 mm or more, preferably 0.03 mm or more, more preferably 0.05 mm or more.
  • the upper limit of the thickness of the sheet-like extensible organic base material of the present invention is, for example, 1 cm, preferably 5 mm, and more preferably 2 mm.
  • the sheet-like extensible organic base material that is easily imparted with designability is a sheet-like extensible organic base material that has extensibility (or further stretchability) and that is easy to impart designability.
  • the sheet-like extensible organic base material that is easily imparted with designability is a sheet having extensibility, in which a cylindrical hardly extensible polymer portion A is partially and integrally formed in an easily extensible polymer base material. It is a sheet-like extensible organic base material which has a printing layer (printing layer) in the at least one surface (single side
  • the printing layer is not particularly limited, and any layer having a surface excellent in printing (printing) with water-based ink and / or oil-based ink, more specifically with a known or common ink jet printer. Can be adopted. Specific examples of the print layer include a layer having excellent ink absorbability (ink absorption layer).
  • the printing layer preferably contains a water-soluble resin.
  • the water-soluble resin may be a known or commonly used water-soluble resin, and is not particularly limited.
  • polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acid, polyethyleneimine, and a copolymer of vinyl pyrrolidone and vinyl acetate At least one water-soluble resin selected from the group consisting of polymers is preferred.
  • the water-soluble resin in the said printing layer can also be used individually by 1 type, and can also be used in combination of 2 or more type.
  • the print layer may contain any other additive depending on the purpose.
  • the additive include a photopolymerization initiator, a silane coupling agent, a mold release agent, a curing agent, a curing accelerator, a diluent, an anti-aging agent, a modifier, a surfactant, a dye, a pigment, and a discoloration preventing agent.
  • the type, number, amount, and the like of additives that can be contained in the print layer can be appropriately set according to the purpose.
  • the printing layer may have a single-layer form or a multi-layer (stacked) form.
  • the printing layer is formed on the entire surface (entire surface) of the sheet-like organic substrate 1 having extensibility (if the intermediate layer described later is present on the sheet-like extensible organic substrate, the intermediate layer). Depending on the application, it may be partially provided only on a necessary portion of the surface of the sheet-like organic substrate 1 having extensibility.
  • the thickness of the printing layer is not particularly limited, but is, for example, 0.1 to 100 ⁇ m, and the lower limit of the thickness is preferably 1 ⁇ m.
  • the thickness of the print layer is not particularly limited, but is, for example, 0.1 to 100 ⁇ m, and the lower limit of the thickness is preferably 1 ⁇ m.
  • the printing layer can be formed by a known or commonly used method.
  • a sheet-like organic substrate such as a sheet-like extensible organic substrate
  • a printing layer material for example, a resin composition containing a water-soluble resin.
  • a method of coating on the intermediate layer a method of laminating the printing layer on a sheet-like organic substrate (or intermediate layer) having extensibility; and a printing layer on an appropriate support
  • the method include a method of transferring to a sheet-like extensible organic base material (or intermediate layer) via an adhesive layer or the like, if necessary.
  • the sheet-like extensible organic base material that is easily imparted with designability can have other extensibility between the sheet-like organic base material 1 having extensibility and the print layer 6 as long as the extensibility is not impaired. It may have a layer (intermediate layer).
  • the sheet-like extensible organic base material of the present invention is easy to impart designability by having a printing layer.
  • the sheet-like extensible organic base material is an easily extensible polymer matrix similar to the sheet-like extensible organic base material (sheet-like extensible organic base material to which designability is imparted) of the aspect (i).
  • the material and / or the cylindrical hardly extensible polymer part A may contain a dye or a pigment. Examples of the types and contents of the dyes and pigments are the same as those in the sheet-like extensible organic substrate of the aspect (i).
  • the sheet-like extensible organic substrate has, for example, a coloring layer described later on the surface opposite to the print layer of the extensible sheet-like organic substrate or the surface of the print layer. May be.
  • the thickness of the sheet-like extensible organic base material to which designability is easily imparted is, for example, 0.01 mm or more, preferably 0.03 mm or more, and more preferably 0.05 mm or more.
  • the upper limit of the thickness of the sheet-like extensible organic base material of the present invention is, for example, 1 cm, preferably 5 mm, and more preferably 2 mm.
  • the sheet-like extensible organic base material has a shape-invariable portion and has a designability imparted (or can be easily imparted with a designability) [or a shape-invariant portion and a design.
  • Stretchable members with added properties (or easy designability)] members for electronic products (transistors, integrated circuits, capacitors, sensors, actuators, etc.), optical products (displays, lighting, optical waveguide circuits, etc.) ) Materials, optoelectronic products (light emitting diodes, photodiodes, solar cells, etc.), car electronics products, home appliances, housing equipment, building materials, band members, binding members, sanitary goods, clothing It can be used as a product part, as a base material for poultices.
  • Sheet-like extensible organic base material with flame retardancy As a sheet-like extensible organic base material having flame retardancy, a sheet-like organic group having extensibility, in which a cylindrical hardly extensible polymer portion A is partially and integrally formed in an easily extensible polymer base material
  • the sheet-like organic base material contains a flame retardant (that is, the sheet-like organic base material (particularly, the easily extensible polymer base material itself) has flame retardancy), and
  • a flame retardant that is, the sheet-like organic base material (particularly, the easily extensible polymer base material itself) has flame retardancy
  • An example is a sheet-like extensible organic base material having a flame retardant layer on at least one surface of the sheet-like organic base material.
  • Such a sheet-like extensible organic base material is excellent in flame retardancy, for example, even if ignited by flame contact, it extinguishes spontaneously when the flame is moved away. Therefore, even if this sheet-like extensible organic base material touches a flame, it can prevent fire spread by self-extinguishing or flame shielding.
  • a sheet-like extensible organic base material having flame retardancy is a sheet-like organic group having extensibility in which a cylindrical hardly extensible polymer portion A is partially and integrally formed in an easily extensible polymer base material.
  • the sheet-like organic substrate may be a sheet-like extensible organic substrate containing a flame retardant, and has a flame-retardant layer on at least one side of the sheet-like organic substrate. It may be a sheet-like extensible organic substrate, the sheet-like organic substrate contains a flame retardant, and the sheet-like extensibility has a flame retardant layer on at least one side of the sheet-like organic substrate.
  • An organic base material may be sufficient.
  • the functional layer 6 is a flame-retardant layer.
  • the functional layer 6 is a flame retardant layer, and the multifunctional sheet-like elongation shown in (3) of FIG.
  • Examples of the organic base material A include those in which the sheet-like organic base material 1 itself having extensibility has flame retardancy.
  • the flame retardant may be contained in the easily extensible polymer matrix constituting the sheet-like organic base material having extensibility, may be contained in the cylindrical hardly extensible polymer portion A, and the easily extensible polymer. It may be contained in the base material and the cylindrical hardly extensible polymer part A.
  • the seed-like organic base material containing a flame retardant uses an easily stretchable polymer base material containing a flame retardant as the easily stretchable polymer base material in the method for producing a sheet-like organic base having stretchability, or An easily extensible polymer base material containing a flame retardant as a material for forming a cylindrical hard extensible polymer portion A containing a flame retardant as a material for forming a cylindrical hard extensible polymer portion A, or containing a flame retardant as an easily extensible polymer base material And a cylindrical difficult-to-extend polymer part A forming material containing a flame retardant as the material for forming a cylindrical difficult-to-extend polymer part A can be produced.
  • the flame retardant contained in the sheet-like organic base material having extensibility is not particularly limited, and known flame retardants can be used, for example, halogen compounds, phosphorus compounds, antimony compounds, metal hydroxides, and Other compounds can be mentioned. These can be used individually by 1 type or in combination of 2 or more types.
  • the halogen compounds include bromine compounds, chlorine compounds and the like.
  • the bromine-based compound include decabromodiphenyl ether; tetrabromobisphenol, tetrabromobisphenol / epoxy oligomer, tetrabromobisphenol / carbonate oligomer, tetrabromobisphenol / bis (dibromopropyl ether), tetrabromobisphenol / bis (aryl ether) ) Tetrabromobisphenol derivatives; bis (pentabromophenyl) ethane, 1,2-bis (2,4,6-tribromophenoxy) ethane, 2,4,6-tris (2,4,6-tribromo) Phenoxy) -1,3,5-triazine, 2,6-dibromophenol, 2,4-dibromophenol and other polybenzene ring compounds; brominated polystyrene, polybrominated styrene; ethyleneb
  • chlorinated compound examples include chlorinated paraffin, polychlorinated biphenyl, dechlorane, chlorendic acid, and chlorendic anhydride.
  • Examples of the phosphorus compound include triphenyl phosphate, cresyl diphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris (t-butylphenyl) phosphate, tris (i-propylphenyl) phosphate, 2-ethylhexyl diphenyl.
  • Aromatic phosphate esters such as phosphate; aromatic condensed phosphate esters such as 1,3-phenylenebis (diphenylphosphate), 1,3-phenylenebis (dixylenyl) phosphate, bisphenol A bis (diphenylphosphate); Tris Halogen-containing phosphates such as (dichloropropyl) phosphate, tris ( ⁇ -chloropropyl) phosphate, tris (chloroethyl) phosphate; 2,2-bis (chloromethyl) trimethyl Nbisu (bis (2-chloroethyl) phosphate), halogen-containing phosphoric condensed phosphate esters such as polyoxyalkylene bis-dichloro alkyl phosphates; may be mentioned red phosphorus Red phosphorus-based compounds such like.
  • antimony compound examples include antimony trioxide, antimony pentoxide, sodium antimonate, zirconium-antimony composite oxide, and the like.
  • metal hydroxide examples include alkali metal hydroxides such as magnesium hydroxide, aluminum hydroxide, and calcium hydroxide.
  • molybdenum compounds such as molybdenum trioxide and molybdate; bismuth trioxide, tungsten trioxide, boron oxide, borates (including borax), zinc borate, calcium aluminate, dihydrate gypsum, metaboric acid
  • molybdenum compounds such as molybdenum trioxide and molybdate; bismuth trioxide, tungsten trioxide, boron oxide, borates (including borax), zinc borate, calcium aluminate, dihydrate gypsum, metaboric acid
  • nitrates such as barium, kaolin clay, and sodium nitrate, zirconium compounds, dawsonite, phlogopite, and silicon-containing inorganic fillers.
  • the content (total amount) of the flame retardant is, for example, 1 to 400% by weight with respect to the whole stretchable polymer base material.
  • the lower limit of the content (total amount) of the flame retardant is preferably 5% by weight, more preferably 10% by weight, still more preferably 20% by weight, and the upper limit is preferably 350% by weight, more preferably 300% by weight, More preferably, it is 250 weight%.
  • the content (total amount) of the flame retardant is, for example, 1 to 400% by weight with respect to the entire cylindrical hard extensible polymer part A.
  • the lower limit of the content (total amount) of the flame retardant is preferably 5% by weight, more preferably 10% by weight, still more preferably 20% by weight, and the upper limit is preferably 350% by weight, more preferably 300% by weight, More preferably, it is 250 weight%.
  • the flame retardant layer may be a layer containing a flame retardant, or may be a layer containing a flame retardant polymer (a flame retardant polymer). Further, it may be a layer containing a flame retardant and a flame retardant polymer.
  • the flame retardant layer may be provided in contact with an extensible sheet-like organic base material, or may be provided via an adhesive layer or the like.
  • the flame retardant layer may be provided on the entire surface of the sheet-like organic base material having extensibility, and is partially applied only to a necessary portion of the surface of the sheet-like organic base material having extensibility. May be provided.
  • the flame retardant layer may be composed of one layer, or may be composed of two or more layers. When comprised by two or more layers, it may be comprised by the layer which has the same composition, and may be comprised by the layer which has a different composition.
  • the above flame retardant can be used without any particular limitation.
  • the flame retardant layer containing a flame retardant may contain a base polymer as necessary.
  • the base polymer it is preferable to use a polymer listed as an example of a polymer constituting the easily extensible polymer base material 2, and in particular, the same kind of polymer as the polymer constituting the easily extensible polymer base material 2, or A sheet having extensibility by selecting and using a polymer having a polymer chain of the same type as the polymer chain (main chain or side chain) of the polymer constituting the easily extensible polymer base material 2 in the main chain or side chain It is preferable at the point which can form the flame retardant layer which is excellent in the adhesiveness to the surface of a glassy organic base material.
  • the flame retardant polymer examples include polyvinyl chloride.
  • the weight average molecular weight of the flame retardant polymer is, for example, 10,000 to 2,000,000, preferably 300,000 to 1,500,000.
  • the flame retardant layer containing the flame retardant polymer may contain only the flame retardant polymer as the base polymer, and can be used for the flame retardant layer containing the flame retardant polymer and the above flame retardant. And may be contained in combination.
  • the flame retardant layer may contain other additives as long as the effects of the present invention are not impaired.
  • Other additives include, for example, crosslinking agents (epoxy crosslinking agents, isocyanate crosslinking agents, melamine crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, metal chelate compounds, etc.), crosslinking accelerators (crosslinking catalysts).
  • Tackifiers eg, rosin derivative resins, polyterpene resins, petroleum resins, oil-soluble phenol resins, etc.
  • thickeners plasticizers
  • fillers foaming agents, anti-aging agents, antioxidants, UV absorbers, charging Examples thereof include an inhibitor, a surfactant, a leveling agent, a colorant, a flame retardant, and a silane coupling agent.
  • the content (total amount) of the flame retardant in the total amount (100% by weight) of the flame retardant layer is, for example, 1 to 85% by weight.
  • the lower limit of the content (total amount) of the flame retardant is preferably 5% by weight, more preferably 10% by weight, still more preferably 20% by weight, and the upper limit is preferably 80% by weight, more preferably 75% by weight, More preferably, it is 70 weight%.
  • the content (total amount) of the flame retardant polymer in the total amount (100% by weight) of the flame retardant layer is, for example, 1 to 100% by weight. That is, the flame retardant layer may be formed of only the flame retardant polymer.
  • the lower limit of the content (total amount) of the flame retardant polymer is preferably 5% by weight, more preferably 10% by weight, still more preferably 20% by weight, and the upper limit is preferably 95% by weight, more preferably 90% by weight. %, More preferably 85% by weight.
  • the content (total amount) of the flame retardant in the total amount (100% by weight) of the flame retardant layer is, for example, 1 to 85% by weight.
  • the lower limit of the content (total amount) of the flame retardant is preferably 5% by weight, more preferably 10% by weight, still more preferably 20% by weight, and the upper limit is preferably 80% by weight, more preferably 75% by weight, More preferably, it is 70 weight%.
  • the content (total amount) of the flame retardant polymer in the total amount (100% by weight) of the flame retardant layer is, for example, 1% by weight or more and less than 100% by weight.
  • the lower limit of the content (total amount) of the flame retardant polymer is preferably 5% by weight, more preferably 10% by weight, still more preferably 20% by weight, and the upper limit is preferably 95% by weight, more preferably 90% by weight. %, More preferably 85% by weight.
  • the same method as the method for forming the easily extensible polymer base material part 2 can be adopted except that a flame retardant is added.
  • the flame retardant layer may be formed directly on the surface of the stretchable sheet-like organic base material, and the flame retardant layer is formed on a suitable separator (release paper, etc.), and this is formed into a sheet form having the stretchability. It may be transferred (transferred) to an organic base material and laminated.
  • the flame retardant layer containing the flame retardant is obtained by melt-extruding the material for forming the flame retardant layer (including at least the flame retardant and the base polymer) and the easily stretchable polymer base material forming the easily stretchable polymer base material. It can also be formed by a method of integrating them.
  • the melt extrusion method any known technique such as an inflation method or a T-die method can be used.
  • a solution or dispersion containing a flame retardant polymer is directly applied to an extensible sheet-like organic base material to form a flame retardant layer.
  • a flame retardant layer is formed by applying a solution or dispersion containing the flame retardant polymer on a method or an appropriate separator (such as release paper), and this is transferred (transferred) to a sheet-like organic substrate having extensibility.
  • a method of laminating and laminating The application can be performed by a coater, an extruder, a printing machine or the like.
  • the thickness of the flame retardant layer can be appropriately selected depending on the application and the like, and is, for example, 5 to 500 ⁇ m, and the lower limit is preferably 10 ⁇ m, more preferably 30 ⁇ m, and even more preferably 50 ⁇ m.
  • the upper limit is preferably 450 ⁇ m, more preferably 400 ⁇ m, and even more preferably 300 ⁇ m.
  • the adhesive constituting the adhesive layer is not particularly limited, and examples thereof include rubber adhesives and acrylic adhesives.
  • One or more known pressure-sensitive adhesives such as creep property-improving pressure-sensitive adhesives containing the following hot-melt resins can be used in combination.
  • the pressure-sensitive adhesive may be any known pressure-sensitive adhesive such as a solvent type, an emulsion type, a hot-melt type, an energy ray curable pressure-sensitive adhesive, and a heat release type, and an appropriate one can be selected depending on the application. Further, the pressure-sensitive adhesive may be any of a weak pressure-sensitive adhesive type, a strong pressure-sensitive adhesive type, a re-peeling type, and the like, and can be appropriately selected according to the application.
  • an acrylic pressure-sensitive adhesive based on an acrylic polymer (weight average molecular weight is, for example, 10,000 to 2,000,000, preferably 300,000 to 1,500,000) is preferably used.
  • the acrylic polymer may be any of a random copolymer, a block copolymer, a graft polymer, and the like.
  • crosslinking agents epoxy crosslinking agents, isocyanate crosslinking agents, melamine crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, metal chelate compounds, etc.
  • crosslinking Accelerator crosslinking catalyst
  • tackifier for example, rosin derivative resin, polyterpene resin, petroleum resin, oil-soluble phenol resin, etc.
  • thickener plasticizer
  • filler foaming agent
  • an anti-aging agent antioxidant
  • an appropriate additive such as an ultraviolet absorber, an antistatic agent, a surfactant, a leveling agent, a colorant, a flame retardant, and a silane coupling agent.
  • the formation of the pressure-sensitive adhesive layer can be performed by a known or conventional method.
  • the pressure-sensitive adhesive composition on a sheet-like organic substrate (sheet-like extensible organic substrate) 1 having extensibility (if the intermediate layer exists on the sheet-like extensible organic substrate, the intermediate layer)
  • the pressure-sensitive adhesive layer is formed into a sheet-like organic substrate 1 having extensibility (the sheet-like extensible organic substrate).
  • a method of transferring (transferring) onto the intermediate layer) may be mentioned.
  • the pressure-sensitive adhesive layer may be provided on the entire surface of the sheet-like organic substrate 1 having extensibility, or may be partially provided only on a necessary portion of the surface of the sheet-like organic substrate 1 having extensibility. Good.
  • the thickness of the pressure-sensitive adhesive layer can be appropriately selected according to the use and the like, and is, for example, 5 to 3000 ⁇ m, the lower limit is preferably 10 ⁇ m, and the upper limit is preferably 500 ⁇ m.
  • a protective film for protecting the surface may be provided on the flame retardant layer 6 until the flame-retardant sheet-like extensible organic base material A is used.
  • the sheet-like extensible organic base material having flame retardancy is an extensible member having flame retardancy and having a shape-invariable portion (or an elastic member having flame retardancy and having a shape-invariant portion. ), Members for electronic products (transistors, integrated circuits, capacitors, sensors, actuators, etc.), members for optical products (displays, lighting, optical waveguide circuits, etc.), optoelectronic products (light emitting diodes, photodiodes, solar cells, etc.) It can be used as a member for automobiles, a member for car electronics products, a member for household electrical appliances, a member for household equipment, a building material, a band member, a binding member, a sanitary article, a clothing part, a base cloth for a poultice.
  • Sheet-like extensible organic base material having thermal conductivity As a sheet-like extensible organic base material having thermal conductivity, a sheet-like organic group having extensibility in which a cylindrical hardly extensible polymer portion A is partially and integrally formed in an easily extensible polymer base material
  • the sheet-like organic base material contains a heat conductive substance (that is, the sheet-like organic base material (particularly, the easily extensible polymer base material itself) has a heat conductivity). And / or those having a thermally conductive layer on at least one side of the sheet-like organic substrate.
  • the thermal conductivity of the sheet-like extensible organic base material is, for example, about 0.5 W / m ⁇ K or more, preferably 1.0 W / m ⁇ K or more. Therefore, such a sheet-like extensible organic substrate can efficiently dissipate heat generated inside and outside the sheet-like extensible organic substrate.
  • the sheet-like extensible organic base material having thermal conductivity when the sheet-like extensible organic base material is extended in one direction (plane direction), the part of the easily extensible polymer base material is extended.
  • the formed cylindrical difficult-to-extend polymer part A does not stretch or hardly stretches. For this reason, it is possible to give the tubular hardly extensible polymer portion A a design whose shape is desired not to change, and to fix and hold other members.
  • the functional layer 6 is a heat conductive layer.
  • the functional layer 6 is a heat conductive layer, and the multifunctional sheet shown in (3) of FIG.
  • the stretchable organic base material A include those in which the stretchable sheet-like organic base material 1 itself has thermal conductivity.
  • the thermal conductivity of the sheet-like extensible organic base material having thermal conductivity is, for example, about 0.5 W / m ⁇ K or more, preferably 1.0 W / m ⁇ K or more. Therefore, this sheet-like extensible organic base material can efficiently dissipate heat generated inside and outside the sheet-like extensible organic base material.
  • the sheet-like extensible organic base material having thermal conductivity when the sheet-like extensible organic base material is extended in one direction (plane direction), the part of the easily extensible polymer base material is extended.
  • the formed cylindrical difficult-to-extend polymer part A does not stretch or hardly stretches. For this reason, it is possible to give the tubular hardly extensible polymer portion A a design whose shape is desired not to change, and to fix and hold other members.
  • the sheet-like extensible organic base material having thermal conductivity is a sheet-like organic group having extensibility in which a cylindrical hardly extensible polymer portion A is partially and integrally formed in an easily extensible polymer base material.
  • the sheet-like organic base material may be a sheet-like extensible organic base material containing a heat conductive substance, and has a heat conductive layer on at least one side of the sheet-like organic base material. It may be a sheet-like extensible organic substrate, the sheet-like organic substrate contains a heat conductive substance, and has a heat conductive layer on at least one side of the sheet-like organic substrate. It may be a sheet-like extensible organic substrate.
  • the sheet-like organic base material contains a heat conductive substance, heat conductivity in the surface direction and the thickness direction can be imparted.
  • heat conductivity in the surface direction can be imparted.
  • the thermally conductive substance may be contained in the easily stretchable polymer base material constituting the stretchable sheet-like organic base material, or may be contained in the cylindrical difficult-to-extend polymer part A. May be contained in the porous polymer base material and the cylindrical hardly extensible polymer part A.
  • a seed-like organic base material containing a thermally conductive substance is an easily stretchable polymer base material containing a thermally conductive substance as an easily stretchable polymer base material in the above-described method for producing a sheet-like organic base having stretchability.
  • a cylindrical hard-to-extend polymer part A-forming material containing a heat-conducting substance as a material for forming a cylindrical hard-to-extend polymer part A, or a heat-conducting substance as an easily-extensible polymer base material can do.
  • the heat conductive material contained in the sheet-like organic substrate having extensibility is not particularly limited, and a known heat conductive material can be used, for example, metal, metal compound, boron compound, graphite, and heat conductivity. Carbon fiber etc. can be mentioned. These can be used alone or in combination of two or more. In this invention, it is preferable to use a metal compound and a boron compound especially at the point which can combine electrical insulation with heat conductivity.
  • the metal examples include a metal (eg, gold, silver, iron, aluminum, copper, nickel, titanium) alone, or an alloy thereof.
  • metal compound examples include metal oxides (for example, SiO2, TiO2, MgO, NiO, CuO, Al2O3, Fe2O3), metal nitrides (for example, AlN, Si3N4), metal hydroxides (for example, Mg (OH 2), metal carbonates (for example, MgCO3), metal borides (for example, TiB2), and the like.
  • metal oxides for example, SiO2, TiO2, MgO, NiO, CuO, Al2O3, Fe2O3
  • metal nitrides for example, AlN, Si3N4
  • metal hydroxides for example, Mg (OH 2)
  • metal carbonates for example, MgCO3
  • metal borides for example, TiB2
  • Examples of the boron compound include BN and B4C.
  • metal oxides, metal nitrides, metal hydroxides, metal carbonates, metal borides, and boron compounds are preferable because they have both heat conductivity and electrical insulation.
  • the shape of the heat conductive material is not particularly limited, and may be any of a bulk shape, a spherical shape, a needle shape, a plate shape, and the like.
  • the average particle diameter of the thermally conductive substance (in the case of needles, the average diameter of the major axis) is, for example, 0.001 to 100 ⁇ m.
  • the upper limit of the average particle diameter of the heat conductive substance (in the case of needles, the average diameter of the major axis) is preferably 50 ⁇ m, more preferably 20 ⁇ m, and the lower limit is preferably 0.005 ⁇ m, more preferably 0.01 ⁇ m. It is.
  • the content (total amount) of the heat conductive substance is, for example, 1 to 400% by weight with respect to the whole easily stretchable polymer base material.
  • the lower limit of the content (total amount) of the heat conductive material is preferably 3% by weight, more preferably 5% by weight, still more preferably 10% by weight, and the upper limit is preferably 300% by weight, more preferably 250% by weight. %, More preferably 200% by weight.
  • the content (total amount) of the heat conductive substance is, for example, 1 to 1000 wt. %.
  • the lower limit of the content (total amount) of the heat conductive material is preferably 3% by weight, more preferably 5% by weight, still more preferably 10% by weight, and the upper limit is preferably 800% by weight, more preferably 500% by weight. %, More preferably 300% by weight.
  • the heat conductive layer contains at least a heat conductive material. Moreover, this heat conductive layer may be provided in the state which contact
  • the above heat conductive material can be used without any particular limitation.
  • the heat conductive layer may contain a base polymer as necessary.
  • a base polymer it is preferable to use a polymer listed as an example of a polymer constituting the easily extensible polymer base material 2, and in particular, the same kind of polymer as the polymer constituting the easily extensible polymer base material 2, or A sheet having extensibility by selecting and using a polymer having a polymer chain of the same type as the polymer chain (main chain or side chain) of the polymer constituting the easily extensible polymer base material 2 in the main chain or side chain It is preferable at the point which can form the heat conductive layer excellent in the adhesiveness to the surface of a glassy organic base material.
  • the heat conductive layer may further contain other additives within a range not impairing the effects of the present invention.
  • additives include, for example, crosslinking agents (epoxy crosslinking agents, isocyanate crosslinking agents, melamine crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, metal chelate compounds, etc.), crosslinking accelerators (crosslinking catalysts).
  • Tackifiers eg, rosin derivative resins, polyterpene resins, petroleum resins, oil-soluble phenol resins, etc.
  • thickeners plasticizers
  • fillers foaming agents, anti-aging agents, antioxidants, UV absorbers, charging Examples thereof include an inhibitor, a surfactant, a leveling agent, a colorant, a thermally conductive substance, and a silane coupling agent.
  • the content (total amount) of the heat conductive material in the total amount (100% by weight) of the heat conductive layer is, for example, 1 to 80% by weight.
  • the lower limit of the content (total amount) of the heat conductive material is preferably 3% by weight, more preferably 5% by weight, still more preferably 10% by weight, and the upper limit is preferably 75% by weight, more preferably 70% by weight. %, More preferably 65% by weight.
  • the same method as the method for forming the easily stretchable polymer base material 2 can be adopted except that a heat conductive material is added.
  • the heat conductive layer may be directly formed on the surface of the sheet-like organic base material having extensibility.
  • the heat conductive layer is formed on an appropriate separator (such as release paper) and has the extensibility. You may transfer (transfer) and laminate
  • the heat conductive layer is obtained by melt-extruding a material for forming a heat conductive layer (including at least a heat conductive material and a base polymer) and a stretchable polymer base material that forms a stretchable polymer base material. It can also be formed by an integrated method.
  • a material for forming a heat conductive layer including at least a heat conductive material and a base polymer
  • a stretchable polymer base material that forms a stretchable polymer base material. It can also be formed by an integrated method.
  • melt extrusion method any known technique such as an inflation method or a T-die method can be used.
  • the thickness of the heat conductive layer can be appropriately selected according to the use and the like, and is, for example, 1 to 500 ⁇ m, and the lower limit is preferably 5 ⁇ m, more preferably 10 ⁇ m, and still more preferably 20 ⁇ m.
  • the upper limit is preferably 400 ⁇ m, more preferably 300 ⁇ m, and even more preferably 200 ⁇ m.
  • the adhesive constituting the adhesive layer is not particularly limited, and examples thereof include rubber adhesives and acrylics.
  • Adhesives, vinyl alkyl ether adhesives, silicone adhesives, polyester adhesives, polyamide adhesives, urethane adhesives, styrene-diene block copolymer adhesives, and these adhesives have a melting point of about 200
  • Known pressure-sensitive adhesives such as creep property-improving pressure-sensitive adhesives blended with a heat-meltable resin at a temperature of 0 ° C. or lower can be used alone or in combination of two or more.
  • the pressure-sensitive adhesive may be any known pressure-sensitive adhesive such as a solvent type, an emulsion type, a hot-melt type, an energy ray curable pressure-sensitive adhesive, and a heat release type, and an appropriate one can be selected depending on the application. Further, the pressure-sensitive adhesive may be any of a weak pressure-sensitive adhesive type, a strong pressure-sensitive adhesive type, a re-peeling type, and the like, and can be appropriately selected according to the application.
  • an acrylic pressure-sensitive adhesive based on an acrylic polymer (weight average molecular weight is, for example, 10,000 to 2,000,000, preferably 300,000 to 1,500,000) is preferably used.
  • the acrylic polymer may be any of a random copolymer, a block copolymer, a graft polymer, and the like.
  • crosslinking agents epoxy crosslinking agents, isocyanate crosslinking agents, melamine crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, metal chelate compounds, etc.
  • crosslinking Accelerator crosslinking catalyst
  • tackifier for example, rosin derivative resin, polyterpene resin, petroleum resin, oil-soluble phenol resin, etc.
  • thickener plasticizer
  • filler foaming agent
  • an appropriate additive such as an ultraviolet absorber, an antistatic agent, a surfactant, a leveling agent, a colorant, a heat conductive substance, or a silane coupling agent may be contained.
  • the formation of the pressure-sensitive adhesive layer can be performed by a known or conventional method. For example, a method of applying a pressure-sensitive adhesive composition onto a sheet-like organic substrate 1 having extensibility (or an intermediate layer when an intermediate layer is present on the sheet-like extensible organic substrate), a pressure-sensitive adhesive composition Is applied onto a suitable separator to form a pressure-sensitive adhesive layer, and then the pressure-sensitive adhesive layer is formed into a sheet-like organic substrate 1 having extensibility (if an intermediate layer is present on the sheet-like extensible organic substrate) And a method of transferring (transferring) onto the intermediate layer).
  • a method of applying a pressure-sensitive adhesive composition onto a sheet-like organic substrate 1 having extensibility or an intermediate layer when an intermediate layer is present on the sheet-like extensible organic substrate
  • a pressure-sensitive adhesive composition Is applied onto a suitable separator to form a pressure-sensitive adhesive layer
  • the pressure-sensitive adhesive layer is formed into a sheet-like organic substrate 1 having extensibility (if an intermediate layer is present on
  • the pressure-sensitive adhesive layer may be provided on the entire surface of the sheet-like organic substrate 1 having extensibility, or may be partially provided only on a necessary portion of the surface of the sheet-like organic substrate 1 having extensibility. Good.
  • the thickness of the pressure-sensitive adhesive layer can be appropriately selected according to the use and the like, and is, for example, 1 to 3000 ⁇ m, the lower limit is preferably 5 ⁇ m, and the upper limit is preferably 500 ⁇ m.
  • the sheet-like organic substrate 1 having extensibility and the heat conductive layer 6 are included as necessary within the range not impairing extensibility other than the adhesive layer. It may be. Moreover, on the heat conductive layer 6, the protective film for protecting the surface may be provided until it uses the sheet-like extensible organic base material A which has heat conductivity.
  • the sheet-like extensible organic base material having thermal conductivity is an extensible member having thermal conductivity and having a shape-invariant portion (or a stretchable member having thermal conductivity and having a shape-invariant portion).
  • Components for electronics products transistors, integrated circuits, capacitors, sensors, actuators, etc.
  • components for optical products dislays, lighting, optical waveguide circuits, etc.
  • components for optoelectronic products light emitting diodes, photodiodes, solar cells, etc.
  • It can be used as a member for car electronics products, a member for household electrical appliances, a member for household equipment, a building material, a band member, a binding member, a sanitary product, a clothing part, a base material for a poultice.
  • Sheet-like extensible organic base material with heat insulation As a sheet-like extensible organic base material having heat insulation properties, a sheet-like organic base material having extensibility in which a cylindrical hard-extensible polymer portion A is partially and integrally formed in an easily extensible polymer base material
  • the sheet-like organic base material contains a heat-insulating agent (that is, the sheet-like organic base material (particularly, the easily extensible polymer base material itself) has heat-insulating properties), and / Or what has a heat insulation layer in the at least single side
  • the thermal conductivity is, for example, about 0.05 W / m ⁇ K or less, preferably 0.03 W / m ⁇ K or less. Therefore, such a sheet-like extensible organic base material can suppress heat conduction to the other surface even when one surface of the base material is in contact with a heat source.
  • a sheet-like extensible organic base material having heat insulation properties when this sheet-like extensible organic base material is extended in one direction (plane direction), the site of the easily extensible polymer base material is extended, but partially formed
  • the formed cylindrical hardly extensible polymer part A does not stretch or hardly stretches. For this reason, it is possible to give the tubular hardly extensible polymer portion A a design whose shape is desired not to change, and to fix and hold other members.
  • the functional layer 6 is a heat-insulating layer.
  • the functional layer 6 is a heat insulating layer, and the multifunctional sheet-like stretchability shown in (3) of FIG.
  • the sheet-like organic base material 1 itself having extensibility has a heat insulating property.
  • the sheet-like extensible organic base material having heat insulation is a sheet-like organic base material having extensibility in which a cylindrical hard-extensible polymer portion A is partially and integrally formed in an easily extensible polymer base material.
  • the sheet-like organic substrate may be a sheet-like extensible organic substrate containing a heat-insulating agent, and has a heat-insulating layer on at least one side of the sheet-like organic substrate.
  • a sheet-like extensible organic base material, the sheet-like organic base material containing a heat-insulating agent, and having a heat-insulating layer on at least one side of the sheet-like organic base material It may be a stretchable organic substrate. Since the sheet-like extensible organic base material of the present invention has heat insulation properties, even if one surface of the base material is in contact with a heat source, heat conduction to the other surface can be suppressed.
  • the heat insulating property imparting agent may be contained in the easily stretchable polymer base material constituting the stretchable sheet-like organic base material, may be contained in the cylindrical hardly stretchable polymer part A, and is easily stretched. May be contained in the porous polymer base material and the cylindrical hardly extensible polymer part A.
  • the seed-like organic base material containing the heat insulating property imparting agent is an easily stretchable polymer base material containing the heat insulating property imparting agent as the easily stretchable polymer base material in the above-described method for producing a sheet-like organic base having extensibility.
  • a cylindrical hard-to-extend polymer part A forming material containing a heat-insulating agent as a material for forming a cylindrical hard-to-extend polymer part A, or a heat-insulating agent as an easily-extensible polymer base material can do.
  • the heat insulating property-imparting agent contained in the sheet-like organic base material having extensibility is not particularly limited, and known heat insulating property imparting agents can be used, and examples thereof include hollow particles such as inorganic hollow particles and organic hollow particles. Can do. These can be used alone or in combination of two or more.
  • Examples of the inorganic hollow particles include a microballoon mainly composed of borosilicate glass, a microballoon mainly composed of sodium boron silica, a microballoon mainly composed of alumina, and a microballoon mainly composed of silica. Can be mentioned.
  • organic hollow particles for example, a styrene polymer, an acrylic polymer, a vinyl chloride polymer, a vinylidene chloride polymer or the like (single polymer or a copolymer in which two or more are copolymerized or may be cross-linked) is a main component. And a microballoon.
  • the average particle diameter of the hollow particles is, for example, 0.1 to 90 ⁇ m, preferably 1 to 75 ⁇ m, particularly preferably 10 to 65 ⁇ m.
  • the bulk specific gravity of the hollow particles is, for example, about 0.01 to 0.5 g / cm 3.
  • the true specific gravity is, for example, about 0.01 to 0.7.
  • the trade name “Q-CEL5020” (manufactured by Potters Barotini Co., Ltd.), the trade name “SX-866 (A)” (manufactured by JSR Corporation), and the trade name “SX-8882 ( A) "(manufactured by JSR Corporation), trade name” Sirinax (registered trademark) "(manufactured by Nittetsu Mining Co., Ltd.), trade name” Matsumoto Microsphere M305 “(manufactured by Matsumoto Yushi Seiyaku Co., Ltd.), etc.
  • Commercially available products can be suitably used.
  • the content (total amount) of the heat insulating property imparting agent is, for example, 0.1 to 100% by weight with respect to the entire easily stretchable polymer base material. is there.
  • the lower limit of the content (total amount) of the heat insulating agent is preferably 0.5% by weight, more preferably 1% by weight, still more preferably 2% by weight, and the upper limit is preferably 90% by weight, more preferably. 80% by weight, more preferably 70% by weight.
  • the content (total amount) of the heat insulating property imparting agent is, for example, 0.1 to 100% by weight.
  • the lower limit of the content (total amount) of the heat insulating agent is preferably 0.5% by weight, more preferably 1% by weight, still more preferably 2% by weight, and the upper limit is preferably 90% by weight, more preferably. 80% by weight, more preferably 70% by weight.
  • the heat insulating layer may be a layer containing at least a heat insulating agent, or may be a layer formed of a heat insulating material such as foamed plastic. Moreover, this heat insulation layer may be provided in the state which contact
  • the heat insulating property imparting agent contained in the heat insulating layer can be used without any particular limitation.
  • the heat-insulating layer may contain a base polymer as necessary.
  • a base polymer it is preferable to use a polymer listed as an example of a polymer constituting the easily extensible polymer base material 2, and in particular, the same kind of polymer as the polymer constituting the easily extensible polymer base material 2, or A sheet having extensibility by selecting and using a polymer having a polymer chain of the same type as the polymer chain (main chain or side chain) of the polymer constituting the easily extensible polymer base material 2 in the main chain or side chain It is preferable at the point which can form the heat insulation layer excellent in the adhesiveness to the surface of a glassy organic base material.
  • the heat insulating layer may further contain other additives within a range not impairing the effects of the present invention.
  • additives include, for example, crosslinking agents (epoxy crosslinking agents, isocyanate crosslinking agents, melamine crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, metal chelate compounds, etc.), crosslinking accelerators (crosslinking catalysts).
  • Tackifiers eg, rosin derivative resins, polyterpene resins, petroleum resins, oil-soluble phenol resins, etc.
  • thickeners plasticizers
  • fillers foaming agents, anti-aging agents, antioxidants, UV absorbers, charging Examples thereof include an inhibitor, a surfactant, a leveling agent, a colorant, a heat-insulating agent, and a silane coupling agent.
  • the content (total amount) of the heat-insulating agent in the total amount (100% by weight) of the heat-insulating layer is, for example, 0.1 to 100% by weight.
  • the lower limit of the content (total amount) of the heat insulating agent is preferably 0.5% by weight, more preferably 1% by weight, still more preferably 2% by weight, and the upper limit is preferably 90% by weight, more preferably. 80% by weight, more preferably 70% by weight.
  • the same method as the method for forming the easily stretchable polymer base material part 2 can be adopted except that the heat insulating property imparting agent is added.
  • the heat insulating layer may be directly formed on the surface of the sheet-like organic base material having extensibility.
  • the heat insulating layer is formed on an appropriate separator (such as release paper), and this is formed into a sheet form having extensibility. It may be transferred (transferred) to an organic base material and laminated.
  • the heat-insulating layer containing the heat-insulating agent includes a heat-insulating layer forming material (including at least a heat-insulating agent and a base polymer) and an easily stretchable polymer base material that forms an easily stretchable polymer base material.
  • a heat-insulating layer forming material including at least a heat-insulating agent and a base polymer
  • an easily stretchable polymer base material that forms an easily stretchable polymer base material.
  • melt extrusion method any known technique such as an inflation method or a T-die method can be used.
  • the heat insulating layer is a layer formed of foamed plastic
  • the foamed plastic include urethane foam, foamed polystyrene, foamed polyethylene, foamed polypropylene, foamed polyester, foamed acrylic, rubber foam (for example, ethylene propylene). Diene rubber (EPDM) foam, etc.), phenol foam, silicone foam, polyvinyl chloride foam, urea foam, acrylic foam, polyimide foam, melamine foam and the like.
  • the thickness of the heat insulating layer can be appropriately selected depending on the application and the like, and is, for example, 10 to 10,000 ⁇ m, and the lower limit is preferably 50 ⁇ m, more preferably 100 ⁇ m, and further preferably 150 ⁇ m.
  • the upper limit is preferably 5000 ⁇ m, more preferably 2000 ⁇ m.
  • the adhesive constituting the adhesive layer is not particularly limited.
  • a rubber-based adhesive an acrylic-based adhesive Adhesives, vinyl alkyl ether adhesives, silicone adhesives, polyester adhesives, polyamide adhesives, urethane adhesives, styrene-diene block copolymer adhesives, melting point of these adhesives is about 200 ° C
  • One or more known pressure-sensitive adhesives such as creep property-improving pressure-sensitive adhesives containing the following hot-melt resins can be used in combination.
  • the pressure-sensitive adhesive may be any known pressure-sensitive adhesive such as a solvent type, an emulsion type, a hot-melt type, an energy ray curable pressure-sensitive adhesive, and a heat release type, and an appropriate one can be selected depending on the application. Further, the pressure-sensitive adhesive may be any of a weak pressure-sensitive adhesive type, a strong pressure-sensitive adhesive type, a re-peeling type, and the like, and can be appropriately selected according to the application.
  • an acrylic pressure-sensitive adhesive based on an acrylic polymer (weight average molecular weight is, for example, 10,000 to 2,000,000, preferably 300,000 to 1,500,000) is preferably used.
  • the acrylic polymer may be any of a random copolymer, a block copolymer, a graft polymer, and the like.
  • crosslinking agents epoxy crosslinking agents, isocyanate crosslinking agents, melamine crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, metal chelate compounds, etc.
  • crosslinking Accelerator crosslinking catalyst
  • tackifier for example, rosin derivative resin, polyterpene resin, petroleum resin, oil-soluble phenol resin, etc.
  • thickener plasticizer
  • filler foaming agent
  • an anti-aging agent antioxidant
  • an appropriate additive such as an ultraviolet absorber, an antistatic agent, a surfactant, a leveling agent, a colorant, a heat-insulating agent, and a silane coupling agent.
  • the formation of the pressure-sensitive adhesive layer can be performed by a known or conventional method. For example, a method of applying a pressure-sensitive adhesive composition onto a sheet-like organic substrate 1 having extensibility (or an intermediate layer when an intermediate layer is present on the sheet-like extensible organic substrate), a pressure-sensitive adhesive composition Is applied onto a suitable separator to form a pressure-sensitive adhesive layer, and then the pressure-sensitive adhesive layer is formed into a sheet-like organic substrate 1 having extensibility (if an intermediate layer is present on the sheet-like extensible organic substrate) And a method of transferring (transferring) onto the intermediate layer).
  • a method of applying a pressure-sensitive adhesive composition onto a sheet-like organic substrate 1 having extensibility or an intermediate layer when an intermediate layer is present on the sheet-like extensible organic substrate
  • a pressure-sensitive adhesive composition Is applied onto a suitable separator to form a pressure-sensitive adhesive layer
  • the pressure-sensitive adhesive layer is formed into a sheet-like organic substrate 1 having extensibility (if an intermediate layer is present on
  • the pressure-sensitive adhesive layer may be provided on the entire surface of the sheet-like organic substrate 1 having extensibility, or may be partially provided only on a necessary portion of the surface of the sheet-like organic substrate 1 having extensibility. Good.
  • the thickness of the pressure-sensitive adhesive layer can be appropriately selected depending on the application, for example, 5 to 300 ⁇ m, the lower limit is preferably 10 ⁇ m, the upper limit is preferably 200 ⁇ m, more preferably 100 ⁇ m, and most preferably 50 ⁇ m. is there.
  • the sheet-like organic substrate 1 having extensibility and the heat-insulating layer 6 are included as necessary within the range not impairing extensibility other than the pressure-sensitive adhesive layer. May be.
  • the protective film for protecting the surface may be provided until it uses the sheet-like extensible organic base material A which has heat insulation.
  • the sheet-like stretchable organic base material having heat insulation properties is an electronic product (or a stretchable member having heat insulation properties and a shape-invariable portion) (or a stretchable member having heat insulation properties and a shape-invariant portion).
  • a sheet-like extensible organic base material having impact resistance a sheet-like organic group having extensibility in which a cylindrical hardly extensible polymer portion A is partially and integrally formed in an easily extensible polymer matrix.
  • the easily stretchable polymer base material includes an impact resistance imparting agent, and the cylindrical stretchable polymer portion A is partially and integrally formed in the easily stretchable polymer base material. The thing which has an impact absorption layer in the at least one surface of the sheet-like organic base material which has a stretching property is mentioned.
  • the functional layer 6 is a shock-absorbing layer in the multifunctional sheet-like stretchable organic substrate A shown in (1) of FIG.
  • the functional layer 6 is an impact absorbing layer, and the multifunctional sheet-like elongation shown in (3) of FIG.
  • the sheet-like organic base material 1 itself having extensibility has a shock absorbing property (excellent shock absorbing property).
  • the sheet-like organic substrate having extensibility When the sheet-like organic substrate having extensibility has impact absorbability, it can be used as a sheet-like extensible organic substrate having excellent impact absorbability.
  • an additive impact resistance imparting agent (also referred to as “impact absorbability imparting agent”)) for imparting impact absorbability to the easily extensible polymer base material, sheet-like extensibility is obtained. Impact absorption can be imparted to the organic substrate. Furthermore, by adding the impact resistance imparting agent to the hardly extensible part, it is possible to impart more excellent impact absorbability to the sheet-like extensible organic base material.
  • the impact resistance imparting agent is formed of hollow particles (inorganic hollow particles) formed of an inorganic material or organic materials. And hollow particles (organic hollow particles), particles formed from a foam material (foam particles), rubber particles, and the like.
  • the inorganic hollow particles include glass hollow balloons (glass balloons) such as hollow balloons (microballoons) formed of glass (particularly borosilicate glass), and metal hollow balloons formed of a metal compound. And porcelain hollow balloons such as hollow ceramic balloons.
  • the organic hollow particles include resin-made hollow balloons such as vinylidene chloride balloons and acrylic balloons.
  • the foam particles include expanded plastic particles such as expanded polystyrene particles, expanded urethane particles (urethane foam particles), expanded polyethylene particles, expanded isoprene rubber particles, expanded butadiene rubber particles, and expanded acrylic rubber particles.
  • the rubber particles include natural rubber particles, butadiene rubber particles, styrene-butadiene rubber particles, chloroprene rubber particles, isoprene rubber particles, urethane rubber particles, acrylic rubber particles, silicone rubber particles, and other synthetic rubber particles, and a core / shell structure. And rubber particles.
  • the impact resistance-imparting agent inorganic hollow particles and foamed plastic particles are preferable.
  • the impact resistance imparting agent can be used alone or in combination of two or more.
  • the shape of the impact resistance imparting agent is not particularly limited, and may be any of, for example, a bulk shape, a spherical shape, a needle shape, and a plate shape.
  • the particle diameter (average particle diameter; in the case of needles, the average diameter of the major axis) is not particularly limited, but is preferably 1 to 500 ⁇ m, for example.
  • the upper limit of the particle diameter of the impact resistance imparting agent is preferably 200 ⁇ m, more preferably 100 ⁇ m, from the viewpoint of dispersibility.
  • the lower limit of the particle size of the impact resistance imparting agent is preferably 5 ⁇ m, more preferably 10 ⁇ m, from the viewpoint of impact absorption.
  • the average particle diameter means a particle diameter (d50) at an integrated value of 50% calculated from a particle size distribution measured by a laser diffraction / scattering method.
  • the specific gravity of the impact resistance-imparting agent is not particularly limited, but is preferably 0.01 to 0.8 g / cm 3, for example.
  • the upper limit of the specific gravity of the impact resistance imparting agent is preferably 0.5 g / cm 3 from the viewpoint of cost and the like.
  • the lower limit of the specific gravity of the impact resistance-imparting agent is preferably 0.1 g / cm 3 from the viewpoint of handleability during blending.
  • the content (total amount) of the impact resistance imparting agent in the easily stretchable polymer base material is not particularly limited, but is, for example, 1 to 50% by weight with respect to the entire easily stretchable polymer base material.
  • the lower limit of the content (total amount) of the impact resistance imparting agent is preferably 2% by weight, more preferably 3% by weight, and still more preferably 5% by weight.
  • the upper limit is preferably 45% by weight, more preferably 40% by weight, and still more preferably 35% by weight. If the content of the impact resistance-imparting agent is less than 1% by weight, sufficient impact absorbability may not be exhibited. On the other hand, when the content of the impact resistance-imparting agent exceeds 50% by weight, the extensibility of the easily extensible polymer base material (organic base material having extensibility) may be lowered.
  • the content (total amount) is not particularly limited, but for example 1 to 50% by weight with respect to the entire cylindrical difficult-to-extend polymer part A It is.
  • the lower limit of the content (total amount) of the impact resistance imparting agent is preferably 2% by weight, more preferably 3% by weight, and still more preferably 5% by weight.
  • the upper limit is preferably 45% by weight, more preferably 40% by weight, and still more preferably 35% by weight. If the content of the impact resistance-imparting agent is less than 1% by weight, sufficient impact absorbability may not be exhibited.
  • the content of the impact resistance-imparting agent exceeds 50% by weight, the shape of the cylindrical hardly extensible polymer part A may be easily changed.
  • the sheet-like extensible organic base material having excellent shock absorption has an extensibility in which a cylindrical hardly extensible polymer portion A is partially and integrally formed in an easily extensible polymer base material.
  • the impact absorbing layer is preferably the following impact absorbing layer.
  • the impact absorbing layer 6 in the sheet-like extensible organic base material is a layer (functional layer) for exerting the impact-absorbing property on the sheet-like extensible organic base material.
  • the impact absorbing layer include a layer containing an impact resistance imparting agent (sometimes referred to as “impact resistance imparting agent-containing layer”); a layer formed from a foam (referred to as “foam layer”). There are).
  • the said shock absorption layer may have a single layer form, and may have the form of the multilayer (lamination
  • the said shock absorption layer is the whole (entire surface) of the surface of the sheet-like organic base material 1 which has extensibility (this intermediate layer when the below-mentioned intermediate
  • it may be partially provided only at a necessary portion of the surface of the sheet-like organic substrate 1 having extensibility.
  • Examples of the impact resistance imparting agent in the impact resistance imparting agent-containing layer include those described above. Among these, as the impact resistance imparting agent contained in the impact resistance imparting agent-containing layer, inorganic hollow particles and foamed plastic particles are preferable.
  • the impact resistance-containing agent-containing layer is not particularly limited, but is preferably a resin layer (resin composition layer) formed from a composition containing an impact resistance imparting agent and a polymer (binder polymer).
  • a resin layer resin composition layer
  • binder polymer polymer which has the extendability illustrated by the term of the above-mentioned [easily stretchable polymer base material]
  • the polymer having the extensibility as a binder polymer, excellent impact absorbability can be exhibited without impairing the extensibility of the sheet-like extensible organic base material.
  • the content (total amount) of the impact imparting agent in the impact imparting agent-containing layer is not particularly limited, but is, for example, 1 to 50% by weight with respect to the entire impact imparting agent-containing layer.
  • the lower limit of the content (total amount) of the impact resistance imparting agent is preferably 2% by weight, more preferably 3% by weight, and still more preferably 5% by weight.
  • the upper limit is preferably 45% by weight, more preferably 40% by weight, and still more preferably 35% by weight. If the content of the impact resistance-imparting agent is less than 1% by weight, sufficient impact absorbability may not be exhibited. On the other hand, if the content of the impact resistance-imparting agent exceeds 50% by weight, the extensibility of the impact resistance imparting agent-containing layer may be lowered.
  • the impact resistance-containing agent-containing layer can be formed by a known or conventional method, and the formation method is not particularly limited. Specifically, a method similar to the method for forming the easily extensible polymer base material, for example, a sheet-like organic base material having extensibility (the intermediate layer described later exists on the sheet-like extensible organic base material) In this case, the intermediate layer is coated with a liquid precursor of the binder polymer containing an impact resistance imparting agent, and then the liquid precursor is converted into a target polymer (binder polymer). It is done.
  • the liquid precursor examples include a monomer that can be derived from the binder polymer (such as an energy ray-curable monomer), a partially polymerized product of the monomer, and a polymer that is precured or crosslinked that can be induced to the binder polymer by curing or crosslinking.
  • the conversion of the liquid precursor into a binder polymer can be performed, for example, by polymerization (polymerization with energy rays or heat, etc.), curing, crosslinking reaction, or the like.
  • the impact resistance-containing agent-containing layer is formed on, for example, a sheet-like organic substrate having extensibility (if the intermediate layer described later is present on the sheet-like extensible organic substrate, the intermediate layer) Coating a solution or dispersion containing an impact resistance-imparting agent and the binder polymer, and then drying and removing the solvent (or dispersion medium); an extensible sheet-like organic substrate (the sheet-like elongation)
  • a layer made of a composition of the impact resistance-imparting agent and the binder polymer alone is formed on the intermediate layer, and a melting / cooling process (hot melt) It can also be formed by a method of performing processing.
  • the impact resistance-imparting agent-containing layer is formed by forming the impact resistance imparting agent-containing layer once on a support (separator or the like), and then forming the impact resistance imparting agent-containing layer into a sheet-like organic material having extensibility. It can also be formed by a method of transferring on a base material (in the case where an intermediate layer described later is present on the sheet-like extensible organic base material).
  • the foam constituting the foam layer a known or conventional foam can be used, and is not particularly limited, but a plastic foam can be particularly preferably used.
  • the plastic (plastic material) constituting the plastic foam include polystyrene, urethane (polyurethane), polyethylene, isoprene rubber, butadiene rubber, and acrylic rubber.
  • the foam layer include a polystyrene foam layer (foamed polystyrene layer), a urethane foam layer, a polyethylene foam layer (foamed polyethylene layer), an isoprene rubber foam layer, a butadiene rubber foam layer, and an acrylic rubber foam. Examples include body layers.
  • the foam layer can be formed by a known or conventional method, and the formation method is not particularly limited. Specifically, for example, a sheet-like foam produced by a well-known method is made into a sheet-like organic substrate 1 having extensibility (when an intermediate layer described later is present on the sheet-like extensible organic substrate) And a method of laminating on the intermediate layer).
  • or usual adhesive for example, acrylic adhesive etc.
  • an adhesive agent can be used for bonding of a sheet-like foam.
  • a commercial item can also be used as said sheet-like foam.
  • the impact absorbing layer (in particular, the impact resistance-containing agent-containing layer and the foam layer) may be a crosslinking agent, a crosslinking accelerator (crosslinking catalyst), a tackifier, a thickener, a plasticizer, as necessary. It may contain appropriate additives such as fillers, foaming agents, anti-aging agents, antioxidants, UV absorbers, antistatic agents, surfactants, leveling agents, colorants, flame retardants, and silane coupling agents. Good.
  • the thickness of the impact absorbing layer is not particularly limited as long as it can provide a desired impact absorbing property to the sheet-like extensible organic base material, but is preferably 0.01 to 10 mm.
  • the lower limit of the thickness of the shock absorbing layer is, for example, preferably 0.1 mm, more preferably 0.5 mm.
  • the upper limit of the thickness of the shock absorbing layer is, for example, preferably 8 mm, more preferably 5 mm.
  • the thickness of the sheet-like extensible organic base material having impact resistance is, for example, 0.01 mm or more, preferably 0.03 mm or more, and more preferably 0.05 mm or more.
  • the upper limit of the thickness of the sheet-like extensible organic base material having impact resistance is, for example, 2 cm, preferably 1 cm, more preferably 5 mm, and further preferably 2 mm.
  • the sheet-like extensible organic base material has an excellent impact absorbability and an extensible member having a shape invariable portion (or an elastic member having an excellent impact absorbability and having a shape invariable portion).
  • Materials for electronics products transistors, integrated circuits, capacitors, sensors, actuators, etc.
  • materials for optical products dislays, lighting, optical waveguide circuits, etc.
  • materials for optoelectronic products light emitting diodes, photodiodes, solar cells, etc.
  • It can be used as a member for car electronics products, a member for household electrical appliances, a member for household equipment, a building material, a band member, a binding member, a sanitary article, a clothing part, a base cloth for a poultice.
  • Sheet-like extensible organic base material having gas barrier properties an extensible sheet-like organic group in which a cylindrical hardly extensible polymer portion A is partially and integrally formed in an easily extensible polymer base material Examples include a sheet-like extensible organic base material having a gas barrier layer on at least one surface of the material and satisfying one or both of the following [i] and [ii].
  • Oxygen permeability oxygen permeability corresponding to a thickness of 100 ⁇ m measured under the conditions of 20 ° C.
  • RH according to JIS K7126-2 method is 10 mL / m 2 /0.1 MPa / day [mL / ( mii ⁇ 0.1 MPa ⁇ day)] or less.
  • the water vapor permeability (water vapor permeability) corresponding to a thickness of 100 ⁇ m measured at 40 ° C. and 90% RH according to JIS K7129B method is 10 g / m 2. /0.1 MPa / day [g / (m 2 ⁇ 0.1 MPa ⁇ day)] or less
  • an extensible sheet-like organic material in which a cylindrical hardly extensible polymer portion A is partially and integrally formed in an easily extensible polymer base material examples include a sheet-like extensible organic base material that satisfies any one or both of the following [i] and [ii].
  • the oxygen permeability corresponding to a thickness of 100 ⁇ m measured under the conditions of 20 ° C. and 70% RH according to JIS K7126-2 method is 10 mL / m 2 /0.1 MPa / day or less.
  • JIS K7129B method The water vapor permeability corresponding to a thickness of 100 ⁇ m measured under the conditions of 40 ° C. and 90% RH is 10 g / m 2 /0.1 MPa / day or less
  • this sheet-like extensible organic base material When such a sheet-like extensible organic base material is extended in one direction (plane direction), the site of the easily extensible polymer base material is extended, but the partially formed cylindrical hardly extensible polymer portion A is Does not stretch or barely stretches. For this reason, it is possible to give the tubular hardly extensible polymer portion A a design whose shape is desired not to change, and to fix and hold other members. Moreover, since this sheet-like extensible organic base material has gas barrier properties (excellent gas barrier properties), for example, deterioration of materials (for example, deterioration of metals) due to gas such as oxygen or water vapor can be suppressed.
  • gas barrier properties excellent gas barrier properties
  • gas barrier property in the present specification means a characteristic (property) that suppresses or suppresses the permeation of gas, for example, a characteristic that satisfies one or both of the above [i] and [ii]. There is a case.
  • the functional layer 6 is a gas barrier layer.
  • the functional layer 6 is a gas barrier layer, and the multifunctional sheet-like extensible organic group shown in (3) of FIG. Examples of the material A include those in which the stretchable sheet-like organic substrate 1 itself has gas barrier properties.
  • the sheet-like organic substrate having extensibility has a gas barrier property (particularly oxygen barrier property and / or water vapor barrier property), it is used as it is as a sheet-like extensible organic substrate having gas barrier property.
  • gas barrier properties can be imparted by configuring the easily stretchable polymer base material with a material having gas barrier properties.
  • the sheet-like extensible organic base material satisfies either one or both of the following [i] and [ii].
  • the oxygen permeability corresponding to a thickness of 100 ⁇ m measured under the conditions of 20 ° C. and 70% RH according to JIS K7126-2 method is 10 mL / m 2 /0.1 MPa / day or less.
  • JIS K7129B method The water vapor permeability corresponding to a thickness of 100 ⁇ m measured under the conditions of 40 ° C. and 90% RH is 10 g / m 2 /0.1 MPa / day or less
  • the oxygen permeability of the sheet-like extensible organic base material is preferably 9 mL / m 2 /0.1 MPa / day or less, and depending on the application, it is 8 mL / m 2 /0.1 MPa / day or less, or 7 mL / m 2/0. It may be 1 MPa / day or less.
  • the water vapor permeability of the sheet-like extensible organic base material is preferably 9 g / m 2 /0.1 MPa / day or less, and depending on the application, it is 8 g / m 2 /0.1 MPa / day or less, or 7 g / m 2 / It may be 0.1 MPa / day or less.
  • Examples of the material having gas barrier properties include polyvinylidene chloride polymers such as polyvinylidene chloride and vinylidene chloride copolymers (for example, copolymers with vinyl chloride, acrylonitrile, etc.); polyacrylonitrile, acrylonitrile copolymers, etc.
  • polyvinylidene chloride polymers such as polyvinylidene chloride and vinylidene chloride copolymers (for example, copolymers with vinyl chloride, acrylonitrile, etc.); polyacrylonitrile, acrylonitrile copolymers, etc.
  • Polyacrylonitrile polymers such as: polyvinyl alcohol, polyvinyl alcohol polymers such as polyvinyl alcohol, partially saponified polyvinyl alcohol, and ethylene-vinyl alcohol copolymers; polyvinyl chloride polymers; polyolefin polymers (eg, high density polyethylene, polypropylene, etc.); polyamides Polymer (eg nylon 6, nylon 66 etc.); polyester polymer (eg polyethylene terephthalate, polyethylene naphthalate etc.); gas barrier material (gas Resin composition comprising the various polymers and materials) for imparting barrier properties (e.g., a resin composition which gas barrier material is dispersed in the polymer) and the like.
  • polyvinyl alcohol polyvinyl alcohol polymers such as polyvinyl alcohol, partially saponified polyvinyl alcohol, and ethylene-vinyl alcohol copolymers
  • polyvinyl chloride polymers polyolefin polymers (eg, high density polyethylene, polypropylene, etc.);
  • Examples of the polymer in the resin composition include the polymers exemplified as the polymer having extensibility in the section of [excellent extensible polymer base material].
  • Examples of the gas barrier substance include silica, calcium carbonate, clay, titanium oxide, talc, layered silicate, clay mineral (for example, layered viscosity mineral), metal powder, glass, glass beads, glass balloon, and alumina balloon. And particles (fine particles, fine particle powder) of ceramic balloon, titanium white, carbon black and the like. The particles may be solid or hollow (balloon).
  • layered viscosity mineral examples include smectites such as montmorillonite, beidellite, hectorite, saponite, nontronite, and stevensite; vermiculite; bentonite; layered sodium silicate such as kanemite, kenyaite, and macanite. .
  • smectites such as montmorillonite, beidellite, hectorite, saponite, nontronite, and stevensite
  • vermiculite bentonite
  • layered sodium silicate such as kanemite, kenyaite, and macanite.
  • 1 type may be used for a gas barrier substance and it may use 2 or more types together.
  • the content of the gas barrier substance in the easily extensible polymer matrix is not particularly limited, For example, 0.1 to 400 parts by weight is preferable with respect to 100 parts by weight of the polymer constituting the polymer base material.
  • the sheet-like extensible organic base material having gas barrier properties is an extensible sheet-like organic material in which the cylindrical hardly extensible polymer portion A is partially and integrally formed in the easily extensible polymer base material.
  • the sheet-like extensible organic substrate is either or both of the following [i] and [ii]: Meet.
  • the oxygen permeability corresponding to a thickness of 100 ⁇ m measured under the conditions of 20 ° C. and 70% RH according to JIS K7126-2 method is 10 mL / m 2 /0.1 MPa / day or less.
  • JIS K7129B method The water vapor permeability corresponding to a thickness of 100 ⁇ m measured under the conditions of 40 ° C. and 90% RH is 10 g / m 2 /0.1 MPa / day or less
  • the oxygen permeability of the sheet-like extensible organic base material (laminate) is preferably 9 mL / m 2 /0.1 MPa / day or less, depending on the application, or 8 mL / m 2 /0.1 MPa / day or less, or 7 mL / It may be less than m2 / 0.1 MPa / day.
  • the water vapor permeability of the sheet-like extensible organic base material (laminate) is preferably 9 g / m 2 /0.1 MPa / day or less, depending on the application, or 8 g / m 2 /0.1 MPa / day or less, or It may be 7 g / m2 / 0.1 MPa / day or less.
  • the thickness of the sheet-like extensible organic base material having gas barrier properties is, for example, 0.01 mm or more, preferably 0.03 mm or more, and more preferably 0.05 mm or more.
  • the upper limit of the thickness of the sheet-like extensible organic base material having gas barrier properties is, for example, 1 cm, preferably 5 mm, and more preferably 2 mm.
  • the gas barrier layer 6 is a layer (functional layer) for imparting gas barrier properties to the sheet-like extensible organic substrate of the present invention.
  • a gas barrier layer that imparts oxygen barrier properties and / or water vapor barrier properties to the sheet-like extensible organic substrate of the present invention is particularly preferable.
  • the “oxygen barrier property” means a property (property) that suppresses or inhibits the permeation of oxygen.
  • the thickness (thickness of the sheet-like extensible organic base material) may be such that the oxygen permeability corresponding to 100 ⁇ m is 10 mL / m 2 /0.1 MPa / day or less.
  • the “water vapor barrier property” means a property (property) that suppresses or inhibits the permeation of water vapor. (Thickness of sheet-like extensible organic substrate)
  • the water vapor transmission rate corresponding to 100 ⁇ m may be 10 g / m 2 /0.1 MPa / day or less.
  • the gas barrier layer is preferably a gas barrier layer that imparts oxygen barrier properties and water vapor barrier properties to the sheet-like extensible organic substrate of the present invention.
  • the gas barrier layer may have a single-layer form or a multi-layer (stacked) form. Further, the gas barrier layer may be provided on the entire surface of the sheet-like organic base material 1 having extensibility (if the below-described intermediate layer is present on the sheet-like extensible organic base material, the intermediate layer). Well, depending on the application, it may be partially provided only on the necessary portion of the surface of the sheet-like organic substrate 1 having extensibility.
  • the gas barrier layer is not particularly limited, and examples thereof include an organic gas barrier layer and an inorganic gas barrier layer.
  • the material (organic material) for forming the organic gas barrier layer is not particularly limited.
  • polyvinylidene chloride polymers such as polyvinylidene chloride and vinylidene chloride copolymers; polyacrylonitrile, acrylonitrile copolymers, and the like.
  • Polyacrylonitrile polymer polyvinyl alcohol, partially saponified polyvinyl alcohol, vinyl alcohol polymer such as ethylene-vinyl alcohol copolymer; polyvinyl chloride polymer such as polyvinyl chloride and polyvinyl chloride copolymer; high density polyethylene Polyolefin polymers such as polypropylene; polyamide polymers such as nylon 6 and nylon 66; oxygen permeability such as polyester polymers such as polyethylene terephthalate and polyethylene naphthalate Material vapor permeability is small and the like.
  • a polyvinylidene chloride polymer is preferable in that both oxygen permeability and water vapor permeability are small.
  • the said organic material may use only 1 type and may use 2 or more types together.
  • the organic gas barrier layer can be formed by a known or conventional method, and the formation method is not particularly limited.
  • the organic material for example, a solution or dispersion containing the organic material
  • the organic material is a sheet-like organic substrate 1 having extensibility (an intermediate layer described later on the sheet-like extensible organic substrate).
  • a method of coating on the intermediate layer and drying as necessary is mentioned.
  • coating of a coating liquid can be performed using a coater, an extruder, a printing machine, etc. which are generally used.
  • the thickness of the organic gas barrier layer is not particularly limited as long as the desired gas barrier property can be imparted to the sheet-like extensible organic base material, but is preferably 0.01 to 1000 ⁇ m.
  • the lower limit of the thickness of the organic gas barrier layer is, for example, preferably 0.1 ⁇ m, more preferably 1 ⁇ m.
  • the upper limit of the thickness of the organic gas barrier layer is preferably, for example, 800 ⁇ m, and more preferably 500 ⁇ m.
  • the material (inorganic material) for forming the inorganic gas barrier layer is not particularly limited, and examples thereof include materials such as silicon oxide, magnesium oxide, aluminum oxide, zinc oxide, and layered silicate. .
  • the said inorganic material may use only 1 type and may use 2 or more types together.
  • the inorganic gas barrier layer can be formed by a known or conventional method, and the formation method is not particularly limited. Specifically, for example, the inorganic material is placed on the sheet-like organic substrate 1 having extensibility (if the intermediate layer described later is present on the sheet-like extensible organic substrate, the intermediate layer). Examples thereof include a method in which a coating liquid containing the coating liquid is applied and dried to form a layer made of the inorganic material (inorganic gas barrier layer), and a method in which the layer made of the inorganic material (inorganic gas barrier layer) is formed by a sputtering method.
  • the thickness of the inorganic gas barrier layer is not particularly limited as long as it can provide a desired gas barrier property to the sheet-like extensible organic base material, but is preferably 1 to 5000 nm.
  • the lower limit of the thickness of the inorganic gas barrier layer is, for example, preferably 5 nm, more preferably 10 nm.
  • the upper limit of the thickness of the inorganic gas barrier layer is preferably, for example, 4000 nm, and more preferably 3000 nm.
  • gas barrier layer in addition to the organic gas barrier layer and the inorganic gas barrier layer described above, for example, a gas barrier layer composed of a resin composition containing a gas barrier substance exemplified as the material having the gas barrier property and various polymers, and the like, A gas barrier layer composed of an organic-inorganic hybrid material can also be used.
  • gas barrier layers can be formed by a known or conventional method.
  • the thickness of these gas barrier layers is not particularly limited as long as the desired gas barrier property can be imparted to the sheet-like extensible organic base material, but is preferably 0.01 to 1000 ⁇ m.
  • the minimum of the thickness of these gas barrier layers is 0.1 micrometer, for example, More preferably, it is 1 micrometer.
  • the upper limit of the thickness of these gas barrier layers is, for example, preferably 800 ⁇ m, and more preferably 500 ⁇ m.
  • the gas barrier layer is optionally provided with a crosslinking agent, a crosslinking accelerator (crosslinking catalyst), a tackifier, a thickener, a plasticizer, a filler, a foaming agent, an anti-aging agent, an antioxidant, and an ultraviolet absorber.
  • a crosslinking agent such as an agent, an antistatic agent, a surfactant, a leveling agent, a colorant, a flame retardant, and a silane coupling agent may be included.
  • an organic gas barrier layer a gas barrier substance can be sufficiently stretched in a sheet-like extensible organic base material, and even when stretched, the gas barrier layer is not easily damaged.
  • a gas barrier layer composed of a resin composition containing a polymer and various polymers and a gas barrier layer composed of an organic-inorganic hybrid material are preferred.
  • the sheet-like extensible organic base material has a gas barrier property (excellent gas barrier property) and an extensible member having a shape-invariable portion (or an elastic member having a gas barrier property and having a shape-invariant portion).
  • Materials for electronics products transistors, integrated circuits, capacitors, sensors, actuators, etc.
  • materials for optical products dislays, lighting, optical waveguide circuits, etc.
  • materials for optoelectronic products light emitting diodes, photodiodes, solar cells, etc.
  • It can be used as a member for car electronics products, a member for household electrical appliances, a member for household equipment, a building material, a band member, a binding member, a sanitary article, a clothing part, a base cloth for a poultice.
  • Sheet-like extensible organic base material having moisture permeability As a sheet-like extensible organic base material having moisture permeability, a sheet-like extensible organic base material in which a cylindrical hard-extensible polymer portion A is partially and integrally formed in an easily extensible polymer base material.
  • the sheet-like extensibility having a water vapor transmission rate (water vapor transmission rate) equivalent to a thickness of 40 ⁇ m measured at 40 ° C. and 90% RH according to JIS K7129A method is 100 g / m 2 /0.1 MPa / day or more.
  • An organic base material is mentioned.
  • the water vapor transmission rate is preferably 300 g / m2 / 0.1 MPa / day or more, and may be 500 g / m2 / 0.1 MPa / day or more, or 1000 g / m2 / 0.1 MPa / day or more depending on the application.
  • the site of the easily extensible polymer base material is extended, but the partially formed cylindrical hardly extensible polymer portion A is Does not stretch or barely stretches. For this reason, it is possible to give the tubular hardly extensible polymer portion A a design whose shape is desired not to change, and to fix and hold other members.
  • this sheet-like extensible organic base material has high moisture permeability, for example, it is possible to suppress stuffiness when pasted on the skin or the like.
  • the sheet-like extensible organic base material is also useful in that it can exhibit high moisture permeability without a multi-dimensional structure (porous structure) (that is, in the form of a non-porous base material).
  • the sheet-like extensible organic substrate may be a porous substrate.
  • the extensible base material is composed of a polymer having extensibility (or further stretchability) and high moisture permeability
  • the following moisture permeability imparting agent is not used or the amount used is kept low.
  • the water vapor transmission rate of the extensible base material can be increased, and as a result, the water vapor transmission rate of the extensible organic base material can be controlled to 100 g / m 2 /0.1 MPa / day or more.
  • polymer having the stretchability (or further stretchability) and having high moisture permeability examples include, for example, a polyurethane polymer, a polyurea polymer, a polyurethane urea polymer, a silicone polymer, a polyester polymer, a polyether polymer, Examples thereof include polyamide polymers and acrylic polymers having a low glass transition temperature (Tg) (Tg is less than 5 ° C., preferably 0 ° C. or less, more preferably ⁇ 5 ° C. or less).
  • Tg glass transition temperature
  • the easily extensible polymer base material 2 may contain a moisture permeability imparting agent.
  • the sheet-like extensible organic base material of the present invention can exhibit particularly high moisture permeability.
  • the moisture permeability imparting agent is not particularly limited, and a known or commonly used additive that can improve the moisture permeability (water vapor permeability) of the easily stretchable polymer base material can be used.
  • the moisture permeability imparting agent include known or commonly used hydrophilic materials, specifically, surfactants, hydrophilic compounds, hydrophilic polymers, and the like.
  • nonionic surfactants nonionic surfactants
  • cationic surfactants cationic surfactants
  • anionic surfactants amphoteric surfactants
  • amphoteric surfactants examples include polyoxyethylene alkyl phenyl ether [eg, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene dodecyl phenyl ether, etc.], polyoxyethylene alkyl allyl ether, Polyoxyethylene alkyl ethers [for example, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, etc.], ether-type nonionic surfactants such as polyoxyethylene polyoxypropylene block polymers; polyethylene glycol fatty acid esters [for example, polyethylene glycol olein Acid ester, etc.], polyoxyethylene sorbitan fatty acid ester [for example, polyoxyethylene sorbitan monopal Ester ether type nonionic surfact
  • cationic surfactant examples include amine salt-based cationic surfactants, quaternary ammonium salt-based cationic surfactants [for example, lauryltrimethylammonium salt, stearyltrimethylammonium salt, trioctylammonium salt, dioctylamine.
  • Aliphatic quaternary ammonium salts such as stearyldimethylammonium salt, aromatic quaternary ammonium salts such as distearyl dibenzylammonium salt], quaternary phosphonium salt-based cationic surfactants [eg, dodecyltriphenylphosphonium salt, Methyltriphenylphosphonium salt, lauryltrimethylphosphonium salt, stearyltrimethylphosphonium salt, distearyldimethylphosphonium salt, distearyldibenzylphosphonium salt, etc.].
  • quaternary phosphonium salt-based cationic surfactants eg, dodecyltriphenylphosphonium salt, Methyltriphenylphosphonium salt, lauryltrimethylphosphonium salt, stearyltrimethylphosphonium salt, distearyldimethylphosphonium salt, distearyldibenzylphosphonium salt, etc.
  • anionic surfactant examples include sulfate ester anionic surfactants [for example, polyoxyethylene alkyl ether sulfate, polyoxyethylene styrenated phenyl ether sulfate, alkyl sulfate, etc.]; Anionic surfactants [for example, alkyl phosphates, polyoxyethylene alkyl ether phosphates, etc.]; sulfonic acid-based anionic surfactants [for example, sulfonates, sulfosuccinates, etc.]; Carboxylic acid-based anionic properties Surfactant [For example, fatty acid salt, polyoxyethylene alkyl ether acetate, polyoxyethylene alkyl sulfosuccinate, etc.] etc. are mentioned.
  • amphoteric surfactants examples include betaine-based amphoteric surfactants [for example, alkyl betaines, amide betaines, etc.] and glycine-based amphoteric surfactants.
  • the surfactant is a reactive group in the molecule (for example, a group containing a carbon-carbon unsaturated bond such as a (meth) acryloyl group, a vinyl group or an allyl group, particularly an active energy ray-curable group). Surfactants having can also be used.
  • hydrophilic compound examples include glycol compounds [eg, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, etc.]; glycerin; glycerin derivatives [eg, Diglycerin, etc.]; ethylene glycol monoether compounds [eg, ethylene glycol monoallyl ether, ethylene glycol monobutyl ether, ethylene glycol isobutyl ether, ethylene glycol monophenyl ether, ethylene glycol monohexyl ether, ethylene glycol mono 2-ethylhexyl ether, etc.] Diethylene glycol monoether compounds [for example, diethylene glycol Monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol mono-2-e
  • hydrophilic polymer examples include acrylic polymers [for example, sodium polyacrylate, ammonium polyacrylate, polyacrylic acid and the like]; polyamide-based polymers; polyalkylene oxide-based polymers [for example, polyethylene oxide and the like]; Polyether glycol-based polymers; alginic acids [for example, sodium alginate, ammonium alginate, propylene glycol ester of alginate]; gelatins; cellulose derivatives [for example, carboxymethylcellulose, hydroxyethylcellulose, etc.]; polyvinylpyrrolidone-based polymers [for example, polyvinylpyrrolidone , Copolymers of vinyl pyrrolidone and vinyl acetate, etc.]; maleic anhydride copolymers or salts thereof [for example, isobutene Len - maleic anhydride copolymer, methyl vinyl ether - maleic anhydride copolymer, styrene - maleic anhydride copo
  • a moisture permeability imparting agent can be used alone or in combination of two or more.
  • a commercial item can also be used as a moisture permeability imparting agent.
  • the moisture permeability imparting agent is not particularly limited.
  • the curable monomer M (the curable monomer M having an energy ray curable group A2) or an organic solvent is used in that the easily stretchable polymer base material can be easily formed. Those which are soluble in are preferable.
  • the easily extensible polymer base material is formed from an aqueous dispersion containing a polymer, it may be water-soluble.
  • the moisture permeability of the sheet-like extensible organic base material is improved by the addition of the moisture permeability-imparting agent.
  • the water-absorbing property of the sheet-like extensible organic base material is improved by the addition of the moisture-permeability imparting agent. It is presumed that the movement of water (moisture) absorbed by the stretchable organic base material becomes easy.
  • the content (total amount) of the moisture permeability imparting agent in the easily stretchable polymer base material 2 is, for example, 0.01 to 80% by weight with respect to the entire easily stretchable polymer base material 2.
  • the lower limit of the content (total amount) of the moisture permeability imparting agent is preferably 0.1% by weight, more preferably 0.5% by weight, still more preferably 1.0% by weight, and the upper limit is preferably 70% by weight. More preferably, it is 60% by weight, and further preferably 50% by weight. If the content is less than 0.01% by weight, moisture permeability may be insufficient depending on the application. On the other hand, if the content exceeds 80% by weight, the mechanical strength of the easily extensible polymer base material portion may be lowered.
  • the easily stretchable polymer base material can be formed according to the method for forming the polymer base material (A).
  • the stretchable polymer base material part 2 is formed by applying a composition in which a moisture permeability imparting agent is added to a liquid precursor of a polymer constituting the stretchable polymer base material, if necessary, on a support. And forming an easily stretchable polymer base material forming material layer, and disposing the forming material of the cylindrical hardly stretchable polymer portion A at a predetermined portion of the easily stretchable polymer base material forming material layer, It can be formed by converting the liquid precursor in the polymer base material forming material layer into a target polymer.
  • the easily stretchable polymer base 2 is coated on a support with a solution or dispersion containing a polymer constituting the easily stretchable polymer base and a moisture permeability imparting agent blended as necessary.
  • the easy stretch It can also be formed by removing the solvent in the conductive polymer base material forming material layer by drying.
  • the easily extensible polymer base material portion 2 is formed by, for example, a polymer simple substance (or a mixture of the polymer simple substance and the moisture permeability imparting agent) constituting the easily extensible polymer base material on the support.
  • a melting / cooling process hot melt process
  • the cylindrical difficult-to-extend polymer part A3 may contain a moisture permeability imparting agent, like the easily-extensible polymer base part 2.
  • the moisture permeability of the sheet-like extensible organic base material can be remarkably improved by adding a moisture permeability imparting agent to the cylindrical hardly extensible polymer portion A.
  • the moisture permeability imparting agent the same ones as described above can be used.
  • the content (total amount) of the moisture permeability imparting agent in the cylindrical difficult-to-extend polymer part A3 is, for example, 0.01 to 80% by weight with respect to the entire cylindrical difficult-to-extend polymer part A3.
  • the lower limit of the content (total amount) of the moisture permeability imparting agent is preferably 0.1% by weight, more preferably 0.5% by weight, still more preferably 1.0% by weight, and the upper limit is preferably 70% by weight. More preferably, it is 60% by weight, and further preferably 50% by weight. If the content is less than 0.01% by weight, moisture permeability may be insufficient depending on the application. On the other hand, if the content exceeds 80% by weight, the mechanical strength of the cylindrical difficult-to-extend polymer part A may be reduced or the film may be easily stretched.
  • the sheet-like extensible organic base material having moisture permeability is, for example, blended with a moisture-permeability imparting agent in the material for forming an easily extensible polymer base material, and is the same as the method for producing the sheet-like extensible organic base material of the present invention. It can manufacture by the method of.
  • the sheet-like extensible organic substrate 1 is used for an electronic product (a transistor, an integrated circuit, a capacitor, a sensor, an actuator, etc.) as an extensible member having a shape-invariant portion (or an elastic member having a shape-invariant portion).
  • an electronic product a transistor, an integrated circuit, a capacitor, a sensor, an actuator, etc.
  • an extensible member having a shape-invariant portion or an elastic member having a shape-invariant portion.
  • members for optical products displays, lighting, optical waveguide circuits, etc.
  • members for optoelectronic products light emitting diodes, photodiodes, solar cells, etc.
  • members for car electronics products members for home appliances, members for housing equipment, It can be used as building materials, band members, binding members, sanitary products, clothing parts, base fabrics for poultices, and the like.
  • Conductive sheet-like extensible organic base material As a sheet-like stretchable organic base material having conductivity, a sheet-like organic base material having extensibility in which a cylindrical difficult-to-extend polymer part A is partially and integrally formed in an easily extensible polymer base material.
  • the sheet-like organic base material contains a conductive substance (that is, the sheet-like organic base material (particularly, the easily extensible polymer base material itself) has conductivity), and / or Or the sheet-like extensible organic base material which has an electroconductive layer on the at least single side
  • the surface resistivity of the sheet-like extensible organic base material having conductivity is, for example, about 1012 ⁇ / ⁇ or less, and particularly preferably less than 106 ⁇ / ⁇ . Therefore, this sheet-like extensible organic base material can flow an electric current on the surface. In addition, charging of the sheet-like extensible organic base material can be suppressed, and damage to the electronic member due to static electricity can be reduced when used around the electronic member. Furthermore, since this conductive sheet-like extensible organic base material has a property that the conductive material contained reflects incoming electromagnetic waves, it can also exhibit electromagnetic shielding properties.
  • the electrically conductive sheet-like extensible organic base material is partially formed when the sheet-like extensible organic base material is stretched in one direction (plane direction), but the part of the easily extensible polymer base material is elongated.
  • the formed cylindrical hardly extensible polymer part A does not stretch or hardly stretches. For this reason, it is possible to give the tubular hardly extensible polymer portion A a design whose shape is desired not to change, and to fix and hold other members.
  • the functional layer 6 is a conductive layer.
  • the functional layer 6 is a conductive layer, and the multifunctional sheet-like stretchability shown in (3) of FIG.
  • the sheet-like organic base material 1 itself having extensibility has a conductive property.
  • the sheet-like extensible organic base material having conductivity is a sheet-like organic base material having extensibility in which a cylindrical hardly extensible polymer portion A is partially and integrally formed in an easily extensible polymer base material.
  • the sheet-like organic base material may be a sheet-like extensible organic base material containing a conductive substance, and has a conductive layer on at least one side of the sheet-like organic base material. It may be a sheet-like extensible organic substrate, and the sheet-like organic substrate contains a conductive substance, and has a conductive layer on at least one side of the sheet-like organic substrate.
  • An organic base material may be used. When a sheet-like organic base material contains a conductive substance, conductivity in the surface direction and the thickness direction can be imparted.
  • a conductive layer is provided on at least one surface of the sheet-like organic base material, conductivity in the surface direction can be imparted. Further, charging can be suppressed, and damage to the electronic member due to static electricity can be reduced when used around the electronic member. Furthermore, electromagnetic wave shielding properties can also be exhibited.
  • the conductive substance may be contained in the easily extensible polymer base material constituting the sheet-like organic base material having extensibility, or may be contained in the cylindrical hardly extensible polymer portion A. It may be contained in the polymer base material and the cylindrical hardly extensible polymer part A.
  • the seed-like organic base material containing a conductive substance uses an easily stretchable polymer base material containing a conductive substance as the easily stretchable polymer base material in the above-described method for producing a stretchable sheet-like organic base.
  • a cylindrical difficult-to-extend polymer part A forming material containing a conductive substance is used as a material for forming a cylindrical difficult-to-extend polymer part A, or an easy extension containing a conductive substance as an easily-extensible polymer base material It can manufacture by using the cylindrical difficult-to-extend polymer part A forming material containing an electroconductive substance as a cylindrical difficult-to-extend polymer part A forming material.
  • Examples of the conductive substance contained in the sheet-like organic substrate having extensibility include a conductive filler, a conductive polymer, a surfactant, a hydrophilic compound, a hydrophilic polymer, and an ionic liquid.
  • Examples of the conductive filler include a carbon-based conductive filler and a metal-based conductive filler. These may be surface-treated with a silane coupling agent or the like in order to improve dispersibility. Moreover, these can be used individually or in combination of 2 or more types.
  • Examples of carbon forming the carbon-based conductive filler include carbon black such as ketjen black, acetylene black, thermal black, and furnace black. These can be used alone or in combination of two or more.
  • metals such as nickel, iron, chromium, cobalt, aluminum, antimony, molybdenum, copper, silver, platinum, and gold, and alloys or oxides thereof (for example, , Titanium oxide, tin oxide, zinc oxide, antimony oxide, indium oxide, potassium titanate, and complex oxides thereof). These can be used alone or in combination of two or more.
  • the shape of the conductive filler is not particularly limited, and examples thereof include a spherical shape, a spike shape, a filament shape, a flake shape, and a dendritic shape.
  • the average particle diameter of the conductive filler is, for example, 0.1 to 100 ⁇ m.
  • the upper limit of the average particle diameter of the conductive filler is preferably 80 ⁇ m, more preferably 60 ⁇ m, and the lower limit is preferably 0.5 ⁇ m, more preferably 1 ⁇ m.
  • Examples of the conductive polymer include polyaniline, polypyrrole, polythiophene, and derivatives thereof. These can be used alone or in combination of two or more.
  • conductive polymer for example, trade name “PPY-12” (manufactured by Maruhishi Oil Chemical Co., Ltd., polypyrrole aqueous dispersion), trade name “Denatron P-502S” (manufactured by Nagase ChemteX Corporation, polythiophene) Commercially available products such as a water-based dispersion) and a trade name “aquaPASS-01” (manufactured by Mitsubishi Rayon Co., Ltd., polyaniline sulfonic acid-based water dispersion) can be suitably used.
  • surfactant examples include nonionic surfactants (nonionic surfactants), cationic surfactants, anionic surfactants, and amphoteric surfactants. These can be used alone or in combination of two or more.
  • nonionic surfactant examples include polyoxyethylene alkyl phenyl ether [eg, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene dodecyl phenyl ether, etc.], polyoxyethylene alkyl allyl ether, Polyoxyethylene alkyl ethers [for example, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, etc.], ether-type nonionic surfactants such as polyoxyethylene polyoxypropylene block polymers; polyethylene glycol fatty acid esters [for example, polyethylene glycol olein Acid ester, etc.], polyoxyethylene sorbitan fatty acid ester [for example, polyoxyethylene sorbitan monopa Ester ether type nonionic surfactants such as mitinate ester, etc .; glycerin fatty acid ester [eg glycerin monostearate etc.], sorbitan fatty acid ester [
  • cationic surfactant examples include amine salt-based cationic surfactants, quaternary ammonium salt-based cationic surfactants [for example, lauryltrimethylammonium salt, stearyltrimethylammonium salt, trioctylammonium salt, dioctylamine.
  • Aliphatic quaternary ammonium salts such as stearyldimethylammonium salt, aromatic quaternary ammonium salts such as distearyl dibenzylammonium salt], quaternary phosphonium salt-based cationic surfactants [eg, dodecyltriphenylphosphonium salt, Methyltriphenylphosphonium salt, lauryltrimethylphosphonium salt, stearyltrimethylphosphonium salt, distearyldimethylphosphonium salt, distearyldibenzylphosphonium salt, etc.].
  • quaternary phosphonium salt-based cationic surfactants eg, dodecyltriphenylphosphonium salt, Methyltriphenylphosphonium salt, lauryltrimethylphosphonium salt, stearyltrimethylphosphonium salt, distearyldimethylphosphonium salt, distearyldibenzylphosphonium salt, etc.
  • anionic surfactant examples include sulfate ester anionic surfactants [for example, polyoxyethylene alkyl ether sulfate, polyoxyethylene styrenated phenyl ether sulfate, alkyl sulfate, etc.]; Anionic surfactants [for example, alkyl phosphates, polyoxyethylene alkyl ether phosphates, etc.]; sulfonic acid-based anionic surfactants [for example, sulfonates, sulfosuccinates, etc.]; Carboxylic acid-based anionic properties Surfactant [For example, fatty acid salt, polyoxyethylene alkyl ether acetate, polyoxyethylene alkyl sulfosuccinate, etc.] etc. can be mentioned.
  • amphoteric surfactant examples include betaine-based amphoteric surfactants [for example, alkyl betaines, amide betaines, etc.], glycine-based amphoteric surfactants, and the like.
  • the surfactant is a reactive group in the molecule (for example, a group containing a carbon-carbon unsaturated bond such as a (meth) acryloyl group, a vinyl group or an allyl group, particularly an active energy ray-curable group). Surfactants having can also be used.
  • surfactant examples include, for example, trade name “Hytenol LA-16” (Daiichi Kogyo Seiyaku Co., Ltd., sulfate ester anionic surfactant), trade name “Katiogen TML” (Daiichi Kogyo Seiyaku Co., Ltd.)
  • Commercially available products such as manufactured and quaternary ammonium salt cationic surfactants) can be suitably used.
  • hydrophilic compound examples include glycol compounds [eg, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, etc.]; glycerin; glycerin derivatives [eg, Diglycerin, etc.]; ethylene glycol monoether compounds [eg, ethylene glycol monoallyl ether, ethylene glycol monobutyl ether, ethylene glycol isobutyl ether, ethylene glycol monophenyl ether, ethylene glycol monohexyl ether, ethylene glycol mono 2-ethylhexyl ether, etc.] Diethylene glycol monoether compounds [for example, diethylene glycol Monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol mono-2-e
  • hydrophilic polymer examples include acrylic polymers [for example, sodium polyacrylate, ammonium polyacrylate, polyacrylic acid and the like]; polyamide-based polymers; polyalkylene oxide-based polymers [for example, polyethylene oxide and the like]; Polyether glycol-based polymers; alginic acids [for example, sodium alginate, ammonium alginate, propylene glycol ester of alginate]; gelatins; cellulose derivatives [for example, carboxymethylcellulose, hydroxyethylcellulose, etc.]; polyvinylpyrrolidone-based polymers [for example, polyvinylpyrrolidone , Copolymers of vinyl pyrrolidone and vinyl acetate, etc.]; maleic anhydride copolymers or salts thereof [for example, isobutene Len - maleic anhydride copolymer, methyl vinyl ether - maleic anhydride copolymer, styrene - maleic anhydride copo
  • various onium salts such as a nitrogen-containing onium salt, a sulfur-containing onium salt, or a phosphorus-containing onium salt can be used.
  • a surfactant By using a surfactant, a hydrophilic compound, or a hydrophilic polymer as the conductive substance, a level of conductivity that can suppress charging can be imparted.
  • the content (total amount) of the conductive substance is, for example, 0.1 to 80% by weight with respect to the whole easily extensible polymer base material.
  • the lower limit of the content (total amount) of the conductive material is preferably 0.5% by weight, more preferably 1% by weight, still more preferably 2% by weight, and the upper limit is preferably 70% by weight, more preferably 60% by weight. % By weight, more preferably 50% by weight.
  • the content (total amount) of the conductive substance is, for example, 0.1 to 100 wt. %.
  • the lower limit of the content (total amount) of the conductive material is preferably 0.5% by weight, more preferably 1% by weight, and still more preferably 2% by weight.
  • the upper limit is preferably 95% by weight, more preferably 90% by weight, and still more preferably 85% by weight.
  • the conductive layer contains at least a conductive substance. Moreover, this electroconductive layer may be provided in the state which contact
  • the conductive substance contained in the conductive layer can be used without any particular limitation.
  • the conductive layer may contain a base polymer as necessary.
  • a base polymer it is preferable to use a polymer listed as an example of a polymer constituting the easily extensible polymer base material 2 as the base polymer, and in particular, a polymer constituting the easily extensible polymer base material 2 It is possible to select and use the same kind of polymer or the polymer having the same kind of polymer chain in the main chain or side chain as the polymer chain (main chain or side chain) of the polymer constituting the stretchable polymer base material 2, It is preferable at the point which can form the electroconductive layer which is excellent in the adhesiveness to the sheet-like organic base material surface which has an extendibility.
  • the conductive layer may further contain other additives as long as the effects of the present invention are not impaired.
  • Other additives include, for example, crosslinking agents (epoxy crosslinking agents, isocyanate crosslinking agents, melamine crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, metal chelate compounds, etc.), crosslinking accelerators (crosslinking catalysts).
  • Tackifiers eg, rosin derivative resins, polyterpene resins, petroleum resins, oil-soluble phenol resins, etc.
  • thickeners plasticizers
  • fillers foaming agents, anti-aging agents, antioxidants, UV absorbers, charging Examples thereof include an inhibitor, a surfactant, a leveling agent, a colorant, a conductive substance, and a silane coupling agent.
  • the content (total amount) of the conductive material in the total amount (100% by weight) of the conductive layer is, for example, 0.1 to 100% by weight.
  • the lower limit of the content (total amount) of the conductive material is preferably 0.5% by weight, more preferably 1% by weight, and still more preferably 2% by weight.
  • the conductive layer may be formed of only a conductive material, but the upper limit is preferably 95% by weight, more preferably 90% by weight, and still more preferably 85% by weight.
  • the same method as the method for forming the easily stretchable polymer base material 2 can be adopted except that a conductive substance is added.
  • the conductive layer may be directly formed on the surface of the sheet-like organic base material having extensibility.
  • the conductive layer is formed on an appropriate separator (such as release paper), and this is formed into a sheet-like form having extensibility. It may be transferred (transferred) to an organic base material and laminated.
  • the conductive layer is formed by melt-extrusion of the material for forming the conductive layer (including at least the conductive material and the base polymer) and the easily stretchable polymer base material forming the easily stretchable polymer base material. It can also be formed by a method. As the melt extrusion method, any known technique such as an inflation method or a T-die method can be used.
  • the thickness of the conductive layer can be appropriately selected depending on the application, for example, 0.1 to 500 ⁇ m, and the lower limit is preferably 0.2 ⁇ m, more preferably 0.5 ⁇ m, and even more preferably 1 ⁇ m. .
  • the upper limit is preferably 400 ⁇ m, more preferably 300 ⁇ m, and even more preferably 200 ⁇ m.
  • the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is not particularly limited, and examples thereof include rubber-based pressure-sensitive adhesives and acrylic-based layers.
  • One or more known pressure-sensitive adhesives such as creep property-improving pressure-sensitive adhesives containing the following hot-melt resins can be used in combination.
  • the pressure-sensitive adhesive may be any known pressure-sensitive adhesive such as a solvent type, an emulsion type, a hot-melt type, an energy ray curable pressure-sensitive adhesive, and a heat release type, and an appropriate one can be selected depending on the application. Further, the pressure-sensitive adhesive may be any of a weak pressure-sensitive adhesive type, a strong pressure-sensitive adhesive type, a re-peeling type, and the like, and can be appropriately selected according to the application.
  • an acrylic pressure-sensitive adhesive based on an acrylic polymer (weight average molecular weight is, for example, 10,000 to 2,000,000, preferably 300,000 to 1,500,000) is preferably used.
  • the acrylic polymer may be any of a random copolymer, a block copolymer, a graft polymer, and the like.
  • crosslinking agents epoxy crosslinking agents, isocyanate crosslinking agents, melamine crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, metal chelate compounds, etc.
  • crosslinking Accelerator crosslinking catalyst
  • tackifier for example, rosin derivative resin, polyterpene resin, petroleum resin, oil-soluble phenol resin, etc.
  • thickener plasticizer
  • filler foaming agent
  • an appropriate additive such as an ultraviolet absorber, an antistatic agent, a surfactant, a leveling agent, a colorant, a conductive substance, or a silane coupling agent may be contained.
  • the formation of the pressure-sensitive adhesive layer can be performed by a known or conventional method. For example, a method of applying a pressure-sensitive adhesive composition onto a sheet-like organic substrate 1 having extensibility (or an intermediate layer when an intermediate layer is present on the sheet-like extensible organic substrate), a pressure-sensitive adhesive composition Is applied onto a suitable separator to form a pressure-sensitive adhesive layer, and then the pressure-sensitive adhesive layer is formed into a sheet-like organic substrate 1 having extensibility (if an intermediate layer is present on the sheet-like extensible organic substrate) And a method of transferring (transferring) onto the intermediate layer).
  • a method of applying a pressure-sensitive adhesive composition onto a sheet-like organic substrate 1 having extensibility or an intermediate layer when an intermediate layer is present on the sheet-like extensible organic substrate
  • a pressure-sensitive adhesive composition Is applied onto a suitable separator to form a pressure-sensitive adhesive layer
  • the pressure-sensitive adhesive layer is formed into a sheet-like organic substrate 1 having extensibility (if an intermediate layer is present on
  • the pressure-sensitive adhesive layer may be provided on the entire surface of the sheet-like organic substrate 1 having extensibility, or may be partially provided only on a necessary portion of the surface of the sheet-like organic substrate 1 having extensibility. Good.
  • the thickness of the pressure-sensitive adhesive layer can be appropriately selected according to the use and the like, and is, for example, 1 to 3000 ⁇ m, the lower limit is preferably 5 ⁇ m, and the upper limit is preferably 500 ⁇ m.
  • a protective film for protecting the surface may be provided on the conductive layer 6 until the conductive sheet-like extensible organic base material A is used.
  • the sheet-like extensible organic base material having conductivity is an electronic product (or a stretchable member having conductivity and having a shape-invariable portion) (or an elastic member having conductivity and having a shape-invariant portion).
  • Sheet-like extensible organic base material having a surface layer As a sheet-like extensible organic base material having a surface layer, a sheet-like organic base material having extensibility in which a cylindrical hardly extensible polymer portion A is partially and integrally formed in an easily extensible polymer base material
  • the sheet-like extensible organic base material which has the surface layer by a fluorine-type compound is mentioned on the at least one surface of these.
  • the “surface layer made of a fluorine-based compound” may be referred to as “fluorine-based surface layer” or “surface layer”.
  • the sheet-like extensible organic base material having a surface layer When the sheet-like extensible organic base material having a surface layer is stretched in one direction (plane direction), the part of the easily extensible polymer base material is elongated, but partially formed.
  • the formed cylindrical hardly extensible polymer part A does not stretch or hardly stretches. For this reason, it is possible to give the tubular hardly extensible polymer portion A a design whose shape is desired not to change, and to fix and hold other members.
  • this sheet-like extensible organic base material is provided with a fluorine-based surface layer, it has characteristics such as scratch resistance, antifouling properties, water repellency, and antireflection properties.
  • the functional layer 6 is a surface layer.
  • the functional layer 6 is a surface layer.
  • the fluorine compound constituting the surface layer 6 is a compound having at least one fluorine atom in the molecule.
  • a fluorine-type compound can be used individually by 1 type or in combination of 2 or more types.
  • the fluorine compound is not particularly limited.
  • fluoroethylene vinyl ether copolymer, fluoroethylene vinyl ester copolymer, fluoroethylene acrylic copolymer, vinylidene fluoride, chlorotrifluoroethylene, tetrafluoroethylene, hexa Preferred examples include fluoropropylene.
  • a fluoroethylene vinyl ether copolymer is particularly preferable.
  • the fluoroethylene vinyl ether copolymer is preferably a copolymer having fluoroethylene units and vinyl ether units alternately.
  • a compound represented by the following formula (1) is more preferable.
  • X represents a fluorine atom, a chlorine atom or a bromine atom
  • Ra represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
  • Rb represents an alkyl group having 1 to 16 carbon atoms
  • Rc represents Represents an alkylene group having 1 to 16 carbon atoms.
  • m and n are integers.
  • the weight average molecular weight of the fluoroethylene vinyl ether alternating copolymer is not particularly limited, but is preferably 1,000 to 2,000,000, more preferably 5,000 to 1,000,000, Preferably, it is 10,000 to 500,000.
  • m and n in the formula (1) are preferably selected so that the weight average molecular weight of the fluoroethylene vinyl ether alternating copolymer falls within the above range.
  • a fluorine-based compound a fluorine-containing resin-based material, a fluorine-containing hybrid material (a material containing at least a fluorine-containing resin and particles), a fluorine-containing sol-gel
  • the resin material is not particularly limited.
  • a fluorine resin a fluorine group-containing polyurethane, a fluorine group-containing polyester, a fluorine group-containing silicone (silicone resin), and a fluorine group.
  • examples thereof include an acrylic resin containing a fluorine group, such as an epoxy resin containing, an ultraviolet curable acrylic resin containing a fluorine group.
  • the hybrid material For example, resin (For example, the polyurethane containing a fluorine group, the polyester containing a fluorine group, the silicone (silicone resin) containing a fluorine group, the epoxy resin containing a fluorine group) And acrylic fine particles containing fluorine groups, fluorine resins, etc.) in which inorganic fine particles such as colloidal silica are dispersed.
  • resin for example, the polyurethane containing a fluorine group, the polyester containing a fluorine group, the silicone (silicone resin) containing a fluorine group, the epoxy resin containing a fluorine group) And acrylic fine particles containing fluorine groups, fluorine resins, etc.
  • inorganic fine particles such as colloidal silica are dispersed.
  • the sol-gel type material For example, the material using metal alkoxy, such as tetraethoxysilane and titanium tetraethoxide, is mentioned. These materials are preferably those having
  • a siloxane oligomer having a number average molecular weight in the range of ethylene glycol equivalent of 500 to 10,000, a polystyrene equivalent number average molecular weight of 5000 or more, a fluoroalkyl structure and a polysiloxane structure
  • the material (The material as described in Unexamined-Japanese-Patent No. 2004-167827) containing the fluorine compound which has this is also mentioned.
  • the surface layer 6 may have a crosslinked structure from the viewpoint of improving strength.
  • a crosslinking agent which forms the said crosslinked structure An isocyanate type crosslinking agent is mentioned preferably.
  • a crosslinking agent can be used individually by 1 type or in combination of 2 or more types.
  • the isocyanate-based crosslinking agent is a compound having two or more isocyanate groups in the molecule.
  • the isocyanate-based crosslinking agent is not particularly limited. For example, hydrogenated xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, ethylene diisocyanate, 1,4-tetramethylene diisocyanate, trimethylhexamethylene diisocyanate.
  • Bifunctional isocyanates such as norbornene diisocyanate, Desmodur N3200 (manufactured by Sumika Bayer Urethane Co., Ltd.), Coronate L, HL, HX (manufactured by Nippon Polyurethane Co., Ltd.), Takenate D-140N, D-127, D-110N Trifunctional isocyanates such as (Mitsui Chemicals Polyurethane Co., Ltd.) are listed.
  • the usage-amount of the said isocyanate type crosslinking agent is not specifically limited, For example, when using the said isocyanate type crosslinking agent for the compound shown by said Formula (1), with respect to 100 weight part of compounds shown by Formula (1).
  • the content is preferably 0.01 to 20 parts by weight, more preferably 0.05 to 15 parts by weight, and still more preferably 0.1 to 10 parts by weight.
  • the surface layer 6 may contain an additive as long as it does not impair the effects of the present invention.
  • additives include, for example, epoxy crosslinking agents, melamine crosslinking agents, peroxide crosslinking agents, urea crosslinking agents, metal alkoxide crosslinking agents, metal chelate crosslinking agents, metal salt crosslinking agents, Crosslinking agents other than the isocyanate crosslinking agents such as carbodiimide crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, amine crosslinking agents, crosslinking accelerators, silane coupling agents, tackifying resins (rosin derivatives, polyterpene resins, Petroleum resins, oil-soluble phenols, etc.), anti-aging agents, fillers, colorants (pigments, dyes, etc.), UV absorbers, antioxidants, plasticizers, softeners, surfactants, antistatic agents, etc. .
  • the surface layer 6 can be formed by a known or conventional method.
  • the surface layer is prepared by mixing the fluoroethylene vinyl ether copolymer, a crosslinking agent (particularly the isocyanate-based crosslinking agent) and an organic solvent (for example, a mixed solvent of xylene, toluene, butyl acetate, ethyl acetate and the solvent).
  • a surface layer can be formed by obtaining a forming composition and drying and curing the surface layer forming composition.
  • a crosslinked structure is formed by drying and curing.
  • the catalyst for example, dibutyltin lauric acid etc.
  • the catalyst for example, dibutyltin lauric acid etc.
  • the drying and curing at the time of forming the surface layer are not particularly limited, and examples thereof include heating at a temperature of 40 to 180 ° C. for 1 to 30 minutes.
  • the surface layer 6 may be provided on the entire surface of the sheet-like organic substrate 1 having extensibility. Depending on the application, the surface layer 6 is only part of the surface of the sheet-like organic substrate 1 having extensibility. It may be provided.
  • the thickness of the surface layer 6 is not particularly limited, but is preferably 2 to 50 ⁇ m, more preferably 5 to 40 ⁇ m. If the thickness is less than 2 ⁇ m, there may be a problem in strength, a defect site where a surface layer such as a pinhole is not formed is likely to occur, and the characteristics of the surface layer may not be fully exhibited. Moreover, when thickness exceeds 50 micrometers, there exists a possibility of having a bad influence on the extensibility of the sheet-like extensible organic base material of this invention.
  • the surface layer may have a single layer structure or a laminated structure having two or more layers.
  • the extensible substrate having a surface layer has another layer (intermediate layer) between the sheet-like substrate 1 having extensibility and the surface layer 6 as needed, as long as the extensibility is not impaired. You may do it.
  • the intermediate layer is not particularly limited, and examples thereof include a pressure-sensitive adhesive layer used for fixing the sheet-like substrate 1 having extensibility and the surface layer 6.
  • the pressure-sensitive adhesive layer is not particularly limited, but may be a known or commonly used pressure-sensitive adhesive layer.
  • a urethane-based pressure-sensitive adhesive layer an acrylic pressure-sensitive adhesive layer, a rubber-based pressure-sensitive adhesive layer, a silicone-based pressure-sensitive adhesive layer
  • examples thereof include a polyester-based pressure-sensitive adhesive layer, a polyamide-based pressure-sensitive adhesive layer, an epoxy-based pressure-sensitive adhesive layer, a vinyl alkyl ether-based pressure-sensitive adhesive layer, and a fluorine-based pressure-sensitive adhesive layer.
  • an acrylic pressure-sensitive adhesive layer is preferable as the pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive layer is formed by a known or conventional method.
  • the thickness of the pressure-sensitive adhesive layer is not particularly limited, but is preferably 1 to 100 ⁇ m, more preferably 5 to 80 ⁇ m.
  • the extensible substrate having a surface layer may be produced using a known or conventional method.
  • the surface layer forming composition is applied onto a sheet-like organic substrate 1 having extensibility (if an intermediate layer is present on the sheet-like substrate, the intermediate layer), and heated. It may be produced by drying and curing the surface layer forming composition to form a surface layer.
  • the surface layer forming composition is applied onto a suitable separator, heated, and the surface layer forming composition is dried and cured to form a surface layer, and then the surface layer is formed into a sheet-like organic group having extensibility. It may be produced by transferring (transferring) onto the material 1 (in the case where an intermediate layer is present on the sheet-like base material, this intermediate layer).
  • the surface layer forming composition is applied on a suitable separator, heated, and the surface layer forming composition is dried and cured to form a surface layer.
  • a pressure-sensitive adhesive layer is provided on the surface layer to obtain a surface layer with a pressure-sensitive adhesive layer, and then the surface layer with the pressure-sensitive adhesive layer is attached to the sheet-like organic substrate 1 having extensibility by the pressure-sensitive adhesive layer. It may be produced by combining them.
  • coating can be performed with the coater, extruder, printer, etc. which are generally used.
  • a sheet-like extensible organic base material having a surface layer is an electronic product (or a stretchable member having a surface layer and having a shape-invariable portion) (or an elastic member having a surface layer and having a shape-invariant portion).
  • Sheet-like extensible organic base material having antireflection properties As a sheet-like extensible organic base material having antireflective properties, a sheet-like organic group having extensibility, in which a cylindrical hardly extensible polymer portion A is partially and integrally formed in an easily extensible polymer base material Examples thereof include a sheet-like extensible organic base material having an antireflection layer on at least one surface of the material.
  • the sheet-like extensible organic base material having antireflection properties when this sheet-like extensible organic base material is stretched in one direction (plane direction), the part of the easily stretchable polymer base material is stretched.
  • the formed cylindrical difficult-to-extend polymer part A does not stretch or hardly stretches. For this reason, it is possible to give the tubular hardly extensible polymer portion A a design whose shape is desired not to change, and to fix and hold other members.
  • this sheet-like extensible organic base material has an antireflection layer, it has antireflection properties. For this reason, for example, when this sheet-like extensible organic base material is attached to a display device or the like, reflection from the outside can be reduced.
  • the functional layer 6 is an antireflection layer.
  • the functional layer 6 is an antireflection layer.
  • the antireflection layer 6 is not particularly limited as long as an antireflection effect is obtained.
  • any appropriate layer such as a known antireflection layer may be adopted.
  • the antireflection layer 6 may be a single layer consisting of only one layer or a plurality of layers consisting of two or more layers.
  • the antireflection layer 6 may be a layer made of only one layer or may be a layer made of two or more kinds of forming materials.
  • the material for forming the antireflection layer 6 is not particularly limited.
  • an acrylic resin such as an ultraviolet curable acrylic resin, a resin material such as polyurethane, polyester, silicone (silicone resin), polyamide, and epoxy resin
  • These forming materials are preferably formed materials having a high content of inorganic components in order to improve the scratch resistance.
  • Examples of the forming material having a large inorganic component content include the sol-gel materials.
  • the sol-gel material may be partially condensed.
  • a hybrid material (a material containing at least a resin and particles) is preferable.
  • Examples of the antireflection layer 6 capable of achieving both scratch resistance and low reflection include, for example, a siloxane oligomer having a number average molecular weight of 500 to 10,000 in terms of ethylene glycol, a polystyrene equivalent number average molecular weight of 5000 or more, An antireflection layer formed from a material containing a fluorine compound having a siloxane structure (a material described in JP-A No. 2004-167827) is also included.
  • an inorganic sol can also be mentioned.
  • the inorganic sol include silica, alumina, and magnesium fluoride.
  • the forming material of the antireflection layer 6 may contain hollow spherical silicon oxide fine particles.
  • hollow spherical silicon oxide fine particles include silica-based fine particles disclosed in JP-A-2001-233611.
  • the antireflection layer 6 is composed of two or more layers, for example, a silicon oxide layer having a low refractive index (refractive index: about 1.) is formed on a titanium oxide layer having a high refractive index (refractive index: about 1.8). 45) is preferred.
  • the antireflection layer 6 may further contain any appropriate additive depending on the purpose.
  • the additive include a photopolymerization initiator, a silane coupling agent, a release agent, a curing agent, a curing accelerator, a diluent, an anti-aging agent, a denaturing agent, a surfactant, a dye, a pigment, and a discoloration preventing agent.
  • the formation of the antireflection layer 6 can be performed by a known or common method.
  • an antireflection layer forming composition (antireflection layer forming material) is obtained by mixing the above-described forming materials, and the antireflection layer is formed by drying and curing the antireflection layer forming composition. be able to.
  • arbitrary appropriate temperature can be employ
  • the antireflection layer forming composition may contain an organic solvent such as butyl acetate.
  • Drying and curing when forming the antireflection layer are not particularly limited, and examples thereof include heating at a temperature of 60 to 160 ° C. for 1 to 30 minutes.
  • the antireflection layer 6 may be provided on the entire surface of the sheet-like organic substrate 1 having extensibility. Depending on the application, the antireflection layer 6 may be provided only on a necessary portion of the surface of the extensible sheet-like organic substrate 1. It may be provided partially.
  • the refractive index of the antireflection layer is not particularly limited, but is preferably from 1.30 to 1.60, more preferably from 1.35 to 1.50 from the viewpoint of obtaining good antireflection properties in the present invention.
  • the thickness of the antireflection layer is not particularly limited, but is preferably from 0.005 to 30 ⁇ m, more preferably from 0.01 to 25 ⁇ m, still more preferably from the viewpoint of obtaining good antireflection properties in the present invention. 01 to 20 ⁇ m.
  • the extensible base material having antireflective property is another layer (intermediate layer) as required between the sheet-like base material 1 having extensibility and the antireflective layer 6 as long as the extensibility and the like are not impaired. You may have.
  • the extensible base material having antireflection properties may be produced using a known or conventional method.
  • the antireflective layer-forming composition is applied onto a stretchable sheet-like organic substrate 1 (or an intermediate layer when an intermediate layer is present on the sheet-like substrate) and heated.
  • the antireflection layer-forming composition may be dried and cured to form an antireflection layer.
  • the antireflection layer-forming composition is applied on a suitable separator, heated, and the antireflection layer-forming composition is dried and cured to form an antireflection layer. It may be produced by transferring (transferring) onto the sheet-like organic base material 1 (in the case where an intermediate layer is present on the sheet-like base material, this intermediate layer).
  • coating can be performed with the coater, extruder, printer, etc. which are generally used.
  • the sheet-like stretchable organic base material having antireflection properties is an extensible member having antireflection properties and having a shape-invariable portion (or an elastic member having antireflection properties and having a shape-invariant portion).
  • Components for electronics products transistors, integrated circuits, capacitors, sensors, actuators, etc.
  • components for optical products dislays, lighting, optical waveguide circuits, etc.
  • components for optoelectronic products light emitting diodes, photodiodes, solar cells, etc.
  • It can be used as a member for car electronics products, a member for household electrical appliances, a member for household equipment, a building material, a band member, a binding member, a sanitary product, a clothing part, a base material for a poultice.
  • the isocyanate group-containing component and polyol (hydroxyl group-containing component) had an NCO / OH (functional group equivalent ratio) of 1.25 and a polymer concentration of 50 wt%.
  • the viscosity (25 ° C.) of the obtained syrup (base material syrup) was 8 Pa ⁇ s.
  • Production Example 2 Manufacture of Syrup for Forming Cylindrical Difficulty Polymer Part A
  • a reaction vessel equipped with a condenser, a thermometer, and a stirrer 51.2 parts by weight of poly (oxytetramethylene) glycol (PTMG650, manufactured by Mitsubishi Chemical Corporation) having a number average molecular weight of 650 as a polyol as a polyol, as a catalyst
  • DBTL dibutyltin dilaurate
  • HXDI hydrogenated xylylene diisocyanate
  • Examples 1-4 The base material syrup obtained in Production Example 1 is coated with an applicator on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 ⁇ m) to form a base material syrup layer having a thickness of 300 ⁇ m. did.
  • a dispenser trade name “SM300DS-S, MPP-1”, manufactured by Musashi Engineering Co., Ltd.
  • Part formation syrup is dropped, and according to the dimensions shown in Table 1, a pattern as shown in FIG. 8 (annular rectangles having a predetermined width (square or rectangle) are arranged at equal intervals in the horizontal and vertical directions, respectively.
  • the cylindrical hardly extensible polymer portion is continuously formed from one surface of the sheet-like extensible organic base material to a depth of 2/3 or more. However, it was not formed up to the other surface (embedded type).
  • X is the lateral length (mm) of the rectangular ring (outer periphery) which is the surface shape of the cylindrical refractory polymer portion forming syrup portion
  • Y is for forming the cylindrical hardly extensible polymer portion.
  • Examples 5-8 The base material syrup obtained in Production Example 1 is coated with an applicator on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 ⁇ m) to form a base material syrup layer having a thickness of 300 ⁇ m. did.
  • a dispenser trade name “SM300DS-S, MPP-1”, manufactured by Musashi Engineering Co., Ltd.
  • the part forming syrup is dropped, and according to the dimensions in Table 2, a pattern as shown in FIG. 9 (annular rectangles (squares or rectangles) having a predetermined width are arranged at equal intervals in the horizontal and vertical directions, respectively.
  • the cylindrical hardly extensible polymer portion is continuously formed from one surface of the sheet-like extensible organic base material to a depth of 2/3 or more. However, it was not formed up to the other surface (embedded type).
  • X is the horizontal length (mm) of the rectangular ring (outer periphery) which is the surface shape of the cylindrical refractory polymer portion forming syrup portion
  • Y is for forming the cylindrical hardly extensible polymer portion.
  • Examples 9-12 The base material syrup obtained in Production Example 1 is coated with an applicator on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 ⁇ m) to form a base material syrup layer having a thickness of 300 ⁇ m. did.
  • a dispenser trade name “SM300DS-S, MPP-1”, manufactured by Musashi Engineering Co., Ltd.
  • Part formation syrup is dropped, and according to the dimensions in Table 3, a pattern as shown in FIG. 10 (annular circles (perfect circles or ellipses) having a predetermined width are arranged at equal intervals in the horizontal and vertical directions, respectively.
  • the cylindrical hardly extensible polymer portion is continuously formed from one surface of the sheet-like extensible organic base material to a depth of 2/3 or more. However, it was not formed up to the other surface (embedded type).
  • Dx is the diameter of the ring (outer periphery) (or the minor axis of the elliptical ring) (mm), which is the surface shape of the syrup part for forming the cylindrical difficult-to-extend polymer part
  • Dy is the difficult cylindrical extension.
  • Examples 13 to 16 The base material syrup obtained in Production Example 1 is coated with an applicator on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 ⁇ m) to form a base material syrup layer having a thickness of 300 ⁇ m. did.
  • a dispenser trade name “SM300DS-S, MPP-1”, manufactured by Musashi Engineering Co., Ltd.
  • the part forming syrup is dropped, and according to the dimensions in Table 4, a pattern as shown in FIG.
  • the cylindrical hardly extensible polymer portion is continuously formed from one surface of the sheet-like extensible organic base material to a depth of 2/3 or more. However, it was not formed up to the other surface (embedded type).
  • Dx is the diameter of the ring (outer periphery) (or the minor axis of the elliptical ring) (mm), which is the surface shape of the syrup portion for forming the cylindrical hardly extensible polymer portion
  • Dy is the hard cylindrical shape.
  • the distance (mm), Ly is the distance (mm) between the centers of the cylindrical refractory polymer part-forming syrup parts adjacent in the oblique direction
  • W is the ring width (mm).
  • the base material syrup obtained in Production Example 1 is coated with an applicator on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 ⁇ m) to form a base material syrup layer having a thickness of 300 ⁇ m. did.
  • a dispenser trade name “SM300DS-S, MPP-1”, manufactured by Musashi Engineering Co., Ltd.
  • the part forming syrup is dropped, and according to the dimensions shown in Table 5, a pattern as shown in FIG. 12 (a pattern in which annular crosses having a predetermined width are arranged at equal intervals in the horizontal and vertical directions; matrix Mold).
  • an ultraviolet lamp (BL type) (ultraviolet illuminance: 3.4 mW / cm 2 , integrated irradiation amount: 100 mJ / cm 2 ), and the base material syrup and cylindrical difficulty elongation
  • the cylindrical hardly extensible polymer portion is continuously formed from one surface of the sheet-like extensible organic base material to a depth of 2/3 or more. However, it was not formed up to the other surface (embedded type).
  • X is the length (mm) of the side (longest part) of the cruciform ring (outer periphery) which is the surface shape of the cylindrically difficult-to-extend polymer part forming syrup part
  • Y is the cylindrical difficultly extended part.
  • the base material syrup obtained in Production Example 1 is coated with an applicator on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 ⁇ m) to form a base material syrup layer having a thickness of 300 ⁇ m. did.
  • a dispenser trade name “SM300DS-S, MPP-1”, manufactured by Musashi Engineering Co., Ltd.
  • Part formation syrup is dropped, and according to the dimensions shown in Table 6, a pattern as shown in FIG. 13 (a pattern in which circular crosses having a predetermined width are arranged so as to be closest packed; closest packed type ) was formed.
  • an ultraviolet lamp (BL type) (ultraviolet illuminance: 3.4 mW / cm 2 , integrated irradiation amount: 100 mJ / cm 2 ), and the base material syrup and cylindrical difficulty elongation
  • the cylindrical hardly extensible polymer portion is continuously formed from one surface of the sheet-like extensible organic base material to a depth of 2/3 or more. However, it was not formed up to the other surface (embedded type).
  • X is the length (mm) of the side (longest part) of the cruciform ring (outer periphery) which is the surface shape of the cylindrically difficult-to-extend polymer part syrup part
  • Y is the cylindrically difficult-to-extend
  • Lx is the syrup part for forming the cylindrical difficult-to-extend polymer part adjacent in the horizontal direction
  • Ly is the center-to-center distance (mm) of the cylindrically stretchable polymer part-forming syrup part adjacent in the oblique direction
  • W is the ring width (mm).
  • Examples 25-28 The base material syrup obtained in Production Example 1 is coated with an applicator on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 ⁇ m) to form a base material syrup layer having a thickness of 300 ⁇ m. did.
  • a dispenser trade name “SM300DS-S, MPP-1”, manufactured by Musashi Engineering Co., Ltd.
  • Part formation syrup was dropped to form a pattern as shown in FIG. 14 (a pattern in which annular circles having a predetermined width were formed in multiple layers) according to the dimensions in Table 7.
  • an ultraviolet lamp (BL type) (ultraviolet illuminance: 3.4 mW / cm 2 , integrated irradiation amount: 100 mJ / cm 2 ), and the base material syrup and cylindrical difficulty elongation
  • the cylindrical hardly extensible polymer portion is continuously formed from one surface of the sheet-like extensible organic base material to a depth of 2/3 or more. However, it was not formed up to the other surface (embedded type).
  • R1 is the diameter (mm) of the outermost ring (outer periphery) which is the surface shape of the cylindrical refractory polymer portion forming syrup portion
  • R2 is the cylindrical hardly extensible polymer portion formation.
  • L 1 and 2 are the distances between the centers of the outermost ring and the second ring from the outside (mm), which are the surface shapes of the cylindrical refractory polymer part forming syrup part
  • L 1 and 3 are distances (mm) between the centers of the outermost annular ring and the third annular ring from the outside, which are the surface shapes of the cylindrical refractory polymer part forming syrup part
  • W is the width of each ring (Mm) is shown.
  • the base material syrup obtained in Production Example 1 is coated with an applicator on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 ⁇ m) to form a base material syrup layer having a thickness of 300 ⁇ m. did.
  • a dispenser trade name “SM300DS-S, MPP-1”, manufactured by Musashi Engineering Co., Ltd.
  • a portion forming syrup is dropped, and according to the dimensions in Table 8, a pattern as shown in FIG. 15 (a pattern in which letters, numbers, and figures having contours with a predetermined width are regularly arranged; matrix type ) was formed.
  • an ultraviolet lamp (BL type) (ultraviolet illuminance: 3.4 mW / cm 2 , integrated irradiation amount: 100 mJ / cm 2 ), and the base material syrup and cylindrical difficulty elongation
  • the cylindrical hardly extensible polymer portion is continuously formed from one surface of the sheet-like extensible organic base material to a depth of 2/3 or more. However, it was not formed up to the other surface (embedded type).
  • W represents the width (mm) of each ring.
  • Example 31 The base material syrup obtained in Production Example 1 is coated with an applicator on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 ⁇ m) to form a base material syrup layer having a thickness of 300 ⁇ m. did.
  • a dispenser trade name “SM300DS-S, MPP-1”, manufactured by Musashi Engineering Co., Ltd.
  • the part forming syrup was dropped to form a pattern as shown in FIG. 16 (a picture composed of a combination of figures having an outline with a predetermined width).
  • an ultraviolet lamp (BL type) (ultraviolet illuminance: 3.4 mW / cm 2 , integrated irradiation amount: 100 mJ / cm 2 ), and the base material syrup and cylindrical difficulty elongation
  • a cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 ⁇ m) is bonded to the semi-cured syrup with a hand roller, and an ultraviolet lamp ( BL type) (ultraviolet light illuminance: 3.4 mW / cm 2 , integrated irradiation amount: 2000 mJ / cm 2 ), and difficult to stretch cylindrically in a cured base material syrup
  • BL type ultraviolet lamp
  • the cylindrical hardly extensible polymer portion is continuously formed from one surface of the sheet-like extensible organic base material to a depth of 2/3 or more. However, it was not formed up to the other surface (embedded type).
  • Example 32 The base material syrup obtained in Production Example 1 is coated with an applicator on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 ⁇ m) to form a base material syrup layer having a thickness of 300 ⁇ m. did.
  • a dispenser trade name “SM300DS-S, MPP-1”, manufactured by Musashi Engineering Co., Ltd.
  • the part forming syrup was dropped to form a pattern as shown in FIG. 17 (a pattern composed of a combination of figures and characters having an outline with a predetermined width; a composite type).
  • an ultraviolet lamp (BL type) (ultraviolet illuminance: 3.4 mW / cm 2 , integrated irradiation amount: 100 mJ / cm 2 ), and the base material syrup and cylindrical difficulty elongation
  • a cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 ⁇ m) is bonded to the semi-cured syrup with a hand roller, and an ultraviolet lamp ( BL type) (ultraviolet light illuminance: 3.4 mW / cm 2 , integrated irradiation amount: 2000 mJ / cm 2 ), and difficult to stretch cylindrically in a cured base material syrup
  • BL type ultraviolet lamp
  • the cylindrical hardly extensible polymer portion is continuously formed from one surface of the sheet-like extensible organic base material to a depth of 2/3 or more. However, it was not formed up to the other surface (embedded type).
  • Elongation rate S 1 (%) is determined by measuring the width in the direction of elongation of the ring-shaped rectangular difficult-to-extend polymer part (rectangular line width of the substrate surface) before and after stretching, and the formula: ⁇ (length after stretching ⁇ Length before stretching) / (Length before stretching) ⁇ ⁇ 100).
  • Elongation rate S 2 (%) is the length between adjacent marks by marking 6 points in the extending direction of the outer part (easily extensible polymer base material part) of the annular rectangular hardly extensible polymer part.
  • S 1 (%) 5
  • S 2 (%) 80
  • (S 2 / S 1 ) 16
  • (S 2 ⁇ S 1 ) (%) 75.
  • the sheet-like extensible organic base material obtained in Example 4 also had stretchability.
  • the shape of the cylindrical difficult-to-extend polymer part hardly changes even when the base material is extended in one direction (plane direction). While having this function, a desired design can be applied to the shape invariant portion, and other members can be held and fixed using appropriate fixing means. Moreover, since the area
  • the sheet-like extensible organic base material of the present invention includes, for example, a band member, a binding member, a sanitary article, a clothing part, a base material for a poultice, an electronic member, an optical member, an optoelectronic member, It can also be used for car electronics members, household appliance members, housing equipment members, building materials, and the like.
  • Sheet-like extensible organic base material Easily extensible polymer base material (excellent extensible polymer base part) 20 Material layer for polymer matrix formation (energy ray curable composition layer for easily stretchable polymer matrix formation) 21 Polymer Base Material Forming Material Layer 22 Polymer Base Material Forming Material Layer 200 Partially Cured Easy Stretchable Polymer Base Material Forming Energy Beam Curable Composition Layer 3 Tubular Difficult Stretchable Polymer Part A 3a Region corresponding to a cylindrical cavity 30 Material for forming a cylindrical hardly stretchable polymer part (energy ray curable composition for forming a cylindrical difficult stretchable polymer part) 31 Cylindrical Difficult-to-Extend Polymer Part Forming Material 32 Cylindrical Difficult-to-Extend Polymer Part Forming Material 300 Partially Cured Cylindrical Difficult-to-Extend Polymer Part Forming Energy Beam Curing Composition 4 Support 5 Cover Film A Multifunctional Sheet-like extensible organic substrate (such as adhesive sheet-like extensible organic substrate) 6 Functional layers

Abstract

This sheet-elongatable organic base material is characterized in that a cylindrical poorly-elongatable polymer part (A), with which the surface shape, or the projection shape from when the surface of the sheet-elongatable organic base material serves as a projection plane, is annular, is partially and integrally formed within a readily-elongatable polymer matrix. The annular outer peripheral shape in the surface shape or the projection shape of the cylindrical poorly-elongatable polymer part (A) may be substantially circular, substantially polygonal, amorphous, or any shape representing a character, symbol, or number. This sheet-elongatable organic base material has a poorly-elongatable part which is elongatable in a planar direction and is less prone to shape deformation even when extended in the planar direction, and also has a readily-elongatable site which can be elongated in the thickness direction into the interior of a region of the poorly-elongatable part.

Description

シート状伸長性有機基材Sheet-like extensible organic substrate
　本発明は、シート状伸長性有機基材、より詳しくは、易伸長性ポリマー母材中に表面形状又は基材表面への投影形状が輪帯状である筒状の難伸長性ポリマー部が一体的に形成されているシート状の伸長性有機基材（特に伸縮性有機基材）に関する。該シート状伸長性有機基材は、その伸長性や伸縮性を利用して、例えば、バンド部材、結束用部材、衛生用品、衣料品の部分、湿布剤の基布等として利用できる。また、このシート状伸長性有機基材は、面方向に伸長させる際、基材全体としては伸長するが、筒状難伸長性ポリマー部は伸長せずにその形状が保持されるため、該筒状難伸長性ポリマー部にキャラクター等の意匠を施したり、他の部材を保持、固定させることができる。さらに、筒状難伸長性ポリマー部の筒状の空洞部に当たる領域は易伸長性ポリマー材料で構成されるため、厚み方向に伸長可能であり、そのため、被装着物の形状に追従しやすく装着性に優れる。従って、このシート状伸長性有機基材は、例えば、エレクトロニクス部材、オプティカル部材、オプトエレクトロニクス部材、カーエレクトロニクス部材、家電製品用部材、住宅設備用部材、建材などにも利用できる。 The present invention relates to a sheet-like extensible organic base material, more specifically, an easily extensible polymer base material and a cylindrical hard-extensible polymer portion whose surface shape or projection shape onto the base material surface is an annular shape. It is related with the sheet-like extensible organic base material (especially elastic organic base material) currently formed. The sheet-like extensible organic base material can be used as, for example, a band member, a binding member, a sanitary article, a clothing part, a base cloth for a poultice, etc. by utilizing its extensibility and stretchability. In addition, when this sheet-like extensible organic base material is extended in the surface direction, the whole base material is extended, but the cylindrical difficult-to-extend polymer part is not extended, but its shape is maintained. Designs such as characters can be applied to the difficult-to-extend polymer part, and other members can be held and fixed. Furthermore, since the region corresponding to the cylindrical cavity of the cylindrical difficult-to-extend polymer part is made of an easily-extensible polymer material, it can be extended in the thickness direction, so it is easy to follow the shape of the object to be attached. Excellent. Therefore, this sheet-like extensible organic base material can be used for, for example, an electronics member, an optical member, an optoelectronic member, a car electronics member, a household appliance member, a housing equipment member, a building material, and the like.
　伸長性や伸縮性を有する有機部材は、バンド部材、結束用部材、衛生用品、衣料品、湿布剤の基布等に幅広く利用されている。伸長性部材は、通常、均質な伸長性を有する組成物により構成されている（特許文献１）。しかし、このような伸長性部材を伸長させると、伸長性部材のあらゆる部分が伸長する。また、伸長性だけでなく伸縮性をも有する部材では、これを伸縮させると、あらゆる部分が伸び縮みする。そのため、ある箇所に意匠を施しても、伸長性部材を伸長させると、該意匠がゆがんでしまう。また、伸長性部材に他の部材を固定する場合には、伸長性部材のあらゆる部分が伸長するので、該他の部材を確実に保持、固定することが困難である。 The organic members having stretchability and stretchability are widely used for band members, binding members, sanitary goods, clothing items, base materials for poultices, and the like. The extensible member is usually composed of a composition having uniform extensibility (Patent Document 1). However, when such an extensible member is extended, every part of the extensible member is extended. Further, in a member having not only extensibility but also elasticity, when this is expanded and contracted, all parts expand and contract. Therefore, even if a design is applied to a certain place, the design is distorted when the extensible member is extended. Moreover, when fixing another member to an extensible member, since every part of an extensible member expand | extends, it is difficult to hold | maintain and fix this other member reliably.
特開２００３−３４２１６９号公報JP 2003-342169 A
　本発明の目的は、面方向に伸長性を有するとともに、面方向に伸長させても形状が変化しにくい難伸長部を有しており、さらに該難伸長部の領域の内部に厚み方向に伸長可能な易伸長部位を有するシート状伸長性基材を提供することにある。
　本発明の他の目的は、面方向に伸縮性を有するとともに、面方向に伸縮させても形状が変化しにくい難伸縮部を有しており、さらに該難伸縮部の内部に厚み方向に伸縮可能な易伸縮部位を有するシート状伸長性基材を提供することにある。 It is an object of the present invention to have a stretchable portion that is extensible in the surface direction and hardly changes in shape even when stretched in the surface direction, and further extends in the thickness direction inside the region of the difficultly stretched portion. An object of the present invention is to provide a sheet-like extensible substrate having a possible easily stretchable portion.
Another object of the present invention is to have a stretchable portion in the surface direction and a hard stretchable portion whose shape hardly changes even when stretched in the plane direction, and further stretches in the thickness direction inside the hard stretchable portion. An object of the present invention is to provide a sheet-like extensible substrate having an easily stretchable part.
　本発明者らは、上記の目的を達成するため鋭意検討した結果、易伸長性のポリマー母材中に、シート厚み方向に延び且つ所定の厚みを有する筒状（中空柱状）の難伸長性ポリマー部を一体的に形成することにより、上記目的を達成できることを見出し、本発明を完成した。 As a result of intensive studies to achieve the above object, the present inventors have found that a tubular (hollow columnar) hardly stretchable polymer having a predetermined thickness and extending in the sheet thickness direction in an easily stretchable polymer base material. The present invention has been completed by finding that the above object can be achieved by integrally forming the portions.
　すなわち、本発明は、易伸長性ポリマー母材中に、表面形状又はシート状伸長性有機基材表面を投影面としたときの投影形状が輪帯状である筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されているシート状伸長性有機基材を提供する。 That is, in the present invention, a cylindrical stretchable polymer portion A having a ring-shaped projection when the surface shape or the sheet-like stretchable organic substrate surface is a projection surface is partially included in the easily stretchable polymer base material. Provided is a sheet-like extensible organic substrate formed integrally and integrally.
　前記筒状難伸長性ポリマー部Ａの前記表面形状又は投影形状における輪帯の外周形状は、略円形、略多角形、無定形、又は文字、記号若しくは数字を表す形状のいずれであってもよい。また、前記筒状難伸長性ポリマー部Ａの前記表面形状又は投影形状における輪帯の外周形状が略多角形であり、且つ該略多角形の内角が９０度以下又は９０度を超える角度であってもよい。 The outer peripheral shape of the annular zone in the surface shape or projected shape of the cylindrical hardly extensible polymer portion A may be any of a substantially circular shape, a substantially polygonal shape, an amorphous shape, or a shape representing a character, a symbol, or a number. . Further, the outer peripheral shape of the annular zone in the surface shape or the projected shape of the cylindrical difficult-to-extend polymer part A is a substantially polygon, and the inner angle of the substantially polygon is an angle of 90 degrees or less or more than 90 degrees. May be.
　前記シート状伸長性有機基材においては、複数の筒状難伸長性ポリマー部Ａが規則的パターンで形成されていてもよい。 In the sheet-like extensible organic base material, a plurality of cylindrical difficult-to-extend polymer parts A may be formed in a regular pattern.
　隣接する筒状難伸長性ポリマー部Ａ間の距離は、例えば０．０５ｍｍ~５０ｃｍである。また、隣接する筒状難伸長性ポリマー部Ａの中心間の距離は、例えば５ｍｍ~８０ｃｍである。 The distance between adjacent cylindrical difficult-to-extend polymer parts A is, for example, 0.05 mm to 50 cm. Further, the distance between the centers of adjacent cylindrical hardly extensible polymer portions A is, for example, 5 mm to 80 cm.
　筒状難伸長性ポリマー部Ａの筒状の空洞部に当たる易伸長性ポリマー材料からなる領域内に、さらに、表面形状又はシート状伸長性有機基材表面を投影面としたときの投影形状が、略円形、略多角形、無定形、又は文字、記号若しくは数字を表す形状、輪帯状、又は線状である難伸長性ポリマー部Ｂを１又は２以上有していてもよい。 In the region made of the easily extensible polymer material that hits the cylindrical cavity of the cylindrical hardly extensible polymer portion A, the projection shape when the surface shape or the sheet-like extensible organic base material surface is the projection surface, You may have 1 or 2 or more or less the difficulty extensible polymer part B which is a substantially circular shape, a substantially polygonal shape, an amorphous shape, the shape showing a character, a symbol, or a number, a ring shape, or linear.
　前記シート状伸長性有機基材の厚みは、例えば０．０１ｍｍ~１ｃｍである。 The thickness of the sheet-like extensible organic base material is, for example, 0.01 mm to 1 cm.
　筒状難伸長性ポリマー部Ａの厚み方向の長さがシート状伸長性有機基材の厚みの少なくとも１／５０であるのが好ましい。また、筒状難伸長性ポリマー部Ａが、シート状伸長性有機基材の一方の表面から他方の表面に至るまで連続して形成されていてもよい。 It is preferable that the length of the cylindrical hardly extensible polymer portion A in the thickness direction is at least 1/50 of the thickness of the sheet-like extensible organic base material. Moreover, the cylindrical difficulty extensible polymer part A may be continuously formed from one surface of the sheet-like extensible organic base material to the other surface.
　筒状難伸長性ポリマー部Ａと易伸長性ポリマー母材の界面近傍において、伸び特性がグラデーションをなしていてもよい。 In the vicinity of the interface between the cylindrical hardly extensible polymer portion A and the easily extensible polymer base material, the elongation characteristics may have a gradation.
　前記シート状伸長性有機基材は、さらに伸縮性を有していてもよい。 The sheet-like extensible organic base material may further have stretchability.
　本明細書では、上記発明のほか、下記のシート状伸長性有機基材（多機能性シート状伸長性有機基材）についても説明する。 In the present specification, in addition to the above invention, the following sheet-like extensible organic base material (multifunctional sheet-like extensible organic base material) will also be described.
　［１−１］易伸長性ポリマー母材中に、表面形状又はシート状有機基材表面を投影面としたときの投影形状が輪帯状である筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されている伸長性を有するシート状有機基材の少なくとも一方の面に粘着剤層を有しており、該粘着剤層の粘着力（温度２３℃、湿度６５％ＲＨ、引張速度３００ｍｍ／分、剥離角度１８０°、対ＳＵＳ３０４）が０．１Ｎ／２０ｍｍ以上である粘着性を有する多機能性シート状伸長性有機基材。 [1-1] In the easily stretchable polymer base material, a cylindrical hardly stretchable polymer portion A having a projection shape when the surface shape or the sheet-like organic base material surface is a projection surface is partially and It has an adhesive layer on at least one surface of an integrally formed sheet-like organic substrate having extensibility, and the adhesive strength of the adhesive layer (temperature 23 ° C., humidity 65% RH, tensile speed) A multifunctional sheet-like extensible organic base material having an adhesiveness of 300 mm / min, peeling angle of 180 °, and SUS304) of 0.1 N / 20 mm or more.
　［１−２］易伸長性ポリマー母材中に、表面形状又はシート状有機基材表面を投影面としたときの投影形状が輪帯状である筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されている伸長性を有するシート状有機基材の少なくとも一方の面の粘着力（温度２３℃、湿度６５％ＲＨ、引張速度３００ｍｍ／分、剥離角度１８０°、対ＳＵＳ３０４）が０．１Ｎ／２０ｍｍ以上である粘着性を有する多機能性シート状伸長性有機基材。 [1-2] In the easily stretchable polymer base material, a cylindrical hardly stretchable polymer portion A having a projection shape when the surface shape or the sheet-like organic base material surface is a projection surface is partially and The adhesive strength (temperature 23 ° C., humidity 65% RH, tensile speed 300 mm / min, peel angle 180 °, vs. SUS304) of at least one surface of the integrally formed sheet-like organic substrate having extensibility is 0. A multifunctional sheet-like extensible organic base material having adhesiveness of 1 N / 20 mm or more.
　［２−１］易伸長性ポリマー母材中に、表面形状又はシート状有機基材表面を投影面としたときの投影形状が輪帯状である筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されている伸長性を有するシート状有機基材であって、前記易伸長性ポリマー母材が耐候剤を含有している多機能性シート状伸長性有機基材。 [2-1] In the easily stretchable polymer base material, a cylindrical hardly stretchable polymer portion A having a projection shape when the surface shape or the sheet-like organic base material surface is a projection surface is partially and A multi-functional sheet-like extensible organic base material which is an integrally formed sheet-like organic base material having extensibility, wherein the easily extensible polymer base material contains a weathering agent.
　［２−２］前記耐候剤が、紫外線吸収剤及び酸化防止剤から選ばれる少なくとも１種である前記［２−１］記載の多機能性シート状伸長性有機基材。 [2-2] The multifunctional sheet-like extensible organic substrate according to [2-1], wherein the weathering agent is at least one selected from an ultraviolet absorber and an antioxidant.
　［３−１］易伸長性ポリマー母材中に、表面形状又はシート状有機基材表面を投影面としたときの投影形状が輪帯状である筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されている伸長性を有するシート状有機基材であって、易伸長性ポリマー母材及び／又は筒状難伸長性ポリマー部が香料を含有している多機能性シート状伸長性有機基材。 [3-1] In the easily stretchable polymer base material, the cylindrical hardly stretchable polymer portion A whose projection shape when the surface shape or the surface of the sheet-like organic base material is a projection surface is an annular shape is partially and Multi-functional sheet-like extensibility, which is an integrally formed sheet-like organic base material having extensibility, in which an easily extensible polymer base material and / or a cylindrical hardly extensible polymer portion contains a fragrance Organic base material.
　［３−２］易伸長性ポリマー母材中に、表面形状又はシート状有機基材表面を投影面としたときの投影形状が輪帯状である筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されている伸長性を有するシート状有機基材の少なくとも一方の面に消臭層を有する多機能性シート状伸長性有機基材。 [3-2] In the easily stretchable polymer base material, a cylindrical hardly stretchable polymer portion A having a projection shape when the surface shape or the surface of the sheet-like organic substrate is a projection surface is partially and A multifunctional sheet-like extensible organic base material having a deodorizing layer on at least one surface of an integrally formed sheet-like organic base material having extensibility.
　［３−３］易伸長性ポリマー母材中に、表面形状又はシート状有機基材表面を投影面としたときの投影形状が輪帯状である筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されている伸長性を有するシート状有機基材を含むシート状伸長性有機基材であって、該シート状伸長性有機基材を１５０℃で３分間加熱した際に発生するモノマー量が３００ｐｐｍ以下である多機能性シート状伸長性有機基材。 [3-3] In the easily stretchable polymer base material, the cylindrical hardly stretchable polymer portion A having a projection shape when the surface shape or the sheet-like organic base material surface is the projection surface is partially and Monomer generated when a sheet-like extensible organic base material including a sheet-like organic base material having extensibility formed integrally is heated at 150 ° C. for 3 minutes. A multifunctional sheet-like extensible organic substrate having an amount of 300 ppm or less.
　［４−１］易伸長性ポリマー母材中に、表面形状又はシート状有機基材表面を投影面としたときの投影形状が輪帯状である筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されている伸長性を有するシート状有機基材であって、易伸長性ポリマー母材及び／又は筒状難伸長性ポリマー部Ａが染料若しくは顔料を含有している多機能性シート状伸長性有機基材。 [4-1] In the easily stretchable polymer base material, a cylindrical hardly stretchable polymer portion A having a projection shape when the surface shape or the sheet-like organic base material surface is a projection surface is partially and A sheet-like organic base material having extensibility formed integrally, wherein the easily extensible polymer base material and / or the cylindrical hardly extensible polymer portion A contains a dye or a pigment Stretchable organic base material.
　［４−２］易伸長性ポリマー母材中に、表面形状又はシート状有機基材表面を投影面としたときの投影形状が輪帯状である筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されている伸長性を有するシート状有機基材の少なくとも一方の面に着色層を有する多機能性シート状伸長性有機基材。 [4-2] In the easily stretchable polymer base material, the cylindrical hardly stretchable polymer portion A having a projection shape when the surface shape or the sheet-like organic substrate surface is the projection surface is partially and A multifunctional sheet-like extensible organic substrate having a colored layer on at least one surface of an integrally formed sheet-like organic substrate having extensibility.
　［４−３］易伸長性ポリマー母材中に、表面形状又はシート状有機基材表面を投影面としたときの投影形状が輪帯状である筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されている伸長性を有するシート状有機基材の少なくとも一方の面に印字層を有する多機能性シート状伸長性有機基材。 [4-3] In the easily stretchable polymer base material, the cylindrical hardly stretchable polymer portion A having a projection shape when the surface shape or the sheet-like organic base material surface is the projection surface is partially and A multifunctional sheet-like extensible organic base material having a printing layer on at least one surface of an integrally formed sheet-like organic base material having extensibility.
　［５−１］易伸長性ポリマー母材中に、表面形状又はシート状有機基材表面を投影面としたときの投影形状が輪帯状である筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されている伸長性を有するシート状有機基材であって、該シート状有機基材が難燃剤を含有している、及び／又は該シート状有機基材の少なくとも片面に難燃層を有している難燃性を有する多機能性シート状伸長性有機基材。 [5-1] In the easily stretchable polymer base material, the cylindrical hardly stretchable polymer portion A having a projection shape when the surface shape or the sheet-like organic base material surface is the projection surface is partially and An integrally formed sheet-like organic base material having extensibility, wherein the sheet-like organic base material contains a flame retardant, and / or flame retardant on at least one side of the sheet-like organic base material A multifunctional sheet-like extensible organic base material having a flame retardancy having a layer.
　［５−２］難燃剤が、ハロゲン系化合物、リン系化合物、アンチモン系化合物、及び金属水酸化物から選ばれる少なくとも１種である前記［５−１］記載の難燃性を有するシート状伸長性有機基材。 [5-2] Sheet-like elongation having flame retardancy according to [5-1], wherein the flame retardant is at least one selected from halogen compounds, phosphorus compounds, antimony compounds, and metal hydroxides. Organic base material.
　［５−３］難燃層が、難燃剤及び／又は難燃性ポリマーを含有する層である前記［５−１］又は［５−２］に記載の難燃性を有する多機能性シート状伸長性有機基材。 [5-3] The multifunctional sheet having flame retardancy according to [5-1] or [5-2], wherein the flame retardant layer is a layer containing a flame retardant and / or a flame retardant polymer. Stretchable organic base material.
　［６−１］易伸長性ポリマー母材中に、表面形状又はシート状有機基材表面を投影面としたときの投影形状が輪帯状である筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されている伸長性を有するシート状有機基材であって、該シート状有機基材が熱伝導性物質を含有している、及び／又は該シート状有機基材の少なくとも片面に熱伝導性層を有している熱伝導性を有する多機能性シート状伸長性有機基材。 [6-1] In the easily stretchable polymer base material, the cylindrical hardly stretchable polymer portion A having a ring shape when the surface shape or the sheet-like organic base material surface is the projection surface is partially and A sheet-like organic substrate having extensibility formed integrally, the sheet-like organic substrate containing a heat conductive substance, and / or on at least one surface of the sheet-like organic substrate A multifunctional sheet-like extensible organic base material having thermal conductivity having a thermal conductive layer.
　［６−２］熱伝導性物質が、金属、金属化合物、ホウ素化合物、グラファイト、及び熱伝導性炭素繊維から選択される少なくとも１種である前記［６−１］記載の熱伝導性を有する多機能性シート状伸長性有機基材。 [6-2] The heat conductive material according to [6-1], wherein the heat conductive material is at least one selected from metals, metal compounds, boron compounds, graphite, and heat conductive carbon fibers. Functional sheet-like extensible organic base material.
　［６−３］熱伝導性層が、金属、金属化合物、ホウ素化合物、グラファイト、又は熱伝導性炭素繊維を含有する層である前記［６−１］又は［６−２］に記載の熱伝導性を有する多機能性シート状伸長性有機基材。 [6-3] The heat conduction according to [6-1] or [6-2], wherein the heat conductive layer is a layer containing a metal, a metal compound, a boron compound, graphite, or a heat conductive carbon fiber. Multifunctional sheet-like extensible organic base material having properties.
　［７−１］易伸長性ポリマー母材中に、表面形状又はシート状有機基材表面を投影面としたときの投影形状が輪帯状である筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されている伸長性を有するシート状有機基材であって、該シート状有機基材が断熱性付与剤を含有している、及び／又は該シート状有機基材の少なくとも片面に断熱性層を有している断熱性を有する多機能性シート状伸長性有機基材。 [7-1] In the easily stretchable polymer base material, the cylindrical hardly stretchable polymer portion A having a projection shape when the surface shape or the sheet-like organic base material surface is the projection surface is partially and A sheet-like organic substrate having extensibility formed integrally, wherein the sheet-like organic substrate contains a heat-insulating agent, and / or on at least one side of the sheet-like organic substrate. A multifunctional sheet-like extensible organic base material having a heat insulating property having a heat insulating layer.
　［７−２］断熱性付与剤が、中空粒子である前記［７−１］記載の断熱性を有する多機能性シート状伸長性有機基材。 [7-2] A multifunctional sheet-like extensible organic base material having heat insulating properties according to [7-1], wherein the heat insulating property imparting agent is hollow particles.
　［７−３］断熱性層が、中空粒子を含有する層、及び／又は発泡プラスチックで形成された層である前記［７−１］又は［７−２］に記載の断熱性を有する多機能性シート状伸長性有機基材。 [7-3] Multifunctional having heat insulating properties according to [7-1] or [7-2], wherein the heat insulating layer is a layer containing hollow particles and / or a layer formed of foamed plastic. Sheet-like extensible organic base material.
　［８−１］易伸長性ポリマー母材中に、表面形状又はシート状有機基材表面を投影面としたときの投影形状が輪帯状である筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されている伸長性を有するシート状有機基材であって、前記易伸長性ポリマー母材が耐衝撃性付与剤を含有しているシート状伸長性有機基材。 [8-1] In the easily stretchable polymer base material, the cylindrical hardly stretchable polymer portion A whose projection shape when the surface shape or the surface of the sheet-like organic base material is a projection surface is an annular shape is partially and A sheet-like organic base material having extensibility formed integrally, wherein the easily extensible polymer base material contains an impact resistance imparting agent.
　［８−２］易伸長性ポリマー母材中に、表面形状又はシート状有機基材表面を投影面としたときの投影形状が輪帯状である筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されている伸長性を有するシート状有機基材の少なくとも一方の面に衝撃吸収層を有する多機能性シート状伸長性有機基材。 [8-2] In the easily stretchable polymer base material, the cylindrical hardly stretchable polymer portion A having a projection shape when the surface shape or the surface of the sheet-like organic base material is a projection surface is partially and A multifunctional sheet-like extensible organic base material having an impact absorbing layer on at least one surface of an integrally formed sheet-like organic base material having extensibility.
　［８−３］前記耐衝撃性付与剤が、無機中空粒子及び発泡プラスチック粒子からなる群より選択された少なくとも１種である前記［８−１］記載の多機能性シート状伸長性有機基材。 [8-3] The multifunctional sheet-like extensible organic base material according to [8-1], wherein the impact resistance-imparting agent is at least one selected from the group consisting of inorganic hollow particles and foamed plastic particles. .
　［８−４］前記衝撃吸収層が、無機中空粒子及び発泡プラスチック粒子からなる群より選択された少なくとも１種を含む耐衝撃性付与剤含有層又はプラスチック発泡体より形成された発泡層である前記［８−２］記載の多機能性シート状伸長性有機基材。 [8-4] The impact absorbing layer is an impact resistance-containing agent-containing layer containing at least one selected from the group consisting of inorganic hollow particles and foamed plastic particles, or a foamed layer formed from a plastic foam. [8-2] Multifunctional sheet-like extensible organic base material.
　［９−１］易伸長性ポリマー母材中に、表面形状又はシート状有機基材表面を投影面としたときの投影形状が輪帯状である筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されている伸長性を有するシート状有機基材の少なくとも一方の面にガスバリア層を有しており、下記［ｉ］及び［ｉｉ］のいずれか一方又は両方を満たす多機能性シート状伸長性有機基材。
［ｉ］ＪＩＳ　Ｋ７１２６−２法に準じて２０℃、７０％ＲＨ条件下で測定される厚さ１００μｍ相当の酸素透過率が１０ｍＬ／ｍ２／０．１ＭＰａ／ｄａｙ以下である
［ｉｉ］ＪＩＳ　Ｋ７１２９Ｂ法に準じて４０℃、９０％ＲＨ条件下で測定される厚さ１００μｍ相当の水蒸気透過率が１０ｇ／ｍ２／０．１ＭＰａ／ｄａｙ以下である [9-1] In the easily stretchable polymer base material, the cylindrical hardly stretchable polymer portion A having a projection shape when the surface shape or the sheet-like organic substrate surface is a projection surface is partially and A multifunctional sheet having a gas barrier layer on at least one surface of an integrally formed sheet-like organic substrate having extensibility and satisfying one or both of the following [i] and [ii] Stretchable organic base material.
[I] The oxygen permeability corresponding to a thickness of 100 μm measured under the conditions of 20 ° C. and 70% RH according to JIS K7126-2 method is 10 mL / m 2 /0.1 MPa / day or less. [Ii] JIS K7129B method The water vapor permeability corresponding to a thickness of 100 μm measured under the conditions of 40 ° C. and 90% RH is 10 g / m 2 /0.1 MPa / day or less
　［９−２］易伸長性ポリマー母材中に、表面形状又はシート状有機基材表面を投影面としたときの投影形状が輪帯状である筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されている伸長性を有するシート状有機基材であって、該シート状有機基材が下記［ｉ］及び［ｉｉ］のいずれか一方又は両方を満たす多機能性シート状伸長性有機基材。
［ｉ］ＪＩＳ　Ｋ７１２６−２法に準じて２０℃、７０％ＲＨ条件下で測定される厚さ１００μｍ相当の酸素透過率が１０ｍＬ／ｍ２／０．１ＭＰａ／ｄａｙ以下である
［ｉｉ］ＪＩＳ　Ｋ７１２９Ｂ法に準じて４０℃、９０％ＲＨ条件下で測定される厚さ１００μｍ相当の水蒸気透過率が１０ｇ／ｍ２／０．１ＭＰａ／ｄａｙ以下である [9-2] In the easily stretchable polymer base material, the cylindrical hardly stretchable polymer portion A having a projection shape when the surface shape or the sheet-like organic base material surface is the projection surface is partially and A sheet-like organic base material having extensibility that is integrally formed, and the multi-functional sheet-like extensibility of the sheet-like organic base material satisfying one or both of the following [i] and [ii] Organic base material.
[I] The oxygen permeability corresponding to a thickness of 100 μm measured under the conditions of 20 ° C. and 70% RH according to JIS K7126-2 method is 10 mL / m 2 /0.1 MPa / day or less. [Ii] JIS K7129B method The water vapor permeability corresponding to a thickness of 100 μm measured under the conditions of 40 ° C. and 90% RH is 10 g / m 2 /0.1 MPa / day or less
　［１０−１］易伸長性ポリマー母材中に、表面形状又はシート状有機基材表面を投影面としたときの投影形状が輪帯状である筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されている伸長性を有するシート状有機基材であって、ＪＩＳ　Ｋ７１２９Ａ法に準じて４０℃、９０％ＲＨ条件下で測定される厚さ４０μｍ相当の水蒸気透過率が１００ｇ／ｍ２／０．１ＭＰａ／ｄａｙ以上である多機能性シート状伸長性有機基材。 [10-1] In the easily stretchable polymer base material, the cylindrical hardly stretchable polymer portion A whose projection shape when the surface shape or the sheet-like organic base material surface is the projection surface is an annular shape is partially and It is an integrally formed sheet-like organic base material having extensibility, and has a water vapor transmission rate corresponding to a thickness of 40 μm measured at 40 ° C. and 90% RH in accordance with JIS K7129A method of 100 g / m 2. Multifunctional sheet-like extensible organic base material that is at least 0.1 MPa / day.
　［１０−２］前記易伸長性ポリマー母材が透湿性付与剤を含有している前記［１０−１］記載の多機能性シート状伸長性有機基材。 [10-2] The multifunctional sheet-like extensible organic base material according to [10-1], wherein the easily extensible polymer base material contains a moisture permeability imparting agent.
　［１１−１］易伸長性ポリマー母材中に、表面形状又はシート状有機基材表面を投影面としたときの投影形状が輪帯状である筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されている伸長性を有するシート状有機基材であって、該シート状有機基材が導電性物質を含有している、及び／又は該シート状有機基材の少なくとも片面に導電性層を有している導電性を有する多機能性シート状伸長性有機基材。 [11-1] In the easily stretchable polymer base material, the cylindrical hardly stretchable polymer portion A having a projection shape when the surface shape or the surface of the sheet-like organic base material is a projection surface is partially and A sheet-like organic substrate having extensibility formed integrally, wherein the sheet-like organic substrate contains a conductive substance, and / or is conductive on at least one surface of the sheet-like organic substrate. Conductive multifunctional sheet-like extensible organic base material having a conductive layer.
　［１１−２］導電性物質が、カーボン系導電性フィラー、金属系導電性フィラー、導電性ポリマー、界面活性剤、親水性化合物、親水性ポリマー及びイオン性液体から選択される少なくとも１種である前記［１１−１］記載の導電性を有する多機能性シート状伸長性有機基材。 [11-2] The conductive substance is at least one selected from a carbon-based conductive filler, a metal-based conductive filler, a conductive polymer, a surfactant, a hydrophilic compound, a hydrophilic polymer, and an ionic liquid. The multifunctional sheet-like extensible organic base material having conductivity according to [11-1].
　［１１−３］導電性層が、カーボン系導電性フィラー、金属系導電性フィラー、導電性ポリマー、界面活性剤、親水性化合物、親水性ポリマー及びイオン性液体から選択される少なくとも１種を含有する層である前記［１１−１］又は［１１−２］に記載の導電性を有する多機能性シート状伸長性有機基材。 [11-3] The conductive layer contains at least one selected from a carbon-based conductive filler, a metal-based conductive filler, a conductive polymer, a surfactant, a hydrophilic compound, a hydrophilic polymer, and an ionic liquid. The multifunctional sheet-like extensible organic base material having conductivity according to [11-1] or [11-2], which is a layer to be used.
　［１２−１］易伸長性ポリマー母材中に、表面形状又はシート状有機基材表面を投影面としたときの投影形状が輪帯状である筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されている伸長性を有するシート状有機基材の少なくとも一方の面にフッ素系化合物による表面層を有する、表面層を有する多機能性シート状伸長性有機基材。 [12-1] In the easily stretchable polymer base material, the cylindrical hardly stretchable polymer portion A whose projection shape when the surface shape or the sheet-like organic base material surface is the projection surface is an annular shape is partially and A multifunctional sheet-like extensible organic base material having a surface layer, which has a surface layer made of a fluorine-based compound on at least one surface of the integrally formed sheet-like organic base material having extensibility.
　［１２−２］前記表面層が、フルオロエチレンビニルエーテル共重合体を含む組成物及びフッ素基を含有するハイブリッド系材料を含む組成物からなる群より選択される少なくとも１の組成物により形成される前記［１２−１］記載の表面層を有する多機能性シート状伸長性有機基材。 [12-2] The surface layer is formed of at least one composition selected from the group consisting of a composition containing a fluoroethylene vinyl ether copolymer and a composition containing a hybrid material containing a fluorine group. [12-1] A multifunctional sheet-like extensible organic base material having the surface layer described in [12-1].
　［１３−１］易伸長性ポリマー母材中に、表面形状又はシート状有機基材表面を投影面としたときの投影形状が輪帯状である筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されている伸長性を有するシート状有機基材の少なくとも一方の面に反射防止層を有する反射防止性を有する多機能性シート状伸長性有機基材。 [13-1] In the easily stretchable polymer base material, the cylindrical hardly stretchable polymer portion A having a ring shape when the surface shape or the sheet-like organic base material surface is the projection surface is partially and An anti-reflective multifunctional sheet-like extensible organic base material having an anti-reflection layer on at least one surface of an integrally formed sheet-like organic base material having extensibility.
　［１３−２］前記反射防止層の厚みが０．００５~３０μｍである前記［１３−１］記載の反射防止性を有するシート状伸長性有機基材。 [13-2] The sheet-like extensible organic base material having antireflection properties according to [13-1], wherein the antireflection layer has a thickness of 0.005 to 30 μm.
　［１４−１］易伸長性ポリマー母材中に筒状難伸長性ポリマー部Ａが前記シート状有機基材の少なくとも一方の表面に露出した状態で又は露出していない状態で部分的に形成されている前記［１−１］~［１−２］、［２−１］~［２−２］、［３−１］~［３−３］、［４−１］~［４−３］、［５−１］~［５−３］、［６−１］~［６−３］、［７−１］~［７−３］、［８−１］~［８−４］、［９−１］~［９−２］、［１０~１］~［１０−２］、［１１−１］~［１１−３］、［１２−１］~［１２−２］、［１３−１］~［１３−２］のいずれかに記載の多機能性シート状伸長性有機基材。 [14-1] In the easily stretchable polymer base material, the tubular hardly stretchable polymer portion A is partially formed in a state where it is exposed on at least one surface of the sheet-like organic base material or not exposed. [1-1] to [1-2], [2-1] to [2-2], [3-1] to [3-3], [4-1] to [4-3] , [5-1] to [5-3], [6-1] to [6-3], [7-1] to [7-3], [8-1] to [8-4], [ 9-1] to [9-2], [10-1] to [10-2], [11-1] to [11-3], [12-1] to [12-2], [13- [1] The multifunctional sheet-like extensible organic substrate according to any one of [13-2].
　［１４−２］筒状難伸長性ポリマー部Ａの表面形状、又は筒状難伸長性ポリマー部Ａのシート状有機基材表面を投影面としたときの投影形状が、略円形、略多角形、無定形、又は文字、記号若しくは数字を表す形状、輪帯状、又は線状である前記［１４−１］記載の多機能性シート状伸長性有機基材。 [14-2] The projection shape when the surface shape of the cylindrical hardly extensible polymer part A or the surface of the sheet-like organic base material of the cylindrical hardly extensible polymer part A is a substantially circular or substantially polygonal shape The multi-functional sheet-like extensible organic base material according to [14-1], which is amorphous, or has a shape representing a character, symbol or number, an annular shape, or a linear shape.
　［１４−３］筒状難伸長性ポリマー部Ａの面方向の長軸の長さが０．０５ｍｍ~１０ｃｍである前記［１−１］~［１−２］、［２−１］~［２−２］、［３−１］~［３−３］、［４−１］~［４−３］、［５−１］~［５−３］、［６−１］~［６−３］、［７−１］~［７−３］、［８−１］~［８−４］、［９−１］~［９−２］、［１０−１］~［１０−２］、［１１−１］~［１１−３］、［１２−１］~［１２−２］、［１３−１］~［１３−２］、［１４−１］~［１４−２］のいずれかに記載の多機能性シート状伸長性有機基材。 [14-3] [1-1] to [1-2], [2-1] to [2-1] wherein the length of the long axis in the surface direction of the cylindrical hardly extensible polymer portion A is 0.05 mm to 10 cm. 2-2], [3-1] to [3-3], [4-1] to [4-3], [5-1] to [5-3], [6-1] to [6- 3], [7-1] to [7-3], [8-1] to [8-4], [9-1] to [9-2], [10-1] to [10-2] , [11-1] to [11-3], [12-1] to [12-2], [13-1] to [13-2], and [14-1] to [14-2] A multifunctional sheet-like extensible organic base material according to claim 1.
　［１４−４］易伸長性ポリマー母材中に複数の筒状難伸長性ポリマー部Ａが規則的パターンで形成されている前記［１−１］~［１−２］、［２−１］~［２−２］、［３−１］~［３−３］、［４−１］~［４−３］、［５−１］~［５−３］、［６−１］~［６−３］、［７−１］~［７−３］、［８−１］~［８−４］、［９−１］~［９−２］、［１０−１］~［１０−２］、［１１−１］~［１１−３］、［１２−１］~［１２−２］、［１３−１］~［１３−２］、［１４−１］~［１４−３］のいずれかに記載の多機能性シート状伸長性有機基材。 [14-4] The above [1-1] to [1-2], [2-1], wherein a plurality of cylindrical hardly extensible polymer portions A are formed in a regular pattern in an easily extensible polymer matrix. ~ [2-2], [3-1] ~ [3-3], [4-1] ~ [4-3], [5-1] ~ [5-3], [6-1] ~ [ 6-3], [7-1] to [7-3], [8-1] to [8-4], [9-1] to [9-2], [10-1] to [10- 2], [11-1] to [11-3], [12-1] to [12-2], [13-1] to [13-2], [14-1] to [14-3] The multifunctional sheet-like extensible organic base material according to any one of the above.
　［１４−５］隣接する筒状難伸長性ポリマー部Ａ間の距離が０．０５ｍｍ~５０ｃｍである前記［１４−４］記載の多機能性シート状伸長性有機基材。 [14-5] The multifunctional sheet-like extensible organic base material according to the above [14-4], wherein the distance between adjacent cylindrical hardly extensible polymer portions A is 0.05 mm to 50 cm.
　［１４−６］厚みが０．０１ｍｍ~１ｃｍである前記［１−１］~［１−２］、［２−１］~［２−２］、［３−１］~［３−３］、［４−１］~［４−３］、［５−１］~［５−３］、［６−１］~［６−３］、［７−１］~［７−３］、［８−１］~［８−４］、［９−１］~［９−２］、［１０−１］~［１０−２］、［１１−１］~［１１−３］、［１２−１］~［１２−２］、［１３−１］~［１３−２］、［１４−１］~［１４−５］のいずれかに記載の多機能性シート状伸長性有機基材。 [14-6] The above [1-1] to [1-2], [2-1] to [2-2], [3-1] to [3-3] having a thickness of 0.01 mm to 1 cm. [4-1] to [4-3], [5-1] to [5-3], [6-1] to [6-3], [7-1] to [7-3], [ 8-1] to [8-4], [9-1] to [9-2], [10-1] to [10-2], [11-1] to [11-3], [12- 1] to [12-2], [13-1] to [13-2], and [14-1] to [14-5].
　［１４−７］筒状難伸長性ポリマー部Ａの厚み方向の長さがシート状有機基材の厚みの少なくとも１／５０である前記［１−１］~［１−２］、［２−１］~［２−２］、［３−１］~［３−３］、［４−１］~［４−３］、［５−１］~［５−３］、［６−１］~［６−３］、［７−１］~［７−３］、［８−１］~［８−４］、［９−１］~［９−２］、［１０−１］~［１０−２］、［１１−１］~［１１−３］、［１２−１］~［１２−２］、［１３−１］~［１３−２］、［１４−１］~［１４−６］のいずれかに記載の多機能性シート状伸長性有機基材。 [14-7] [1-1] to [1-2], [2-] wherein the length in the thickness direction of the cylindrical hardly extensible polymer portion A is at least 1/50 of the thickness of the sheet-like organic base material. 1] to [2-2], [3-1] to [3-3], [4-1] to [4-3], [5-1] to [5-3], [6-1] ~ [6-3], [7-1] ~ [7-3], [8-1] ~ [8-4], [9-1] ~ [9-2], [10-1] ~ [ 10-2], [11-1] to [11-3], [12-1] to [12-2], [13-1] to [13-2], [14-1] to [14- 6] The multifunctional sheet-like extensible organic base material according to any one of [6].
　［１４−８］難伸長性ポリマー部が、シート状有機基材の一方の表面から他方の表面に至るまで連続して形成されている前記［１−１］~［１−２］、［２−１］~［２−２］、［３−１］~［３−３］、［４−１］~［４−３］、［５−１］~［５−３］、［６−１］~［６−３］、［７−１］~［７−３］、［８−１］~［８−４］、［９−１］~［９−２］、［１０−１］~［１０−２］、［１１−１］~［１１−３］、［１２−１］~［１２−２］、［１３−１］~［１３−２］、［１４−１］~［１４−７］のいずれかに記載の多機能性シート状伸長性有機基材。 [14-8] [1-1] to [1-2], [2] wherein the hardly extensible polymer portion is continuously formed from one surface of the sheet-like organic base material to the other surface. -1] to [2-2], [3-1] to [3-3], [4-1] to [4-3], [5-1] to [5-3], [6-1 ] To [6-3], [7-1] to [7-3], [8-1] to [8-4], [9-1] to [9-2], [10-1] to [10-2], [11-1] to [11-3], [12-1] to [12-2], [13-1] to [13-2], [14-1] to [14 The multifunctional sheet-like extensible organic base material according to any one of [7].
　［１４−９］難伸長性ポリマー部と易伸長性ポリマー母材の界面近傍において、伸び特性がグラデーションをなしている前記［１−１］~［１−２］、［２−１］~［２−２］、［３−１］~［３−３］、［４−１］~［４−３］、［５−１］~［５−３］、［６−１］~［６−３］、［７−１］~［７−３］、［８−１］~［８−４］、［９−１］~［９−２］、［１０−１］~［１０−２］、［１１−１］~［１１−３］、［１２−１］~［１２−２］、［１３−１］~［１３−２］、［１４−１］~［１４−８］のいずれかに記載の多機能性シート状伸長性有機基材。 [14-9] The above [1-1] to [1-2], [2-1] to [2-1] in which the elongation characteristics form gradation near the interface between the hardly extensible polymer portion and the easily extensible polymer base material. 2-2], [3-1] to [3-3], [4-1] to [4-3], [5-1] to [5-3], [6-1] to [6- 3], [7-1] to [7-3], [8-1] to [8-4], [9-1] to [9-2], [10-1] to [10-2] , [11-1] to [11-3], [12-1] to [12-2], [13-1] to [13-2], and [14-1] to [14-8] A multifunctional sheet-like extensible organic base material according to claim 1.
　［１４−１０］さらに伸縮性を有する前記［１−１］~［１−２］、［２−１］~［２−２］、［３−１］~［３−３］、［４−１］~［４−３］、［５−１］~［５−３］、［６−１］~［６−３］、［７−１］~［７−３］、［８−１］~［８−４］、［９−１］~［９−２］、［１０−１］~［１０−２］、［１１−１］~［１１−３］、［１２−１］~［１２−２］、［１３−１］~［１３−２］、［１４−１］~［１４−９］のいずれかに記載の多機能性シート状伸長性有機基材。 [14-10] [1-1] to [1-2], [2-1] to [2-2], [3-1] to [3-3], [4- 1] to [4-3], [5-1] to [5-3], [6-1] to [6-3], [7-1] to [7-3], [8-1] ~ [8-4], [9-1] ~ [9-2], [10-1] ~ [10-2], [11-1] ~ [11-3], [12-1] ~ [ 12-2], [13-1] to [13-2], [14-1] to [14-9], the multifunctional sheet-like extensible organic base material described in any one of [14-9].
　本発明のシート状伸長性有機基材によれば、該基材をある一方向（面方向）に伸長させても、筒状難伸長性ポリマー部の形状がほとんど変化しないので、伸長性部材としての機能を有しつつ、その形状不変部に所望の意匠を施したり、他の部材を適宜な固定手段を用いて保持、固定することができる。また、筒状難伸長性ポリマー部の筒状の空洞部に当たる領域は易伸長性ポリマー材料で構成されるので、該領域においては厚み方向に伸長可能である。そのため、当該シート状伸長性有機基材を被装着物に装着する際、該被装着物の形状に良好に追従させることができ、優れた装着性を発揮する。
　また、さらに伸縮性を有するシート状伸長性有機基材によれば、該基材を伸縮させても、筒状難伸長性ポリマー部の形状がほとんど変化しないので、伸縮性部材としての機能を有しつつ、その形状不変部に所望の意匠を施したり、他の部材を容易に保持、固定することが可能となる。また、筒状難伸長性ポリマー部の筒状の空洞部に当たる領域は厚み方向に伸長又は伸縮が可能であるため、被着物装着性に優れる。 According to the sheet-like extensible organic base material of the present invention, even if the base material is extended in one direction (plane direction), the shape of the cylindrical hardly extensible polymer portion hardly changes. While having this function, a desired design can be applied to the shape invariant portion, and other members can be held and fixed using appropriate fixing means. Moreover, since the area | region which hits the cylindrical cavity part of a cylindrical difficulty extensible polymer part is comprised with an easily extensible polymer material, it can extend | expand in the thickness direction in this area | region. For this reason, when the sheet-like extensible organic base material is attached to an object to be attached, the shape of the object to be attached can be satisfactorily followed, and excellent wearability is exhibited.
Furthermore, according to the stretchable sheet-like stretchable organic base material, the shape of the cylindrical difficult-to-extend polymer part hardly changes even when the base is stretched, so that it has a function as a stretchable member. However, it is possible to give a desired design to the shape-invariant portion and to easily hold and fix other members. Moreover, since the area | region which hits the cylindrical cavity part of a cylindrical difficulty extensible polymer part can be expand | extended or expanded / contracted in the thickness direction, it is excellent in the adherence | attachment mounting property.
本発明のシート状伸長性有機基材の一例を示す概略斜視図である。It is a schematic perspective view which shows an example of the sheet-like extensible organic base material of this invention. 図１のシート状伸長性有機基材のＩＩ−ＩＩ線断面を示す概略斜視図である。It is a schematic perspective view which shows the II-II line cross section of the sheet-like extensible organic base material of FIG. 本発明のシート状伸長性有機基材の例を示す断面図（筒状難伸長性ポリマー部の表面形状又は筒状難伸長性ポリマー部のシート状伸長性有機基材表面を投影面としたときの投影形状である輪帯の延びる方向に対して垂直な面で切断したときの断面図）（筒の片側の断面のみを示す）である。Sectional drawing which shows the example of the sheet-like extensible organic base material of this invention (When the surface shape of a cylindrical hardly extensible polymer part or the sheet-like extensible organic base material surface of a cylindrical hardly extensible polymer part is made into a projection surface. FIG. 6 is a cross-sectional view taken along a plane perpendicular to the direction in which the annular zone extends, which is the projected shape of FIG. 本発明のシート状伸長性有機基材の製造方法の一例を示す概略図（断面図）である。It is the schematic (sectional drawing) which shows an example of the manufacturing method of the sheet-like extensible organic base material of this invention. 本発明のシート状伸長性有機基材の製造方法の他の例を示す概略図（断面図）である。It is the schematic (sectional drawing) which shows the other example of the manufacturing method of the sheet-like extensible organic base material of this invention. 本発明のシート状伸長性有機基材の製造方法のさらに他の例を示す概略図（断面図）である。It is the schematic (sectional drawing) which shows the other example of the manufacturing method of the sheet-like extensible organic base material of this invention. 引張試験及びヒステリシス試験で用いるシート状伸長性有機基材のサンプルを示す図である。It is a figure which shows the sample of the sheet-like extensible organic base material used with a tension test and a hysteresis test. 実施例１~４で得られたシート状伸長性有機基材の表面における筒状難伸長性ポリマー部Ａのパターン形状を示す概略図である。FIG. 4 is a schematic view showing a pattern shape of a cylindrical hardly extensible polymer portion A on the surface of the sheet-like extensible organic base material obtained in Examples 1 to 4. 実施例５~８で得られたシート状伸長性有機基材の表面における筒状難伸長性ポリマー部Ａのパターン形状を示す概略図である。FIG. 6 is a schematic view showing a pattern shape of a cylindrical hardly extensible polymer portion A on the surface of the sheet-like extensible organic base material obtained in Examples 5 to 8. 実施例９~１２で得られたシート状伸長性有機基材の表面における筒状難伸長性ポリマー部Ａのパターン形状を示す概略図である。FIG. 3 is a schematic view showing a pattern shape of a cylindrical hardly extensible polymer portion A on the surface of a sheet-like extensible organic base material obtained in Examples 9 to 12. 実施例１３~１６で得られたシート状伸長性有機基材の表面における筒状難伸長性ポリマー部Ａのパターン形状を示す概略図である。FIG. 6 is a schematic view showing a pattern shape of a cylindrical hardly extensible polymer portion A on the surface of a sheet-like extensible organic base material obtained in Examples 13 to 16. 実施例１７~２０で得られたシート状伸長性有機基材の表面における筒状難伸長性ポリマー部Ａのパターン形状を示す概略図である。FIG. 3 is a schematic view showing a pattern shape of a cylindrical hardly extensible polymer portion A on the surface of a sheet-like extensible organic base material obtained in Examples 17 to 20. 実施例２１~２４で得られたシート状伸長性有機基材の表面における筒状難伸長性ポリマー部Ａのパターン形状を示す概略図である。FIG. 2 is a schematic view showing a pattern shape of a cylindrical hardly extensible polymer portion A on the surface of a sheet-like extensible organic base material obtained in Examples 21 to 24. 実施例２５~２８で得られたシート状伸長性有機基材の表面における筒状難伸長性ポリマー部Ａの形状を示す概略図である。FIG. 3 is a schematic view showing the shape of a cylindrical hardly extensible polymer portion A on the surface of a sheet-like extensible organic base material obtained in Examples 25 to 28. 実施例２９~３０で得られたシート状伸長性有機基材の表面における筒状難伸長性ポリマー部Ａの形状を示す概略図である。FIG. 3 is a schematic view showing the shape of a cylindrical hardly extensible polymer portion A on the surface of a sheet-like extensible organic base material obtained in Examples 29-30. 実施例３１で得られたシート状伸長性有機基材の表面における筒状難伸長性ポリマー部Ａの形状を示す概略図である。6 is a schematic view showing the shape of a cylindrical hardly extensible polymer portion A on the surface of a sheet-like extensible organic base material obtained in Example 31. FIG. 実施例３２で得られたシート状伸長性有機基材の表面における筒状難伸長性ポリマー部Ａの形状を示す概略図である。It is the schematic which shows the shape of the cylindrical difficulty extensible polymer part A in the surface of the sheet-like extensible organic base material obtained in Example 32. 本発明のシート状伸長性有機基材の他の例（多機能性シート状伸長性有機基材）を示す概略断面図である。It is a schematic sectional drawing which shows the other example (multifunctional sheet-like extensible organic base material) of the sheet-like extensible organic base material of this invention.
　［シート状伸長性有機基材］
　本発明のシート状伸長性有機基材においては、易伸長性ポリマー母材中に筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されている。筒状難伸長性ポリマー部Ａの表面形状、又はシート状伸長性有機基材表面を投影面としたときの投影形状（シート状伸長性有機基材の表面側から見た形状；以下、「基材表面投影形状」と称する場合がある）は輪帯状である。この有機基材を一方向（面方向）に伸長させると、易伸長性ポリマー母材の部位は伸長するが、部分的に形成された筒状難伸長性ポリマー部Ａは伸長しないか、又はほとんど伸長しない。このため、筒状難伸長性ポリマー部Ａに、形状が変化しないことが望まれる意匠を施したり、他の部材を固定、保持することができる。また、筒状難伸長性ポリマー部Ａの筒状の空洞部に当たる領域は易伸長性ポリマー材料で構成されるので、厚み方向に伸長可能である。 [Sheet-like extensible organic substrate]
In the sheet-like extensible organic base material of the present invention, a cylindrical hardly extensible polymer portion A is partially and integrally formed in an easily extensible polymer base material. The surface shape of the cylindrical hardly extensible polymer part A or the projected shape when the surface of the sheet-like extensible organic substrate is the projection surface (the shape seen from the surface side of the sheet-like extensible organic substrate; The material surface projection shape is sometimes referred to as “ring surface shape”. When this organic base material is stretched in one direction (plane direction), the part of the easily stretchable polymer base material is stretched, but the partially formed cylindrical hardly stretchable polymer part A is not stretched or is hardly stretched. Does not stretch. For this reason, it is possible to give the tubular hardly extensible polymer portion A a design whose shape is desired not to change, and to fix and hold other members. Moreover, since the area | region which hits the cylindrical cavity part of the cylindrical difficulty extensible polymer part A is comprised with an easily extensible polymer material, it can expand | extend in the thickness direction.
　図１は本発明のシート状伸長性有機基材の一例を示す概略斜視図である。図２は図１のシート状伸長性有機基材のＩＩ−ＩＩ断面を示す概略斜視図である。図１及び２において、シート状伸長性有機基材１は、易伸長性ポリマー母材２（易伸長性ポリマー母材部）と、該易伸長性ポリマー母材２中に一体的に形成されている筒状難伸長性ポリマー部Ａ３とで構成されている。３ａは筒状難伸長性ポリマー部Ａ３の筒状の空洞部に当たる領域（部位）であり、易伸長性ポリマー材料で構成されている。この易伸長性ポリマー材料は易伸長性ポリマー母材部２を構成する材料と同一であっても異なっていてもよい。 FIG. 1 is a schematic perspective view showing an example of a sheet-like extensible organic substrate of the present invention. FIG. 2 is a schematic perspective view showing a II-II section of the sheet-like extensible organic base material of FIG. 1 and 2, a sheet-like extensible organic base material 1 is formed integrally with an easily extensible polymer base material 2 (easily extensible polymer base material portion) and the easily extensible polymer base material 2. It is comprised with the cylindrical difficulty extensible polymer part A3. 3a is a region (part) corresponding to the cylindrical hollow portion of the cylindrical hardly extensible polymer portion A3, and is made of an easily extensible polymer material. This easily extensible polymer material may be the same as or different from the material constituting the easily extensible polymer base material portion 2.
　筒状難伸長性ポリマー部Ａ３は易伸長性ポリマー母材２中に一体的に形成されていればよく、例えば、１箇所のみに形成されていてもよく、複数の箇所に非連続的に散在若しくは点在していてもよい。 The cylindrical difficult-to-extend polymer part A3 only needs to be formed integrally in the easily-extensible polymer base material 2, for example, it may be formed only at one place, and is discontinuously scattered at a plurality of places. Or it may be scattered.
　筒状難伸長性ポリマー部Ａ３の表面形状又は基材表面投影形状は輪帯状であり、所定の幅を有する環状を呈している。前記輪帯の形状（外周形状及び／又は内周形状、特に外周形状）は特に限定されず、目的に応じて適宜選択でき、例えば、略円形（真円、楕円等）、略多角形（略三角形、略矩形、略五角形、略六角形等）、無定形（不定形）、あるいは、文字、記号若しくは数字を表す形状；周知の図形、マークを表す形状などのいずれであってもよい。筒状難伸長性ポリマー部Ａ３の表面形状又は基材表面投影形状が略多角形の場合、その内角は９０度以下であってもよく、９０度を超える角度であってもよい。製造のし易さの点からは、筒状難伸長性ポリマー部Ａ３の表面形状又は基材表面投影形状（外周形状及び／又は内周形状、特に外周形状）は略円形、略矩形であるのが好ましい。 The surface shape or base material surface projection shape of the cylindrical hardly extensible polymer portion A3 is a ring-like shape and has an annular shape having a predetermined width. The shape of the annular zone (outer peripheral shape and / or inner peripheral shape, particularly outer peripheral shape) is not particularly limited and can be appropriately selected according to the purpose. For example, it can be selected from a substantially circular shape (perfect circle, ellipse, etc.), a substantially polygonal shape (substantially Any of a triangle, a substantially rectangular shape, a substantially pentagonal shape, a substantially hexagonal shape, etc.), an amorphous shape (indefinite shape), a shape representing a character, a symbol, or a number; a well-known figure, a shape representing a mark, etc. When the surface shape or base material surface projection shape of the cylindrical hardly extensible polymer portion A3 is a substantially polygon, the inner angle may be 90 degrees or less, or may be an angle exceeding 90 degrees. From the viewpoint of ease of manufacturing, the surface shape of the cylindrical difficult-to-extend polymer part A3 or the projected surface shape of the base material (outer peripheral shape and / or inner peripheral shape, particularly outer peripheral shape) is substantially circular or substantially rectangular. Is preferred.
　本発明のシート状伸長性有機基材において、筒状難伸長性ポリマー部Ａ３の面方向の長軸（外周をなす形状の最長部）の長さ（例えば、直径）は、例えば０．０５ｍｍ~１０ｃｍである。この長さが小さすぎると、筒状難伸長性ポリマー部Ａの利用価値が小さくなり、逆に大きすぎると、製造しにくくなる。また、例えば、複数の筒状難伸長性ポリマー部Ａ３が形成されており、隣接する筒状難伸長性ポリマー部Ａ３間の距離（最短距離）が、例えば０．０５ｍｍ~５０ｃｍの場合、筒状難伸長性ポリマー部Ａ３の面方向の長軸（外周をなす形状の最長部）の長さが０．０５ｍｍ未満では、シート状伸長性有機基材１全体を一方向に伸長させた場合でも形状不変部位を有するという技術的意義が小さくなる。また、この長さが１０ｃｍを超える場合には、製造が困難になるだけでなく、前記の技術的意義も小さくなりやすい。 In the sheet-like extensible organic base material of the present invention, the length (for example, the diameter) of the long axis (the longest part of the shape forming the outer periphery) of the cylindrical difficult-to-extend polymer part A3 is, for example, 0.05 mm to 10 cm. When this length is too small, the utility value of the cylindrical difficult-to-extend polymer part A becomes small, and when it is too large, it becomes difficult to manufacture. Further, for example, when a plurality of cylindrical difficult-to-extend polymer parts A3 are formed and the distance (shortest distance) between adjacent cylindrical difficult-to-extend polymer parts A3 is, for example, 0.05 mm to 50 cm, the cylindrical shape If the length of the long axis in the surface direction of the hardly extensible polymer part A3 (the longest part of the shape forming the outer periphery) is less than 0.05 mm, the shape is obtained even when the entire sheet-like extensible organic substrate 1 is extended in one direction. The technical significance of having an invariant site is reduced. Moreover, when this length exceeds 10 cm, not only manufacture becomes difficult, but the said technical significance tends to become small.
　筒状難伸長性ポリマー部Ａ３の面方向の長軸（外周をなす形状の最長部）の長さは、好ましくは０．１ｍｍ以上、より好ましくは０．５ｍｍ以上、さらに好ましくは１ｍｍ以上、特に好ましくは２ｍｍ以上であり、とりわけ５ｍｍ以上が好ましい。また、筒状難伸長性ポリマー部Ａ３の面方向の長軸の長さ（外周をなす形状の最長部）の上限は、８ｃｍが好ましく、５ｃｍが特に好ましい。 The length of the long axis in the surface direction of the cylindrical hardly extensible polymer portion A3 (the longest portion of the shape forming the outer periphery) is preferably 0.1 mm or more, more preferably 0.5 mm or more, and even more preferably 1 mm or more, particularly Preferably it is 2 mm or more, and especially 5 mm or more is preferable. Further, the upper limit of the length of the long axis in the surface direction of the cylindrical hardly extensible polymer portion A3 (the longest portion of the shape forming the outer periphery) is preferably 8 cm, and particularly preferably 5 cm.
　筒状難伸長性ポリマー部Ａ３の表面形状又は基材表面投影形状である輪帯の幅（すなわち、筒状難伸長性ポリマー部Ａ３の外周面と内周面との距離；厚さ）は、目的に応じて適宜選択できるが、通常、筒状難伸長性ポリマー部Ａ３の面方向の長軸（外周をなす形状の最長部）の長さの１~４０％である。前記輪帯の幅（筒状難伸長性ポリマー部Ａ３の厚さ）の下限は、筒状難伸長性ポリマー部Ａ３の面方向の長軸（外周をなす形状の最長部）の長さに対して、好ましくは２％、さらに好ましくは５％である。また、前記輪帯の幅（筒状難伸長性ポリマー部Ａ３の厚さ）の上限は、筒状難伸長性ポリマー部Ａ３の面方向の長軸（外周をなす形状の最長部）の長さに対して、好ましくは３０％、さらに好ましくは２０％である。また、前記輪帯の幅（筒状難伸長性ポリマー部Ａ３の厚さ）は、より具体的には、例えば０．０１ｍｍ~４ｃｍであり、その下限は、好ましくは０．０２ｍｍ、より好ましくは０．１ｍｍ、さらに好ましくは０．２ｍｍ、特に好ましくは０．４ｍｍ、とりわけ１ｍｍであり、上限は、好ましくは３ｃｍ、より好ましくは２ｃｍである。 The width of the annular zone (that is, the distance between the outer peripheral surface and the inner peripheral surface of the cylindrical hardly extensible polymer portion A3; the thickness) which is the surface shape of the cylindrical hardly extensible polymer portion A3 or the projected surface shape of the base material is Although it can be appropriately selected depending on the purpose, it is usually 1 to 40% of the length of the long axis (longest part of the shape forming the outer periphery) in the surface direction of the cylindrical hardly extensible polymer part A3. The lower limit of the width of the annular zone (thickness of the cylindrical hardly extensible polymer portion A3) is relative to the length of the long axis in the surface direction of the cylindrical hardly extensible polymer portion A3 (the longest part of the shape forming the outer periphery). Therefore, it is preferably 2%, more preferably 5%. The upper limit of the width of the annular zone (thickness of the cylindrical hardly extensible polymer portion A3) is the length of the long axis (the longest part of the shape forming the outer periphery) in the surface direction of the cylindrical hardly extensible polymer portion A3. On the other hand, it is preferably 30%, more preferably 20%. Further, the width of the annular zone (thickness of the cylindrical hardly extensible polymer portion A3) is more specifically 0.01 mm to 4 cm, for example, and the lower limit thereof is preferably 0.02 mm, more preferably It is 0.1 mm, more preferably 0.2 mm, particularly preferably 0.4 mm, especially 1 mm, and the upper limit is preferably 3 cm, more preferably 2 cm.
　筒状難伸長性ポリマー部Ａ３と易伸長性ポリマー母材部２の界面（境界部）近傍においては、組成及び／又は物性（伸び特性、硬度等）が徐々に変化するグラデーション（グラディエント）をなしていてもよい。筒状難伸長性ポリマー部Ａ３と易伸長性ポリマー母材部２の界面近傍にこのようなグラデーション（例えば、後述する伸長率についてのグラデーション）を有するシート状伸長性有機基材１は、例えば該シート状伸長性有機基材１を伸長させた時、筒状難伸長性ポリマー部Ａ３と易伸長性ポリマー母材部２との界面で切れにくいという特性を有する。また、筒状難伸長性ポリマー部Ａ３と易伸長性ポリマー母材部２の界面（境界部）近傍だけでなく、筒状難伸長性ポリマー部Ａ３及び／又は易伸長性ポリマー母材部２の多くの部分或いは全体に亘ってグラデーションを呈していてもよい。グラデーション部を有するシート状伸長性有機基材において、筒状難伸長性ポリマー部Ａ３と易伸長性ポリマー母材部２との境界は、易伸長性ポリマー母材部２の非グラデーション部の硬度［易伸長性ポリマー母材部の全体に亘ってグラデーションを呈している場合は、硬度の最も低い箇所の硬度］と、筒状難伸長性ポリマー部Ａ３の非グラデーション部の硬度［筒状難伸長性ポリマー部Ａ３の全体に亘ってグラデーションを呈している場合には、硬度の最も高い箇所の硬度］の平均値を結ぶ線によって定めることができる。 In the vicinity of the interface (boundary part) between the cylindrical hardly extensible polymer part A3 and the easily extensible polymer base part 2, there is a gradation in which the composition and / or physical properties (elongation characteristics, hardness, etc.) gradually change. It may be. The sheet-like extensible organic base material 1 having such gradation (for example, gradation about the elongation rate described later) in the vicinity of the interface between the cylindrical hardly extensible polymer portion A3 and the easily extensible polymer base portion 2 is, for example, When the sheet-like extensible organic base material 1 is extended, the sheet-like extensible organic base material 1 has a characteristic that it is difficult to cut at the interface between the cylindrical hardly extensible polymer portion A3 and the easily extensible polymer base material portion 2. Further, not only in the vicinity of the interface (boundary part) between the cylindrical hardly extensible polymer part A3 and the easily extensible polymer base part 2, but also the cylindrical hardly extensible polymer part A3 and / or the easily extensible polymer base part 2 A gradation may be exhibited over many parts or the whole. In the sheet-like extensible organic base material having a gradation part, the boundary between the cylindrical hardly extensible polymer part A3 and the easily extensible polymer base part 2 is the hardness of the non-gradient part of the easily extensible polymer base part 2 [ When gradation is exhibited over the entire stretchable polymer base material, the hardness of the lowest hardness portion and the hardness of the non-gradient portion of the tubular hardly extensible polymer portion A3 [tubular difficult stretchability] In the case where gradation is exhibited over the entire polymer part A3, the gradation can be determined by a line connecting the average values of the hardness of the highest hardness portion.
　本発明において、筒状難伸長性ポリマー部Ａ３は易伸長性ポリマー母材２中のどの部位に形成されていてもよい。例えば、筒状難伸長性ポリマー部Ａ３は、シート状伸長性有機基材１の少なくとも一方の表面に露出した状態で形成されていてもよく、またシート状伸長性有機基材１の表面に露出していない状態で形成されていてもよい。筒状難伸長性ポリマー部３がシート状伸長性有機基材１の少なくとも一方の表面に露出した状態で形成されている場合、筒状難伸長性ポリマー部Ａ３の表面形状と基材表面投影形状とは、形状や大きさが異なっていてもよい（内部で膨らみがある場合等）。筒状難伸長性ポリマー部Ａ３がシート状伸長性有機基材１の表面に露出していない状態で形成されている場合には、筒状難伸長性ポリマー部Ａ３のシート状伸長性有機基材１の表面（少なくとも一方の表面）を投影面としたときの投影形状（シート状伸長性有機基材１表面側から見た形状）が輪帯状である。 In the present invention, the cylindrical hardly extensible polymer part A3 may be formed in any part of the easily extensible polymer base material 2. For example, the cylindrical difficult-to-extend polymer part A3 may be formed in a state of being exposed on at least one surface of the sheet-like extensible organic base material 1 or exposed on the surface of the sheet-like extensible organic base material 1 It may be formed in a state where it is not. When the cylindrical hardly extensible polymer part 3 is formed in a state of being exposed on at least one surface of the sheet-like extensible organic substrate 1, the surface shape of the cylindrical hardly extensible polymer part A3 and the substrate surface projection shape May be different in shape and size (such as when there is a bulge inside). When the cylindrical hardly extensible polymer portion A3 is formed in a state where it is not exposed on the surface of the sheet extensible organic substrate 1, the sheet extensible organic substrate of the cylindrical hardly extensible polymer portion A3 is used. The projected shape (shape viewed from the surface side of the sheet-like extensible organic base material 1) when the surface of 1 (at least one surface) is used as a projection surface is a ring-shaped shape.
　筒状難伸長性ポリマー部Ａ３を有効に活用できる観点からは、筒状難伸長性ポリマー部Ａ３はシート状伸長性有機基材１の少なくとも一方の表面に露出した状態で形成されているのが好ましい。また、シート状伸長性有機基材１の円滑な伸長性を担保するため、筒状難伸長性ポリマー部Ａ３は、易伸長性ポリマー母材２の面方向の端部以外の箇所に形成されているのが好ましい。すなわち、筒状難伸長性ポリマー部Ａ３は易伸長性ポリマー母材２に包含される状態（但し、両表面を除く）で形成されているのが好ましい。但し、易伸長性ポリマー母材２の面方向の端部を補強したり、該端部に異なる特性を出すため、筒状難伸長性ポリマー部３を該端部に形成する場合がある。 From the viewpoint of effectively utilizing the cylindrical hardly extensible polymer portion A3, the cylindrical hardly extensible polymer portion A3 is formed in a state of being exposed on at least one surface of the sheet-like extensible organic base material 1. preferable. Moreover, in order to ensure smooth extensibility of the sheet-like extensible organic base material 1, the cylindrical hardly extensible polymer portion A <b> 3 is formed at a place other than the end portion in the surface direction of the easily extensible polymer base material 2. It is preferable. That is, it is preferable that the cylindrical hardly extensible polymer portion A3 is formed in a state of being included in the easily extensible polymer base material 2 (excluding both surfaces). However, in order to reinforce the end portion in the surface direction of the easily stretchable polymer base material 2 or to give different characteristics to the end portion, the cylindrical hardly stretchable polymer portion 3 may be formed at the end portion.
　前記易伸長性ポリマー母材２中に筒状難伸長性ポリマー部Ａ３が複数形成されている場合、該複数の筒状難伸長性ポリマー部Ａ３はランダムに形成されていてもよく、規則的パターンで形成されていてもよい。複数の筒状難伸長性ポリマー部Ａ３が規則的パターンで形成されている場合、隣接する筒状難伸長性ポリマー部Ａ３間の距離（最短距離）は、例えば、０．０５ｍｍ~５０ｃｍであり、該距離の上限は、好ましくは３０ｃｍ、より好ましくは２０ｃｍ、さらに好ましくは１５ｃｍ、特に好ましくは１０ｃｍである。また、該距離の下限は、好ましくは０．１ｍｍ、より好ましくは１ｍｍ、さらに好ましくは３ｍｍ、特に好ましくは５ｍｍである。 When a plurality of cylindrical hardly extensible polymer portions A3 are formed in the easily extensible polymer base material 2, the plurality of cylindrical hardly extensible polymer portions A3 may be randomly formed, and a regular pattern May be formed. When the plurality of cylindrical difficult-to-extend polymer parts A3 are formed in a regular pattern, the distance between the adjacent cylindrical difficult-to-extend polymer parts A3 (shortest distance) is, for example, 0.05 mm to 50 cm, The upper limit of the distance is preferably 30 cm, more preferably 20 cm, still more preferably 15 cm, and particularly preferably 10 cm. The lower limit of the distance is preferably 0.1 mm, more preferably 1 mm, still more preferably 3 mm, and particularly preferably 5 mm.
　また、複数の筒状難伸長性ポリマー部Ａ３が規則的パターンで形成されている場合、隣接する筒状難伸長性ポリマー部Ａ３の中心（重心）間の距離は、例えば、５ｍｍ~８０ｃｍであり、該距離の上限は、好ましくは５０ｃｍ、より好ましくは３０ｃｍ、さらに好ましくは２０ｃｍ、特に好ましくは１２ｃｍである。また、該距離の下限は、好ましくは１０ｍｍ、より好ましくは１５ｍｍ、さらに好ましくは２０ｍｍ、特に好ましくは２５ｍｍである。 When a plurality of cylindrical difficult-to-extend polymer parts A3 are formed in a regular pattern, the distance between the centers (centers of gravity) of adjacent cylindrical difficult-to-extend polymer parts A3 is, for example, 5 mm to 80 cm. The upper limit of the distance is preferably 50 cm, more preferably 30 cm, still more preferably 20 cm, and particularly preferably 12 cm. Further, the lower limit of the distance is preferably 10 mm, more preferably 15 mm, still more preferably 20 mm, and particularly preferably 25 mm.
　予め筒状難伸長性ポリマー部Ａ３を規則的パターンで形成しておけば、切断により、多数のシート状伸長性有機基材１を効率よく製造できる。なお、筒状難伸長性ポリマー部Ａ３が複数形成されている場合、複数の筒状難伸長性ポリマー部Ａ３の形状、大きさは同一であっても異なっていてもよい。複数の筒状難伸長性ポリマー部Ａ３が同じ形状及び大きさである場合には、同一の形状及び大きさを有するシート状伸長性有機基材を生産効率よく製造できる。 If the cylindrical difficult-to-extend polymer part A3 is formed in a regular pattern in advance, a large number of sheet-like extensible organic base materials 1 can be efficiently manufactured by cutting. In addition, when multiple cylindrical difficulty extensible polymer part A3 is formed, the shape and magnitude | size of several cylindrical difficulty extensible polymer part A3 may be the same, or may differ. When the plurality of cylindrical hardly extensible polymer portions A3 have the same shape and size, a sheet-like extensible organic base material having the same shape and size can be produced with high production efficiency.
　筒状難伸長性ポリマー部Ａ３の筒状の空洞部に当たる領域３ａは、易伸長性ポリマー材料で構成されている。この易伸長性ポリマー材料からなる領域内には、さらに、表面形状又はシート状伸長性有機基材表面を投影面としたときの投影形状（基材表面投影形状）が、（ｉ）略円形、略多角形、無定形、又は文字、記号若しくは数字を表す形状、（ｉｉ）輪帯状、又は（ｉｉｉ）線状である難伸長性ポリマー部Ｂが１又は２以上形成されていてもよい。難伸長性ポリマー部Ｂの表面形状又は基材表面投影形状が輪帯状である場合、すなわち難伸長性ポリマー部Ｂが筒状である場合、該筒状の空洞部に相当する領域は、筒状難伸長性ポリマー部Ａの筒状の空洞部に相当する領域と同様、易伸長性ポリマー材料で構成される。 The region 3a corresponding to the cylindrical cavity of the cylindrical hardly extensible polymer portion A3 is made of an easily extensible polymer material. In the region made of the easily extensible polymer material, the projection shape (substrate surface projection shape) when the surface shape or the sheet-like extensible organic substrate surface is the projection surface is (i) a substantially circular shape, 1 or 2 or more of the hardly extensible polymer part B which is substantially polygonal, amorphous, or a shape representing a character, a symbol or a number, (ii) an annular shape, or (iii) a linear shape may be formed. When the surface shape of the hardly extensible polymer part B or the projected shape of the substrate surface is a ring shape, that is, when the hardly extensible polymer part B is cylindrical, the region corresponding to the cylindrical cavity is cylindrical. Like the region corresponding to the cylindrical cavity of the hardly extensible polymer portion A, it is made of an easily extensible polymer material.
　本発明のシート状伸長性有機基材１の厚みは、例えば０．０１ｍｍ以上であり、好ましくは０．０３ｍｍ以上、さらに好ましくは０．０５ｍｍ以上である。シート状伸長性有機基材１の厚みの上限は、例えば１ｃｍであり、好ましくは５ｍｍ、さらに好ましくは２ｍｍである。 The thickness of the sheet-like extensible organic substrate 1 of the present invention is, for example, 0.01 mm or more, preferably 0.03 mm or more, and more preferably 0.05 mm or more. The upper limit of the thickness of the sheet-like extensible organic substrate 1 is, for example, 1 cm, preferably 5 mm, and more preferably 2 mm.
　前記筒状難伸長性ポリマー部Ａ３は、シート状伸長性有機基材１の一方の表面から連続して形成されていてもよく、シート状伸長性有機基材１の一方の表面から他方の表面に至るまで連続して形成されていてもよい。また、前記筒状難伸長性ポリマー部Ａ３は、シート状伸長性有機基材１の内部に埋没されて形成されてもよい。前記筒状難伸長性ポリマー部Ａ３の厚み方向の長さ（厚み）は、有用性の観点等から、上記何れの場合も、シート状伸長性有機基材１の厚みの少なくとも１／５０が好ましく、より好ましくは少なくとも１／２０、さらに好ましくは少なくとも１／１０、特に好ましくは少なくとも１／４である。また、他の部材の保持性等の観点から、例えば、筒状難伸長性ポリマー部Ａ３がシート状伸長性有機基材１の一方の表面から連続して形成されている場合などには、前記筒状難伸長性ポリマー部Ａ３の厚み方向の長さ（厚み）は、さらに、シート状伸長性有機基材１の厚みの少なくとも１／３、中でも少なくとも１／２（とりわけ、少なくとも２／３）であるのが望ましい。 The cylindrical difficult-to-extend polymer part A3 may be continuously formed from one surface of the sheet-like extensible organic substrate 1, and from one surface of the sheet-like extensible organic substrate 1 to the other surface It may be formed continuously up to. Moreover, the said cylindrical difficulty extensible polymer part A3 may be embedded and formed in the inside of the sheet-like extensible organic base material 1. In any case, the length (thickness) in the thickness direction of the cylindrical difficult-to-extend polymer part A3 is preferably at least 1/50 of the thickness of the sheet-like extensible organic base material 1 in any of the above cases. More preferably at least 1/20, even more preferably at least 1/10, particularly preferably at least 1/4. In addition, from the viewpoint of the retention of other members, for example, when the cylindrical hardly extensible polymer portion A3 is continuously formed from one surface of the sheet-like extensible organic substrate 1, The length (thickness) in the thickness direction of the cylindrical hardly extensible polymer portion A3 is further at least 1/3, especially at least 1/2 (especially at least 2/3) of the thickness of the sheet-like extensible organic base material 1. It is desirable that
　図３の（１）~（７）は、それぞれ、本発明のシート状伸長性有機基材の例を示す断面図（筒状難伸長性ポリマー部の表面形状又は筒状難伸長性ポリマー部のシート状伸長性有機基材表面を投影面としたときの投影形状である輪帯の延びる方向に対して垂直な面で切断したときの断面図）（筒の片側の断面のみを示す）である。この図に示されるように、筒状難伸長性ポリマー部３の断面形状（筒壁の断面）は、矩形、蹄形、弓形、半円形、円形、楕円形、ダンベル形など種々の形状をとり得る。筒状難伸長性ポリマー部Ａ３の上記断面形状は、易伸長性ポリマー母材形成用材料及び筒状難伸長性ポリマー部形成用材料の種類、組成、粘度；筒状難伸長性ポリマー部形成用材料の易伸長性ポリマー母材形成用材料層への適用方法（滴下、注入等）、適用箇所、適用量；易伸長性ポリマー母材及び筒状難伸長性ポリマー部を形成する際の条件等により調整できる。筒状難伸長性ポリマー部形成用の塗布液を易伸長性ポリマー母材形成用材料層へ適用した後、硬化等により筒状難伸長性ポリマー部が形成されるまでの時間が長い場合には、塗布液が横方向に拡散して、図３の（７）のようなダンベル形状の筒状難伸長性ポリマー部が形成される場合がある。 (1) to (7) in FIG. 3 are cross-sectional views showing examples of the sheet-like extensible organic base material of the present invention (the surface shape of the cylindrical hardly extensible polymer portion or the cylindrical hardly extensible polymer portion). Sectional view when cut along a plane perpendicular to the direction in which the annular zone extends, which is a projected shape when the surface of the sheet-like extensible organic base material is a projection plane) (only the cross section on one side of the cylinder is shown) . As shown in this figure, the cross-sectional shape (cross-section of the cylinder wall) of the cylindrical hardly extensible polymer portion 3 has various shapes such as a rectangle, a hoof, an arc, a semicircle, a circle, an ellipse, and a dumbbell. obtain. The cross-sectional shape of the cylindrical hardly extensible polymer part A3 is the kind, composition, viscosity of the easily extensible polymer base material forming material and the cylindrical hardly extensible polymer part forming material; for forming the cylindrical hardly extensible polymer part. Application method (e.g., dropping, pouring, etc.) to material layer for forming easily stretchable polymer base material, application location, application amount; conditions for forming easily stretchable polymer base material and cylindrical hardly stretchable polymer part, etc. Can be adjusted. When it takes a long time to apply the coating liquid for forming the cylindrically difficult-to-extend polymer part to the material layer for forming the easily-extensible polymer base material, and to form the cylindrically-extensible polymer part by curing, etc. In some cases, the coating solution diffuses in the lateral direction, and a dumbbell-shaped cylindrical hardly extensible polymer portion as shown in (7) of FIG. 3 is formed.
　本発明のシート状伸長性有機基材の引張試験（試験片の幅３０ｍｍ、チャック間距離５０ｍｍ、温度２５℃、引張速度２００ｍｍ／ｍｉｎ）における伸度（破断伸度）は、好ましくは５０％以上、より好ましくは７０％以上、さらに好ましくは１２０％以上であり、強度（破断応力）は、好ましくは１．０ＭＰａ以上、より好ましくは２．０ＭＰａ以上、さらに好ましくは３．０ＭＰａ以上である。前記強度は高いほどよいが、上限は、例えば１００ＭＰａであり、通常は５０ＭＰａ以下である。引張試験機を用いた引張試験等に用いるシート状伸長性有機基材サンプルの例を図７に示す。 The elongation (breaking elongation) of the sheet-like extensible organic base material of the present invention in a tensile test (test piece width 30 mm, distance between chucks 50 mm, temperature 25 ° C., tensile speed 200 mm / min) is preferably 50% or more. More preferably, it is 70% or more, more preferably 120% or more, and the strength (breaking stress) is preferably 1.0 MPa or more, more preferably 2.0 MPa or more, and further preferably 3.0 MPa or more. The higher the strength, the better, but the upper limit is, for example, 100 MPa, and usually 50 MPa or less. FIG. 7 shows an example of a sheet-like extensible organic base material sample used for a tensile test using a tensile tester.
　本発明のシート状伸長性有機基材においては、易伸長性ポリマー母材２は伸長性に優れるが、筒状難伸長性ポリマー部Ａ３は伸長性が低い。本発明のシート状伸長性有機基材は、引張試験機を用いた伸長試験（温度２５℃）において、該シート状伸長性有機基材を１．５倍（元の長さの１５０％）まで伸長させた際（但し、１．５倍まで伸長しないシート状有機基材については、１．２５倍まで伸長させた際、また、１．２５倍まで伸長しないシート状有機基材については、１．１倍まで伸長させた際）、筒状難伸長性ポリマー部Ａ３の伸長率Ｓ１（％）（元の長さに対する伸びた長さの割合）は、４９％以下が好ましく、より好ましくは４０％以下、さらに好ましくは２５％以下、特に好ましくは１０％以下である。 In the sheet-like extensible organic base material of the present invention, the easily extensible polymer base material 2 is excellent in extensibility, but the cylindrical hardly extensible polymer portion A3 has low extensibility. The sheet-like extensible organic substrate of the present invention is 1.5 times (150% of the original length) of the sheet-like extensible organic substrate in an elongation test (temperature 25 ° C.) using a tensile tester. When stretched (however, for a sheet-like organic substrate that does not stretch up to 1.5 times, when stretched up to 1.25 times, and for a sheet-like organic substrate that does not stretch up to 1.25 times, 1 When stretched up to 1 time), the elongation rate S 1 (%) of the cylindrical difficult-to-extend polymer part A3 (ratio of the stretched length to the original length) is preferably 49% or less, more preferably It is 40% or less, more preferably 25% or less, and particularly preferably 10% or less.
　また、本発明のシート状伸長性有機基材は、引張試験機を用いた伸長試験（温度２５℃）において、該シート状伸長性有機基材を１．５倍（元の長さの１５０％）まで伸長させた際（但し、１．５倍まで伸長しないシート状有機基材については、１．２５倍まで伸長させた際、また、１．２５倍まで伸長しないシート状有機基材については、１．１倍まで伸長させた際）、易伸長性ポリマー母材部２の伸長率Ｓ２（％）（元の長さに対する伸びた長さの割合）と筒状難伸長性ポリマー部の伸長率Ｓ１（％）の比率［Ｓ２（％）／Ｓ１（％）］が１より大きいのが好ましい。このようなシート状伸長性有機基材では、該基材を一方向に伸長させた際、易伸長性ポリマー母材部２が伸長しても、筒状難伸長性ポリマー部Ａ３が伸長しにくく、形状が変化しにくいため、筒状難伸長性ポリマー部Ａ３に所望の意匠を施したり、所望の部材を固定、保持させることができる。前記比率［Ｓ２（％）／Ｓ１（％）］は、より好ましくは２以上であり、さらに好ましくは５以上（特に１０以上）である。 Further, the sheet-like extensible organic substrate of the present invention is 1.5 times (150% of the original length) of the sheet-like extensible organic substrate in an elongation test (temperature 25 ° C.) using a tensile tester. (However, for a sheet-like organic base material that does not extend up to 1.5 times, when it is extended up to 1.25 times, and for a sheet-like organic base material that does not extend up to 1.25 times) , When stretched to 1.1 times), the elongation rate S 2 (%) of the stretchable polymer base material part 2 (the ratio of the stretched length to the original length) and the cylindrical stretchable polymer part It is preferable that the ratio [S 2 (%) / S 1 (%)] of the elongation rate S 1 (%) is larger than 1. In such a sheet-like extensible organic base material, when the base material is extended in one direction, even if the easy-extensible polymer base material part 2 is extended, the cylindrical hardly-extensible polymer part A3 is difficult to extend. Since the shape hardly changes, it is possible to give a desired design to the cylindrical difficult-to-extend polymer part A3 or to fix and hold a desired member. The ratio [S 2 (%) / S 1 (%)] is more preferably 2 or more, and further preferably 5 or more (particularly 10 or more).
　さらに、本発明のシート状伸長性有機基材は、引張試験機を用いた伸長試験（温度２５℃）において、該シート状伸長性有機基材を１．５倍（元の長さの１５０％）まで伸長させた際（但し、１．５倍まで伸長しないシート状有機基材については、１．２５倍まで伸長させた際、また、１．２５倍まで伸長しないシート状有機基材については、１．１倍まで伸長させた際）、易伸長性ポリマー母材部２の伸長率Ｓ２（％）と筒状難伸長性ポリマー部Ａ３の伸長率Ｓ１（％）の差［Ｓ２（％）−Ｓ１（％）］は、２０％以上であるのが好ましく、４０％以上であるのがより好ましい。 Furthermore, the sheet-like extensible organic substrate of the present invention is 1.5 times (150% of the original length) of the sheet-like extensible organic substrate in an elongation test (temperature 25 ° C.) using a tensile tester. (However, for a sheet-like organic base material that does not extend up to 1.5 times, when it is extended up to 1.25 times, and for a sheet-like organic base material that does not extend up to 1.25 times) , when is extended up to 1.1 times), the difference in the elongation S 2 easily stretched polymer matrix section 2 (%) and the elongation rate S 1 of the tubular flame stretch polymer unit A3 (%) [S 2 (%)-S 1 (%)] is preferably 20% or more, and more preferably 40% or more.
　本発明において、シート状伸長性有機基材の伸長性は等方向性であるのが好ましい。例えば、一方向における前記易伸長性ポリマー母材部２の伸長率Ｓ２（１）（％）と、該方向に対して直交する方向における前記易伸長性ポリマー母材部２の伸長率Ｓ２（２）（％）との比［Ｓ２（１）／Ｓ２（２）］［但し、Ｓ２（１）≧Ｓ２（２）とする］は、１~１．３が好ましく、１~１．２がより好ましく、１~１．１が特に好ましい。 In the present invention, the extensibility of the sheet-like extensible organic base material is preferably isotropic. For example, the elongation rate S 2 (1) (%) of the stretchable polymer base material portion 2 in one direction and the stretch rate S 2 of the stretchable polymer base material portion 2 in a direction orthogonal to the direction. (2) The ratio [S 2 (1) / S 2 (2)] [where S 2 (1) ≧ S 2 (2)] is preferably 1 to 1.3. ~ 1.2 is more preferable, and 1 to 1.1 is particularly preferable.
　本発明のシート状伸長性有機基材はさらに伸縮性を有していてもよい。シート状伸長性有機基材が伸縮性を有する場合には、バンド部材等の伸縮性が要求される分野で好適に使用できる。易伸長性ポリマー母材２を構成するポリマーとして伸縮性を有するポリマーを選択することにより、シート状伸長性有機基材１に伸縮性を付与できる。このような伸縮性を有するシート状伸長性有機基材において、引張試験機を用いた５０％伸長時のヒステリシス試験（試験片の幅３０ｍｍ、チャック間距離５０ｍｍ、温度２５℃、引張速度２００ｍｍ／ｍｉｎ）により得られる伸長回復率は、１０％以上であるのが好ましく、より好ましくは３０％以上、さらに好ましくは５０％以上（特に好ましくは７０％以上）である。 The sheet-like extensible organic base material of the present invention may further have stretchability. When the sheet-like extensible organic base material has stretchability, it can be suitably used in fields where stretchability is required such as band members. By selecting a polymer having stretchability as the polymer constituting the easily stretchable polymer base material 2, stretchability can be imparted to the sheet-like stretchable organic substrate 1. In such a stretchable sheet-like stretchable organic substrate, a hysteresis test at 50% elongation using a tensile tester (test piece width 30 mm, chuck-to-chuck distance 50 mm, temperature 25 ° C., tensile speed 200 mm / min. ) Is preferably 10% or more, more preferably 30% or more, still more preferably 50% or more (particularly preferably 70% or more).
　また、本発明のシート状伸長性有機基材では、通常、易伸長性ポリマー母材２は軟質であり、筒状難伸長性ポリマー部Ａ３は硬質である。例えば、本発明のシート状伸長性有機基材においては、ゴム硬度計を用いた硬さ試験（試験片３０ｍｍ×３０ｍｍのシート状伸長性有機基材１の１０枚積層品、針押し込み１０秒後の硬さ、温度２５℃）により求めた筒状難伸長性ポリマー部Ａ３の硬さＨ１と易伸長性ポリマー母材２の硬さＨ２との比（Ｈ１／Ｈ２）が１より大きいことが好ましく、より好ましくは１．０１以上、さらに好ましくは１．１０以上、特に好ましくは１．２０以上である。 Moreover, in the sheet-like extensible organic base material of the present invention, the easily extensible polymer base material 2 is usually soft, and the cylindrical hardly extensible polymer portion A3 is hard. For example, in the sheet-like extensible organic substrate of the present invention, a hardness test using a rubber hardness tester (10-sheet laminate product of the sheet-like extensible organic substrate 1 having a test piece of 30 mm × 30 mm, after 10 seconds of pushing in the needle hardness of the ratio of the hardness H 1 and hardness of H 2 easily extensible polymer matrix 2 of the tubular flame stretch polymer unit A3 as determined by the temperature of 25 ℃) (H 1 / H 2) is from 1 It is preferably large, more preferably 1.01 or more, further preferably 1.10 or more, and particularly preferably 1.20 or more.
　また、易伸長性ポリマー母材２及び筒状難伸長性ポリマー部Ａ３の硬さの尺度として引張弾性率を用いることもできる。本発明のシート状伸長性有機基材においては、固体粘弾性測定装置（サンプルサイズ：長さ２５ｍｍ×幅３ｍｍ、チャック間距離：５ｍｍ、モード：時間分散、温度：２７℃、周波数：１Ｈｚ、初期歪み：０．２％、測定時間：１２０秒、測定回数：１０回）により測定した筒状難伸長性ポリマー部Ａ３の引張弾性率Ｅ’１（Ｐａ）と易伸長性ポリマー母材２の引張弾性率Ｅ’２（Ｐａ）の比（Ｅ’１／Ｅ’２）が１より大きいことが好ましく、より好ましくは５以上、さらに好ましくは１０以上、特に好ましくは１００以上である。 Moreover, a tensile elasticity modulus can also be used as a scale of the hardness of the easily extensible polymer base material 2 and the cylindrical hardly extensible polymer part A3. In the sheet-like extensible organic base material of the present invention, a solid viscoelasticity measuring device (sample size: length 25 mm × width 3 mm, distance between chucks: 5 mm, mode: time dispersion, temperature: 27 ° C., frequency: 1 Hz, initial stage The tensile elastic modulus E ′ 1 (Pa) of the cylindrical hardly extensible polymer portion A3 and the tensile strength of the easily extensible polymer base material 2 measured by strain: 0.2%, measurement time: 120 seconds, measurement count: 10 times) The elastic modulus E ′ 2 (Pa) ratio (E ′ 1 / E ′ 2 ) is preferably greater than 1, more preferably 5 or more, still more preferably 10 or more, and particularly preferably 100 or more.
　さらに、易伸長性ポリマー母材２及び筒状難伸長性ポリマー部Ａ３の硬さの尺度としてナノインデンテーション測定における荷重を用いることもできる。前記シート状伸長性有機基材においては、ナノインデンテーション測定（押し込み深さ４μｍ、押し込み速度１．５μｍ／秒、温度２５℃）における筒状難伸長性ポリマー部Ａ３の荷重Ｐ１と易伸長性ポリマー母材２の荷重Ｐ２との比（Ｐ１／Ｐ２）が１より大きいことが好ましく、より好ましくは１．０１以上、さらに好ましくは１．１０以上、特に好ましくは１．５０以上である。 Furthermore, the load in the nanoindentation measurement can also be used as a measure of the hardness of the easily extensible polymer base material 2 and the cylindrical hardly extensible polymer portion A3. In the sheet-like extensible organic base material, the load P 1 of the cylindrical hardly extensible polymer portion A3 and the easy extensibility in nanoindentation measurement (indentation depth 4 μm, indentation speed 1.5 μm / second, temperature 25 ° C.). The ratio of the polymer base material 2 to the load P 2 (P 1 / P 2 ) is preferably greater than 1, more preferably 1.01 or more, further preferably 1.10 or more, and particularly preferably 1.50 or more. is there.
　なお、易伸長性ポリマー母材部２の表面（少なくとも一方の表面）、筒状難伸長性ポリマー部Ａ３の形成部位の表面（少なくとも一方の表面）の表面粗さＲａは、それぞれ、１００ｎｍ以下が好ましく、５０ｎｍ以下がより好ましく、３０ｎｍ以下がさらに好ましい。特に、各表面に精密な部材や部品等を搭載する場合には、表面粗さが小さいほど部材や部品等を精度よく設置することができ、部材や部品等の有する機能、性能を確実に発揮させることができる。なお、ＲａはＡＦＭ（原子間力顕微鏡）により測定することができる。 The surface roughness Ra of the surface (at least one surface) of the easily extensible polymer base material portion 2 and the surface (at least one surface) of the formation site of the cylindrical hardly extensible polymer portion A3 is 100 nm or less, respectively. Preferably, 50 nm or less is more preferable, and 30 nm or less is more preferable. In particular, when precise members and parts are mounted on each surface, the smaller the surface roughness, the more accurately the members and parts can be installed, and the functions and performances of the members and parts are reliably exhibited. Can be made. Ra can be measured by an AFM (atomic force microscope).
　［易伸長性ポリマー母材］
　本発明において、易伸長性ポリマー母材２は、伸長性（又はさらに伸縮性）を有するポリマーにより構成することができる。伸長性（又はさらに伸縮性）を有するポリマーとしては、例えば、ポリウレタン系ポリマー、ポリウレア系ポリマー、ポリウレタンウレア系ポリマー、ポリオレフィン系ポリマー（特に、ポリジエン系ポリマー）、シリコーン系ポリマー、ポリエステル系ポリマー、ポリエーテル系ポリマー、ポリアミド系ポリマー、ポリスチレン系ポリマー、ガラス転移温度（Ｔｇ）の低いアクリル系ポリマー（Ｔｇが、例えば５℃未満、好ましくは０℃以下、さらに好ましくは−５℃以下のアクリル系ポリマー）などが挙げられる。これらのポリマーは、通常、柔軟性を有している。これらのポリマーは、単独で、又は２種以上を組み合わせて使用できる。これらのポリマーの易伸長性ポリマー母材を構成するポリマー全体に占める割合は、３０重量％以上が好ましく、より好ましくは５０重量％以上、さらに好ましくは７０重量％以上、特に好ましくは９０重量％以上である。 [Easily stretchable polymer matrix]
In the present invention, the easily extensible polymer base material 2 can be composed of a polymer having extensibility (or further stretchability). Examples of stretchable (or even stretchable) polymers include polyurethane polymers, polyurea polymers, polyurethane urea polymers, polyolefin polymers (particularly polydiene polymers), silicone polymers, polyester polymers, and polyethers. Polymer, polyamide polymer, polystyrene polymer, acrylic polymer having a low glass transition temperature (Tg) (Tg is, for example, less than 5 ° C, preferably 0 ° C or less, more preferably -5 ° C or less) Is mentioned. These polymers are usually flexible. These polymers can be used alone or in combination of two or more. The proportion of these polymers in the polymer constituting the easily stretchable polymer matrix is preferably 30% by weight or more, more preferably 50% by weight or more, still more preferably 70% by weight or more, and particularly preferably 90% by weight or more. It is.
　これらの中でも、ポリウレタン系ポリマー、ポリウレア系ポリマー、ポリウレタンウレア系ポリマー、ポリオレフィン系ポリマー（特に、ポリジエン系ポリマー）、シリコーン系ポリマー、ポリスチレン系ポリマー（例えば、スチレン−イソプレン−スチレンブロック共重合体、スチレン−ブタジエン−スチレンブロック共重合体等のスチレン系熱可塑性エラストマー等）が特に好ましい。伸長性（又はさらに伸縮性）を有するポリマーとしては、市販品（ポリマー単体、ポリマーの水分散液、ポリマーの有機溶媒溶液等）を使用することもできる。 Among these, polyurethane polymers, polyurea polymers, polyurethane urea polymers, polyolefin polymers (particularly polydiene polymers), silicone polymers, polystyrene polymers (for example, styrene-isoprene-styrene block copolymers, styrene- Styrenic thermoplastic elastomers such as butadiene-styrene block copolymers are particularly preferred. Commercially available products (polymer alone, polymer aqueous dispersion, polymer organic solvent solution, etc.) can also be used as the polymer having extensibility (or further stretchability).
　易伸長性ポリマー母材部２は、例えば支持体上に、易伸長性ポリマー母材を構成するポリマーの液状前駆体を塗工して易伸長性ポリマー母材形成用材料層を形成し、該易伸長性ポリマー母材形成用材料層の所定部位に筒状難伸長性ポリマー部の形成材料を配した後、該易伸長性ポリマー母材形成用材料層中の液状前駆体を目的のポリマーへ転化することにより形成できる。前記液状前駆体としては、前記ポリマーに誘導できるモノマー（エネルギー線硬化性モノマー等）、該モノマーの部分重合物、硬化又は架橋により前記ポリマーに誘導できる硬化又は架橋前ポリマーなどが挙げられる。前記液状前駆体の目的のポリマーへ転化は、例えば、重合（エネルギー線や熱による重合等）、硬化、架橋反応などにより行うことができる。 The easily stretchable polymer base material part 2 is formed by, for example, coating a liquid precursor of a polymer constituting the easily stretchable polymer base material on a support to form a material layer for easily stretchable polymer base material, After the forming material of the cylindrical hardly extensible polymer portion is arranged at a predetermined portion of the easily extensible polymer base material forming material layer, the liquid precursor in the easily extensible polymer base material forming material layer is changed to the target polymer. It can be formed by conversion. Examples of the liquid precursor include a monomer that can be derived from the polymer (such as an energy ray-curable monomer), a partially polymerized product of the monomer, and a polymer that is precured or crosslinked that can be induced to the polymer by curing or crosslinking. The conversion of the liquid precursor into a target polymer can be performed by, for example, polymerization (energy ray or heat polymerization), curing, cross-linking reaction, or the like.
　また、易伸長性ポリマー母材部２は、例えば支持体上に、易伸長性ポリマー母材を構成するポリマーを含む溶液若しくは分散液を塗工して易伸長性ポリマー母材形成用材料層を形成し、該易伸長性ポリマー母材形成用材料層の所定部位に筒状難伸長性ポリマー部の形成材料を配した後、該易伸長性ポリマー母材形成用材料層中の溶媒を乾燥除去することにより形成することもできる。前記ポリマーを含む溶液に用いる溶媒としては、前記ポリマーを溶解できる溶媒であればよく、例えば、酢酸エチル等のエステル；トルエン等の芳香族炭化水素等の炭化水素；アセトン等のケトン；塩化メチレン等のハロゲン化炭化水素；ラクトン；アミド；ラクタム；水；これらの混合溶媒等が挙げられる。前記ポリマーを含む分散液としては、水分散液（乳化重合後の反応液等）などが挙げられる。 In addition, the easily stretchable polymer base material part 2 is formed, for example, by applying a solution or dispersion containing a polymer constituting the easily stretchable polymer base material onto the support to form the easily stretchable polymer base material forming material layer. After forming and arranging the forming material of the cylindrical difficult-to-extend polymer part at a predetermined portion of the easily-extensible polymer base material forming material layer, the solvent in the easily-extensible polymer base material forming material layer is dried and removed It can also be formed. The solvent used in the solution containing the polymer may be any solvent that can dissolve the polymer. Examples thereof include esters such as ethyl acetate; hydrocarbons such as aromatic hydrocarbons such as toluene; ketones such as acetone; methylene chloride and the like. Halocarbons; lactones; amides; lactams; water; and mixed solvents thereof. Examples of the dispersion containing the polymer include an aqueous dispersion (such as a reaction liquid after emulsion polymerization).
　さらに、易伸長性ポリマー母材部２は、例えば支持体上に、易伸長性ポリマー母材を構成するポリマー単体により易伸長性ポリマー母材形成用材料層を形成し、該易伸長性ポリマー母材形成用材料層の所定部位に筒状難伸長性ポリマー部の形成材料を配した後、溶融・冷却処理（ホットメルト処理）を行うことにより形成することもできる。この場合の易伸長性ポリマー母材形成用材料層は、前記ポリマー単体を一般的なフィルム成形法（押出成形、射出成形、圧縮成形、ホットメルト処理等）に付すことにより形成できる。この場合、易伸長性ポリマー母材形成用材料層と易伸長性ポリマー母材は実質的に同一の材料組成で構成されることが多い。なお、溶融・冷却処理とは、溶融した後、冷却することを意味する。 Furthermore, the easily extensible polymer base material part 2 forms an easily extensible polymer base material forming material layer from a single polymer constituting the easily extensible polymer base material on a support, for example, It can also be formed by performing a melting / cooling process (hot melt process) after disposing a forming material for the cylindrical difficult-to-extend polymer part at a predetermined portion of the material forming material layer. In this case, the easily stretchable polymer base material forming material layer can be formed by subjecting the polymer alone to a general film molding method (extrusion molding, injection molding, compression molding, hot melt treatment, etc.). In this case, the easily stretchable polymer base material forming material layer and the easily stretchable polymer base material are often composed of substantially the same material composition. The melting / cooling treatment means cooling after melting.
　本発明において、易伸長性ポリマー母材部２は、例えば、ポリウレタン鎖、ポリウレア鎖、ポリウレタンウレア鎖、ポリオレフィン鎖（特に、ポリジエン鎖）、シリコーン鎖、ポリエステル鎖、ポリエーテル鎖、ポリアミド鎖、ポリスチレン系ポリマー鎖及びポリアクリル鎖からなる群より選択される少なくとも１種のポリマー鎖を有し、且つ主鎖又は側鎖にエネルギー線硬化性基Ａ１を有する硬化性ポリマーＰ、又は該硬化性ポリマーＰとエネルギー線硬化性基Ａ２を有する硬化性モノマーＭとの混合物にエネルギー線を照射して硬化させることにより形成できる。前記硬化性ポリマーＰ、該硬化性ポリマーＰとエネルギー線硬化性基Ａ２を有する硬化性モノマーＭとの混合物は、前記ポリマーの前駆体である。 In the present invention, the easily extensible polymer base material part 2 includes, for example, a polyurethane chain, a polyurea chain, a polyurethane urea chain, a polyolefin chain (particularly, a polydiene chain), a silicone chain, a polyester chain, a polyether chain, a polyamide chain, and a polystyrene series. A curable polymer P having at least one polymer chain selected from the group consisting of a polymer chain and a polyacrylic chain, and having an energy ray-curable group A 1 in the main chain or side chain, or the curable polymer P And a mixture of the curable monomer M having the energy ray curable group A 2 and irradiating it with an energy ray to cure. The curable polymer P and the mixture of the curable polymer P and the curable monomer M having the energy ray curable group A 2 are precursors of the polymer.
　エネルギー線としては、α線、β線、γ線、中性子線、電子線などの電離性放射線、紫外線、可視光線などが挙げられる。中でも、紫外線及び電子線が好ましく、特に紫外線が好ましい。 Examples of energy rays include ionizing radiation such as α rays, β rays, γ rays, neutron rays, and electron rays, ultraviolet rays, and visible rays. Among these, ultraviolet rays and electron beams are preferable, and ultraviolet rays are particularly preferable.
　前記エネルギー線硬化性基Ａ１、Ａ２としては、それぞれ、例えば、（メタ）アクリロイル基、ビニル基等の炭素−炭素不飽和結合を含む基（ラジカル重合性基を含む基）；エポキシ基、オキセタニル基等のカチオン重合性基などが挙げられる。主鎖又は側鎖にエネルギー線硬化性基Ａ１を有する硬化性ポリマーＰにおけるエネルギー線硬化性基Ａ１がラジカル重合性基を含む基である場合には、エネルギー線硬化性基Ａ２を有する硬化性モノマーＭにおけるエネルギー線硬化性基Ａ２もラジカル重合性基を含む基であるのが好ましく、主鎖又は側鎖にエネルギー線硬化性基Ａ１を有する硬化性ポリマーＰにおけるエネルギー線硬化性基Ａ１がカチオン重合性基である場合には、エネルギー線硬化性基Ａ２を有する硬化性モノマーＭにおけるエネルギー線硬化性基Ａ２もカチオン重合性基であるのが好ましい。 Examples of the energy ray-curable groups A 1 and A 2 include a group containing a carbon-carbon unsaturated bond (a group containing a radical polymerizable group) such as a (meth) acryloyl group or a vinyl group, an epoxy group, And cationically polymerizable groups such as oxetanyl group. When the energy ray-curable groups A 1 in the curable polymer P having an energy ray-curable groups A 1 is a group containing a radically polymerizable group in the main chain or side chain, having an energy ray-curable groups A 2 The energy ray curable group A 2 in the curable monomer M is also preferably a group containing a radical polymerizable group, and the energy ray curable property in the curable polymer P having the energy ray curable group A 1 in the main chain or side chain. When the group A 1 is a cationic polymerizable group, the energy ray curable group A 2 in the curable monomer M having the energy ray curable group A 2 is also preferably a cationic polymerizable group.
　前記硬化性ポリマーＰは、エネルギー線硬化性基Ａ１及び反応性官能基Ｒ１を有する化合物と、分子内に前記反応性官能基Ｒ１に対して反応性を有する反応性官能基Ｒ２を有し、且つポリウレタン鎖、ポリウレア鎖、ポリウレタンウレア鎖、ポリオレフィン鎖（特に、ポリジエン鎖）、シリコーン鎖、ポリエステル鎖、ポリエーテル鎖、ポリアミド鎖及びポリアクリル鎖からなる群より選択される少なくとも１種のポリマー鎖を有するポリマーとを反応させることにより得ることができる。 The curable polymer P includes a compound having an energy ray curable group A 1 and a reactive functional group R 1 , and a reactive functional group R 2 having reactivity to the reactive functional group R 1 in the molecule. And at least one selected from the group consisting of a polyurethane chain, a polyurea chain, a polyurethane urea chain, a polyolefin chain (particularly a polydiene chain), a silicone chain, a polyester chain, a polyether chain, a polyamide chain, and a polyacryl chain. It can be obtained by reacting with a polymer having a polymer chain.
　前記反応性官能基Ｒ１と反応性官能基Ｒ２の組合せ（順序を問わない）としては、例えば、ヒドロキシル基とイソシアネート基との組合せ、ヒドロキシル基とエポキシ基との組合せ、カルボキシル基又は酸無水物基とイソシアネート基との組合せ、カルボキシル基又は酸無水物基とエポキシ基との組合せ、アミノ基とイソシアネート基との組合せ、アミノ基とエポキシ基との組合せ、Ｓｉ−Ｈ基と炭素−炭素二重結合を有する基との組合せなどが挙げられる。 Examples of the combination (regardless of order) of the reactive functional group R 1 and the reactive functional group R 2 include a combination of a hydroxyl group and an isocyanate group, a combination of a hydroxyl group and an epoxy group, a carboxyl group, or an acid anhydride. A combination of a compound group and an isocyanate group, a combination of a carboxyl group or an acid anhydride group and an epoxy group, a combination of an amino group and an isocyanate group, a combination of an amino group and an epoxy group, a Si-H group and a carbon-carbon group. A combination with a group having a heavy bond is exemplified.
　反応性官能基Ｒ２を有し且つポリウレタン鎖を有するポリマーは、ポリイソシアネート化合物と、長鎖ポリオール化合物、及び必要に応じて用いられる鎖伸長剤や他のイソシアネート反応性化合物とを、慣用の方法で反応させることにより得ることができる。 A polymer having a reactive functional group R 2 and a polyurethane chain is prepared by combining a polyisocyanate compound, a long-chain polyol compound, and a chain extender and other isocyanate-reactive compounds used as necessary. It can obtain by making it react.
　ポリイソシアネート化合物としては、例えば、ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート等の脂肪族ジイソシアネート；イソホロンジイソシアネート、ジシクロヘキシルメタンジイソシアネート、水添キシリレンジイソシアネート、ノルボルネンジイソシアネート、ノルボルナンジイソシアネート等の脂環式ジイソシアネート；ナフタレンジイソシアネート、フェニレンジイソシアネート、トリレンジイソシアネート、ジフェニルジイソシアネート、ジフェニルメタンジイソシアネート、ジフェニルエーテルジイソシアネート、ジフェニルプロパンジイソシアネート等の芳香族ジイソシアネート；キシリレンジイソシアネート、テトラメチレンキシリレンジイソシアネート等の芳香脂肪族ジイソシアネート；ダイマー酸ジイソシアネートなどが挙げられる。 Examples of the polyisocyanate compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; alicyclic diisocyanates such as isophorone diisocyanate, dicyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, norbornene diisocyanate, and norbornane diisocyanate; naphthalene diisocyanate, Aromatic diisocyanates such as phenylene diisocyanate, tolylene diisocyanate, diphenyl diisocyanate, diphenylmethane diisocyanate, diphenyl ether diisocyanate, diphenylpropane diisocyanate; araliphatic diisocyanates such as xylylene diisocyanate and tetramethylene xylylene diisocyanate DOO; and dimer acid diisocyanate.
　長鎖ポリオール化合物としては、例えば、ポリエーテルポリオール、ポリエステルポリオール、ポリカーボネートポリオール、ポリオレフィンポリオール、ポリアクリルポリオールなどが挙げられる。長鎖ポリオールの数平均分子量は、通常、５００以上であり、好ましくは５００~１００００、より好ましくは５５０~４０００である。長鎖ポリオールは単独で又は２種以上を組み合わせて使用できる。 Examples of the long-chain polyol compound include polyether polyol, polyester polyol, polycarbonate polyol, polyolefin polyol, and polyacryl polyol. The number average molecular weight of the long-chain polyol is usually 500 or more, preferably 500 to 10,000, more preferably 550 to 4000. Long chain polyols can be used alone or in combination of two or more.
　ポリエーテルポリオールとしては、例えば、ポリエチレンエーテルグリコール、ポリプロピレンエーテルグリコール、ポリテトラメチレンエーテルグリコール（ＰＴＭＧ）などのポリアルキレンエーテルグリコールの他、エチレンオキシド−プロピレンオキシド共重合体などのモノマー成分として複数のアルキレンオキシドを含む（アルキレンオキサイド−他のアルキレンオキサイド）共重合体などが挙げられる。 Examples of the polyether polyol include polyalkylene ether glycols such as polyethylene ether glycol, polypropylene ether glycol, polytetramethylene ether glycol (PTMG), and a plurality of alkylene oxides as monomer components such as an ethylene oxide-propylene oxide copolymer. (Alkylene oxide-other alkylene oxide) copolymer containing etc. are mentioned.
　ポリエステルポリオールとしては、例えば、多価アルコールと多価カルボン酸との縮合重合物；環状エステル（ラクトン）の開環重合物；多価アルコール、多価カルボン酸及び環状エステルの３種類の成分による反応物などを用いることができる。多価アルコールと多価カルボン酸との縮合重合物において、多価アルコールとしては、例えば、エチレングリコール、ジエチレングリコール、プロピレングリコール、１，３−プロパンジオール、１，４−ブタンジオール、２−メチル−１，３−プロパンジオール、１，５−ペンタンジオール、ネオペンチルグリコール、１，６−ヘキサンジオール、１，９−ノナンジオール、１，１０−デカンジオール、グリセリン、トリメチロールプロパン、トリメチロールエタン、シクロヘキサンジオール類（１，４−シクロヘキサンジオールなど）、シクロヘキサンジメタノール類（１，４−シクロヘキサンジメタノールなど）、ビスフェノール類（ビスフェノールＡなど）、糖アルコール類（キシリトールやソルビトールなど）などを用いることができる。一方、多価カルボン酸としては、例えば、マロン酸、マレイン酸、コハク酸、アジピン酸、スベリン酸、アゼライン酸、セバシン酸、ドデカンジオン酸等の脂肪族ジカルボン酸；１，４−シクロヘキサンジカルボン酸等の脂環式ジカルボン酸；テレフタル酸、イソフタル酸、オルトフタル酸、２，６−ナフタレンジカルボン酸、トリメリット酸等の芳香族ジカルボン酸などが挙げられる。また、環状エステルの開環重合物において、環状エステルとしては、例えば、プロピオラクトン、β−メチル−δ−バレロラクトン、ε−カプロラクトンなどが挙げられる。３種類の成分による反応物において、多価アルコール、多価カルボン酸、環状エステルとしては、前記例示のものなどを用いることができる。 Examples of the polyester polyol include a condensation polymer of a polyhydric alcohol and a polyvalent carboxylic acid; a ring-opening polymer of a cyclic ester (lactone); a reaction by three kinds of components: a polyhydric alcohol, a polyvalent carboxylic acid, and a cyclic ester. Things can be used. In the condensation polymerization product of polyhydric alcohol and polycarboxylic acid, examples of polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 2-methyl-1 , 3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, glycerin, trimethylolpropane, trimethylolethane, cyclohexanediol (Such as 1,4-cyclohexanediol), cyclohexanedimethanols (such as 1,4-cyclohexanedimethanol), bisphenols (such as bisphenol A), sugar alcohols (such as xylitol and sorbitol), etc. Kill. On the other hand, examples of the polyvalent carboxylic acid include aliphatic dicarboxylic acids such as malonic acid, maleic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid; 1,4-cyclohexanedicarboxylic acid, etc. And aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid and trimellitic acid. In the ring-opening polymer of cyclic ester, examples of the cyclic ester include propiolactone, β-methyl-δ-valerolactone, and ε-caprolactone. In the reaction product of the three types of components, those exemplified above can be used as the polyhydric alcohol, polycarboxylic acid, and cyclic ester.
　ポリカーボネートポリオールとしては、例えば、多価アルコールとホスゲン、クロロギ酸エステル、ジアルキルカーボネート又はジアリールカーボネートとの反応物；環状炭酸エステル（アルキレンカーボネートなど）の開環重合物などが挙げられる。具体的には、多価アルコールとホスゲンとの反応物において、多価アルコールとしては、前記例示の多価アルコール（例えば、エチレングリコール、プロピレングリコール、１，３−ブタンジオール、１，４−ブタンジオール、ネオペンチルグリコール、１，６−ヘキサンジオール等）を用いることができる。また、環状炭酸エステルの開環重合物において、アルキレンカーボネートとしては、例えば、エチレンカーボネート、トリメチレンカーボネート、テトラメチレンカーボネート、ヘキサメチレンカーボネートなどが挙げられる。なお、ポリカーボネートポリオールは、分子内にカーボネート結合を有し、末端がヒドロキシル基である化合物であればよく、カーボネート結合とともにエステル結合を有していてもよい。ポリカーボネートポリオールの代表的な例として、ポリヘキサメチレンカーボネートジオール、ポリヘキサメチレンカーボネートジオールにラクトンを開環付加重合して得られるジオール、ポリヘキサメチレンカーボネートジオールとポリエステルジオール又はポリエーテルジオールとの共縮合物などが挙げられる。 Examples of the polycarbonate polyol include a reaction product of a polyhydric alcohol and phosgene, chloroformate, dialkyl carbonate or diaryl carbonate; a ring-opening polymer of a cyclic carbonate (such as alkylene carbonate). Specifically, in the reaction product of polyhydric alcohol and phosgene, the polyhydric alcohol includes the polyhydric alcohols exemplified above (for example, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol). , Neopentyl glycol, 1,6-hexanediol, etc.) can be used. In the ring-opening polymer of cyclic carbonate, examples of the alkylene carbonate include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, hexamethylene carbonate, and the like. In addition, the polycarbonate polyol should just be a compound which has a carbonate bond in a molecule | numerator, and the terminal is a hydroxyl group, and may have an ester bond with a carbonate bond. Representative examples of polycarbonate polyols include polyhexamethylene carbonate diol, diol obtained by ring-opening addition polymerization of lactone to polyhexamethylene carbonate diol, and co-condensate of polyhexamethylene carbonate diol with polyester diol or polyether diol. Etc.
　ポリオレフィンポリオールは、オレフィンを重合体又は共重合体の骨格（又は主鎖）の成分とし且つ分子内に（特に末端に）ヒドロキシル基を少なくとも２つ有するポリオールである。前記オレフィンとしては、末端に炭素−炭素二重結合を有するオレフィン（例えば、エチレン、プロピレン等のα−オレフィンなど）であってもよく、また末端以外の部位に炭素−炭素二重結合を有するオレフィン（例えば、イソブテンなど）であってもよく、さらにはジエン（例えば、ブタジエン、イソプレンなど）であってもよい。ポリオレフィンポリオールの代表的な例として、ブタジエンホモポリマー、イソプレンホモポリマー、ブタジエン−スチレンコポリマー、ブタジエン−イソプレンコポリマー、ブタジエン−アクリロニトリルコポリマーなどのブタジエン若しくはイソプレン系ポリマーの末端をヒドロキシル基に変性したものが挙げられる。 The polyolefin polyol is a polyol having an olefin as a component of the skeleton (or main chain) of the polymer or copolymer and having at least two hydroxyl groups in the molecule (particularly at the terminal). The olefin may be an olefin having a carbon-carbon double bond at the terminal (for example, an α-olefin such as ethylene or propylene), or an olefin having a carbon-carbon double bond at a position other than the terminal. (For example, isobutene and the like) and diene (for example, butadiene, isoprene and the like) may be used. Typical examples of polyolefin polyols include butadiene homopolymers, isoprene homopolymers, butadiene-styrene copolymers, butadiene-isoprene copolymers, butadiene-isoprene copolymers such as butadiene-modified polymers modified with hydroxyl groups at the ends. .
　ポリアクリルポリオールは、（メタ）アクリレートを重合体又は共重合体の骨格（又は主鎖）の成分とし且つ分子内に（特に末端に）ヒドロキシル基を少なくとも２つ有するポリオールである。（メタ）アクリレートとしては、（メタ）アクリル酸アルキルエステル［例えば、（メタ）アクリル酸Ｃ１−２０アルキルエステルなど］が好適に用いられる。 The polyacrylic polyol is a polyol having (meth) acrylate as a component of the polymer (or copolymer) skeleton (or main chain) and having at least two hydroxyl groups in the molecule (particularly at the terminal). As the (meth) acrylate, (meth) acrylic acid alkyl ester [for example, (meth) acrylic acid C 1-20 alkyl ester, etc.] is preferably used.
　前記鎖伸長剤としては、熱可塑性ポリウレタンの製造に通常用いられる鎖伸長剤を使用でき、その種類は特に制限されないが、低分子量のポリオール、ポリアミン等を用いることができる。鎖伸長剤の分子量は、通常、５００未満であり、好ましくは３００以下である。鎖伸長剤は単独で又は２種以上を組み合わせて使用できる。 As the chain extender, a chain extender usually used in the production of thermoplastic polyurethane can be used, and the kind thereof is not particularly limited, but a low molecular weight polyol, polyamine or the like can be used. The molecular weight of the chain extender is usually less than 500, preferably 300 or less. A chain extender can be used individually or in combination of 2 or more types.
　鎖伸長剤の代表的な例として、例えば、エチレングリコール、プロピレングリコール、１，３−プロパンジオール、１，４−ブタンジオール、１，５−ペンタンジオール、ネオペンチルグリコール、１，６−ヘキサンジオール、１，４−シクロヘキサンジオール、１，４−シクロヘキサンジメタノールなどのポリオール（特に、ジオール）；ヘキサメチレンジアミン、３，３′−ジメチル−４，４′−ジアミノジシクロヘキシルメタン、４，４′−メチレンビス−２−クロロアニリンなどのポリアミン（特に、ジアミン）などが挙げられる。 Representative examples of chain extenders include, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, Polyols (especially diols) such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol; hexamethylenediamine, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 4,4'-methylenebis- Examples include polyamines (particularly diamines) such as 2-chloroaniline.
　ポリウレタン鎖を有するポリマーとしては、ポリイシソアネート化合物、長鎖ポリオール化合物、及び必要に応じて鎖伸長剤、他のイソシアネート反応性化合物とを、ポリイソシアネートのイソシアネート基のモル数と、長鎖ポリオール及び鎖伸長剤等が有するイソシアネート反応性基（水酸基、アミノ基等）のモル数との比（ＮＣＯ／イソシアネート反応性基）が、０．８~２．０、特に０．９５~１．５となる範囲で反応させて得られたものが好ましい。上記反応には、反応を促進するため、必要に応じて、第３級アミン、有機金属化合物、スズ化合物等の触媒を用いてもよい。 Examples of the polymer having a polyurethane chain include a polyisocyanate compound, a long-chain polyol compound, and, if necessary, a chain extender and another isocyanate-reactive compound, the number of moles of isocyanate groups of the polyisocyanate, and a long-chain polyol. And the ratio (NCO / isocyanate reactive group) to the number of moles of isocyanate reactive groups (hydroxyl group, amino group, etc.) of the chain extender and the like is 0.8 to 2.0, particularly 0.95 to 1.5. What was obtained by making it react in the range which becomes is preferable. In order to accelerate the reaction, a catalyst such as a tertiary amine, an organometallic compound, or a tin compound may be used in the above reaction as necessary.
　ポリウレタン鎖を有するポリマーの末端がイソシアネート基である場合には、該イソシアネート基を反応性官能基Ｒ２として利用できる。この場合、前記エネルギー線硬化性基Ａ１及び反応性官能基Ｒ１を有する化合物として、ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレートなどを用いることができる。 If the end of a polymer having a polyurethane chain is an isocyanate group can utilize the isocyanate group as a reactive functional group R 2. In this case, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, etc. can be used as the compound having the energy ray curable group A 1 and the reactive functional group R 1 .
　また、ポリウレタン鎖を有するポリマーの末端がヒドロキシル基である場合には、該ヒドロキシル基を反応性官能基Ｒ２として利用できる。この場合、前記エネルギー線硬化性基Ａ１及び反応性官能基Ｒ１を有する化合物として、（メタ）アクリロイルオキシエチルイソシアネートなどを用いることができる。 Further, when the end of the polymer having a polyurethane chain is a hydroxyl group, it can be used the hydroxyl groups as reactive functional groups R 2. In this case, as the compound having the energy ray-curable groups A 1 and reactive functional groups R 1, or the like can be used (meth) acryloyloxyethyl isocyanate.
　反応性官能基Ｒ２を有し且つポリウレア鎖を有するポリマー、反応性官能基Ｒ２を有し且つポリウレタンウレア鎖を有するポリマー、反応性官能基Ｒ２を有し且つポリオレフィン鎖（特に、ポリジエン鎖）を有するポリマー、反応性官能基Ｒ２を有し且つシリコーン鎖を有するポリマー、反応性官能基Ｒ２を有し且つポリエステル鎖を有するポリマー、反応性官能基Ｒ２を有し且つポリエーテル鎖を有するポリマー、反応性官能基Ｒ２を有し且つポリアミド鎖を有するポリマー、反応性官能基Ｒ２を有し且つポリアクリル鎖を有するポリマーも公知乃至慣用の方法により得ることができる。 Polymer having reactive functional group R 2 and having polyurea chain, polymer having reactive functional group R 2 and having polyurethane urea chain, polyolefin having reactive functional group R 2 and polyolefin chain (particularly polydiene chain) ), A reactive functional group R 2 and a silicone chain, a reactive functional group R 2 and a polyester chain, a reactive functional group R 2 and a polyether chain , A polymer having a reactive functional group R 2 and a polyamide chain, and a polymer having a reactive functional group R 2 and a polyacryl chain can also be obtained by known or conventional methods.
　そして、これらの反応性官能基Ｒ２を有し且つ特定のポリマー鎖を有するポリマーに、該ポリマーの有する反応性官能基Ｒ２の種類に応じて、前記エネルギー線硬化性基Ａ１及び反応性官能基Ｒ１を有する化合物を反応させることにより、前記主鎖又は側鎖にエネルギー線硬化性基Ａ１を有する硬化性ポリマーＰを製造できる。 Then, the polymer and having a specific polymer chains having these reactive functional groups R 2, depending on the type of reactive functional group R 2 having the said polymer, said energy ray-curable groups A 1 and reactive by reacting a compound having a functional group R 1, it may produce a curable polymer P having an energy ray-curable groups a 1 in the main chain or side chain.
　本発明において、前記エネルギー線硬化性基Ａ２を有する硬化性モノマーＭとしては、（メタ）アクリロイル基、ビニル基等の炭素−炭素不飽和結合を含む基（ラジカル重合性基）を有する化合物；エポキシ基、オキセタニル基等のカチオン重合性基を有する化合物が挙げられる。これらの中でも、ラジカル重合性基を含む化合物が好ましい。なお、エネルギー線硬化性基Ａ２を有する硬化性モノマーＭは１種単独で又は２種以上を組み合わせて使用できる。 In the present invention, the curable monomers M having said energy ray-curable groups A 2, (meth) acryloyl group, carbon atoms such as a vinyl group - a compound having a group containing a carbon-carbon unsaturated bond (radical polymerizable group); Examples thereof include compounds having a cationically polymerizable group such as an epoxy group and an oxetanyl group. Among these, a compound containing a radical polymerizable group is preferable. Incidentally, curable monomers M having an energy ray-curable groups A 2 may be used in combination of at least one kind alone, or two or.
　エネルギー線硬化性基Ａ２を有する硬化性モノマーＭにおいて、エネルギー線硬化性基Ａ２がラジカル重合性基である化合物としては、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ−ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｓ−ブチル、（メタ）アクリル酸ｔ−ブチル、（メタ）アクリル酸ペンチル、（メタ）アクリル酸イソペンチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸ヘプチル、（メタ）アクリル酸オクチル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸ノニル、（メタ）アクリル酸イソノニル、（メタ）アクリル酸デシル、（メタ）アクリル酸イソデシル、（メタ）アクリル酸ウンデシル、（メタ）アクリル酸ドデシル、（メタ）アクリル酸トリデシル、（メタ）アクリル酸テトラデシル、（メタ）アクリル酸ペンタデシル、（メタ）アクリル酸ヘキサデシル、（メタ）アクリル酸ヘプタデシル、（メタ）アクリル酸オクタデシル、（メタ）アクリル酸ノナデシル、（メタ）アクリル酸エイコシルなどの（メタ）アクリル酸Ｃ１−２０アルキルエステル；（メタ）アクリル酸シクロペンチル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸イソボルニルなどの脂環式基を有する（メタ）アクリル酸エステル；（メタ）アクリル酸フェニル、（メタ）アクリル酸ベンジル、（メタ）アクリル酸フェノキシエチルなどの芳香族炭化水素基を有する（メタ）アクリル酸エステル；（メタ）アクリル酸メトキシエチル、（メタ）アクリル酸エトキシエチルなどの（メタ）アクリル酸アルコキシアルキル；（メタ）アクリル酸２−ヒドロキシエチル、（メタ）アクリル酸２−ヒドロキシプロピル、（メタ）アクリル酸３−ヒドロキシプロピル、（メタ）アクリル酸４−ヒドロキシブチル、（メタ）アクリル酸６−ヒドロキシヘキシル、ビニルアルコール、アリルアルコールなどの水酸基（ヒドロキシル基）含有モノマー；（メタ）アクリル酸、イタコン酸、クロトン酸、マレイン酸、フマル酸、イソクロトン酸、無水マレイン酸、無水イタコン酸、２−カルボキシエチル（メタ）アクリレート、２−（メタ）アクリロイルオキシエチルコハク酸、２−（メタ）アクリロイルオキシエチルフタル酸などのカルボキシル基又は酸無水物基含有モノマー；ビニルスルホン酸ナトリウム、アリルスルホン酸、スチレンスルホン酸、（メタ）アクリルアミドプロパンスルホン酸、スルホプロピル（メタ）アクリレートなどのスルホン酸基含有モノマー；２−ヒドロキシエチルアクリロイルフォスフェートなどのリン酸基含有モノマー；（メタ）アクリル酸グリシジル、（メタ）アクリル酸メチルグリシジルなどのエポキシ基含有モノマー；（メタ）アクリルアミド、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド、Ｎ−メチロール（メタ）アクリルアミド、Ｎ−メトキシメチル（メタ）アクリルアミド、Ｎ−ブトキシメチル（メタ）アクリルアミド、Ｎ−ヒドロキシエチル（メタ）アクリルアミドなどアミド基含有モノマー；Ｎ−ビニル−２−ピロリドン、Ｎ−ビニル−２−ピペリドン、Ｎ−ビニル−２−カプロラクタム、Ｎ−ビニルピペラジン、Ｎ−ビニルピロール、Ｎ−ビニルイミダゾール、（メタ）アクリロイルモルホリンなどの含窒素複素環含有モノマー；（メタ）アクリル酸テトラヒドロフルフリルなどの含酸素複素環含有モノマー；（メタ）アクリル酸アミノエチル、（メタ）アクリル酸ジメチルアミノエチル、（メタ）アクリル酸ｔ−ブチルアミノエチルなどのアミノ基含有モノマー；アクリロニトリルやメタクリロニトリルなどのシアノ基含有モノマー；シクロヘキシルマレイミド、イソプロピルマレイミドなどのイミド基含有モノマー；２−メタクリロイルオキシエチルイソシアネートなどのイソシアネート基含有モノマー；スチレン、α−メチルスチレン、ビニルトルエンなどのスチレン系モノマー；エチレン、プロピレン、イソプレン、ブタジエン、イソブチレンなどのオレフィン系モノマー；酢酸ビニル、プロピオン酸ビニルなどのビニルエステル系モノマー；ビニルアルキルエーテルなどのビニルエーテル系モノマー；塩化ビニル；塩化ビニリデン；フッ素原子含有基を有する（メタ）アクリル酸エステル；ケイ素原子含有基を有する（メタ）アクリル酸エステルなどが挙げられる。 In the curable monomer M having energy ray-curable group A 2, a compound energy ray-curable groups and A 2 is a radical polymerizable group, e.g., methyl (meth) acrylate, (meth) acrylate, ( Meth) propyl acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, (meth) Pentyl acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, (meth ) Nonyl acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, (meth Isodecyl acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, (meth) acrylic (Meth) acrylic acid C 1-20 alkyl esters such as heptadecyl acid, octadecyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate; cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate (Meth) acrylic acid ester having an alicyclic group such as isobornyl (meth) acrylate; aromatic hydrocarbon group such as phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate (Meth) acrylic Esters; alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) Hydroxyl group-containing monomers such as 3-hydroxypropyl acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, vinyl alcohol and allyl alcohol; (meth) acrylic acid, itaconic acid , Crotonic acid, maleic acid, fumaric acid, isocrotonic acid, maleic anhydride, itaconic anhydride, 2-carboxyethyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalate Carboxy such as acid Sulfonic acid group-containing monomers such as sodium vinyl sulfonate, allyl sulfonic acid, styrene sulfonic acid, (meth) acrylamide propane sulfonic acid, sulfopropyl (meth) acrylate; 2-hydroxyethylacryloyl Phosphoric acid group-containing monomers such as phosphate; Epoxy group-containing monomers such as glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-methylol ( Amide group-containing monomers such as (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide; N-vinyl-2-pyrrolidone, N-vinyl Nitrogen-containing heterocycle-containing monomers such as 2-piperidone, N-vinyl-2-caprolactam, N-vinylpiperazine, N-vinylpyrrole, N-vinylimidazole, (meth) acryloylmorpholine; tetrahydrofurfuryl (meth) acrylate, etc. Oxygen-containing heterocycle-containing monomers; amino group-containing monomers such as aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, and t-butylaminoethyl (meth) acrylate; cyano such as acrylonitrile and methacrylonitrile Group-containing monomers; Imido group-containing monomers such as cyclohexylmaleimide and isopropylmaleimide; Isocyanate group-containing monomers such as 2-methacryloyloxyethyl isocyanate; Styrene such as styrene, α-methylstyrene and vinyltoluene Olefin monomers such as ethylene, propylene, isoprene, butadiene, and isobutylene; vinyl ester monomers such as vinyl acetate and vinyl propionate; vinyl ether monomers such as vinyl alkyl ether; vinyl chloride; vinylidene chloride; (Meth) acrylic acid ester having a (meth) acrylic acid ester having a silicon atom-containing group.
　エネルギー線硬化性基Ａ２を有する硬化性モノマーＭにおいて、エネルギー線硬化性基Ａ２がラジカル重合性基である化合物としては、上記のほか、１，６−ヘキサンジオールジ（メタ）アクリレート、１，４−ブタンジオールジ（メタ）アクリレート、（ポリ）エチレングリコールジ（メタ）アクリレート、（ポリ）プロピレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、テトラメチロールメタントリ（メタ）アクリレート、トリメチロールプロパンＥＯ付加トリ（メタ）アクリレート、グリセリンＰＯ付加トリ（メタ）アクリレート、アリル（メタ）アクリレート、ビニル（メタ）アクリレート、ジビニルベンゼン、エポキシアクリレート、ポリエステルアクリレート、ウレタンアクリレートなどの多官能性モノマーを使用することもできる。なお、「ＥＯ」はエチレンオキサイド、「ＰＯ」はプロピレンオキサイドを示す。 In the curable monomer M having energy ray-curable group A 2, a compound energy ray-curable groups and A 2 is a radical polymerizable group, In addition to the above, 1,6-hexanediol di (meth) acrylate, 1 , 4-butanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tri Uses polyfunctional monomers such as tyrolpropane EO-added tri (meth) acrylate, glycerin PO-added tri (meth) acrylate, allyl (meth) acrylate, vinyl (meth) acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, urethane acrylate You can also “EO” represents ethylene oxide, and “PO” represents propylene oxide.
　エネルギー線硬化性基Ａ２を有する硬化性モノマーＭにおいて、エネルギー線硬化性基Ａ２がカチオン重合性基である化合物としては、エポキシ基、オキセタニル基等のカチオン重合性基を有する公知の化合物を使用できる。 In the curable monomer M having energy ray-curable group A 2, a compound energy ray-curable groups and A 2 is a cationic polymerizable group, an epoxy group, a known compound having a cationically polymerizable group such as oxetanyl group Can be used.
　前記エネルギー線硬化性基Ａ２を有する硬化性モノマーＭの中でも、ラジカル重合性基を有する硬化性モノマーが好ましい。特に、前記硬化性モノマーＭとして、少なくとも、（メタ）アクリル酸Ｃ１−２０アルキルエステルを用いるのが好ましい。また、易伸長性ポリマー母材２と筒状難伸長性ポリマー部Ａ３との界面における密着強度を向上させるため、硬化性モノマーＭとして筒状難伸長性ポリマー部を構成するポリマーのモノマーと同種のモノマー（特に、同一モノマー）を用いるのも好ましい。 Among curable monomers M having said energy ray-curable groups A 2, curable monomer having a radical polymerizable group is preferred. In particular, it is preferable to use at least (meth) acrylic acid C 1-20 alkyl ester as the curable monomer M. Further, in order to improve the adhesion strength at the interface between the easily extensible polymer base material 2 and the cylindrical hardly extensible polymer portion A3, the same kind of monomer as the polymer constituting the cylindrical hardly extensible polymer portion as the curable monomer M is used. It is also preferable to use a monomer (particularly the same monomer).
　硬化性モノマーＭとして（メタ）アクリル酸Ｃ１−２０アルキルエステルを用いる場合、硬化性モノマー全体に占める（メタ）アクリル酸Ｃ１−２０アルキルエステルの割合は、例えば、４０重量％以上（４０~１００重量％）、好ましくは５０重量％以上（５０~１００重量％）、さらに好ましくは６０重量％以上（６０~１００重量％）である。また、硬化性モノマーＭとして（メタ）アクリル酸Ｃ１−２０アルキルエステルとともに、（メタ）アクリル酸等のカルボキシル基又は酸無水物基含有モノマーや（メタ）アクリル酸２−ヒドロキシエチル等のヒドロキシル基含有モノマーを用いてもよい。この場合、カルボキシル基又は酸無水物基含有モノマー、ヒドロキシル基含有モノマーの使用量は、硬化性モノマー全体に対して、それぞれ、例えば０~５０重量％（０．１~５０重量％程度）の範囲から選択することができ、１~４５重量％程度用いてもよい。 When (meth) acrylic acid C 1-20 alkyl ester is used as curable monomer M, the proportion of (meth) acrylic acid C 1-20 alkyl ester in the entire curable monomer is, for example, 40% by weight or more (40 ~ 100% by weight), preferably 50% by weight or more (50 to 100% by weight), and more preferably 60% by weight or more (60 to 100% by weight). Further, as the curable monomer M, together with a (meth) acrylic acid C 1-20 alkyl ester, a carboxyl group such as (meth) acrylic acid or an acid anhydride group-containing monomer, or a hydroxyl group such as 2-hydroxyethyl (meth) acrylate Containing monomers may be used. In this case, the amount of the carboxyl group- or acid anhydride group-containing monomer and the hydroxyl group-containing monomer is, for example, in the range of 0 to 50% by weight (about 0.1 to 50% by weight), respectively, with respect to the entire curable monomer. From about 1 to 45% by weight may be used.
　易伸長性ポリマー母材２は、前記のように、硬化性ポリマーＰ、又は該硬化性ポリマーＰと硬化性モノマーＭとの混合物にエネルギー線を照射して硬化させることにより形成できる。この際、通常、光重合開始剤が用いられる。 As described above, the easily extensible polymer base material 2 can be formed by irradiating an energy ray to the curable polymer P or a mixture of the curable polymer P and the curable monomer M and curing it. At this time, a photopolymerization initiator is usually used.
　エネルギー線硬化性基Ａ１、Ａ２がラジカル重合性基の場合には、光重合開始剤として、例えば、ベンゾインエーテル系光重合開始剤、アセトフェノン系光重合開始剤、α−ケトール系光重合開始剤、芳香族スルホニルクロリド系光重合開始剤、光活性オキシム系光重合開始剤、ベンゾイン系光重合開始剤、ベンジル系光重合開始剤、ベンゾフェノン系光重合開始剤、ケタール系光重合開始剤、チオキサントン系光重合開始剤等が用いられる。 When the energy ray curable groups A 1 and A 2 are radical polymerizable groups, examples of the photopolymerization initiator include a benzoin ether photopolymerization initiator, an acetophenone photopolymerization initiator, and an α-ketol photopolymerization initiator. Agent, aromatic sulfonyl chloride photopolymerization initiator, photoactive oxime photopolymerization initiator, benzoin photopolymerization initiator, benzyl photopolymerization initiator, benzophenone photopolymerization initiator, ketal photopolymerization initiator, thioxanthone A photopolymerization initiator or the like is used.
　上記ベンゾインエーテル系光重合開始剤としては、例えば、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインプロピルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル、２，２−ジメトキシ−１，２−ジフェニルエタン−１−オン、アニソールメチルエーテルなどが挙げられる。上記アセトフェノン系光重合開始剤としては、例えば、２，２−ジエトキシアセトフェノン、２，２−ジメトキシ−２−フェニルアセトフェノン、１−ヒドロキシシクロヘキシルフェニルケトン、４−フェノキシジクロロアセトフェノン、４−（ｔ−ブチル）ジクロロアセトフェノンなどが挙げられる。上記α−ケトール系光重合開始剤としては、例えば、２−メチル−２−ヒドロキシプロピオフェノン、１−［４−（２−ヒドロキシエチル）フェニル］−２−メチルプロパン−１−オンなどが挙げられる。上記芳香族スルホニルクロリド系光重合開始剤としては、例えば、２−ナフタレンスルホニルクロライドなどが挙げられる。上記光活性オキシム系光重合開始剤としては、例えば、１−フェニル−１，１−プロパンジオン−２−（ｏ−エトキシカルボニル）−オキシムなどが挙げられる。上記ベンゾイン系光重合開始剤としては、例えば、ベンゾインなどが挙げられる。上記ベンジル系光重合開始剤としては、例えば、ベンジルなどが挙げられる。上記ベンゾフェノン系光重合開始剤としては、例えば、ベンゾフェノン、ベンゾイル安息香酸、３，３′−ジメチル−４−メトキシベンゾフェノン、ポリビニルベンゾフェノン、α−ヒドロキシシクロヘキシルフェニルケトンなどが挙げられる。上記ケタール系光重合開始剤としては、例えば、ベンジルジメチルケタールなどが挙げられる。上記チオキサントン系光重合開始剤としては、例えば、チオキサントン、２−クロロチオキサントン、２−メチルチオキサントン、２，４−ジメチルチオキサントン、イソプロピルチオキサントン、２，４−ジイソプロピルチオキサントン、ドデシルチオキサントンなどが挙げられる。 Examples of the benzoin ether photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethane-1-one, Anisole methyl ether etc. are mentioned. Examples of the acetophenone photopolymerization initiator include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 4-phenoxydichloroacetophenone, and 4- (t-butyl). ) Dichloroacetophenone and the like. Examples of the α-ketol photopolymerization initiator include 2-methyl-2-hydroxypropiophenone and 1- [4- (2-hydroxyethyl) phenyl] -2-methylpropan-1-one. It is done. Examples of the aromatic sulfonyl chloride photopolymerization initiator include 2-naphthalenesulfonyl chloride. Examples of the photoactive oxime photopolymerization initiator include 1-phenyl-1,1-propanedione-2- (o-ethoxycarbonyl) -oxime. Examples of the benzoin photopolymerization initiator include benzoin. Examples of the benzyl photopolymerization initiator include benzyl. Examples of the benzophenone photopolymerization initiator include benzophenone, benzoylbenzoic acid, 3,3′-dimethyl-4-methoxybenzophenone, polyvinyl benzophenone, α-hydroxycyclohexyl phenyl ketone, and the like. Examples of the ketal photopolymerization initiator include benzyl dimethyl ketal. Examples of the thioxanthone photopolymerization initiator include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, dodecylthioxanthone, and the like.
　エネルギー線硬化性基Ａ１、Ａ２がカチオン重合性基である場合には、光重合開始剤として、公知乃至慣用のカチオン硬化触媒を用いることができる。 In the case where the energy beam curable groups A 1 and A 2 are cationic polymerizable groups, a known or conventional cationic curing catalyst can be used as a photopolymerization initiator.
　光重合開始剤の使用量としては、特に限定されないが、硬化性化合物全量１００重量部に対して、例えば０．０１~３重量部であり、その上限は、好ましくは１重量部、さらに好ましくは０．５重量部であり、その下限は、好ましくは０．０２重量部、さらに好ましくは０．０５重量部である。 The amount of the photopolymerization initiator used is not particularly limited, but for example 0.01 to 3 parts by weight with respect to 100 parts by weight of the total amount of the curable compound, and the upper limit is preferably 1 part by weight, more preferably The lower limit is preferably 0.02 parts by weight, more preferably 0.05 parts by weight.
　本発明において、易伸長性ポリマー母材２を構成する伸長性（又はさらに伸縮性）を有するポリマーにおいて、ポリウレタン鎖、ポリウレア鎖、ポリウレタンウレア鎖、ポリオレフィン鎖（特に、ポリジエン鎖）、シリコーン鎖、ポリエステル鎖、ポリエーテル鎖及びポリアミド鎖からなる群より選択される少なくとも１種のポリマー鎖を有する場合には、該少なくとも１種のポリマー鎖部のポリマー全体に占める割合は、２０重量％以上（例えば、２０~１００重量％）が好ましく、より好ましくは２５重量％以上（例えば、２５~９０重量％）、さらに好ましくは３０重量％以上（例えば、３０~７５重量％）程度である。この割合が小さすぎると、伸長性が低下しやすくなる。なお、易伸長性ポリマー母材２を構成する伸長性（又はさらに伸縮性）を有するポリマーが、ガラス転移温度（Ｔｇ）の低いアクリル系ポリマー（Ｔｇが、例えば５℃未満、好ましくは０℃以下、さらに好ましくは−５℃以下のアクリル系ポリマー）である場合には、ポリマー全体に占めるポリアクリル鎖の割合は１００重量％であってもよい。 In the present invention, in the polymer having stretchability (or further stretchability) constituting the easily stretchable polymer matrix 2, polyurethane chain, polyurea chain, polyurethaneurea chain, polyolefin chain (particularly polydiene chain), silicone chain, polyester In the case of having at least one polymer chain selected from the group consisting of a chain, a polyether chain and a polyamide chain, the proportion of the at least one polymer chain portion in the whole polymer is 20% by weight or more (for example, 20 to 100% by weight) is preferable, more preferably 25% by weight or more (for example, 25 to 90% by weight), and still more preferably about 30% by weight or more (for example, 30 to 75% by weight). If this ratio is too small, the extensibility tends to decrease. In addition, the polymer having stretchability (or further stretchability) constituting the stretchable polymer base material 2 is an acrylic polymer having a low glass transition temperature (Tg) (Tg is, for example, less than 5 ° C., preferably 0 ° C. or less. In the case of an acrylic polymer having a temperature of −5 ° C. or lower), the ratio of the polyacryl chain in the whole polymer may be 100% by weight.
　易伸長性ポリマー母材部２には、必要に応じて、例えば、架橋剤（例えば、イソシアネート系架橋剤、エポキシ系架橋剤、メラミン系架橋剤、過酸化物系架橋剤、尿素系架橋剤、金属アルコキシド系架橋剤、金属キレート系架橋剤、金属塩系架橋剤、カルボジイミド系架橋剤、オキサゾリン系架橋剤、アジリジン系架橋剤、アミン系架橋剤など）、架橋促進剤、シランカップリング剤、粘着付与樹脂（ロジン誘導体、ポリテルペン樹脂、石油樹脂、油溶性フェノールなど）、老化防止剤、充填剤、着色剤（顔料や染料など）、紫外線吸収剤、酸化防止剤、可塑剤、軟化剤、界面活性剤、帯電防止剤などの添加剤が、本発明の特性を損なわない範囲で含まれていてもよい。 In the easily extensible polymer base material part 2, for example, a crosslinking agent (for example, an isocyanate crosslinking agent, an epoxy crosslinking agent, a melamine crosslinking agent, a peroxide crosslinking agent, a urea crosslinking agent, Metal alkoxide crosslinking agent, metal chelate crosslinking agent, metal salt crosslinking agent, carbodiimide crosslinking agent, oxazoline crosslinking agent, aziridine crosslinking agent, amine crosslinking agent, etc.), crosslinking accelerator, silane coupling agent, adhesive Giving resins (rosin derivatives, polyterpene resins, petroleum resins, oil-soluble phenols, etc.), anti-aging agents, fillers, colorants (pigments and dyes, etc.), UV absorbers, antioxidants, plasticizers, softeners, surface activity Additives such as an agent and an antistatic agent may be included as long as the characteristics of the present invention are not impaired.
　［筒状難伸長性ポリマー部Ａ（筒状難伸長部）］
　本発明において、筒状難伸長性ポリマー部Ａ３を構成する材料は、通常、ポリマーを少なくとも含有するポリマー材料であり、このポリマー材料は、フィラー（無機フィラー、有機フィラー）を含有していてもよい。前記ポリマー材料中のポリマーは１種単独であってもよく、２種以上の混合物であってもよい。 [Cylindrically difficult-to-extend polymer part A (cylindrical difficult-to-extend part)]
In the present invention, the material constituting the cylindrical hardly extensible polymer part A3 is usually a polymer material containing at least a polymer, and this polymer material may contain a filler (inorganic filler, organic filler). . The polymer in the polymer material may be a single type or a mixture of two or more types.
　筒状難伸長性ポリマー部Ａとしては、例えば、（ｉ）ホモポリマーのＴｇが５℃以上（より好ましくは１５℃以上、さらに好ましくは５０℃以上）であるモノマー［特に、（メタ）アクリル系モノマー］に由来する構成単位を、ポリマーの全構成単位に対して、５０重量％以上（より好ましくは６０重量％以上、さらに好ましくは８０重量％以上）含むポリマー［例えば、Ｔｇが５℃以上、好ましくは１５℃以上のポリマー（特に、アクリル系ポリマー）］を含有するポリマー材料、（ｉｉ）硬化性基（ラジカル重合性基、カチオン重合性基）を分子内に２以上有する多官能モノマーに由来する構成単位を、ポリマーの全構成単位に対して、５０重量％以上（より好ましくは６０重量％以上、さらに好ましくは８０重量％以上）含むポリマー［とりわけ、ラジカル重合性基を分子内に２以上有する多官能モノマー（特に、アクリル系多官能モノマー）に由来する構成単位が、ポリマーの全構成単位に対して、５０重量％以上（より好ましくは６０重量％以上、さらに好ましくは８０重量％以上）含むポリマー］を含有するポリマー材料、（ｉｉｉ）フィラー含有ポリマー材料、（ｉｖ）引張弾性率が０．１ＭＰａ以上（より好ましくは０．５ＭＰａ以上、さらに好ましくは１ＭＰａ以上、特に好ましくは５ＭＰａ以上）のポリマー材料で構成できる。 Examples of the cylindrical difficult-to-extend polymer part A include (i) a monomer having a Tg of a homopolymer of 5 ° C. or higher (more preferably 15 ° C. or higher, more preferably 50 ° C. or higher) [particularly, (meth) acrylic Monomer] is a polymer containing 50% by weight or more (more preferably 60% by weight or more, and still more preferably 80% by weight or more) with respect to all the structural units of the polymer [for example, Tg is 5 ° C. or more, Preferably derived from a polymer material containing a polymer (especially an acrylic polymer) at 15 ° C. or higher, (ii) a polyfunctional monomer having two or more curable groups (radical polymerizable groups, cationic polymerizable groups) in the molecule A polymer containing 50% by weight or more (more preferably 60% by weight or more, more preferably 80% by weight or more) based on the total structural units of the polymer. [In particular, the structural unit derived from a polyfunctional monomer having 2 or more radical polymerizable groups in the molecule (particularly an acrylic polyfunctional monomer) is 50% by weight or more (more preferably Polymer material containing], (iii) filler-containing polymer material, and (iv) tensile elastic modulus of 0.1 MPa or more (more preferably 0.5 MPa or more), More preferably, it can be composed of a polymer material of 1 MPa or more, particularly preferably 5 MPa or more.
　前記（ｉ）の場合、ホモポリマーのＴｇが５℃以上であるモノマーに由来する構成単位をポリマーの全構成単位に対して５０重量％以上含むポリマーの、筒状難伸長性ポリマー部Ａを構成するポリマー材料全体に占める割合は、例えば５重量％以上、好ましくは１０重量％以上、さらに好ましくは１５重量％以上であり、５０重量％以上（例えば９０重量％以上）であってもよい。前記（ｉｉ）の場合、硬化性基を分子内に２以上有する多官能モノマーに由来する構成単位をポリマーの全構成単位に対して５０重量％以上含むポリマーの、筒状難伸長性ポリマー部Ａを構成するポリマー材料全体に占める割合は、例えば５重量％以上、好ましくは１０重量％以上、さらに好ましくは１５重量％以上であり、５０重量％以上（例えば９０重量％以上）であってもよい。 In the case of the above (i), the cylindrical hard-extensible polymer portion A of a polymer containing 50% by weight or more of a structural unit derived from a monomer having a Tg of 5 ° C. or higher with respect to the total structural unit of the homopolymer is formed. The proportion of the polymer material in the entire polymer material is, for example, 5% by weight or more, preferably 10% by weight or more, more preferably 15% by weight or more, and may be 50% by weight or more (for example, 90% by weight or more). In the case of (ii) above, the cylindrical hard-to-extend polymer part A of a polymer containing 50% by weight or more of structural units derived from a polyfunctional monomer having two or more curable groups in the molecule based on the total structural units of the polymer The proportion of the polymer material constituting the total is, for example, 5% by weight or more, preferably 10% by weight or more, more preferably 15% by weight or more, and may be 50% by weight or more (for example, 90% by weight or more). .
　前記（ｉ）において、ホモポリマーのＴｇが５℃以上であるモノマーとして、例えば、イソボルニルアクリレート（ホモポリマーのＴｇ：９７℃）、シクロヘキシルアクリレート（ホモポリマーのＴｇ：１５℃）などの脂環式基を有する（メタ）アクリル酸エステル；ｔ−ブチルアクリレート（ホモポリマーのＴｇ：４１℃）などの（メタ）アクリル酸第３級アルキルエステル；メタクリル酸メチル（ホモポリマーのＴｇ：１０５℃）、メタクリル酸エチル（ホモポリマーのＴｇ：６５℃）、メタクリル酸ブチル（ホモポリマーのＴｇ：２０℃）、メタクリル酸イソブチル（ホモポリマーのＴｇ：６７℃）などのメタクリル酸Ｃ１−４アルキルエステル；スチレン（ホモポリマーのＴｇ：１００℃）などのスチレン系モノマー；アクリロニトリル（ホモポリマーのＴｇ：１００℃）などが挙げられる。 In (i) above, examples of the monomer having a Tg of homopolymer of 5 ° C. or higher include alicyclic rings such as isobornyl acrylate (homopolymer Tg: 97 ° C.) and cyclohexyl acrylate (homopolymer Tg: 15 ° C.). (Meth) acrylic acid ester having a formula group; (meth) acrylic acid tertiary alkyl ester such as t-butyl acrylate (homopolymer Tg: 41 ° C.); methyl methacrylate (homopolymer Tg: 105 ° C.); Methacrylic acid C 1-4 alkyl esters such as ethyl methacrylate (Tg of homopolymer: 65 ° C.), butyl methacrylate (Tg of homopolymer: 20 ° C.), isobutyl methacrylate (Tg of homopolymer: 67 ° C.); styrene Styrenic monomers such as (Tg of homopolymer: 100 ° C.); acrylonite Ril (homopolymer Tg: 100 ° C.) and the like.
　前記（ｉｉ）において、多官能モノマーとして、例えば、１，６−ヘキサンジオールジ（メタ）アクリレート、１，４−ブタンジオールジ（メタ）アクリレート、（ポリ）エチレングリコールジ（メタ）アクリレート、（ポリ）プロピレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、テトラメチロールメタントリ（メタ）アクリレート、トリメチロールプロパンＥＯ付加トリ（メタ）アクリレート、グリセリンＰＯ付加トリ（メタ）アクリレートなどが挙げられる。多官能モノマーの中でも３官能以上（例えば、３~６官能）の多官能モノマーが最も好ましい。 In the above (ii), examples of the polyfunctional monomer include 1,6-hexanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly ) Propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate , Trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, trimethylolpropane EO-added tri (meth) acrylate, glycerin PO-added tri (meth) Acrylate and the like. Of the polyfunctional monomers, those having 3 or more functional groups (for example, 3 to 6 functional groups) are most preferable.
　前記（ｉｉｉ）において、フィラーとしては、例えば、シリカ、アルミナ、酸化チタン、酸化ジルコニウム、酸化鉄、酸化銅、酸化亜鉛、酸化スズ等の無機酸化物；窒化ホウ素、窒化アルミニウム等の窒化物；炭酸カルシウム、炭酸マグネシウム等の炭酸塩；雲母、スメクタイト、カオリナイト、モンモリロナイト、バーミキュライト等の粘土鉱物；金、銀、銅、鉄、ニッケル、亜鉛、アルミニウム、スズ等の金属（金属合金を含む）；ガラス等の無機フィラー；有機フィラーなどが挙げられる。前記フィラーは、適宜な成分により、表面処理、表面被覆がなされたコア・シェル構造を有するものであってもよい。さらに、フィラーは、ガラスバルーン、セラミックバルーン、フライアッシュバルーン、中空シリカ等の中空構造を有するものであってもよい。フィラーは１種単独で又は２種以上を組み合わせて使用できる。フィラーを用いることで、筒状難伸長性ポリマー部Ａ３に難伸長性や硬度を付与できるだけでなく、フィラーの種類により、導電性、熱伝導性等の種々の機能を付与できる。 In (iii), examples of the filler include inorganic oxides such as silica, alumina, titanium oxide, zirconium oxide, iron oxide, copper oxide, zinc oxide and tin oxide; nitrides such as boron nitride and aluminum nitride; Carbonates such as calcium and magnesium carbonate; clay minerals such as mica, smectite, kaolinite, montmorillonite, vermiculite; metals such as gold, silver, copper, iron, nickel, zinc, aluminum, tin (including metal alloys); glass And inorganic fillers; organic fillers and the like. The filler may have a core / shell structure that is surface-treated and coated with an appropriate component. Furthermore, the filler may have a hollow structure such as a glass balloon, a ceramic balloon, a fly ash balloon, or hollow silica. A filler can be used individually by 1 type or in combination of 2 or more types. By using the filler, not only can the stretchability and hardness be imparted to the tubular hardly stretchable polymer part A3, but various functions such as conductivity and thermal conductivity can be imparted depending on the type of filler.
　フィラーの形状は、特に限定されず、バルク、球状、針状、板状等の何れであってもよい。また、フィラーの平均粒子径（針状の場合は、長径の平均径）は、例えば、０．００１~１００μｍである。フィラーの平均粒子径（針状の場合は、長径の平均径）の上限は、好ましくは５０μｍ、さらに好ましくは２０μｍであり、下限は、好ましくは０．００５μｍ、さらに好ましくは０．００８μｍである。 The shape of the filler is not particularly limited, and may be any of a bulk shape, a spherical shape, a needle shape, a plate shape, and the like. Further, the average particle diameter of the filler (in the case of needles, the average diameter of the major axis) is, for example, 0.001 to 100 μm. The upper limit of the average particle diameter of the filler (in the case of needles, the average diameter of the major axis) is preferably 50 μm, more preferably 20 μm, and the lower limit is preferably 0.005 μm, more preferably 0.008 μm.
　フィラー含有ポリマー材料における「ポリマー」としては、特に限定されず、前記易伸長性ポリマー母材を構成するポリマーとして例示したポリマー、筒状難伸長性ポリマー部Ａを構成するポリマーとして例示した前記（ｉ）ホモポリマーのＴｇが５℃以上であるモノマーに由来する構成単位をポリマーの全構成単位に対して５０重量％以上含むポリマー、筒状難伸長性ポリマー部Ａを構成するポリマーとして例示した前記（ｉｉ）硬化性基を分子内に２以上有する多官能モノマーに由来する構成単位を、ポリマーの全構成単位に対して５０重量％以上含むポリマー、筒状難伸長性ポリマー部Ａを構成するポリマーとして後述する（ｉｖ）引張弾性率が０．１ＭＰａ以上のポリマーなどの何れであってもよい。該ポリマーは、エネルギー線硬化型ポリマーであってもよい。 The “polymer” in the filler-containing polymer material is not particularly limited, and the polymer exemplified as the polymer constituting the easily stretchable polymer base material, the polymer exemplified as the polymer constituting the cylindrical hardly stretchable polymer portion A (i ) The polymer exemplified above as a polymer comprising the structural unit derived from a monomer having a Tg of 5 ° C. or higher with respect to the homopolymer, 50% by weight or more based on the total structural units of the polymer, and the polymer constituting the cylindrical hardly extensible polymer part A ii) a polymer comprising 50% by weight or more of a structural unit derived from a polyfunctional monomer having two or more curable groups in the molecule, based on the total structural unit of the polymer, and a polymer constituting the cylindrical hardly extensible polymer part A (Iv) Any of a polymer having a tensile elastic modulus of 0.1 MPa or more, which will be described later, may be used. The polymer may be an energy ray curable polymer.
　前記（ｉｖ）において、引張弾性率が０．１ＭＰａ以上のポリマーとしては、引張弾性率が０．１ＭＰａ以上のポリマー（１種又は２種以上のポリマーの混合物）であれば特に限定されず、例えば、ポリウレタン系ポリマー、ポリウレア系ポリマー、ポリウレタンウレア系ポリマー、ポリオレフィン系ポリマー、シリコーン系ポリマー、ポリエステル系ポリマー、ポリエーテル系ポリマー、ポリアミド系ポリマー、ポリスチレン系ポリマー、アクリル系ポリマー等の中から選択して使用できる。ポリマーを２種以上含む場合は、ポリマー混合物の引張弾性率が０．１ＭＰａ以上であればよい。 In (iv), the polymer having a tensile modulus of elasticity of 0.1 MPa or more is not particularly limited as long as the polymer has a tensile modulus of elasticity of 0.1 MPa or more (a mixture of one or two or more polymers). , Polyurethane polymer, polyurea polymer, polyurethane urea polymer, polyolefin polymer, silicone polymer, polyester polymer, polyether polymer, polyamide polymer, polystyrene polymer, acrylic polymer, etc. it can. When two or more kinds of polymers are contained, the tensile modulus of the polymer mixture may be 0.1 MPa or more.
　引張弾性率が０．１ＭＰａ以上のポリマーの代表的な例として、例えば、Ｔｇが５℃以上（より好ましくは２０℃以上）であるポリウレタン系ポリマー；スチレン−ブタジエン−スチレンブロック共重合体（ＳＢＳ）の水素添加物（ＳＥＢＳ）やスチレン−イソプレン−スチレンブロック共重合体（ＳＩＳ）の水素添加物（ＳＥＰＳ）等のポリスチレン系ポリマー；ポリメタクリル酸メチル等のアクリル系ポリマーなどが挙げられる。引張弾性率が０．１ＭＰａ以上のポリマー材料としては、これらのポリマーを、例えば５０重量％以上、特に８０重量％以上含むのが好ましい。 As a typical example of a polymer having a tensile modulus of elasticity of 0.1 MPa or more, for example, a polyurethane-based polymer having a Tg of 5 ° C. or more (more preferably 20 ° C. or more); a styrene-butadiene-styrene block copolymer (SBS) Polystyrene polymers such as hydrogenated product (SEBS) and hydrogenated product (SEPS) of styrene-isoprene-styrene block copolymer (SIS); and acrylic polymers such as polymethyl methacrylate. As a polymer material having a tensile modulus of elasticity of 0.1 MPa or more, it is preferable to contain these polymers, for example, 50% by weight or more, particularly 80% by weight or more.
　筒状難伸長性ポリマー部Ａは、該筒状難伸長性ポリマー部Ａを構成するポリマー材料の前駆体を該ポリマー材料に転化して形成されたポリマー部、前記ポリマー材料を含む溶液若しくは分散液中の溶媒を乾燥除去して形成されたポリマー部、前記ポリマー材料を溶融・冷却処理して形成されたポリマー部等の何れであってもよい。 The cylindrical difficult-to-extend polymer part A is a polymer part formed by converting a polymer material precursor constituting the cylindrical difficult-to-extend polymer part A to the polymer material, a solution or dispersion containing the polymer material Any of a polymer part formed by drying and removing the solvent therein, a polymer part formed by melting and cooling the polymer material, and the like may be used.
　筒状難伸長性ポリマー部Ａを、前記（ｉ）ホモポリマーのＴｇが５℃以上であるモノマーに由来する構成単位をポリマーの全構成単位に対して５０重量％以上含むポリマーを含有するポリマー材料で構成する場合は、例えば、前記ホモポリマーのＴｇが５℃以上であるモノマーをモノマー全体の５０重量％以上含むモノマー成分を易伸長性ポリマー母材形成用材料層の所定部位に配した後、エネルギー線を照射して硬化（重合）させることにより形成できる。この場合、ホモポリマーのＴｇが５℃以上であるモノマー以外の他のモノマーとして、例えば、前記エネルギー線硬化性基Ａ２を有する硬化性モノマーＭとして例示したモノマーを適宜選択して使用できる。 A polymer material comprising a cylindrical hard-extensible polymer part A, the polymer comprising (i) 50% by weight or more of a structural unit derived from a monomer having a Tg of a homopolymer of 5 ° C. or higher based on the total structural unit of the polymer For example, after arranging a monomer component containing 50% by weight or more of the monomer having a Tg of 5 ° C. or higher of the homopolymer at a predetermined portion of the easily stretchable polymer base material forming material layer, It can be formed by irradiating with energy rays and curing (polymerization). In this case, as a monomer other than the monomer having a homopolymer Tg of 5 ° C. or more, for example, a monomer exemplified as the curable monomer M having the energy ray curable group A 2 can be appropriately selected and used.
　筒状難伸長性ポリマー部Ａを、前記（ｉｉ）硬化性基を分子内に２以上有する多官能モノマーに由来する構成単位をポリマーの全構成単位に対して５０重量％以上含むポリマーを含有するポリマー材料で構成する場合は、例えば、前記多官能モノマーをモノマー全体の５０重量％以上含むモノマー成分を易伸長性ポリマー母材形成用材料層の所定部位に配した後、エネルギー線を照射して硬化（重合）させることにより形成できる。この場合、前記多官能モノマー以外の他のモノマーとして、前記エネルギー線硬化性基Ａ２を有する硬化性モノマーＭとして例示したモノマーのうち単官能モノマーを適宜選択して使用できる。 The cylindrical difficult-to-extend polymer part A contains (ii) a polymer containing 50% by weight or more of a structural unit derived from a polyfunctional monomer having two or more curable groups in the molecule based on the total structural unit of the polymer. In the case of a polymer material, for example, a monomer component containing 50% by weight or more of the polyfunctional monomer in the whole monomer is disposed at a predetermined portion of the easily stretchable polymer base material forming material layer, and then irradiated with energy rays. It can be formed by curing (polymerization). In this case, examples of monomer other than the polyfunctional monomer, a monofunctional monomer of the monomers exemplified as the curable monomer M having said energy ray-curable groups A 2 appropriately selected and can be used.
　筒状難伸長性ポリマー部Ａを形成する際には、通常、硬化性基を硬化させるため光重合開始剤が用いられる。光重合開始剤としては、特に限定されず、前記易伸長性ポリマー母材２を形成する場合と同様の光重合開始剤を使用できる。光重合開始剤の使用量としては、特に限定されないが、硬化性化合物全量１００重量部に対して、例えば０．０１~３重量部であり、その上限は、好ましくは１重量部、さらに好ましくは０．５重量部であり、その下限は、好ましくは０．０２重量部、さらに好ましくは０．０５重量部である。 When forming the cylindrical difficult-to-extend polymer part A, a photopolymerization initiator is usually used to cure the curable group. It does not specifically limit as a photoinitiator, The photoinitiator similar to the case where the said easily extensible polymer base material 2 is formed can be used. The amount of the photopolymerization initiator used is not particularly limited, but for example 0.01 to 3 parts by weight with respect to 100 parts by weight of the total amount of the curable compound, and the upper limit is preferably 1 part by weight, more preferably The lower limit is preferably 0.02 parts by weight, more preferably 0.05 parts by weight.
　筒状難伸長性ポリマー部Ａを、前記（ｉｉｉ）フィラー含有ポリマーで構成する場合には、易伸長性ポリマー母材形成用材料層の所定部位に、フィラーを含有する分散液（水分散液、有機溶媒分散液等）を配した後、分散液中の溶媒を乾燥除去することにより筒状難伸長性ポリマー部Ａを形成することができる。この場合、筒状難伸長性ポリマー部Ａは、該フィラーと、易伸長性ポリマー母材２を構成するポリマーと同じポリマーとで構成される。なお、前記易伸長性ポリマー母材形成用材料層を該層を構成するポリマーの有機溶媒溶液により形成する場合には、フィラーの有機溶媒分散液を用いるのが好ましく、前記易伸長性ポリマー母材形成用材料層を該層を構成するポリマーの水分散液により形成する場合には、フィラーの水分散液を用いるのが好ましい。また、易伸長性ポリマー母材形成用材料層の所定部位に、フィラーと、筒状難伸長性ポリマー部Ａを構成すべきポリマーに誘導できるモノマー（エネルギー線硬化性モノマー等）又はその部分重合物と、必要に応じて溶媒とを含む混合液を配した後、前記モノマー又はその部分重合物を重合することにより前記筒状難伸長性ポリマー部Ａを形成できる。さらに、易伸長性ポリマー母材形成用材料層の所定部位に、フィラーと、筒状難伸長性ポリマー部Ａを構成すべきポリマーに架橋により誘導できる架橋前ポリマーと架橋剤とを含む混合液を配した後、前記架橋前ポリマーを架橋することにより筒状難伸長性ポリマー部Ａを形成できる。さらにまた、易伸長性ポリマー母材形成用材料層の所定部位に、フィラー単体（粉体）を配した後、易伸長性ポリマー母材形成用材料層を易伸長性ポリマー母材に転化することにより、同時に筒状難伸長性ポリマー部Ａを形成できる。この場合、筒状難伸長性ポリマー部Ａは、該フィラーと、易伸長性ポリマー母材を構成するポリマーと同じポリマーとで構成される。フィラーの使用量は、形成する筒状難伸長性ポリマー部Ａの大きさ、所望する筒状難伸長性ポリマー部Ａの強度等により適宜調整できる。例えば、筒状難伸長性ポリマー部Ａ中のフィラーの含有量は、例えば０．１~９９重量％程度であり、その上限は、好ましくは９５重量％、さらに好ましくは９０重量％、特に好ましくは８０重量％であり、下限は、好ましくは１重量％、さらに好ましくは５重量％、特に好ましくは１０重量％である。 In the case where the cylindrical hardly extensible polymer part A is composed of the (iii) filler-containing polymer, a dispersion containing a filler (an aqueous dispersion, a predetermined portion of the easily extensible polymer base material forming material layer) After disposing the organic solvent dispersion or the like, the cylindrical hardly extensible polymer portion A can be formed by drying and removing the solvent in the dispersion. In this case, the cylindrical hardly extensible polymer portion A is composed of the filler and the same polymer as the polymer constituting the easily extensible polymer base material 2. In the case where the material layer for forming an easily stretchable polymer base material is formed from an organic solvent solution of a polymer constituting the layer, it is preferable to use an organic solvent dispersion of a filler. When the forming material layer is formed with an aqueous dispersion of the polymer constituting the layer, it is preferable to use an aqueous dispersion of filler. In addition, a monomer (energy ray-curable monomer or the like) or a partial polymer thereof that can be derived from a filler and a polymer that constitutes the cylindrical difficult-to-extend polymer part A at a predetermined portion of the easily stretchable polymer base material forming material layer And after arrange | positioning the liquid mixture containing a solvent as needed, the said cylindrical difficulty extensible polymer part A can be formed by superposing | polymerizing the said monomer or its partial polymer. Furthermore, a mixture liquid containing a filler, a pre-crosslinking polymer that can be induced by crosslinking in a polymer that should form the cylindrical difficult-to-extend polymer part A, and a crosslinking agent at a predetermined portion of the easily stretchable polymer base material forming material layer After placement, the cylindrical difficult-to-extend polymer part A can be formed by crosslinking the pre-crosslinking polymer. Furthermore, after placing the filler alone (powder) at a predetermined part of the easily stretchable polymer matrix forming material layer, the easily stretchable polymer matrix forming material layer is converted into an easily stretchable polymer matrix. Thereby, the cylindrical difficult-to-extend polymer part A can be formed simultaneously. In this case, the cylindrical hardly extensible polymer part A is composed of the filler and the same polymer as the polymer constituting the easily extensible polymer base material. The usage-amount of a filler can be suitably adjusted with the magnitude | size of the cylindrical difficulty extensible polymer part A to form, the intensity | strength of the desired cylindrical difficult extensible polymer part A, etc. For example, the content of the filler in the cylindrical difficult-to-extend polymer part A is, for example, about 0.1 to 99% by weight, and the upper limit thereof is preferably 95% by weight, more preferably 90% by weight, particularly preferably. The lower limit is preferably 1% by weight, more preferably 5% by weight, and particularly preferably 10% by weight.
　筒状難伸長性ポリマー部Ａを、前記（ｉｖ）引張弾性率が０．１ＭＰａ以上のポリマー材料で構成する場合には、前記ポリマーに誘導できるモノマー（エネルギー線硬化性モノマー等）又はその部分重合物を重合するか、又は前記ポリマーに硬化又は架橋により誘導できる硬化又は架橋前ポリマーを硬化又は架橋することにより筒状難伸長性ポリマー部Ａを形成することができる。 When the cylindrical difficult-to-extend polymer part A is composed of (iv) a polymer material having a tensile modulus of elasticity of 0.1 MPa or more, a monomer (such as an energy ray-curable monomer) that can be derived from the polymer or a partial polymerization thereof The cylindrical difficult-to-extend polymer part A can be formed by polymerizing a product, or curing or crosslinking a polymer before curing or crosslinking that can be induced by curing or crosslinking.
　筒状難伸長性ポリマー部Ａには、必要に応じて、例えば、架橋剤（例えば、イソシアネート系架橋剤、エポキシ系架橋剤、メラミン系架橋剤、過酸化物系架橋剤、尿素系架橋剤、金属アルコキシド系架橋剤、金属キレート系架橋剤、金属塩系架橋剤、カルボジイミド系架橋剤、オキサゾリン系架橋剤、アジリジン系架橋剤、アミン系架橋剤など）、架橋促進剤、シランカップリング剤、粘着付与樹脂（ロジン誘導体、ポリテルペン樹脂、石油樹脂、油溶性フェノールなど）、老化防止剤、充填剤、着色剤（顔料や染料など）、紫外線吸収剤、酸化防止剤、可塑剤、軟化剤、界面活性剤、帯電防止剤などの添加剤が、本発明の特性を損なわない範囲で含まれていてもよい。 For the cylindrical difficult-to-extend polymer part A, for example, a crosslinking agent (for example, an isocyanate-based crosslinking agent, an epoxy-based crosslinking agent, a melamine-based crosslinking agent, a peroxide-based crosslinking agent, a urea-based crosslinking agent, Metal alkoxide crosslinking agent, metal chelate crosslinking agent, metal salt crosslinking agent, carbodiimide crosslinking agent, oxazoline crosslinking agent, aziridine crosslinking agent, amine crosslinking agent, etc.), crosslinking accelerator, silane coupling agent, adhesive Giving resins (rosin derivatives, polyterpene resins, petroleum resins, oil-soluble phenols, etc.), anti-aging agents, fillers, colorants (pigments and dyes, etc.), UV absorbers, antioxidants, plasticizers, softeners, surface activity Additives such as an agent and an antistatic agent may be included as long as the characteristics of the present invention are not impaired.
　筒状難伸長性ポリマー部Ａを構成する材料のうちポリマーとしては、易伸長性ポリマー母材と筒状難伸長性ポリマー部材の一体性、密着性等の観点から、易伸長性ポリマー母材を構成するポリマーと同種のポリマー、或いは易伸長性ポリマー母材を構成するポリマーが有するポリマー鎖（主鎖又は側鎖）と同種のポリマー鎖を主鎖又は側鎖に有するポリマーであることが好ましい。 Among the materials constituting the cylindrical hardly extensible polymer part A, as the polymer, from the viewpoint of the integrity and adhesion of the easily extensible polymer base material and the cylindrical hardly extensible polymer member, an easily extensible polymer base material is used. A polymer having the same type of polymer chain as the polymer constituting the polymer or a polymer chain (main chain or side chain) of the polymer constituting the easily extensible polymer matrix in the main chain or side chain is preferable.
　より具体的には、易伸長性ポリマー母材を構成するポリマーと筒状難伸長性ポリマー部Ａを構成するポリマーの好ましい組合せとして、ポリウレタン系ポリマー同士の組合せ、ポリウレア系ポリマー同士の組合せ、ポリウレタンウレア系ポリマー同士の組合せ、ポリオレフィン系ポリマー同士の組合せ、シリコーン系ポリマー同士の組合せ、ポリエステル系ポリマー同士の組合せ、ポリエーテル系ポリマー同士の組合せ、ポリアミド系ポリマー同士の組合せ、ポリスチレン系ポリマー同士の組合せ、アクリル系ポリマー同士の組合せが挙げられる。また、ポリスチレン系ポリマーとアクリル系ポリマーとの組合せも好ましい。さらに、前記好ましい組合せとして、ポリウレタン鎖を有するポリマー同士の組合せ、ポリウレア鎖を有するポリマー同士の組合せ、ポリウレタンウレア鎖を有するポリマー同士の組合せ、ポリオレフィン鎖を有するポリマー同士の組合せ、シリコーン鎖を有するポリマー同士の組合せ、ポリエステル鎖を有するポリマー同士の組合せ、ポリエーテル鎖を有するポリマー同士の組合せ、ポリアミド鎖を有するポリマー同士の組合せ、ポリスチレン系ポリマー鎖を有するポリマー同士の組合せ、ポリアクリル鎖を有するポリマー同士の組合せが挙げられる。 More specifically, as a preferred combination of the polymer constituting the easily stretchable polymer base material and the polymer constituting the cylindrical hardly stretchable polymer part A, a combination of polyurethane polymers, a combination of polyurea polymers, polyurethane urea Combinations of polymers, combinations of polyolefin polymers, combinations of silicone polymers, combinations of polyester polymers, combinations of polyether polymers, combinations of polyamide polymers, combinations of polystyrene polymers, acrylic A combination of the base polymers may be mentioned. A combination of a polystyrene polymer and an acrylic polymer is also preferable. Furthermore, as the preferred combination, a combination of polymers having a polyurethane chain, a combination of polymers having a polyurea chain, a combination of polymers having a polyurethane urea chain, a combination of polymers having a polyolefin chain, and a polymer having a silicone chain Combination of polymers having a polyester chain, combination of polymers having a polyether chain, combination of polymers having a polyamide chain, combination of polymers having a polystyrene-based polymer chain, between polymers having a polyacryl chain Combinations are mentioned.
　これらの中でも、易伸長性ポリマー母材を構成するポリマーと筒状難伸長性ポリマー部Ａを構成するポリマーの好ましい組合せとして、ポリウレタン系ポリマー同士の組合せ、ポリウレタン鎖を有するポリマー同士の組合せ、ポリスチレン系ポリマー同士の組合せ、ポリスチレン系ポリマー鎖を有するポリマー同士の組合せ、アクリル系ポリマー同士の組合せ、ポリアクリル鎖を有するポリマー同士の組合せ、ポリスチレン系ポリマーとアクリル系ポリマーとの組合せが特に好ましい。 Among these, as a preferable combination of the polymer constituting the easily stretchable polymer base material and the polymer constituting the cylindrical hardly stretchable polymer part A, a combination of polyurethane polymers, a combination of polymers having a polyurethane chain, a polystyrene series A combination of polymers, a combination of polymers having a polystyrene polymer chain, a combination of acrylic polymers, a combination of polymers having a polyacryl chain, and a combination of a polystyrene polymer and an acrylic polymer are particularly preferable.
　［シート状伸長性有機基材の製造］
　本発明のシート状伸長性有機基材は、例えば、下記の工程Ａ、工程Ｂ及び工程Ｃを経ることにより製造できる。
　工程Ａ：支持体上に、易伸長性ポリマー母材を構成するポリマー（ａ）の液状前駆体、前記ポリマー（ａ）を含む溶液若しくは分散液、又は前記ポリマー（ａ）単体により易伸長性ポリマー母材形成用材料層を形成する工程
　工程Ｂ：前記易伸長性ポリマー母材形成用材料層の所定部位に、筒状難伸長性ポリマー部形成用材料を配する工程
　工程Ｃ：筒状難伸長性ポリマー部形成用材料を所定部位に配した易伸長性ポリマー母材形成用材料層に対して、反応、溶媒の乾燥除去処理、及び溶融・冷却処理から選択された少なくとも１つの処理を施して、易伸長性ポリマー母材中に筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されたシート状伸長性有機基材を得る工程 [Production of sheet-like extensible organic substrate]
The sheet-like extensible organic base material of this invention can be manufactured by passing through the following process A, process B, and process C, for example.
Step A: A polymer (a) liquid precursor constituting the easily stretchable polymer matrix, a solution or dispersion containing the polymer (a), or the polymer (a) alone, on the support. Step B: Forming a Base Material Forming Material Layer Step B: Placing a Cylindrical Difficulty Polymer Part Forming Material at a Predetermined Part of the Easy-Extensible Polymer Base Material Forming Material Layer Step C: Cylindrical Difficulty Stretching The easily stretchable polymer base material forming material layer in which the polymer material forming material is disposed at a predetermined site is subjected to at least one treatment selected from a reaction, a solvent dry removal treatment, and a melting / cooling treatment. , A step of obtaining a sheet-like extensible organic base material in which a cylindrical hardly extensible polymer portion A is partially and integrally formed in an easily extensible polymer base material
　まず、工程Ａでは、支持体上に、易伸長性ポリマー母材を構成するポリマー（ａ）の液状前駆体、前記ポリマー（ａ）を含む溶液若しくは分散液、又は前記ポリマー（ａ）単体により易伸長性ポリマー母材形成用材料層を形成する。 First, in step A, the polymer (a) liquid precursor constituting the easily stretchable polymer matrix, the solution or dispersion containing the polymer (a), or the polymer (a) alone is easily formed on the support. An extensible polymer base material forming material layer is formed.
　工程Ａにおいて、支持体としては、特に限定されないが、例えばセパレータを用いることができる。セパレータとしては、特に限定されず、慣用の剥離紙、剥離処理層を有するセパレータ、フッ素ポリマーからなる低接着性基材、無極性ポリマーからなる低接着性基材などを使用できる。上記剥離処理層を有するセパレータとしては、例えば、シリコーン系、長鎖アルキル系、フッ素系、硫化モリブデン等の剥離処理剤により表面処理されたプラスチックフィルムや紙等が挙げられる。上記フッ素ポリマーからなる低接着性基材におけるフッ素系ポリマーとしては、例えば、ポリテトラフルオロエチレン、ポリクロロトリフルオロエチレン、ポリフッ化ビニル、ポリフッ化ビニリデン、テトラフルオロエチレン−ヘキサフルオロプロピレン共重合体、クロロフルオロエチレン−フッ化ビニリデン共重合体等が挙げられる。また、上記無極性ポリマーとしては、例えば、オレフィン系樹脂（例えば、ポリエチレン、ポリプロピレンなど）等が挙げられる。なお、セパレータは公知乃至慣用の方法により製造することができる。また、セパレータの厚さ等も特に限定されない。 In step A, the support is not particularly limited, and for example, a separator can be used. The separator is not particularly limited, and a conventional release paper, a separator having a release treatment layer, a low adhesive substrate made of a fluoropolymer, a low adhesive substrate made of a nonpolar polymer, and the like can be used. Examples of the separator having the release treatment layer include a plastic film or paper surface-treated with a release treatment agent such as silicone-based, long-chain alkyl-based, fluorine-based, or molybdenum sulfide. Examples of the fluorine-based polymer in the low-adhesive substrate made of the above-described fluoropolymer include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, chloro Examples include fluoroethylene-vinylidene fluoride copolymer. Moreover, as said nonpolar polymer, olefin resin (for example, polyethylene, a polypropylene, etc.) etc. are mentioned, for example. The separator can be manufactured by a known or conventional method. Further, the thickness of the separator is not particularly limited.
　易伸長性ポリマー母材を構成するポリマー（ａ）の液状前駆体としては、ポリマー（ａ）に誘導できるモノマー（エネルギー線硬化性モノマー等）、該モノマーの部分重合物、硬化又は架橋によりポリマー（ａ）に誘導できる硬化又は架橋前ポリマーなどが挙げられる。これらの混合物であってもよい。ポリマー（ａ）を含む溶液若しくは分散液としては、ポリマー（ａ）の水溶液又は有機溶媒溶液、ポリマー（ａ）の水分散液、有機溶媒分散液が挙げられる。溶媒としては、前記［易伸長性ポリマー母材］の項で例示したものを使用できる。 Examples of the liquid precursor of the polymer (a) constituting the easily stretchable polymer matrix include monomers that can be derived into the polymer (a) (energy ray curable monomers, etc.), partial polymers of the monomers, polymers by curing or crosslinking ( Examples thereof include a polymer that can be derived into a), a polymer before curing or crosslinking. A mixture thereof may be used. Examples of the solution or dispersion containing the polymer (a) include an aqueous solution or an organic solvent solution of the polymer (a), an aqueous dispersion of the polymer (a), and an organic solvent dispersion. As the solvent, those exemplified in the above section [Easily stretchable polymer matrix] can be used.
　易伸長性ポリマー母材を構成するポリマー（ａ）の液状前駆体、又は前記ポリマー（ａ）を含む溶液若しくは分散液により易伸長性ポリマー母材形成用材料層を形成する場合には、例えば、支持体上に、これらを塗工することにより、易伸長性ポリマー母材形成用材料層を形成できる。塗工液の粘度は、作業性等の観点から、塗工する際の温度（例えば１０~４０℃の範囲内の所定温度、特に２５℃）において、例えば、０．１~５０Ｐａ・ｓであり、その上限は、好ましくは３０Ｐａ・ｓ、さらに好ましくは２０Ｐａ・ｓであり、下限は、好ましくは０．５Ｐａ・ｓ、さらに好ましくは１Ｐａ・ｓである。この粘度が低すぎると形状の保持が困難になりやすく、逆に高すぎると塗工作業性が低下しやすくなる。 When forming the stretchable polymer matrix forming material layer from the liquid precursor of the polymer (a) constituting the stretchable polymer matrix, or a solution or dispersion containing the polymer (a), for example, By coating these on the support, an easily extensible polymer base material forming material layer can be formed. The viscosity of the coating liquid is, for example, 0.1 to 50 Pa · s at a coating temperature (for example, a predetermined temperature within a range of 10 to 40 ° C., particularly 25 ° C.) from the viewpoint of workability and the like. The upper limit is preferably 30 Pa · s, more preferably 20 Pa · s, and the lower limit is preferably 0.5 Pa · s, more preferably 1 Pa · s. If the viscosity is too low, the shape tends to be difficult to maintain. Conversely, if the viscosity is too high, the coating workability tends to decrease.
　塗工方法は特に限定されず、例えば、マイヤーバー、ブレードコーター、エアナイフコーター、ロールコーター、ダイコーター等のコーター、押出機、印刷機などを使用できる。 The coating method is not particularly limited, and for example, a coater such as a Meyer bar, a blade coater, an air knife coater, a roll coater or a die coater, an extruder or a printing machine can be used.
　前記ポリマー（ａ）単体により易伸長性ポリマー母材形成用材料層を形成する場合には、例えば、支持体上に、所定量のポリマー（ａ）単体を置き、その上にさらに支持体（セパレータ等）を載せ、これを加熱下（ポリマーの溶融温度以上の温度）でプレスすることにより易伸長性ポリマー母材形成用材料層を形成できる。また、支持体上に、ポリマー（ａ）を押出成形することにより易伸長性ポリマー母材形成用材料層を形成できる。さらに、ポリマー（ａ）を用いて、適宜な成形法により別途易伸長性ポリマー母材形成用材料層となる層を作製しておき、これを支持体上に転写することにより易伸長性ポリマー母材形成用材料層を形成することもできる。 When the easily stretchable polymer base material forming material layer is formed of the polymer (a) alone, for example, a predetermined amount of the polymer (a) is placed on the support, and a support (separator) is further provided thereon. Etc.), and this is pressed under heating (at a temperature equal to or higher than the melting temperature of the polymer) to form an easily stretchable polymer base material forming material layer. Moreover, the easily extensible polymer base material forming material layer can be formed on the support by extruding the polymer (a). Furthermore, by using the polymer (a), a layer that becomes a material layer for forming an easily stretchable polymer base material is separately prepared by an appropriate molding method, and the layer is transferred onto a support to thereby easily stretch the polymer base material. A material forming material layer can also be formed.
　なお、易伸長性ポリマー母材形成用材料層の形成は、適宜な型を用いて行うこともできる。この場合には、前記形成用材料の粘度は前記範囲より低くてもよい。 In addition, formation of the material layer for easily stretchable polymer base material formation can also be performed using a suitable type | mold. In this case, the viscosity of the forming material may be lower than the above range.
　前記易伸長性ポリマー母材形成用材料層の厚みは、例えば、０．０１ｍｍ~１ｃｍであり、その上限は、好ましくは５ｍｍ、さらに好ましくは２ｍｍであり、下限は、好ましくは０．０３ｍｍ、さらに好ましくは０．０５ｍｍである。 The thickness of the easily stretchable polymer base material forming material layer is, for example, 0.01 mm to 1 cm. The upper limit is preferably 5 mm, more preferably 2 mm, and the lower limit is preferably 0.03 mm. Preferably it is 0.05 mm.
　次に、工程Ｂでは、前記易伸長性ポリマー母材形成用材料層の所定部位に、筒状難伸長性ポリマー部形成用材料を配する。筒状難伸長性ポリマー部形成用材料は、固体、液体、気体、溶液、分散液等の何れであってもよい。筒状難伸長性ポリマー部形成用材料としては、筒状難伸長性ポリマー部Ａを構成する材料（ポリマー材料）（ｂ）の前駆体（例えば、エネルギー線硬化性組成物）、筒状難伸長性ポリマー部Ａを構成する材料（ポリマー材料）（ｂ）自体、筒状難伸長性ポリマー部Ａを構成する材料（ポリマー材料）（ｂ）を含む溶液若しくは分散液などを用いることができる。 Next, in Step B, a cylindrical difficult-to-extend polymer part forming material is disposed on a predetermined portion of the easily-extensible polymer base material forming material layer. The material for forming the cylindrical difficult-to-extend polymer part may be any of solid, liquid, gas, solution, dispersion and the like. As a material for forming a cylindrical hardly stretchable polymer part, a precursor (for example, an energy beam curable composition) of the material (polymer material) (b) constituting the tubular hardly stretchable polymer part A, a cylindrical difficult stretch The material (polymer material) (b) itself constituting the conductive polymer part A, or a solution or dispersion containing the material (polymer material) (b) constituting the cylindrical difficult-to-extend polymer part A can be used.
　工程Ｂにおいて、筒状難伸長性ポリマー部形成用材料としては、筒状難伸長性ポリマー部Ａを、前記（ｉ）ホモポリマーのＴｇが５℃以上であるモノマーに由来する構成単位をポリマーの全構成単位に対して５０重量％以上含むポリマーを含有するポリマー材料で構成する場合には、該ホモポリマーのＴｇが５℃以上であるモノマーをモノマー全体の５０重量％以上含むモノマー成分、又はその部分重合物を含有する硬化性組成物（エネルギー線硬化性組成物等）を使用できる。この硬化性組成物は、通常、重合開始剤を含んでいる。 In step B, as the material for forming the cylindrical hardly-extensible polymer part, the cylindrical difficult-to-extend polymer part A is a structural unit derived from a monomer whose Tg of the homopolymer is 5 ° C. or higher. In the case of comprising a polymer material containing a polymer containing 50% by weight or more with respect to all the structural units, a monomer component containing 50% by weight or more of the monomer having a Tg of 5 ° C. or more of the homopolymer, or its A curable composition (such as an energy beam curable composition) containing a partial polymer can be used. This curable composition usually contains a polymerization initiator.
　筒状難伸長性ポリマー部Ａを、前記（ｉｉ）硬化性基を分子内に２以上有する多官能モノマーに由来する構成単位をポリマーの全構成単位に対して５０重量％以上含むポリマーを含有するポリマー材料で構成する場合には、筒状難伸長性ポリマー部形成用材料として、該硬化性基を分子内に２以上有する多官能モノマーを５０重量％以上含むモノマー成分、又はその部分重合物を含有する硬化性組成物（エネルギー線硬化性組成物等）を使用できる。この硬化性組成物は、通常、重合開始剤を含んでいる。 The cylindrical difficult-to-extend polymer part A contains (ii) a polymer containing 50% by weight or more of a structural unit derived from a polyfunctional monomer having two or more curable groups in the molecule based on the total structural unit of the polymer. When the polymer material is used, a monomer component containing 50% by weight or more of a polyfunctional monomer having two or more curable groups in the molecule as a material for forming a cylindrical difficult-to-extend polymer part, or a partial polymer thereof. The curable composition (energy beam curable composition etc.) to contain can be used. This curable composition usually contains a polymerization initiator.
　筒状難伸長性ポリマー部Ａを、前記（ｉｉｉ）フィラー含有ポリマー材料で構成する場合には、筒状難伸長性ポリマー部形成用材料として、フィラーを含有する分散液（水分散液、有機溶媒分散液等）、該フィラーと、筒状難伸長性ポリマー部を構成すべきポリマーに誘導できるモノマー（エネルギー線硬化性モノマー等）またはその部分重合物とを含む硬化性組成物、フィラーと、筒状難伸長性ポリマー部Ａを構成すべきポリマーに硬化又は架橋により誘導できる硬化又は架橋前ポリマーと架橋剤等との混合液、又はフィラー単体（粉体）等を使用できる。 When the cylindrical difficult-to-extend polymer part A is composed of the above-mentioned (iii) filler-containing polymer material, a dispersion liquid (an aqueous dispersion or an organic solvent) containing a filler is used as the cylindrical difficult-to-extend polymer part forming material. Dispersion, etc.), a curable composition containing the filler, and a monomer (energy ray curable monomer, etc.) or a partial polymer thereof that can be derived into a polymer that constitutes the cylindrical hardly extensible polymer part, a filler, and a cylinder A mixture of a pre-curing or cross-linking polymer that can be induced by curing or cross-linking and a cross-linking agent or the like, or a filler alone (powder) can be used.
　筒状難伸長性ポリマー部Ａを、前記（ｉｖ）引張弾性率が０．１ＭＰａ以上のポリマー材料で構成する場合には、筒状難伸長性ポリマー部形成用材料として、前記引張弾性率０．１ＭＰａ以上のポリマーに誘導できるモノマー（エネルギー線硬化性モノマー等）又はその部分重合物を含有する硬化性組成物（エネルギー線硬化性組成物等）を使用できる。 In the case where the cylindrical hardly extensible polymer part A is composed of the polymer material having (iv) a tensile elastic modulus of 0.1 MPa or more, the tensile elastic modulus of 0. A curable composition (such as an energy beam curable composition) containing a monomer (such as an energy beam curable monomer) that can be derived into a polymer of 1 MPa or more or a partial polymer thereof can be used.
　前記易伸長性ポリマー母材形成用材料層の所定部位に、筒状難伸長性ポリマー部形成用材料を配する方法（手段）としては、特に限定されず、例えば、（１）筒状難伸長性ポリマー部形成用材料を、易伸長性ポリマー母材形成用材料層の所定箇所に、上から、筒状難伸長性ポリマー部Ａの表面形状又は基材表面投影形状が所望の形状となるように、塗工、滴下、載置、打ち込み又は印刷する方法、（２）筒状難伸長性ポリマー部形成用材料を、液状の形態で、易伸長性ポリマー母材形成用材料層の所定箇所に、筒状難伸長性ポリマー部Ａの表面形状又は基材表面投影形状が所望の形状となるように、注入する方法、（３）前記易伸長性ポリマー母材形成用材料層を形成した支持体とは別の支持体上に、筒状難伸長性ポリマー部の形成材料を、筒状難伸長性ポリマー部Ａの表面形状又は基材表面投影形状が所望の形状となるように、塗工、滴下、載置又は印刷し、これを前記易伸長性ポリマー母材形成用材料層上へ転写する方法などが挙げられる。 There is no particular limitation on the method (means) for arranging the cylindrically difficult-to-extend polymer part forming material at a predetermined site of the easily-extensible polymer base material-forming material layer. For example, (1) cylindrically difficult-to-extend The surface shape of the cylindrical hardly extensible polymer portion A or the projected surface shape of the base material becomes a desired shape from above, at a predetermined position of the easily stretchable polymer base material forming material layer. Coating, dripping, placing, driving or printing, and (2) cylindrical hard-to-extend polymer part forming material in a liquid form at a predetermined position of the easily-extensible polymer base material forming material layer. , A method of injecting so that the surface shape of the cylindrical hardly extensible polymer portion A or the projected shape of the substrate surface is a desired shape, and (3) a support on which the material layer for forming the easily extensible polymer base material is formed. A material for forming the cylindrical difficult-to-extend polymer part on a support different from Coating, dripping, mounting or printing is performed so that the surface shape of the cylindrical hardly extensible polymer portion A or the projected shape of the substrate surface is a desired shape, and this is used as the material layer for forming the easily extensible polymer base material. Examples include a method of transferring up.
　筒状難伸長性ポリマー部形成用材料が液状である場合には、該液の粘度は、作業性等の観点から、塗工、滴下等する際の温度（例えば１０~４０℃の範囲内の所定温度、特に２５℃）において、例えば、１０~５００００ｍＰａ・ｓであり、その上限は、好ましくは３００００ｍＰａ・ｓ、さらに好ましくは２００００ｍＰａ・ｓであり、下限は、好ましくは２０ｍＰａ・ｓ、さらに好ましくは３０ｍＰａ・ｓである。この粘度が低すぎると所望の形状の筒状難伸長性ポリマー部Ａが得られにくくなり、逆に高すぎると塗工作業性が低下しやすくなる。 When the material for forming a cylindrical hardly extensible polymer part is in a liquid state, the viscosity of the liquid is the temperature at the time of coating, dripping, etc. from the viewpoint of workability and the like (for example, within a range of 10 to 40 ° C. At a predetermined temperature, particularly 25 ° C., for example, 10 to 50000 mPa · s, the upper limit is preferably 30000 mPa · s, more preferably 20000 mPa · s, and the lower limit is preferably 20 mPa · s, more preferably 30 mPa · s. If this viscosity is too low, it will be difficult to obtain a cylindrical difficult-to-extend polymer part A having a desired shape, and conversely if too high, the coating workability will tend to be reduced.
　塗工、滴下、載置、打ち込み、印刷、注入、転写は、特に限定されず、公知乃至慣用の方法で行うことができる。例えば、滴下は適宜な滴下装置、注入は、注射器等を使用できる。印刷としては、例えば、スクリーン印刷などが挙げられる。 Coating, dripping, placing, driving, printing, pouring, and transfer are not particularly limited, and can be performed by a known or common method. For example, an appropriate dropping device can be used for dropping, and a syringe or the like can be used for injection. Examples of printing include screen printing.
　前記易伸長性ポリマー母材形成用材料層の所定部位に配する筒状難伸長性ポリマー部形成用材料の種類、使用量、粘度等を選択、調整することにより、筒状難伸長性ポリマー部Ａの大きさ（面方向の大きさ及び高さ）をコントロールできる。筒状難伸長性ポリマー部Ａを複数形成する場合は、適宜な間隔をおいて、筒状難伸長性ポリマー部形成用材料を適用する。なお、筒状難伸長性ポリマー部形成用材料の滴下、注入箇所を規制する手段を用いることにより、筒状難伸長性ポリマー部Ａの形状を制御できる。筒状難伸長性ポリマー部Ａの大きさが比較的大きい場合は滴下法を用いることが多く、筒状難伸長性ポリマー部Ａの大きさが比較的小さい場合は注入法を用いることが多い。滴下法の場合は、滴下装置の先端部が易伸長性ポリマー母材形成用材料に接触しないため汚れないという利点がある。注入法の場合は、滴下法よりも筒状難伸長性ポリマー部形成用材料が易伸長性ポリマー母材形成用材料層に対して拡散しにくいという利点がある。 By selecting and adjusting the kind, amount of use, viscosity, etc. of the cylindrical difficult-to-extend polymer part forming material disposed in a predetermined portion of the easily-extensible polymer base material-forming material layer, the cylindrical difficult-to-extend polymer part The size of A (the size and height in the surface direction) can be controlled. In the case of forming a plurality of cylindrical difficult-to-extend polymer parts A, a cylindrical hard-to-extend polymer part forming material is applied at an appropriate interval. In addition, the shape of the cylindrical difficult-to-extend polymer part A can be controlled by using a means for regulating dropping and injection of the cylindrical hard-to-extend polymer part forming material. The drop method is often used when the size of the cylindrical difficult-to-extend polymer part A is relatively large, and the injection method is often used when the size of the cylindrical hardly-extensible polymer part A is relatively small. In the case of the dropping method, there is an advantage that the tip of the dropping device does not come into contact with the material for forming an easily stretchable polymer base material, so that it does not get dirty. In the case of the injection method, there is an advantage that the cylindrical hardly extensible polymer part forming material is less likely to diffuse into the easily extensible polymer base material forming material layer than the dropping method.
　なお、筒状難伸長性ポリマー部形成用材料として、筒状難伸長性ポリマー部Ａを構成する材料（ｂ）の前駆体であるエネルギー線硬化性組成物を用いる場合には、該エネルギー線硬化性組成物（塗布液）を易伸長性ポリマー母材形成用材料層の所定部位に配する際、エネルギー線硬化性組成物（塗布液）の周辺部（易伸長性ポリマー母材形成用材料層）への拡散を抑制するため、該エネルギー線硬化性組成物にポリマーを含有させるのが好ましい。特に、易伸長性ポリマー母材中に筒状難伸長性ポリマー部Ａを多数形成する場合には、塗布液を易伸長性ポリマー母材形成用材料層の所定部位に所定の個数配した後、エネルギー線を照射する工程に移行すると、初期に塗布液を配した箇所では、時間の経過により塗布液が周辺部に拡散し（滲み）、その状態で硬化して、所望する形状や大きさの筒状難伸長性ポリマー部Ａが得られなかったり、筒状難伸長性ポリマー部Ａの輪郭が鮮明でなくなったりすることがある。このような場合、エネルギー線硬化性組成物（塗布液）中にポリマーを含有させておくと、該塗布液中に含まれているモノマー等が周辺部（易伸長性ポリマー母材形成用材料層）へ拡散するのを抑制でき、多数の筒状難伸長性ポリマー部Ａを形成する場合でも、形状、大きさの揃った、輪郭が鮮明な筒状難伸長性ポリマー部Ａを形成することができる。この方法は、特に、エネルギー線硬化性組成物（塗布液）を易伸長性ポリマー母材形成用材料層の多数の所定部位に滴下により配する場合に大きな拡散抑制効果が得られる。 In addition, when using the energy ray curable composition which is a precursor of the material (b) which comprises the cylindrical difficulty extensible polymer part A as a material for cylindrical difficulty extensible polymer part formation, this energy ray hardening When disposing an adhesive composition (coating liquid) on a predetermined part of an easily stretchable polymer base material forming material layer, a peripheral portion of the energy ray curable composition (coating liquid) (easy stretchable polymer base material forming material layer) ) Is preferably contained in the energy ray-curable composition. In particular, when a large number of cylindrical difficult-to-extend polymer parts A are formed in the easily-extensible polymer base material, after a predetermined number of coating liquids are arranged in a predetermined part of the easily-extensible polymer base material forming layer, When shifting to the process of irradiating energy rays, the coating liquid diffuses to the peripheral part (bleeds) with the passage of time at the place where the coating liquid is initially disposed, and cures in that state to have a desired shape and size. The cylindrical difficult-to-extend polymer part A may not be obtained, or the outline of the cylindrical difficult-to-extend polymer part A may not be clear. In such a case, if a polymer is contained in the energy beam curable composition (coating liquid), the monomer and the like contained in the coating liquid are in the periphery (material layer for forming an easily extensible polymer base material). ) Can be suppressed, and even when a large number of cylindrically difficult-to-extend polymer parts A are formed, it is possible to form a cylindrically-extensible polymer part A having a uniform shape and size with a clear outline. it can. This method provides a great diffusion suppressing effect particularly when the energy beam curable composition (coating liquid) is disposed by dropping at a plurality of predetermined sites of the easily stretchable polymer base material forming material layer.
　前記エネルギー線硬化性組成物中に配合するポリマーの重量平均分子量としては、特に限定されないが、例えば１０００以上、好ましくは２０００以上、さらに好ましくは３０００以上である。ポリマーの重量平均分子量が低すぎると、拡散抑制効果が小さくなりやすい。また、ポリマーの重量平均分子量があまりに大きすぎると、組成物（塗布液）の粘度が高くなりすぎて塗布作業性が低下する場合がある。この観点からは、ポリマーの重量平均分子量の上限は、例えば、５００００００、好ましくは１００００００、さらに好ましくは１０００００である。前記エネルギー線硬化性組成物（塗布液）中のポリマーの含有量は、例えば５重量％以上、好ましくは１０重量％以上、さらに好ましくは２０重量％以上である。ポリマーの含有量が５重量％未満の場合には前記拡散抑制効果が小さい。また、ポリマーの含有量が多すぎると、エネルギー線硬化性組成物（塗布液）の粘度が高くなりすぎて塗布作業性が低下しやすくなる。この観点から、前記エネルギー線硬化性組成物（塗布液）中のポリマーの含有量の上限は、例えば９５重量％、好ましくは９０重量％、さらに好ましくは８５重量％である。 The weight average molecular weight of the polymer blended in the energy beam curable composition is not particularly limited, but is, for example, 1000 or more, preferably 2000 or more, and more preferably 3000 or more. If the weight average molecular weight of the polymer is too low, the diffusion suppressing effect tends to be small. On the other hand, if the weight average molecular weight of the polymer is too large, the viscosity of the composition (coating solution) becomes too high, and the coating workability may be reduced. From this viewpoint, the upper limit of the weight average molecular weight of the polymer is, for example, 5000000, preferably 1000000, and more preferably 100,000. The polymer content in the energy ray-curable composition (coating liquid) is, for example, 5% by weight or more, preferably 10% by weight or more, and more preferably 20% by weight or more. When the polymer content is less than 5% by weight, the diffusion suppressing effect is small. Moreover, when there is too much content of a polymer, the viscosity of an energy-beam curable composition (coating liquid) will become high too much, and coating workability | operativity will fall easily. From this viewpoint, the upper limit of the content of the polymer in the energy beam curable composition (coating liquid) is, for example, 95% by weight, preferably 90% by weight, and more preferably 85% by weight.
　前記エネルギー線硬化性組成物中に配合するポリマーとしては、筒状難伸長性ポリマー部Ａに要求される物性（特性）を損なわないポリマーであれば特に制限はなく、前記易伸長性ポリマー母材を構成するポリマーとして例示したポリマー、前記筒状難伸長性ポリマー部Ａを構成するポリマーとして例示したポリマー等のいずれであってもよいが、易伸長性ポリマー母材と筒状難伸長性ポリマー部Ａの一体性、密着性等の観点から、易伸長性ポリマー母材を構成するポリマーと同種のポリマー、或いは易伸長性ポリマー母材を構成するポリマーが有するポリマー鎖（主鎖又は側鎖）と同種のポリマー鎖を主鎖又は側鎖に有するポリマーであることが好ましい。 The polymer blended in the energy ray-curable composition is not particularly limited as long as it does not impair the physical properties (characteristics) required for the cylindrical difficult-to-extend polymer part A, and the easily-extensible polymer base material. The polymer exemplified as the polymer constituting the polymer, the polymer exemplified as the polymer constituting the cylindrical hardly extensible polymer part A, etc. may be used, but the easily extensible polymer base material and the cylindrical hardly extensible polymer part From the viewpoint of the integrity, adhesion, etc. of A, a polymer of the same type as the polymer constituting the easily extensible polymer matrix, or the polymer chain (main chain or side chain) of the polymer constituting the easily extensible polymer matrix A polymer having the same type of polymer chain in the main chain or side chain is preferred.
　前記エネルギー線硬化性組成物（塗布液）としては、該塗布液を易伸長性ポリマー母材形成用材料層上に滴下して（滴下量０．０３μＬ）から６０秒後における易伸長性ポリマー母材形成用材料層上の塗布液の直径が、滴下直後の塗布液の直径に対して１．２倍以下となるものが好ましく、１．１５倍以下となるものがより好ましい。また、該塗布液を易伸長性ポリマー母材形成用材料層上に滴下して（滴下量０．０３μＬ）から１２０秒後における易伸長性ポリマー母材形成用材料層上の塗布液の直径が、滴下直後の塗布液の直径に対して１．４倍以下となるものが好ましく、１．３倍以下となるものがより好ましい。滴下して６０秒後或いは１２０秒後の塗布液の前記直径が滴下直後の塗布液の直径と比較して大きくなるような塗布液からは、狙った形状のパターンシート［易伸長性ポリマー母材中に筒状難伸長性ポリマー部Ａが多数形成された（例えば、規則的パターンで形成された）シート状伸長性有機基材］が得られないことがある。 As the energy ray curable composition (coating liquid), the easy-extensible polymer matrix 60 seconds after dropping the coating liquid onto the material layer for forming an easily extensible polymer matrix (drop amount 0.03 μL). The diameter of the coating liquid on the material forming material layer is preferably 1.2 times or less, more preferably 1.15 times or less than the diameter of the coating liquid immediately after dropping. In addition, the diameter of the coating liquid on the easily stretchable polymer base material forming material layer 120 seconds after dropping the coating liquid on the easily stretchable polymer base material forming material layer (drop amount 0.03 μL) is Those that are 1.4 times or less the diameter of the coating solution immediately after dropping are preferred, and those that are 1.3 times or less are more preferred. From a coating solution in which the diameter of the coating solution after 60 seconds or 120 seconds after dropping is larger than the diameter of the coating solution immediately after dropping, a pattern sheet [easily stretchable polymer base material] In some cases, a sheet-like extensible organic base material in which a large number of cylindrical hardly extensible polymer portions A are formed (for example, formed in a regular pattern) may not be obtained.
　筒状難伸長性ポリマー部形成用材料の塗工、滴下、載置、打ち込み、印刷、注入又は転写の後、必要に応じて、筒状難伸長性ポリマー部形成用材料が易伸長性ポリマー母材形成用材料層の所定の深さまで浸透、移行、沈降するまで放置する。 After coating, dripping, placing, driving in, printing, pouring or transferring of the material for forming a cylindrical difficult-to-extend polymer part, if necessary, the material for forming a cylindrically-extensible polymer part is an easily extensible polymer base. It is allowed to stand until it penetrates, moves and settles to a predetermined depth of the material forming material layer.
　そして、工程Ｃでは、筒状難伸長性ポリマー部形成用材料を所定部位に配した易伸長性ポリマー母材形成用材料層に対して、反応、溶媒の乾燥除去処理、及び溶融・冷却処理（ホットメルト処理）から選択された少なくとも１つの処理を施して、易伸長性ポリマー母材中に筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されたシート状伸長性有機基材を得る。 In step C, the reaction, the solvent drying and removal treatment, and the melting / cooling treatment are performed on the easily stretchable polymer base material forming material layer in which the cylindrical hardly stretchable polymer portion forming material is arranged at a predetermined site. A sheet-like extensible organic base material in which a cylindrical hardly extensible polymer portion A is partially and integrally formed in an easily extensible polymer base material by performing at least one treatment selected from hot melt treatment) Get.
　反応としては、エネルギー線や熱による重合反応、硬化又は架橋反応等が挙げられる。溶媒の乾燥除去は、溶媒の種類等に応じて、適当な温度で行う。溶媒の乾燥除去は、常圧で行ってもよく、減圧下に行ってもよい。前記溶融は、易伸長性ポリマー母材形成用材料層と筒状難伸長性ポリマー部形成用材料がともに溶融する温度で行うのが好ましい。 Examples of the reaction include polymerization reaction by energy rays and heat, curing or cross-linking reaction. The solvent is removed by drying at an appropriate temperature according to the type of the solvent. The solvent may be removed by drying at normal pressure or under reduced pressure. The melting is preferably performed at a temperature at which both the easily stretchable polymer base material forming material layer and the cylindrical hardly stretchable polymer portion forming material are melted.
　本発明において、工程Ａにおいて用いる易伸長性ポリマー母材形成用材料の形態と、工程Ｂにおいて用いる筒状難伸長性ポリマー部形成用材料の形態との組合せは特に制限はなく、任意に組み合わせることができる。例えば、易伸長性ポリマー母材形成用材料として、エネルギー線硬化性材料［ポリマー（ａ）の液状前駆体（シロップ等）］を用いる場合、溶剤系材料［ポリマー（ａ）を含む溶液］を用いる場合、分散液系材料［ポリマー（ａ）を含むエマルション等］を用いる場合、ホットメルト性材料［ポリマー（ａ）単体］を用いる場合のそれぞれにおいて、筒状難伸長性ポリマー部形成用材料としては、溶剤系材料（ポリマー溶液）、分散液系材料（ポリマーエマルション等）、エネルギー線硬化性材料［ポリマーの液状前駆体（シロップ等）］、固体［ホットメルト性材料（ポリマー単体）、フィラー（粉体）等］などの何れの形態の材料を用いることもできる。より具体的には、前記易伸長性ポリマー母材形成用材料と前記筒状難伸長性ポリマー部形成用材料の形態は、エネルギー線硬化性材料（エネルギー線硬化性シロップ等）同士の組合せ、溶剤系材料（溶液）同士の組合せ、分散液系材料（エマルション等）同士の組合せ、ホットメルト性材料同士の組合せのほか、溶剤系材料（溶液）と分散液系材料（エマルション等）との組合せ（順序不同）、ホットメルト性材料と溶剤系材料（溶液）との組合せ（順序不同）、ホットメルト性材料と分散液系材料（エマルション等）との組合せ（順序不同）、溶剤系材料（溶液）とフィラー（粉体）との組合せ、分散液系材料（エマルション等）とフィラー（粉体）との組合せ、ホットメルト性材料とフィラー（粉体）との組合せなどの何れであってもよい。工程Ｃにおいて、それぞれの材料の形態に適した処理を行うことにより、易伸長性ポリマー母材中に筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されたシート状伸長性有機基材を得ることができる。 In the present invention, the combination of the form of the easily stretchable polymer base material forming material used in step A and the form of the cylindrical hardly stretchable polymer part forming material used in step B is not particularly limited, and may be arbitrarily combined. Can do. For example, when an energy ray curable material [liquid precursor of polymer (a) (syrup or the like)] is used as the material for forming an easily stretchable polymer base material, a solvent-based material [solution containing polymer (a)] is used. In the case of using a dispersion-based material [emulsion containing polymer (a), etc.] or in the case of using a hot-melt material [polymer (a) alone], , Solvent-based materials (polymer solutions), dispersion-based materials (polymer emulsions, etc.), energy ray-curable materials [polymeric liquid precursors (syrups, etc.)], solids [hot melt materials (polymer alone), fillers (powder) Any form of material such as (body) and the like] can be used. More specifically, the form of the easily stretchable polymer base material forming material and the cylindrical hardly stretchable polymer part forming material is a combination of energy ray curable materials (energy ray curable syrup, etc.), solvent Combinations of system materials (solutions), combinations of dispersion materials (emulsions, etc.), combinations of hot-melt materials, and combinations of solvent materials (solutions) and dispersion materials (emulsions, etc.) (In no particular order), a combination of a hot-melt material and a solvent-based material (solution) (no order), a combination of a hot-melt material and a dispersion-based material (emulsion, etc.) (in no particular order), a solvent-based material (solution) And a filler (powder), a dispersion material (emulsion, etc.) and a filler (powder), a hot-melt material and a filler (powder), etc. . In step C, a sheet-like stretchable organic material in which the cylindrical stretchable polymer portion A is partially and integrally formed in the stretchable polymer base material by performing a treatment suitable for the form of each material. A substrate can be obtained.
　なお、筒状難伸長性ポリマー部Ａと易伸長性ポリマー母材部の界面近傍において、組成及び／又は物性（伸び特性、硬度等）に関してグラデーションをなしているシート状伸長性有機基材は、例えば、易伸長性ポリマー母材形成用材料及び筒状難伸長性ポリマー部形成用材料として、互いに共通又は類似する材料（溶媒、モノマー等）を用いたり、互いに親和性のある材料（溶媒、モノマー等）を用いることにより製造することができる。具体的には、例えば、易伸長性ポリマー母材形成用材料及び筒状難伸長性ポリマー部形成用材料を、ともにアクリル系モノマーを含む材料（ポリマーの液状前駆体等）で構成することにより、上記のグラデーションを得ることができる。このようなグラデーションは、モノマー成分、溶媒等の拡散、移行と、その後の硬化、溶媒の乾燥除去等により形成される。従って該グラデーションを有するシート状伸長性有機基材のグラデーション部では、各部位［筒状難伸長性ポリマー部Ａ、易伸長性ポリマー母材部］の形成用材料から想定される組成とは異なるものとなる。なお、グラデーションの程度（幅）は、易伸長性ポリマー母材形成用材料及び筒状難伸長性ポリマー部形成用材料（溶媒、モノマー等）の種類や量により調整できる。また、前記のように、筒状難伸長性ポリマー部形成用材料としてエネルギー線硬化性組成物を用いる場合において、該エネルギー線硬化性組成物中にポリマーを配合する場合には、該ポリマーの種類、量、重量平均分子量等によりグラデーションの程度（幅）を調整することもできる。 In addition, in the vicinity of the interface between the cylindrical hardly extensible polymer part A and the easily extensible polymer base material part, the sheet-like extensible organic base material having a gradation regarding the composition and / or physical properties (elongation characteristics, hardness, etc.) For example, materials that are common or similar to each other (solvent, monomer, etc.) or materials that are compatible with each other (solvent, monomer) are used as the material for forming the easily stretchable polymer base material and the material for forming the cylindrical difficult stretchable polymer part. Etc.) can be used. Specifically, for example, by configuring both the easily stretchable polymer base material forming material and the cylindrical hardly stretchable polymer part forming material with materials containing acrylic monomers (polymer liquid precursors, etc.), The above gradation can be obtained. Such gradation is formed by diffusion and migration of monomer components, solvents, and the like, and subsequent curing, solvent removal, and the like. Therefore, the gradation part of the sheet-like extensible organic base material having the gradation is different from the composition assumed from the material for forming each part [tubular hardly extensible polymer part A, easily extensible polymer base part]. It becomes. In addition, the grade (width | variety) of gradation can be adjusted with the kind and quantity of the easily extensible polymer base material forming material and the cylindrical difficulty extensible polymer part forming material (solvent, monomer, etc.). In addition, as described above, in the case where an energy beam curable composition is used as the material for forming a cylindrical difficult-to-extend polymer part, when the polymer is blended in the energy beam curable composition, the type of the polymer The degree of gradation (width) can be adjusted by the amount, weight average molecular weight, and the like.
　なお、筒状難伸長性ポリマー部Ａの筒状の空洞部に当たる易伸長性ポリマー材料からなる領域内に、さらに、表面形状又はシート状伸長性有機基材表面を投影面としたときの投影形状が、略円形、略多角形、無定形、又は文字、記号若しくは数字を表す形状、輪帯状、又は線状である難伸長性ポリマー部Ｂを１又は２以上形成する場合、該難伸長性ポリマー部Ｂは、前記筒状難伸長性ポリマー部Ａを形成する場合と同様にして形成することができる。 In addition, in the area | region which consists of an easily extensible polymer material which hits the cylindrical cavity part of the cylindrical hardly extensible polymer part A, surface shape or projection shape when using a sheet-like extensible organic base material surface as a projection surface In the case of forming one or more hardly extensible polymer portions B that are substantially circular, substantially polygonal, amorphous, or in the form of letters, symbols or numbers, ring zones, or lines, The part B can be formed in the same manner as in the case of forming the cylindrical difficult-to-extend polymer part A.
　本発明のシート状伸長性有機基材の製造法においては、シート状伸長性有機基材を効率よく製造できる観点から、以下の態様（Ｉ）~（ＩＩＩ）が好ましい。 In the method for producing a sheet-like extensible organic substrate of the present invention, the following modes (I) to (III) are preferable from the viewpoint of efficiently producing a sheet-like extensible organic substrate.
　（Ｉ）工程Ａにおいて、支持体上に、前記ポリマー（ａ）の液状前駆体であるエネルギー線硬化性組成物により易伸長性ポリマー母材形成用材料層を形成し、工程Ｂにおいて、前記易伸長性ポリマー母材形成用材料層の所定部位に、筒状難伸長性ポリマー部Ａを構成する材料（ｂ）の前駆体であるエネルギー線硬化性組成物を配し、工程Ｃにおいて、前記材料（ｂ）の前駆体であるエネルギー線硬化性組成物を所定部位に配した易伸長性ポリマー母材形成用材料層にエネルギー線を照射し、前記２つのエネルギー線硬化性組成物を硬化させて、易伸長性ポリマー母材中に筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されたシート状伸長性有機基材を得る方法。 (I) In step A, an easily extensible polymer base material-forming material layer is formed on the support using an energy ray-curable composition that is a liquid precursor of the polymer (a). An energy ray-curable composition that is a precursor of the material (b) constituting the cylindrical difficult-to-extend polymer part A is disposed at a predetermined portion of the extensible polymer base material forming material layer. The energy beam curable composition that is the precursor of (b) is irradiated with energy rays on the easily stretchable polymer base material forming material layer arranged at a predetermined site, and the two energy beam curable compositions are cured. The method of obtaining the sheet-like extensible organic base material in which the cylindrical difficulty extensible polymer part A was partially and integrally formed in the easily extensible polymer matrix.
　（ＩＩ）工程Ａにおいて、支持体上に、前記ポリマー（ａ）を含む溶液若しくは分散液により易伸長性ポリマー母材形成用材料層を形成し、工程Ｂにおいて、前記易伸長性ポリマー母材形成用材料層の所定部位に、筒状難伸長性ポリマー部をＡ構成する材料（ｂ）［例えば、ポリマー、フィラー（粉体）等］又は該材料（ｂ）を含む溶液若しくは分散液を配し、工程Ｃにおいて、筒状難伸長性ポリマー部Ａを構成する材料（ｂ）又は該材料（ｂ）を含む溶液若しくは分散液を所定部位に配した易伸長性ポリマー母材形成用材料層に対し、溶媒の乾燥除去処理を施して、易伸長性ポリマー母材中に筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されたシート状伸長性有機基材を得る方法。 (II) In step A, an easily stretchable polymer base material forming material layer is formed on the support using a solution or dispersion containing the polymer (a), and in step B, the easily stretchable polymer base material is formed. The material (b) [for example, polymer, filler (powder), etc.] constituting the cylindrical difficult-to-extend polymer part or a solution or dispersion containing the material (b) is disposed at a predetermined portion of the material layer for use. In the step C, the material (b) constituting the cylindrical hardly extensible polymer part A or the easily extensible polymer base material forming material layer in which the solution or dispersion containing the material (b) is disposed at a predetermined site A method for obtaining a sheet-like extensible organic base material in which a cylindrical hardly extensible polymer portion A is partially and integrally formed in an easily extensible polymer base material by subjecting the solvent to dry removal treatment.
　（ＩＩＩ）工程Ａにおいて、支持体上に、前記ポリマー（ａ）単体により易伸長性ポリマー母材形成用材料層を形成し、工程Ｂにおいて、前記易伸長性ポリマー母材形成用材料層の所定部位に、筒状難伸長性ポリマー部Ａを構成する材料（ｂ）［例えば、ポリマー、フィラー（粉体）等］を配し、工程Ｃにおいて、筒状難伸長性ポリマー部Ａを構成する材料（ｂ）を所定部位に配した易伸長性ポリマー母材形成用材料層に対し、溶融・冷却処理（ホットメルト処理）を施して、易伸長性ポリマー母材（Ａ）中に筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されたシート状伸長性有機基材を得る方法。 (III) In step A, an easily stretchable polymer base material forming material layer is formed on the support by the polymer (a) alone, and in step B, the easily stretchable polymer base material forming material layer is predetermined. The material (b) [for example, polymer, filler (powder), etc.] constituting the cylindrical hardly extensible polymer part A is arranged at the site, and the material constituting the cylindrical hardly extensible polymer part A in Step C The material layer for forming an easily stretchable polymer base material (b) arranged at a predetermined site is subjected to a melting / cooling process (hot melt process) to form a cylindrical difficult stretch in the easily stretchable polymer base material (A). To obtain a sheet-like extensible organic base material in which the conductive polymer part A is partially and integrally formed.
　本発明のシート状伸長性有機基材は、より具体的には、例えば、下記の工程を経ることにより製造できる。
　工程Ａ１：支持体上に易伸長性ポリマー母材形成用エネルギー線硬化性組成物層を形成する工程
　工程Ｂ１：前記易伸長性ポリマー母材形成用エネルギー線硬化性組成物層の所定部位に、筒状難伸長性ポリマー部Ａの表面形状又は基材表面投影形状が所望の形状となるように、筒状難伸長性ポリマー部形成用エネルギー線硬化性組成物を配する（含有させる）工程
　工程Ｃ１：前記筒状難伸長性ポリマー部形成用エネルギー線硬化性組成物を配した易伸長性ポリマー母材形成用エネルギー線硬化性組成物層にエネルギー線を照射して、前記筒状難伸長性ポリマー部形成用エネルギー線硬化性組成物及び易伸長性ポリマー母材形成用エネルギー線硬化性組成物層を硬化させて、易伸長性ポリマー母材中に筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成された伸長性を有するシート状有機基材を得る工程 More specifically, the sheet-like extensible organic substrate of the present invention can be produced, for example, through the following steps.
Step A1: Step of forming an easily extensible polymer matrix-forming energy beam curable composition layer on a support Step B1: In a predetermined part of the easily extensible polymer matrix-forming energy beam curable composition layer, The step of arranging (containing) the energy ray-curable composition for forming a cylindrical difficult-to-extend polymer part so that the surface shape of the cylindrical difficult-to-extend polymer part A or the projected shape of the substrate surface becomes a desired shape. C1: An energy ray curable composition layer for forming an easily extensible polymer base material in which the energy ray curable composition for forming a cylindrical hardly extensible polymer part is disposed, and then irradiating the energy ray to the cylindrical difficult extensible property. The energy ray curable composition for forming a polymer part and the energy ray curable composition layer for forming an easily extensible polymer matrix are cured, and the cylindrical hardly extensible polymer part A is partially in the easily extensible polymer matrix. And Obtaining a sheet-shaped organic substrate having a body-formed extensibility
　この方法は、上記（Ｉ）の態様の具体例であり、図４はその概略説明図（断面図）である。図４の（ａ）は工程Ａ１、（ｂ）は工程Ｂ１、（ｃ）、（ｄ）、（ｅ）、（ｆ）［又は、（ｄ′）、（ｅ′）、（ｆ）］は工程Ｃ１に該当する。 This method is a specific example of the above aspect (I), and FIG. 4 is a schematic explanatory view (sectional view). In FIG. 4, (a) is a process A1, (b) is a process B1, (c), (d), (e), (f) [or (d '), (e'), (f)] Corresponds to step C1.
　工程Ａ１では、支持体４上に易伸長性ポリマー母材形成用エネルギー線硬化性組成物層２０を形成する。支持体４としては前記のものを使用できる。 In step A1, the energy ray-curable composition layer 20 for forming an easily extensible polymer base material is formed on the support 4. As the support 4, those described above can be used.
　前記易伸長性ポリマー母材形成用エネルギー線硬化性組成物層２０は、例えば、前記のポリウレタン鎖、ポリウレア鎖、ポリウレタンウレア鎖、ポリオレフィン鎖（特に、ポリジエン鎖）、シリコーン鎖、ポリエステル鎖、ポリエーテル鎖、ポリアミド鎖、ポリスチレン系ポリマー鎖及びポリアクリル鎖からなる群より選択される少なくとも１種のポリマー鎖を有し、且つ主鎖又は側鎖にエネルギー線硬化性基Ａ１を有する硬化性ポリマーＰ、又は該硬化性ポリマーＰとエネルギー線硬化性基Ａ２を有する硬化性モノマーＭとの混合物、及び光重合開始剤を含むエネルギー線硬化性組成物を支持体４上に塗工することにより形成できる。 The energy-extensible curable composition layer 20 for forming an easily stretchable polymer base material includes, for example, the polyurethane chain, polyurea chain, polyurethane urea chain, polyolefin chain (particularly, polydiene chain), silicone chain, polyester chain, and polyether. A curable polymer P having at least one polymer chain selected from the group consisting of a chain, a polyamide chain, a polystyrene polymer chain, and a polyacryl chain, and having an energy ray-curable group A 1 in the main chain or side chain Or a mixture of the curable polymer P and a curable monomer M having an energy beam curable group A 2 and an energy beam curable composition containing a photopolymerization initiator are coated on the support 4. it can.
　前記硬化性組成物には、必要に応じて溶剤を添加してもよいが、後で溶剤を除去する工程が増えるので、溶剤を使用しないのが好ましい。また、前記硬化性組成物には、熱による重合を防止するため、必要に応じて重合禁止剤を添加してもよい。 In the curable composition, a solvent may be added as necessary, but it is preferable not to use a solvent because a step of removing the solvent later increases. Moreover, in order to prevent the superposition | polymerization by a heat | fever, you may add a polymerization inhibitor to the said curable composition as needed.
　前記硬化性組成物はシロップ状であるのが好ましい。前記硬化性組成物の粘度、塗工方法は前記と同様である。なお、易伸長性ポリマー母材形成用エネルギー線硬化性組成物層２０の形成は、適宜な型を用いて行うこともできる。この場合には、前記硬化性組成物の粘度は前記範囲より低くてもよい。 The curable composition is preferably syrup-like. The viscosity of the curable composition and the coating method are the same as described above. In addition, formation of the energy-beam curable composition layer 20 for easily extensible polymer base material formation can also be performed using a suitable type | mold. In this case, the viscosity of the curable composition may be lower than the above range.
　前記易伸長性ポリマー母材形成用エネルギー線硬化性組成物層２０の厚みは前記と同様である。 The thickness of the energy-beam curable composition layer 20 for forming the easily stretchable polymer base material is the same as described above.
　工程Ｂ１では、前記易伸長性ポリマー母材形成用エネルギー線硬化性組成物層２０中に、筒状難伸長性ポリマー部形成用エネルギー線硬化性組成物３０を配する（含有させる）。 In Step B1, the energy ray-curable composition 30 for forming a cylindrical difficult-to-extend polymer part is disposed (included) in the energy-ray-curable composition layer 20 for forming an easily extensible polymer base material.
　工程Ｂ１は、例えば、前記ホモポリマーのＴｇが５℃以上（より好ましくは１５℃以上、さらに好ましくは５０℃以上）であるモノマー［特に、（メタ）アクリル系モノマー］を５０重量％以上（より好ましくは６０重量％以上、さらに好ましくは８０重量％以上）含むモノマー成分、或いは硬化性基を分子内に２以上有する多官能モノマーを５０重量％以上（より好ましくは６０重量％以上、さらに好ましくは８０重量％以上）含むモノマー成分と、光重合開始剤とを含有するエネルギー線硬化性組成物を、前記易伸長性ポリマー母材形成用エネルギー線硬化性組成物層２０の所定箇所に上から添加（滴下）したり、前記易伸長性ポリマー母材形成用エネルギー線硬化性組成物層２０中の所定箇所に注入したりすることにより行うことができる。また、前記モノマー成分と、光重合開始剤とを含有するエネルギー線硬化性組成物を塗工・滴下した支持体から前記易伸長性ポリマー母材形成用エネルギー線硬化性組成物層２０上へ転写することによっても行うことができる。 In the step B1, for example, a monomer [particularly, a (meth) acrylic monomer] having a Tg of the homopolymer of 5 ° C. or higher (more preferably 15 ° C. or higher, more preferably 50 ° C. or higher) is 50% by weight or more (more A monomer component containing preferably 60% by weight or more, more preferably 80% by weight or more, or a polyfunctional monomer having two or more curable groups in the molecule is 50% by weight or more (more preferably 60% by weight or more, more preferably 80% by weight or more) An energy ray-curable composition containing a monomer component and a photopolymerization initiator is added to a predetermined portion of the easily extensible polymer base material forming energy ray-curable composition layer 20 from above. (Dropping) or by injecting into a predetermined location in the energy-beam curable composition layer 20 for forming the easily stretchable polymer base material. Kill. Also, transfer onto the energy ray curable composition layer 20 for forming an easily extensible polymer base material from a support on which an energy ray curable composition containing the monomer component and a photopolymerization initiator is coated and dropped. This can also be done.
　前記筒状難伸長性ポリマー部形成用エネルギー線硬化性組成物３０はシロップ状であるのが好ましい。筒状難伸長性ポリマー部形成用エネルギー線硬化性組成物３０の粘度は、作業性等の観点から、塗工する際の温度（例えば１０~４０℃の範囲内の所定温度、特に２５℃）において、例えば、１０~５００００ｍＰａ・ｓであり、その上限は、好ましくは３００００ｍＰａ・ｓ、さらに好ましくは２００００ｍＰａ・ｓであり、下限は、好ましくは２０ｍＰａ・ｓ、さらに好ましくは３０ｍＰａ・ｓである。この粘度が低すぎると所望の形状が得られにくくなり、逆に高すぎると塗工作業性が低下しやすくなる。 It is preferable that the energy ray-curable composition 30 for forming a cylindrical difficult-to-extend polymer part is in a syrup shape. The viscosity of the energy ray-curable composition 30 for forming a cylindrical difficult-to-extend polymer part is the temperature at the time of coating (for example, a predetermined temperature within a range of 10 to 40 ° C., particularly 25 ° C.) from the viewpoint of workability and the like. The upper limit is preferably 30000 mPa · s, more preferably 20000 mPa · s, and the lower limit is preferably 20 mPa · s, more preferably 30 mPa · s. If the viscosity is too low, it is difficult to obtain a desired shape.
　筒状難伸長性ポリマー部形成用エネルギー線硬化性組成物３０の添加、注入方法は特に限定されず、例えば、注射器、適宜な滴下装置等を使用できる。また、筒状難伸長性ポリマー部形成用エネルギー線硬化性組成物３０の転写方法は特に限定されず、例えば、グラビアコーターなどの凹版塗工機を用いる方法、筒状難伸長性ポリマー部形成用エネルギー線硬化性組成物３０を塗工・滴下した支持体と伸長性ポリマー母材形成用エネルギー線硬化性組成物層２０を貼り合わせる方法等を使用できる。 The addition and injection method of the energy ray-curable composition 30 for forming a cylindrical difficult-to-extend polymer part is not particularly limited, and for example, a syringe, an appropriate dropping device, or the like can be used. Moreover, the transfer method of the energy ray-curable composition 30 for forming a cylindrical hardly extensible polymer part is not particularly limited. For example, a method using an intaglio coating machine such as a gravure coater, for forming a cylindrical hardly extensible polymer part The support etc. which apply | coated and dripped the energy-beam curable composition 30 and the method of bonding the energy-beam curable composition layer 20 for extensible polymer base material formation etc. can be used.
　筒状難伸長性ポリマー部形成用エネルギー線硬化性組成物３０の使用量及び粘度を調整することにより、硬化後の筒状難伸長性ポリマー部Ａ３の大きさ（面方向の大きさ及び高さ）をコントロールできる。筒状難伸長性ポリマー部Ａ３を複数形成する場合は、適宜な間隔をおいて、筒状難伸長性ポリマー部形成用エネルギー線硬化性組成物３０を適用する。なお、筒状難伸長性ポリマー部形成用エネルギー線硬化性組成物３０の添加又は注入箇所を規制する手段を用いることにより、硬化後の筒状難伸長性ポリマー部Ａ３の形状を制御することができる。 By adjusting the amount of use and viscosity of the energy ray-curable composition 30 for forming the cylindrical hardly extensible polymer part, the size (size and height in the plane direction) of the cylindrical hardly extensible polymer part A3 after curing is adjusted. ) Can be controlled. When a plurality of cylindrical hardly extensible polymer portions A3 are formed, the energy ray curable composition 30 for forming a cylindrical hardly extensible polymer portion is applied at an appropriate interval. In addition, it is possible to control the shape of the cylindrical difficult-to-extend polymer part A3 after curing by using means for regulating the addition or injection of the energy ray-curable composition 30 for forming the cylindrical hardly-extensible polymer part. it can.
　工程Ｃ１では、前記筒状難伸長性ポリマー部形成用エネルギー線硬化性組成物３０を含有させた易伸長性ポリマー母材形成用エネルギー線硬化性組成物層２０にエネルギー線を照射して、前記筒状難伸長性ポリマー部形成用エネルギー線硬化性組成物３０及び易伸長性ポリマー母材形成用エネルギー線硬化性組成物層２０を硬化させ、易伸長性ポリマー母材２中に筒状難伸長性ポリマー部Ａ３が部分的に且つ一体的に形成された伸長性を有するシート状有機基材を得る。 In step C1, the energy ray-curable composition layer 20 for forming an easily extensible polymer base material containing the energy ray-curable composition 30 for forming a cylindrical hardly extensible polymer portion is irradiated with energy rays, The energy ray curable composition 30 for forming a cylindrical hardly extensible polymer part and the energy ray curable composition layer 20 for forming an easily extensible polymer base material are cured, and the cylindrical difficult extension in the easily extensible polymer base material 2 is cured. The sheet-like organic base material which has the extensibility in which the property polymer part A3 was partially and integrally formed is obtained.
　図４ではエネルギー線として紫外線（ＵＶ）を用いているが、前記のように、α線、β線、γ線、中性子線、電子線などの電離性放射線や、可視光線であってもよい。 In FIG. 4, ultraviolet rays (UV) are used as energy rays, but as described above, ionizing radiation such as α rays, β rays, γ rays, neutron rays, electron rays, or visible rays may be used.
　エネルギー線の照射エネルギー、照射時間、照射方法などは特に限定されず、光重合開始剤を活性化させて、モノマー成分の反応を生じさせることができればよい。 The irradiation energy, irradiation time, irradiation method and the like of the energy beam are not particularly limited as long as the photopolymerization initiator can be activated to cause the monomer component to react.
　エネルギー線の照射装置としては、慣用のものを使用できる。例えば、紫外線を照射する場合には、水銀灯、蛍光灯、ナトリウムランプ、メタルハライドランプ、キセノンランプ、ネオン管、ネオンランプ、高輝度放電灯などを用いることができる。 As the energy beam irradiation device, a conventional device can be used. For example, when irradiating ultraviolet rays, a mercury lamp, a fluorescent lamp, a sodium lamp, a metal halide lamp, a xenon lamp, a neon tube, a neon lamp, a high-intensity discharge lamp, or the like can be used.
　エネルギー線照射の際、酸素による硬化阻害を防止する目的や、表面を平滑にする目的のため、前記筒状難伸長性ポリマー部形成用エネルギー線硬化性組成物３０を含有させた易伸長性ポリマー母材形成用エネルギー線硬化性組成物層２０の表面にカバーフィルム５を積層してもよい。カバーフィルム５としては、前記支持体４と同様のセパレータなどを使用できる。カバーフィルム５の積層は、例えば、ハンドローラー等を用いて行うことができる。 An easily extensible polymer containing the energy ray curable composition 30 for forming a cylindrical hardly extensible polymer portion for the purpose of preventing curing inhibition by oxygen and the purpose of smoothing the surface during irradiation with energy rays The cover film 5 may be laminated on the surface of the base material forming energy beam curable composition layer 20. As the cover film 5, the same separator as the support 4 can be used. Lamination | stacking of the cover film 5 can be performed using a hand roller etc., for example.
　エネルギー線照射は数段階に分けて行ってもよい。例えば、紫外線を照射する場合、図４の（ｃ）に示すように、予め高い照度（例えば、５０~１０００ｍＷ／ｃｍ２）にて短時間照射（例えば、積算照射量１０~１０００ｍＪ／ｃｍ２）した後、図４の（ｄ）に示すように、前記カバーフィルム５を積層し、その後、図４の（ｅ）に示すように、低い照度（例えば、１~４０ｍＷ／ｃｍ２）にて長時間照射（例えば、積算照射量５００~１００００ｍＪ／ｃｍ２）してもよい。このように、エネルギー線照射を数段階に分けて照射することにより、ハンドローラーによるカバーフィルム５の積層時の作業性を向上することができる。図中、２００は部分硬化した易伸長性ポリマー母材形成用エネルギー線硬化性組成物層であり、３００は部分硬化した筒状難伸長性ポリマー部形成用エネルギー線硬化性組成物である。 Energy beam irradiation may be performed in several stages. For example, when irradiated with ultraviolet rays, as shown in FIG. 4 (c), advance high illuminance (e.g., 50 ~ 1000mW / cm 2) irradiation briefly at (e.g., integrated radiation, 10 ~ 1000mJ / cm 2) After that, as shown in FIG. 4 (d), the cover film 5 is laminated, and then, as shown in FIG. 4 (e), it is long with a low illuminance (for example, 1 to 40 mW / cm 2 ). Time irradiation (for example, an integrated dose of 500 to 10,000 mJ / cm 2 ) may be performed. Thus, the workability at the time of lamination | stacking of the cover film 5 by a hand roller can be improved by dividing energy beam irradiation in several steps. In the figure, 200 is a partially cured energy ray-curable composition layer for forming an easily extensible polymer base material, and 300 is a partially cured energy ray curable composition for forming a cylindrical hardly extensible polymer portion.
　エネルギー線照射を１段で行う場合には、例えば、工程Ｂ１の後、図４の（ｄ′）に示すように、前記筒状難伸長性ポリマー部形成用エネルギー線硬化性組成物３０を含有させた易伸長性ポリマー母材形成用エネルギー線硬化性組成物層２０の表面にカバーフィルム５を積層し、図４の（ｅ′）に示すように紫外線を照射してもよい。この場合の紫外線の照度は、例えば１~４０ｍＷ／ｃｍ２、積算照射量は、例えば５００~１００００ｍＪ／ｃｍ２である。 In the case where the energy beam irradiation is performed in a single stage, for example, after the step B1, as shown in FIG. The cover film 5 may be laminated on the surface of the energy ray-curable composition layer 20 for forming an easily stretchable polymer base material, and irradiated with ultraviolet rays as shown in FIG. In this case, the illuminance of ultraviolet rays is, for example, 1 to 40 mW / cm 2 , and the integrated irradiation amount is, for example, 500 to 10000 mJ / cm 2 .
　上記のようにして筒状難伸長性ポリマー部形成用エネルギー線硬化性組成物３０及び易伸長性ポリマー母材形成用エネルギー線硬化性組成物層２０を硬化させた後、図４の（ｆ）に示されるように、必要に応じてカバーフィルム５、支持体４を剥離し、必要に応じて適宜な大きさに切断し、シート状伸長性有機基材１として使用に供される。切断操作はカバーフィルム５や支持体４の剥離前に行ってもよい。 After the energy ray-curable composition 30 for forming a cylindrical hardly extensible polymer portion and the energy ray-curable composition layer 20 for forming an easily extensible polymer base material are cured as described above, (f) in FIG. As shown in FIG. 4, the cover film 5 and the support 4 are peeled off as necessary, cut into an appropriate size as necessary, and used as the sheet-like extensible organic substrate 1. The cutting operation may be performed before the cover film 5 or the support 4 is peeled off.
　また、本発明のシート状伸長性有機基材は、より具体的に、下記の工程を経ることにより製造することもできる。
　工程Ａ２：支持体上に易伸長性ポリマー母材を構成するポリマーａを含む溶液又は分散液を塗工して、易伸長性ポリマー母材形成用材料層を形成する工程
　工程Ｂ２：前記易伸長性ポリマー母材形成用材料層の所定部位に、筒状難伸長性ポリマー部を構成するポリマーを含有する溶液若しくは分散液、又は筒状難伸長性ポリマー部Ａを構成するフィラー（粉体）を、筒状難伸長性ポリマー部Ａの表面形状又は基材表面投影形状が所望の形状となるように、塗工、滴下、載置、打ち込み、印刷等により配する（含有させる）工程
　工程Ｃ２：前記筒状難伸長性ポリマー部Ａを構成するポリマーを含有する溶液若しくは分散液、又は筒状難伸長性ポリマー部Ａを構成するフィラー（粉体）を配した易伸長性ポリマー母材形成用材料層を乾燥して、溶媒を除去し、易伸長性ポリマー母材中に筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成された伸長性を有するシート状有機基材を得る工程 In addition, the sheet-like extensible organic base material of the present invention can be more specifically manufactured through the following steps.
Step A2: A step of coating a solution or dispersion containing polymer a constituting the easily stretchable polymer matrix on the support to form a material layer for easily stretchable polymer matrix formation Step B2: The easy stretch A solution or dispersion containing a polymer constituting the cylindrical hardly extensible polymer part or a filler (powder) constituting the cylindrical hardly extensible polymer part A at a predetermined portion of the material layer for forming the porous polymer base material The step of arranging (including) by coating, dripping, placing, driving in, printing or the like so that the surface shape of the cylindrical difficult-to-extend polymer part A or the projected shape of the substrate surface becomes a desired shape Step C2: A material for forming an easily stretchable polymer base material provided with a solution or dispersion containing a polymer constituting the cylindrical hardly extensible polymer part A or a filler (powder) constituting the cylindrical hardly extensible polymer part A Dry the layer and dissolve It was removed to obtain a sheet-shaped organic substrate having elongation properties of the tubular flame stretch polymer unit A to easily extensible polymer matrix is partially and integrally formed
　この方法は、上記（ＩＩ）の態様の具体例であり、図５はその概略説明図（断面図）である。図５の（ｇ）は工程Ａ２、（ｈ）は工程Ｂ２、（ｉ）、（ｊ）は工程Ｃ２に相当する。符号２１は易伸長性ポリマー母材を構成するポリマーを含む溶液又は分散液からなる層（易伸長性ポリマー母材形成用材料層）、符号３１は筒状難伸長性ポリマー部を構成するポリマーを含有する溶液若しくは分散液、又は筒状難伸長性ポリマー部を構成するフィラー（粉体）を示す。符号１、２、３、４は前記と同じである。 This method is a specific example of the aspect (II) above, and FIG. 5 is a schematic explanatory view (cross-sectional view) thereof. In FIG. 5, (g) corresponds to step A2, (h) corresponds to step B2, and (i) and (j) correspond to step C2. Reference numeral 21 denotes a layer (material layer for forming an easily extensible polymer base material) made of a solution or dispersion containing a polymer constituting the easily extensible polymer matrix, and reference numeral 31 denotes a polymer constituting the cylindrical hardly extensible polymer portion. The filler (powder) which comprises the solution or dispersion liquid to contain or a cylindrical difficulty extensible polymer part is shown. Reference numerals 1, 2, 3, and 4 are the same as described above.
　さらに、本発明のシート状伸長性有機基材は、より具体的に、下記の工程を経ることにより製造することもできる。
　工程Ａ３：支持体上に易伸長性ポリマー母材を構成するポリマーａを、熱プレス、押出成形等によりシート化して、易伸長性ポリマー母材形成用材料層を形成する工程
　工程Ｂ３：前記易伸長性ポリマー母材形成用材料層の所定部位に、筒状難伸長性ポリマー部Ａ構成するポリマー又はフィラー（粉体）を、筒状難伸長性ポリマー部Ａの表面形状又は基材表面投影形状が所望の形状となるように、載置又は滴下（溶融物）等により配する（含有させる）工程
　工程Ｃ３：前記筒状難伸長性ポリマー部を構成するポリマー又はフィラー（粉体）を配した易伸長性ポリマー母材形成用材料層を加熱溶融した後、冷却して、易伸長性ポリマー母材中に筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成された伸長性を有するシート状有機基材を得る工程 Furthermore, the sheet-like extensible organic base material of the present invention can be more specifically manufactured through the following steps.
Step A3: Step of forming a material layer for forming an easily stretchable polymer base material by forming the polymer a constituting the easily stretchable polymer base material on a support by sheeting by hot pressing, extrusion molding or the like Step B3: The polymer or filler (powder) constituting the cylindrical difficult-to-extend polymer part A is applied to a predetermined portion of the extensible polymer base material forming material layer, and the surface shape of the cylindrical difficult-to-extend polymer part A or the projected surface of the base material Is placed (added) by placing or dropping (melt) or the like so as to have a desired shape. Step C3: A polymer or filler (powder) constituting the cylindrical difficult-to-extend polymer part is placed. After the material layer for forming an easily stretchable polymer base material is heated and melted, it is cooled, and the stretchability in which the cylindrical difficult stretchable polymer portion A is partially and integrally formed in the easily stretchable polymer base material is obtained. Obtain a sheet-like organic base material A process
　この方法は、上記（ＩＩＩ）の態様の具体例であり、図６はその概略説明図（断面図）である。図６の（ｋ）は工程Ａ３、（ｌ）は工程Ｂ３、（ｍ）、（ｎ）は工程Ｃ３に該当する。符号２２は易伸長性ポリマー母材を構成するポリマーからなるシート（易伸長性ポリマー母材形成用材料層）、符号３２は筒状難伸長性ポリマー部Ａを構成するポリマー又はフィラー（粉体）を示す。符号１、２、３、４は前記と同じである。 This method is a specific example of the above aspect (III), and FIG. 6 is a schematic explanatory view (cross-sectional view) thereof. 6K corresponds to the step A3, (l) corresponds to the step B3, and (m) and (n) correspond to the step C3. Reference numeral 22 denotes a sheet (material layer for forming an easily extensible polymer base material) made of a polymer constituting the easily extensible polymer matrix, and reference numeral 32 denotes a polymer or filler (powder) constituting the cylindrical hardly extensible polymer portion A. Indicates. Reference numerals 1, 2, 3, and 4 are the same as described above.
　こうして得られるシート状伸長性有機基材１は、形状不変部を有する伸長性部材（又は、形状不変部を有する伸縮性部材）として、エレクトロニクス製品（トランジスタ、集積回路、コンデンサ、センサ、アクチュエータ等）用部材、オプティカル製品（ディスプレイ、照明、光導波回路等）用部材、オプトエレクトロニクス製品（発光ダイオード、フォトダイオード、太陽電池等）用部材、カーエレクトロニクス製品用部材、家電製品用部材、住宅設備用部材、建材、バンド部材、結束用部材、衛生用品、衣料品の部分、湿布剤の基布等として利用できる。また、筒状難伸長性ポリマー部がシート状伸長性有機基材の一方の表面から他方の表面に至るまで連続して形成され（貫通しており）、且つ筒状難伸長性ポリマー部が導電性フィラーを含有している場合には、例えば、異方導電シート、オンチップで導通試験可能なダイシングテープ又はその基材等として使用できる。さらに、筒状難伸長性ポリマー部がシート状伸長性有機基材の一方の表面から他方の表面に至るまで連続して形成され（貫通しており）、且つ筒状難伸長性ポリマー部が熱伝導性フィラーを含有している場合には、例えば、伸長又は伸縮可能な伝熱シート等として使用できる。 The sheet-like extensible organic base material 1 obtained in this way is an electronic product (transistor, integrated circuit, capacitor, sensor, actuator, etc.) as an extensible member having a shape-invariant portion (or an elastic member having a shape-invariant portion). Materials, optical products (displays, lighting, optical waveguide circuits, etc.), optoelectronics products (light emitting diodes, photodiodes, solar cells, etc.), car electronics products, home appliances, housing equipment It can be used as a building material, a band member, a binding member, a sanitary article, a clothing part, a base material for a poultice. In addition, the cylindrical difficult-to-extend polymer part is continuously formed (penetrated) from one surface of the sheet-like extensible organic base to the other surface, and the cylindrical difficult-to-extend polymer part is electrically conductive. In the case of containing a conductive filler, it can be used as, for example, an anisotropic conductive sheet, a dicing tape capable of conducting an on-chip conduction test, or a base material thereof. Furthermore, the cylindrical difficult-to-extend polymer part is continuously formed (penetrated) from one surface of the sheet-like extensible organic base material to the other surface, and the cylindrical difficult-to-extend polymer part is heated. When it contains a conductive filler, it can be used as, for example, a heat transfer sheet that can be stretched or stretched.
　［多機能性シート状伸長性有機基材］
　前記シート状伸長性有機基材は、伸長性若しくは伸縮性以外の他の特性、機能をさらに具備していてもよい。本発明のシート状伸長性有機基材には、このような多機能、多特性を有するシート状伸長性有機基材（多機能性シート状伸長性有機基材）も含まれる。以下、多機能性シート状伸長性有機基材について説明する。なお、多機能性シート状伸長性有機基材は、基本的に、前記本発明のシート状伸長性有機基材の製造方法に準じて、又は前記本発明のシート状伸長性有機基材の製造方法を利用することにより製造できる。 [Multifunctional sheet-like extensible organic substrate]
The sheet-like extensible organic substrate may further have other characteristics and functions other than extensibility or stretchability. The sheet-like extensible organic base material of the present invention includes such a multi-functional and multi-functional sheet-like extensible organic base material (multi-functional sheet-like extensible organic base material). Hereinafter, the multifunctional sheet-like extensible organic base material will be described. In addition, the multifunctional sheet-like extensible organic substrate basically conforms to the method for producing the sheet-like extensible organic substrate of the present invention or the production of the sheet-like extensible organic substrate of the present invention. It can be manufactured by using the method.
　図１８の（１）、（２）、（３）は、それぞれ、本発明のシート状伸長性有機基材のうち多機能性シート状伸長性有機基材の例を示す概略断面図である。図１８の（１）に示される多機能性シート状伸長性有機基材Ａは、易伸長性ポリマー母材２中に筒状難伸長性ポリマー部Ａ３が部分的に且つ一体的に形成されている伸長性を有するシート状有機基材（シート状伸長性有機基材）１の一方の面に機能性層６を有している例である。図１８の（２）に示される多機能性シート状伸長性有機基材Ａは、易伸長性ポリマー母材２中に筒状難伸長性ポリマー部Ａ３が部分的に且つ一体的に形成されている伸長性を有するシート状有機基材（シート状伸長性有機基材）１の両面に機能性層６を有している例である。図１８の（３）に示される多機能性シート状伸長性有機基材Ａは、易伸長性ポリマー母材２中に筒状難伸長性ポリマー部Ａ３が部分的に且つ一体的に形成されている伸長性を有するシート状有機基材（シート状伸長性有機基材）１自体が、伸長性若しくは伸縮性以外の他の機能、特性を有している例である。 18 (1), (2), and (3) are schematic cross-sectional views showing examples of a multifunctional sheet-like extensible organic substrate among the sheet-like extensible organic substrates of the present invention. The multifunctional sheet-like extensible organic base A shown in (1) of FIG. 18 has a cylindrical hardly extensible polymer portion A3 partially and integrally formed in the easily extensible polymer base material 2. It is an example which has the functional layer 6 on one surface of the sheet-like organic base material (sheet-like extensible organic base material) 1 having extensibility. The multifunctional sheet-like extensible organic base material A shown in (2) of FIG. 18 has a cylindrical hardly extensible polymer portion A3 partially and integrally formed in the easily extensible polymer base material 2. It is an example which has the functional layer 6 on both surfaces of the sheet-like organic base material (sheet-like extensible organic base material) 1 which has the extendibility which is. In the multifunctional sheet-like extensible organic base material A shown in (3) of FIG. 18, the cylindrical hardly extensible polymer portion A3 is partially and integrally formed in the easily extensible polymer base material 2. This is an example in which the extensible sheet-like organic base material (sheet-like extensible organic base material) 1 itself has functions and characteristics other than extensibility or stretchability.
　［粘着性を有するシート状伸長性有機基材］
　粘着性を有するシート状伸長性有機基材として、（ｉ）易伸長性ポリマー母材中に筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されている伸長性を有するシート状有機基材の少なくとも一方の面に粘着剤層を有しており、該粘着剤層の粘着力（温度２３℃、湿度６５％ＲＨ、引張速度３００ｍｍ／分、剥離角度１８０°、対ＳＵＳ３０４）が０．１Ｎ／２０ｍｍ以上であるシート状伸長性有機基材、（ｉｉ）易伸長性ポリマー母材中に筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されている伸長性を有するシート状有機基材であって、該シート状有機基材の少なくとも一方の面の粘着力（温度２３℃、湿度６５％ＲＨ、引張速度３００ｍｍ／分、剥離角度１８０°、対ＳＵＳ３０４）が０．１Ｎ／２０ｍｍ以上であるシート状伸長性有機基材が挙げられる。前記（ｉｉ）のシート状伸長性有機基材は、易伸長性ポリマー母材中に筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されている伸長性を有するシート状有機基材（特に、易伸長性ポリマー母材）そのものが粘着性を有している。 [Adhesive sheet-like extensible organic substrate]
As a sheet-like extensible organic base material having adhesiveness, (i) a sheet-like form having extensibility in which a cylindrical hardly extensible polymer portion A is partially and integrally formed in an easily extensible polymer matrix. It has an adhesive layer on at least one surface of the organic substrate, and the adhesive strength of the adhesive layer (temperature 23 ° C., humidity 65% RH, tensile speed 300 mm / min, peel angle 180 °, vs. SUS304) A sheet-like extensible organic base material having a thickness of 0.1 N / 20 mm or more, and (ii) an extensibility in which a cylindrical hardly extensible polymer portion A is partially and integrally formed in an easily extensible polymer base material. A sheet-like organic base material having an adhesive strength (temperature 23 ° C., humidity 65% RH, tensile speed 300 mm / min, peeling angle 180 °, vs. SUS 304) on at least one side of the sheet-like organic base material .1N / 20mm or more A toroidal organic base material. The sheet-like extensible organic base material of (ii) is a sheet-like organic group having extensibility in which a cylindrical hardly extensible polymer portion A is partially and integrally formed in an easily extensible polymer base material. The material (particularly, the easily stretchable polymer base material) itself has adhesiveness.
　上記の粘着性を有するシート状伸長性有機基材は、このシート状伸長性有機基材を一方向（面方向）に伸長させると、易伸長性ポリマー母材の部位は伸長するが、部分的に形成された筒状難伸長性ポリマー部Ａは伸長しないか、又はほとんど伸長しない。このため、筒状難伸長性ポリマー部Ａに、形状が変化しないことが望まれる意匠を施したり、他の部材を固定、保持することができる。また、このシート状伸長性有機基材は粘着性を有するので、任意の被着体に貼着することができる。 When the sheet-like extensible organic base material having the above-mentioned adhesive property is stretched in one direction (plane direction), the part of the easily extensible polymer base material is extended, but partially. The cylindrical difficult-to-extend polymer part A formed in the film does not stretch or hardly stretches. For this reason, it is possible to give the tubular hardly extensible polymer portion A a design whose shape is desired not to change, and to fix and hold other members. Moreover, since this sheet-like extensible organic base material has adhesiveness, it can be attached to any adherend.
　粘着性を有するシート状伸長性有機基材の代表例として、図１８の（１）に示される多機能性シート状伸長性有機基材Ａにおいて、機能性層６が粘着剤層であるもの、図１８の（２）に示される多機能性シート状伸長性有機基材Ａにおいて、機能性層６が粘着剤層であるもの、図１８の（３）に示される多機能性シート状伸長性有機基材Ａにおいて、伸長性を有するシート状有機基材１自体が粘着性を有しているものが挙げられる。 As a representative example of a sheet-like extensible organic substrate having adhesiveness, in the multifunctional sheet-like extensible organic substrate A shown in (1) of FIG. 18, the functional layer 6 is an adhesive layer. In the multifunctional sheet-like stretchable organic substrate A shown in (2) of FIG. 18, the functional layer 6 is an adhesive layer, and the multifunctional sheet-like stretchability shown in (3) of FIG. Examples of the organic base material A include those in which the sheet-like organic base material 1 itself having extensibility has adhesiveness.
　上述のように、前記シート状有機基材が粘着性を有している場合には、そのまま粘着性を有するシート状伸長性有機基材として用いることができる。この場合、例えば、易伸長性ポリマー母材２を、ガラス転移温度（Ｔｇ）の低いポリマー（Ｔｇが、例えば５℃未満、好ましくは０℃以下、さらに好ましくは−５℃以下のポリマー；特に、ポリアクリル鎖を有するアクリル系ポリマー）で構成することにより粘着性を付与できる。この場合、該シート状有機基材の少なくとも一方の面の粘着力（温度２３℃、湿度６５％ＲＨ、引張速度３００ｍｍ／分、剥離角度１８０°、対ＳＵＳ３０４）が０．１Ｎ／２０ｍｍ以上である。該粘着力は、好ましくは０．２Ｎ／２０ｍｍ以上であり、用途によっては０．５Ｎ／２０ｍｍ以上、あるいは１．０Ｎ／２０ｍｍ以上であってもよい。 As described above, when the sheet-like organic base material has adhesiveness, it can be used as it is as an adhesive sheet-like extensible organic base material. In this case, for example, the stretchable polymer base material 2 is a polymer having a low glass transition temperature (Tg) (a polymer having a Tg of, for example, less than 5 ° C., preferably 0 ° C. or less, more preferably −5 ° C. or less; Acrylic polymer having a polyacrylic chain) can be used to impart tackiness. In this case, the adhesive strength (temperature 23 ° C., humidity 65% RH, tensile speed 300 mm / min, peel angle 180 °, vs. SUS304) of at least one surface of the sheet-like organic base material is 0.1 N / 20 mm or more. . The adhesive strength is preferably 0.2 N / 20 mm or more, and may be 0.5 N / 20 mm or more, or 1.0 N / 20 mm or more depending on the application.
　一方、本発明の粘着性を有するシート状伸長性有機基材が、易伸長性ポリマー母材中に筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されている伸長性を有するシート状有機基材の少なくとも一方の面に粘着剤層を設けた積層体で構成する場合には、該粘着剤層の粘着力（温度２３℃、湿度６５％ＲＨ、引張速度３００ｍｍ／分、剥離角度１８０°、対ＳＵＳ３０４）が０．１Ｎ／２０ｍｍ以上である。該粘着力は、好ましくは０．２Ｎ／２０ｍｍ以上であり、用途によっては０．５Ｎ／２０ｍｍ以上、あるいは１．０Ｎ／２０ｍｍ以上（特に、２．０Ｎ／２０ｍｍ以上）であってもよい。 On the other hand, the sheet-like extensible organic base material having adhesiveness according to the present invention has extensibility in which a cylindrical hardly extensible polymer portion A is partially and integrally formed in an easily extensible polymer base material. In the case of a laminate comprising an adhesive layer on at least one surface of a sheet-like organic base material, the adhesive strength of the adhesive layer (temperature 23 ° C., humidity 65% RH, tensile speed 300 mm / min, peeling The angle is 180 ° and SUS304 is 0.1 N / 20 mm or more. The adhesive strength is preferably 0.2 N / 20 mm or more, and may be 0.5 N / 20 mm or more, or 1.0 N / 20 mm or more (particularly 2.0 N / 20 mm or more) depending on the application.
　粘着性を有するシート状伸長性有機基材Ａの厚みは、例えば０．０１ｍｍ以上であり、好ましくは０．０３ｍｍ以上、さらに好ましくは０．０５ｍｍ以上である。粘着性を有するシート状伸長性有機基材の厚みの上限は、例えば１ｃｍであり、好ましくは５ｍｍ、さらに好ましくは２ｍｍである。 The thickness of the adhesive sheet-like extensible organic substrate A is, for example, 0.01 mm or more, preferably 0.03 mm or more, and more preferably 0.05 mm or more. The upper limit of the thickness of the adhesive sheet-like extensible organic substrate is, for example, 1 cm, preferably 5 mm, and more preferably 2 mm.
　粘着剤層６（粘着層）を構成する粘着剤としては、特に限定されず、例えば、ゴム系粘着剤、アクリル系粘着剤、ビニルアルキルエーテル系粘着剤、シリコーン系粘着剤、ポリエステル系粘着剤、ポリアミド系粘着剤、ウレタン系粘着剤、スチレン−ジエンブロック共重合体系粘着剤、これらの粘着剤に融点が約２００℃以下の熱溶融性樹脂を配合したクリープ特性改良型粘着剤などの公知の粘着剤を１種又は２種以上組み合わせて用いることができる。粘着剤は、溶剤型、エマルジョン型、ホットメルト型、エネルギー線硬化型粘着剤、加熱剥離型等の公知のいずれの粘着剤であってもよく、用途に応じて適切なものを選択できる。また、粘着剤は、弱粘着型、強粘着型、再剥離型等の何れであってもよく、用途に応じて適宜選択できる。 It does not specifically limit as an adhesive which comprises the adhesive layer 6 (adhesion layer), For example, a rubber adhesive, an acrylic adhesive, a vinyl alkyl ether adhesive, a silicone adhesive, a polyester adhesive, Known adhesives such as polyamide-based adhesives, urethane-based adhesives, styrene-diene block copolymer-based adhesives, and adhesives with improved creep characteristics in which a hot-melt resin having a melting point of about 200 ° C. or less is blended with these adhesives An agent can be used 1 type or in combination of 2 or more types. The pressure-sensitive adhesive may be any known pressure-sensitive adhesive such as a solvent type, an emulsion type, a hot-melt type, an energy ray curable pressure-sensitive adhesive, and a heat release type, and an appropriate one can be selected depending on the application. Further, the pressure-sensitive adhesive may be any of a weak pressure-sensitive adhesive type, a strong pressure-sensitive adhesive type, a re-peeling type, and the like, and can be appropriately selected according to the application.
　一般には、前記粘着剤として、天然ゴムや各種の合成ゴムをベースポリマーとしたゴム系粘着剤；（メタ）アクリル酸アルキルエステルの１種又は２種以上を単量体成分として用いたアクリル系ポリマー（単独重合体又は共重合体）をベースポリマーとするアクリル系粘着剤などが用いられる。本発明においては、特にアクリル系ポリマーをベースポリマーとするアクリル系粘着剤が好ましく使用される。 In general, as the pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive using natural rubber or various synthetic rubbers as a base polymer; an acrylic polymer using one or more (meth) acrylic acid alkyl esters as monomer components An acrylic pressure-sensitive adhesive having a base polymer (homopolymer or copolymer) is used. In the present invention, an acrylic adhesive having an acrylic polymer as a base polymer is particularly preferably used.
　前記アクリル系ポリマーの単量体成分として用いられる（メタ）アクリル酸アルキルエステルとしては、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｓ−ブチル、（メタ）アクリル酸ｔ−ブチル、（メタ）アクリル酸ペンチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸ヘプチル、（メタ）アクリル酸オクチル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸イソデシル、（メタ）アクリル酸ドデシル、（メタ）アクリル酸トリデシル、（メタ）アクリル酸ペンタデシル、（メタ）アクリル酸ヘキサデシル、（メタ）アクリル酸ヘプタデシル、（メタ）アクリル酸オクタデシル、（メタ）アクリル酸ノナデシル、（メタ）アクリル酸エイコシルなどの（メタ）アクリル酸Ｃ１−２０アルキルエステルなどが挙げられる。 Examples of the (meth) acrylic acid alkyl ester used as the monomer component of the acrylic polymer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and (meth) acrylic acid. Isopropyl, butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, (meth ) Heptyl acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, ( Pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, ( Data) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl and the like (meth) (meth) acrylic acid C 1-20 alkyl esters such as eicosyl acrylate.
　前記アクリル系ポリマーは、凝集力、耐熱性、架橋性などの改質を目的として、必要に応じて、前記（メタ）アクリル酸アルキルエステルと共重合可能な他の単量体成分（共重合性単量体成分）由来の構成単位を含んでいてもよい。このような単量体成分として、例えば、（メタ）アクリル酸シクロペンチル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸シクロヘキシルメチル、（メタ）アクリル酸ボルニル、（メタ）アクリル酸イソボルニルなどの脂肪族環状骨格を有する（メタ）アクリル酸エステル；（メタ）アクリル酸フェニル、（メタ）アクリル酸ベンジルなどの芳香族炭素環を有する（メタ）アクリル酸エステル；アクリル酸、メタクリル酸、カルボキシエチルアクリレート、カルボキシペンチルアクリレート、イタコン酸、マレイン酸、フマル酸、クロトン酸などのカルボキシル基含有モノマー；無水マレイン酸、無水イコタン酸などの酸無水物基含有モノマー；（メタ）アクリル酸ヒドロキシエチル、（メタ）アクリル酸ヒドロキシプロピル、（メタ）アクリル酸ヒドロキシブチル、（メタ）アクリル酸ヒドロキシヘキシル、（メタ）アクリル酸ヒドロキシオクチル、（メタ）アクリル酸ヒドロキシデシル、（メタ）アクリル酸ヒドロキシラウリル、（４−ヒドロキシメチルシクロヘキシル）メチルメタクリレートなどのヒドロキシル基含有モノマー；スチレンスルホン酸、アリルスルホン酸、２−（メタ）アクリルアミド−２−メチルプロパンスルホン酸、（メタ）アクリルアミドプロパンスルホン酸、スルホプロピル（メタ）アクリレート、（メタ）アクリロイルオキシナフタレンスルホン酸などのスルホン酸基含有モノマー；（メタ）アクリルアミド、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド、Ｎ−ブチル（メタ）アクリルアミド、Ｎ−メチロール（メタ）アクリルアミド、Ｎ−メチロールプロパン（メタ）アクリルアミドなどの（Ｎ−置換）アミド基含有モノマー；（メタ）アクリル酸アミノエチル、（メタ）アクリル酸Ｎ，Ｎ−ジメチルアミノエチル、（メタ）アクリル酸ｔ−ブチルアミノエチルなどの（メタ）アクリル酸アミノアルキル系モノマー；（メタ）アクリル酸メトキシエチル、（メタ）アクリル酸エトキシエチルなどの（メタ）アクリル酸アルコキシアルキル系モノマー；Ｎ−シクロヘキシルマレイミド、Ｎ−イソプロピルマレイミド、Ｎ−ラウリルマレイミド、Ｎ−フェニルマレイミドなどのマレイミド系モノマー；Ｎ−メチルイタコンイミド、Ｎ−エチルイタコンイミド、Ｎ−ブチルイタコンイミド、Ｎ−オクチルイタコンイミド、Ｎ−２−エチルヘキシルイタコンイミド、Ｎ−シクロヘキシルイタコンイミド、Ｎ−ラウリルイタコンイミドなどのイタコンイミド系モノマー；Ｎ−（メタ）アクリロイルオキシメチレンスクシンイミド、Ｎ−（メタ）アクルロイル−６−オキシヘキサメチレンスクシンイミド、Ｎ−（メタ）アクリロイル−８−オキシオクタメチレンスクシンイミドなどのスクシンイミド系モノマー；酢酸ビニル、プロピオン酸ビニル、Ｎ−ビニルピロリドン、メチルビニルピロリドン、ビニルピリジン、ビニルピペリドン、ビニルピリミジン、ビニルピペラジン、ビニルピラジン、ビニルピロール、ビニルイミダゾール、ビニルオキサゾール、ビニルモルホリン、Ｎ−ビニルカルボン酸アミド類、スチレン、α−メチルスチレン、Ｎ−ビニルカプロラクタムなどのビニル系モノマー；アクリロニトリル、メタクリロニトリルなどのシアノ基含有モノマー；（メタ）アクリル酸グリシジルなどのエポキシ基含有アクリル系モノマー；（メタ）アクリル酸ポリエチレングリコール、（メタ）アクリル酸ポリプロピレングリコール、（メタ）アクリル酸メトキシエチレングリコール、（メタ）アクリル酸メトキシポリプロピレングリコールなどのグリコール系アクリルエステルモノマー；Ｎ−（メタ）アクリロイルモルホリン、（メタ）アクリル酸テトラヒドロフルフリル、フッ素（メタ）アクリレート、シリコーン（メタ）アクリレートなどの複素環、ハロゲン原子、ケイ素原子などを有するアクリル酸エステル系モノマー；ヘキサンジオールジ（メタ）アクリレート、（ポリ）エチレングリコールジ（メタ）アクリレート、（ポリ）プロピレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、エポキシアクリレート、ポリエステルアクリレート、ウレタンアクリレートなどの多官能モノマー；イソプレン、ブタジエン、イソブチレンなどのオレフィン系モノマー；ビニルエーテルなどのビニルエーテル系モノマー等が挙げられる。これらの共重合性単量体成分は単独で又は２種以上を組み合わせて使用することができる。これらの共重合性単量体成分の中でも、特に、カルボキシル基含有モノマー、酸無水物基含有モノマー、ヒドロキシル基含有モノマー、（Ｎ−置換）アミド基含有モノマー、（メタ）アクリル酸アミノアルキル系モノマー、（メタ）アクリル酸アルコキシアルキル系モノマー、マレイミド系モノマー、多官能モノマーなどが好ましい。 For the purpose of modifying the cohesive strength, heat resistance, crosslinkability, and the like, the acrylic polymer may contain other monomer components (copolymerizable) that can be copolymerized with the (meth) acrylic acid alkyl ester as necessary. A structural unit derived from a monomer component) may be included. Examples of such monomer components include aliphatic groups such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, bornyl (meth) acrylate, and isobornyl (meth) acrylate. (Meth) acrylic acid ester having a cyclic skeleton; (meth) acrylic acid ester having an aromatic carbocyclic ring such as phenyl (meth) acrylate and benzyl (meth) acrylate; acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxy Carboxyl group-containing monomers such as pentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid; acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride; hydroxyethyl (meth) acrylate, (meth) acrylic acid Hydroxypropyl, Such as hydroxybutyl methacrylate, hydroxyhexyl (meth) acrylate, hydroxyoctyl (meth) acrylate, hydroxydecyl (meth) acrylate, hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl methacrylate, etc. Hydroxyl group-containing monomer: styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (meth) acrylamide propane sulfonic acid, sulfopropyl (meth) acrylate, (meth) acryloyloxynaphthalene sulfonic acid Sulfonic acid group-containing monomers such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-butyl (meth) acrylamide, N-methylol (meth) acrylamide, -(N-substituted) amide group-containing monomers such as methylolpropane (meth) acrylamide; aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate (Meth) acrylic acid aminoalkyl monomers such as (meth) acrylic acid methoxyethyl, (meth) acrylic acid alkoxyalkyl monomers such as ethoxyethyl; N-cyclohexylmaleimide, N-isopropylmaleimide, N -Maleimide monomers such as laurylmaleimide and N-phenylmaleimide; N-methylitaconimide, N-ethylitaconimide, N-butylitaconimide, N-octylitaconimide, N-2-ethylhexylitaconimide, N-cyclohexyl Itaconimide-based monomers such as itaconimide and N-laurylitaconimide; N- (meth) acryloyloxymethylenesuccinimide, N- (meth) acryloyl-6-oxyhexamethylenesuccinimide, N- (meth) acryloyl-8-oxyoctamethylenesuccinimide Succinimide monomers such as vinyl acetate, vinyl propionate, N-vinyl pyrrolidone, methyl vinyl pyrrolidone, vinyl pyridine, vinyl piperidone, vinyl pyrimidine, vinyl piperazine, vinyl pyrazine, vinyl pyrrole, vinyl imidazole, vinyl oxazole, vinyl morpholine, N- Vinyl monomers such as vinylcarboxylic amides, styrene, α-methylstyrene, N-vinylcaprolactam; acrylonitrile, methacryloni Cyano group-containing monomers such as ril; epoxy group-containing acrylic monomers such as glycidyl (meth) acrylate; polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxyethylene glycol (meth) acrylate, (meta ) Glycol acrylic ester monomers such as methoxypolypropylene glycol acrylate; N- (meth) acryloylmorpholine, tetrahydrofurfuryl (meth) acrylate, fluorine (meth) acrylate, silicone (meth) acrylate and other heterocycles, halogen atoms, Acrylic acid ester monomers having silicon atoms, etc .; hexanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (me Acrylate), neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, epoxy acrylate, Polyfunctional monomers such as polyester acrylate and urethane acrylate; olefin monomers such as isoprene, butadiene, and isobutylene; vinyl ether monomers such as vinyl ether, and the like. These copolymerizable monomer components can be used alone or in combination of two or more. Among these copolymerizable monomer components, in particular, carboxyl group-containing monomers, acid anhydride group-containing monomers, hydroxyl group-containing monomers, (N-substituted) amide group-containing monomers, (meth) acrylic acid aminoalkyl monomers , (Meth) acrylic acid alkoxyalkyl monomers, maleimide monomers, polyfunctional monomers and the like are preferable.
　前記アクリル系ポリマーにおいて、（メタ）アクリル酸Ｃ１−２０アルキルエステルに由来する構成単位の割合は、ポリマーの全構成単位に対して、例えば、５０重量％以上、好ましくは６０重量％以上、さらに好ましくは８０重量％以上、特に好ましくは８５重量％以上である。その上限は１００重量％であるが、好ましくは９９重量％、より好ましくは９８重量％である。また、特に、粘着性能の観点から、前記アクリル系ポリマーにおいて、（メタ）アクリル酸Ｃ４−１２アルキルエステルに由来する構成単位の割合が、ポリマーの全構成単位に対して、６０重量％以上であるのが好ましく、８０重量％以上であるのがより好ましい。その上限は１００重量％であるが、好ましくは９９重量％、より好ましくは９８重量％である。また、前記アクリル系ポリマーにおいて、前記共重合性単量体成分に由来する構成単位の割合は、ポリマーの全構成単位に対して、例えば、０．１~５０重量％であり、その下限は、好ましくは１重量％、より好ましくは２重量％であり、その上限は、好ましくは４０重量％、より好ましくは２０重量％である。また、架橋反応性や被着体に対する接着性等の観点から、前記アクリル系ポリマーにおいて、カルボキシル基含有モノマー、酸無水物基含有モノマー、ヒドロキシル基含有モノマーからなる群より選択される少なくとも１種のモノマー成分由来の構成単位の割合が、ポリマーの全構成単位に対して、０．１~４０重量％であるのが好ましく、その下限は、より好ましくは０．５重量％、特に好ましくは１重量％、その上限は、より好ましくは３０重量％、特に好ましくは２０重量％である。 In the acrylic polymer, the proportion of the structural unit derived from the (meth) acrylic acid C 1-20 alkyl ester is, for example, 50% by weight or more, preferably 60% by weight or more, based on all the structural units of the polymer. Preferably it is 80 weight% or more, Most preferably, it is 85 weight% or more. The upper limit is 100% by weight, preferably 99% by weight, more preferably 98% by weight. In particular, from the viewpoint of adhesive performance, in the acrylic polymer, the proportion of structural units derived from (meth) acrylic acid C 4-12 alkyl ester is 60% by weight or more based on the total structural units of the polymer. It is preferable that it is 80% by weight or more. The upper limit is 100% by weight, preferably 99% by weight, more preferably 98% by weight. In the acrylic polymer, the proportion of the structural unit derived from the copolymerizable monomer component is, for example, 0.1 to 50% by weight with respect to all the structural units of the polymer, and the lower limit is The upper limit is preferably 1% by weight, more preferably 2% by weight, and the upper limit is preferably 40% by weight, more preferably 20% by weight. In addition, from the viewpoint of cross-linking reactivity and adhesion to an adherend, at least one selected from the group consisting of a carboxyl group-containing monomer, an acid anhydride group-containing monomer, and a hydroxyl group-containing monomer in the acrylic polymer. The proportion of the structural unit derived from the monomer component is preferably 0.1 to 40% by weight with respect to the total structural unit of the polymer, and the lower limit thereof is more preferably 0.5% by weight, particularly preferably 1% by weight. %, The upper limit thereof is more preferably 30% by weight, particularly preferably 20% by weight.
　アクリル系ポリマーは、溶液重合、塊状重合、乳化重合などの公知のラジカル重合法等により製造できる。アクリル系ポリマーは、ランダム共重合体、ブロック共重合体、グラフト重合体等のいずれであってもよい。重合においては、通常用いられる重合開始剤、連鎖移動剤を使用できる。 The acrylic polymer can be produced by a known radical polymerization method such as solution polymerization, bulk polymerization, and emulsion polymerization. The acrylic polymer may be any of a random copolymer, a block copolymer, a graft polymer, and the like. In polymerization, a commonly used polymerization initiator or chain transfer agent can be used.
　粘着剤を構成するベースポリマーの重量平均分子量は、例えば、１万~２００万、好ましくは３０万~１５０万である。ベースポリマーの重量平均分子量が低すぎると、被着体との追従性の点では優れるものの、例えば加熱剥離する場合、被着体に糊残り等の汚染が生じやすくなる。一方、ベースポリマーの重量平均分子量が高すぎると、被着体への追従性が低下しやすくなる。 The weight average molecular weight of the base polymer constituting the pressure-sensitive adhesive is, for example, 10,000 to 2,000,000, preferably 300,000 to 1,500,000. When the weight average molecular weight of the base polymer is too low, although excellent in the followability with the adherend, for example, when peeling by heating, contamination such as adhesive residue tends to occur on the adherend. On the other hand, if the weight average molecular weight of the base polymer is too high, the followability to the adherend tends to decrease.
　粘着剤には、ベースポリマーのほか、必要に応じて、架橋剤（エポキシ系架橋剤、イソシアネート系架橋剤、メラミン系架橋剤、オキサゾリン系架橋剤、アジリジン系架橋剤、金属キレート化合物等）、架橋促進剤（架橋触媒）、粘着付与剤（例えば、ロジン誘導体樹脂、ポリテルペン樹脂、石油樹脂、油溶性フェノール樹脂など）、増粘剤、可塑剤、充填剤、発泡剤、老化防止剤、酸化防止剤、紫外線吸収剤、帯電防止剤、界面活性剤、レベリング剤、着色剤、難燃剤、シランカップリング剤などの適宜な添加剤を含んでいてもよい。 For adhesives, in addition to the base polymer, if necessary, crosslinking agents (epoxy crosslinking agents, isocyanate crosslinking agents, melamine crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, metal chelate compounds, etc.), crosslinking Accelerator (crosslinking catalyst), tackifier (for example, rosin derivative resin, polyterpene resin, petroleum resin, oil-soluble phenol resin, etc.), thickener, plasticizer, filler, foaming agent, anti-aging agent, antioxidant And an appropriate additive such as an ultraviolet absorber, an antistatic agent, a surfactant, a leveling agent, a colorant, a flame retardant, and a silane coupling agent.
　粘着剤層６の形成は公知乃至慣用の方法により行うことができる。例えば、粘着剤組成物を伸長性を有するシート状有機基材１（該シート状伸長性有機基材上に中間層が存在する場合は、該中間層）上に塗布する方法、粘着剤組成物を適当なセパレータ上に塗布して粘着剤層を形成した後、該粘着剤層を伸長性を有するシート状有機基材１（該シート状伸長性有機基材上に中間層が存在する場合は、該中間層）上に転写（移着）する方法等が挙げられる。塗布は、一般に粘着剤層の形成に用いられるコーター、押出機、印刷機などにより行うことができる。 The formation of the pressure-sensitive adhesive layer 6 can be performed by a known or common method. For example, a method of applying a pressure-sensitive adhesive composition onto a sheet-like organic substrate 1 having extensibility (or an intermediate layer when an intermediate layer is present on the sheet-like extensible organic substrate), a pressure-sensitive adhesive composition Is applied onto a suitable separator to form a pressure-sensitive adhesive layer, and then the pressure-sensitive adhesive layer is formed into a sheet-like organic substrate 1 having extensibility (if an intermediate layer is present on the sheet-like extensible organic substrate) And a method of transferring (transferring) onto the intermediate layer). The coating can be performed by a coater, an extruder, a printing machine or the like generally used for forming the pressure-sensitive adhesive layer.
　粘着剤層６は、伸長性を有するシート状有機基材１の表面の全体に設けてもよく、用途によっては、伸長性を有するシート状有機基材１の表面のうち必要な箇所のみに部分的に設けてもよい。 The pressure-sensitive adhesive layer 6 may be provided on the entire surface of the sheet-like organic substrate 1 having extensibility, and depending on the application, the adhesive layer 6 is only part of the surface of the sheet-like organic substrate 1 having extensibility. May be provided.
　粘着剤層６の厚さとしては、用途等に応じて適宜選択でき、例えば、５~３０００μｍであり、下限は、好ましくは１０μｍ、上限は、好ましくは５００μｍである。 The thickness of the pressure-sensitive adhesive layer 6 can be appropriately selected depending on the application and the like, and is, for example, 5 to 3000 μm, the lower limit is preferably 10 μm, and the upper limit is preferably 500 μm.
　伸長性を有するシート状有機基材１と粘着剤層６との間に、伸長性等を損なわない範囲で、必要に応じて他の層（中間層）を有していてもよい。また、粘着剤層６上には、粘着性を有するシート状伸長性有機基材Ａを使用するまでの間、粘着剤層６を保護するためのセパレータが設けられていてもよい。 Between the sheet-like organic base material 1 having extensibility and the pressure-sensitive adhesive layer 6, other layers (intermediate layers) may be provided as necessary as long as extensibility and the like are not impaired. In addition, a separator for protecting the pressure-sensitive adhesive layer 6 may be provided on the pressure-sensitive adhesive layer 6 until the adhesive sheet-like extensible organic base material A is used.
　粘着性を有するシート状伸長性有機基材は、粘着性を有し且つ形状不変部を有する伸長性部材（又は、粘着性を有し且つ形状不変部を有する伸縮性部材）として、エレクトロニクス製品（トランジスタ、集積回路、コンデンサ、センサ、アクチュエータ等）用部材、オプティカル製品（ディスプレイ、照明、光導波回路等）用部材、オプトエレクトロニクス製品（発光ダイオード、フォトダイオード、太陽電池等）用部材、カーエレクトロニクス製品用部材、家電製品用部材、住宅設備用部材、建材、バンド部材、結束用部材、衛生用品、衣料品の部分、湿布剤の基布等として利用できる。 An adhesive sheet-like extensible organic base material has an adhesive property and an extensible member having a shape-invariable portion (or an elastic member having an adhesive shape and a shape-invariable portion) as an electronic product ( Transistors, integrated circuits, capacitors, sensors, actuators, etc.) members, optical products (displays, lighting, optical waveguide circuits, etc.) members, optoelectronics products (light emitting diodes, photodiodes, solar cells, etc.), car electronics products It can be used as a member for home appliances, a member for home appliances, a member for housing equipment, a building material, a band member, a member for binding, a sanitary article, a clothing part, a base cloth for a poultice.
　［耐候性を有するシート状伸長性有機基材］
　耐候性を有するシート状伸長性有機基材としては、耐候剤を含有する易伸長性ポリマー母材中に筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されているシート状伸長性有機基材が挙げられる。図１８の（３）に示される多機能性シート状伸長性有機基材Ａにおいて、伸長性を有するシート状有機基材１自体が耐候性を有しているものに相当する。 [Sheet-like extensible organic base material having weather resistance]
As a sheet-like extensible organic base material having weather resistance, a sheet-like extension in which a cylindrical hardly extensible polymer portion A is partially and integrally formed in an easily extensible polymer base material containing a weathering agent An organic base material. In the multifunctional sheet-like extensible organic base material A shown in (3) of FIG. 18, the sheet-like organic base material 1 itself having extensibility corresponds to that having weather resistance.
　このようなシート状伸長性有機基材を一方向（面方向）に伸長させると、易伸長性ポリマー母材の部位は伸長するが、部分的に形成された筒状難伸長性ポリマー部Ａは伸長しないか、又はほとんど伸長しない。このため、筒状難伸長性ポリマー部Ａに、形状が変化しないことが望まれる意匠を施したり、他の部材を固定、保持することができる。また、このシート状伸長性有機基材は耐候剤を含んでいるので、屋外での長期使用が可能である。 When such a sheet-like extensible organic base material is extended in one direction (plane direction), the site of the easily extensible polymer base material is extended, but the partially formed cylindrical hardly extensible polymer portion A is Does not stretch or barely stretches. For this reason, it is possible to give the tubular hardly extensible polymer portion A a design whose shape is desired not to change, and to fix and hold other members. Moreover, since this sheet-like extensible organic base material contains a weathering agent, it can be used for a long time outdoors.
　上記の耐候性を有するシート状伸長性有機基材においては、易伸長性ポリマー母材２が耐候剤を含有している。耐候剤としては、特に限定されず、公知の耐候剤を使用できる。耐候剤としては、紫外線吸収剤及び酸化防止剤から選ばれる少なくとも１種であるのが好ましい。耐候剤は１種単独で又は２種以上を組み合わせて使用できる。 In the sheet-like extensible organic base material having the above weather resistance, the easily extensible polymer base material 2 contains a weathering agent. It does not specifically limit as a weathering agent, A well-known weathering agent can be used. The weathering agent is preferably at least one selected from ultraviolet absorbers and antioxidants. A weathering agent can be used individually by 1 type or in combination of 2 or more types.
　耐候剤としての紫外線吸収剤としては、例えば、ベンゾトリアゾール系化合物、ヒドロキシフェニルトリアジン系化合物、サリチル酸エステル系化合物、ベンゾフェノン系化合物、オキシベンゾフェノン系化合物、シアノアクリレート系化合物から選ばれる少なくとも１種が挙げられる。耐候剤としての紫外線吸収剤は、１種のみを用いてもよいし、２種以上を併用してもよい。 Examples of the ultraviolet absorber as the weathering agent include at least one selected from benzotriazole compounds, hydroxyphenyltriazine compounds, salicylic acid ester compounds, benzophenone compounds, oxybenzophenone compounds, and cyanoacrylate compounds. . Only 1 type may be used for the ultraviolet absorber as a weathering agent, and it may use 2 or more types together.
　ベンゾトリアゾール系化合物としては、例えば、２−（２−ヒドロキシ−５−ｔｅｒｔ−ブチルフェニル）−２Ｈ−ベンゾトリアゾール（ＴＩＮＵＶＩＮ　ＰＳ、ＢＡＳＦ社製）、ベンゼンプロパン酸および３−（２Ｈ−ベンゾトリアゾール−２−イル）−５−（１，１−ジメチルエチル）−４−ヒドロキシ（Ｃ７−９側鎖および直鎖アルキル）のエステル化合物（ＴＩＮＵＶＩＮ３８４−２、ＢＡＳＦ社製）、オクチル３−［３−ｔｅｒｔ−ブチル−４−ヒドロキシ−５−（５−クロロ−２Ｈ−ベンゾトリアゾール−２−イル）フェニル］プロピオネートおよび２−エチルヘキシル−３−［３−ｔｅｒｔ−ブチル−４−ヒドロキシ−５−（５−クロロ−２Ｈ−ベンゾトリアゾール−２イル）フェニル］プロピオネートの混合物（ＴＩＮＵＶＩＮ１０９、ＢＡＳＦ社製）、２−（２Ｈ−ベンゾトリアゾール−２−イル）−４，６−ビス（１−メチル−１−フェニルエチル）フェノール（ＴＩＮＵＶＩＮ９００、ＢＡＳＦ社製）、２−（２Ｈ−ベンゾトリアゾール−２−イル）−６−（１−メチル−１−フェニルエチル）−４−（１，１，３，３−テトラメチルブチル）フェノール（ＴＩＮＵＶＩＮ９２８、ＢＡＳＦ社製）、メチル−３−（３−（２Ｈ−ベンゾトリアゾール−２−イル）−５−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート／ポリエチレングリコール３００の反応生成物（ＴＩＮＵＶＩＮ１１３０、ＢＡＳＦ社製）、２−（２Ｈ−ベンゾトリアゾール−２−イル）−ｐ−クレゾール（ＴＩＮＵＶＩＮ　Ｐ、ＢＡＳＦ社製）、２（２Ｈ−ベンゾトリアゾール−２−イル）−４−６−ビス（１−メチル−１−フェニルエチル）フェノール（ＴＩＮＵＶＩＮ２３４、ＢＡＳＦ社製）、２−〔５−クロロ（２Ｈ）−ベンゾトリアゾール−２−イル〕−４−メチル−６−（ｔｅｒｔ−ブチル）フェノール（ＴＩＮＵＶＩＮ３２６、ＢＡＳＦ社製）、２−（２Ｈ−ベンゾトリアゾール−２−イル）−４，６−ジ−ｔｅｒｔ−ペンチルフェノール（ＴＩＮＵＶＩＮ３２８、ＢＡＳＦ社製）、２−（２Ｈ−ベンゾトリアゾール−２−イル）−４−（１，１，３，３−テトラメチルブチル）フェノール（ＴＩＮＵＶＩＮ３２９、ＢＡＳＦ社製）、２−２’−メチレンビス〔６−（２Ｈ−ベンゾトリアゾール−２−イル）−４−（１，１，３，３−テトラメチルブチル）フェノール〕（ＴＩＮＵＶＩＮ３６０、ＢＡＳＦ社製）、メチル３−（３−（２Ｈ−ベンゾトリアゾール−２−イル）−５−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネートとポリエチレングリコール３００との反応生成物（ＴＩＮＵＶＩＮ２１３、ＢＡＳＦ社製）、２−（２Ｈ−ベンゾトリアゾール−２−イル）−６−ドデシル−４−メチルフェノール（ＴＩＮＵＶＩＮ５７１、ＢＡＳＦ社製）、２−［２−ヒドロキシ−３−（３、４、５，６−テトラヒドロフタルイミド−メチル）−５−メチルフェニル］ベンゾトリアゾール（Ｓｕｍｉｓｏｒｂ２５０、住友化学工業社製）、２，２’−メチレンビス［６−（ベンゾトリアゾール−２イル）−４−ｔｅｒｔ−オクチルフェノール］（ＡＤＫ　ＳＴＡＢ　ＬＡ３１、ＡＤＥＫＡ社製）などが挙げられる。 Examples of the benzotriazole compounds include 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole (TINUVIN PS, manufactured by BASF), benzenepropanoic acid and 3- (2H-benzotriazole-2). - yl) -5- (1,1-dimethylethyl) -4-ester compound of a hydroxy (C 7-9 side chain and straight chain alkyl) (TINUVIN384-2, manufactured by BASF), octyl 3- [3-tert -Butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro -2H-benzotriazol-2-yl) phenyl] propionate (TINUV N109, manufactured by BASF), 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (TINUVIN900, manufactured by BASF), 2- (2H-benzo Triazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol (TINUVIN 928, manufactured by BASF), methyl-3- (3 -(2H-benzotriazol-2-yl) -5-t-butyl-4-hydroxyphenyl) propionate / polyethylene glycol 300 reaction product (TINUVIN 1130, manufactured by BASF), 2- (2H-benzotriazol-2- Yl) -p-cresol (TINUVIN P, manufactured by BASF), 2 (2H-benzotriazole-2) Yl) -4-6-bis (1-methyl-1-phenylethyl) phenol (TINUVIN234, manufactured by BASF), 2- [5-chloro (2H) -benzotriazol-2-yl] -4-methyl-6 -(Tert-butyl) phenol (TINUVIN 326, manufactured by BASF), 2- (2H-benzotriazol-2-yl) -4,6-di-tert-pentylphenol (TINUVIN 328, manufactured by BASF), 2- (2H -Benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol (TINUVIN 329, manufactured by BASF), 2-2'-methylenebis [6- (2H-benzotriazole-2- Yl) -4- (1,1,3,3-tetramethylbutyl) phenol] (TINUVIN 360, manufactured by BASF) , Methyl 3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate and polyethylene glycol 300 (TINUVIN 213, manufactured by BASF), 2- ( 2H-benzotriazol-2-yl) -6-dodecyl-4-methylphenol (TINUVIN571, manufactured by BASF), 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimide-methyl)- 5-methylphenyl] benzotriazole (Sumisorb 250, manufactured by Sumitomo Chemical Co., Ltd.), 2,2′-methylenebis [6- (benzotriazol-2-yl) -4-tert-octylphenol] (ADK STAB LA31, manufactured by ADEKA), etc. Is mentioned.
　ヒドロキシフェニルトリアジン系化合物としては、例えば、２−（４，６−ビス（２，４−ジメチルフェニル）−１，３，５−トリアジン−２−イル）−５−ヒドロキシフェニルと［（Ｃ１０−Ｃ１６（主としてＣ１２−Ｃ１３）アルキルオキシ）メチル］オキシランとの反応生成物（ＴＩＮＵＶＩＮ４００、ＢＡＳＦ社製；２−［４，６−ビス（２，４−ジメチルフェニル）−１，３，５−トリアジン−２−イル］−５−［３−（ドデシルオキシ）−２−ヒドロキシプロポキシ］フェノール）、２−（２，４−ジヒドロキシフェニル）−４，６−ビス−（２，４−ジメチルフェニル）−１，３，５−トリアジンと（２−エチルヘキシル）−グリシド酸エステルの反応生成物（ＴＩＮＵＶＩＮ４０５、ＢＡＳＦ社製）、２，４−ビス「２−ヒドロキシ−４−ブトキシフェニル」−６−（２，４−ジブトキシフェニル）−１，３−５−トリアジン（ＴＩＮＵＶＩＮ４６０、ＢＡＳＦ社製）、２−（４，６−ジフェニル−１，３，５−トリアジン−２−イル）−５−［（ヘキシル）オキシ］−フェノール（ＴＩＮＵＶＩＮ１５７７、ＢＡＳＦ社製）、２−（４，６−ジフェニル−１，３，５−トリアジン−２−イル）−５−［２−（２−エチルヘキサノイルオキシ）エトキシ］−フェノール（ＡＤＫ　ＳＴＡＢ　ＬＡ４６、ＡＤＥＫＡ社製）、２−（２−ヒドロキシ−４−［１−オクチルオキシカルボニルエトキシ］フェニル）−４，６−ビス（４−フェニルフェニル）−１，３，５−トリアジン（ＴＩＮＵＶＩＮ４７９、ＢＡＳＦ社製）などが挙げられる。 Examples of the hydroxyphenyl triazine compound include 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hydroxyphenyl and [(C 10- Reaction product with C 16 (mainly C 12 -C 13 ) alkyloxy) methyl] oxirane (TINUVIN 400, manufactured by BASF; 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5 -Triazin-2-yl] -5- [3- (dodecyloxy) -2-hydroxypropoxy] phenol), 2- (2,4-dihydroxyphenyl) -4,6-bis- (2,4-dimethylphenyl) ) -1,3,5-triazine and (2-ethylhexyl) -glycidic acid ester reaction product (TINUVIN405, manufactured by BASF), 2,4-bis " -Hydroxy-4-butoxyphenyl "-6- (2,4-dibutoxyphenyl) -1,3-5-triazine (TINUVIN460, manufactured by BASF), 2- (4,6-diphenyl-1,3,5 -Triazin-2-yl) -5-[(hexyl) oxy] -phenol (TINUVIN 1577, manufactured by BASF), 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5 [2- (2-Ethylhexanoyloxy) ethoxy] -phenol (ADK STAB LA46, manufactured by ADEKA), 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine (TINUVIN479, manufactured by BASF) and the like.
　ベンゾフェノン系化合物、オキシベンゾフェノン系化合物としては、例えば、２，４−ジヒドロキシベンゾフェノン、２−ヒドロキシ−４−メトキシベンゾフェノン、２−ヒドロキシ−４−メトキシベンゾフェノン−５−スルホン酸（無水及び三水塩）、２−ヒドロキシ−４−オクチルオキシベンゾフェノン、４−ドデシルオキシ−２−ヒドロキシベンゾフェノン、４−ベンジルオキシ−２−ヒドロキシベンゾフェノン、２，２´，４，４´−テトラヒドロキシベンゾフェノン、２，２´−ジヒドロキシ−４，４´−ジメトキシベンゾフェノンなどが挙げられる。 Examples of benzophenone compounds and oxybenzophenone compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid (anhydrous and trihydrate), 2-hydroxy-4-octyloxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy Examples include -4,4'-dimethoxybenzophenone.
　サリチル酸エステル系化合物としては、例えば、フェニル−２−アクリロイルオキシベンゾエート、フェニル−２−アクロリイルオキシ−３−メチルベンゾエート、フェニル−２−アクリロイルオキシ−４−メチルベンゾエート、フェニル−２−アクリロイルオキシ−５−メチルベンゾエート、フェニル−２−アクリロイルオキシ−３−メトキシベンゾエート、フェニル−２−ヒドロキシベンゾエート、フェニル−２−ヒドロキシ−３−メチルベンゾエート、フェニル−２−ヒドロキシ−４メチルベンゾエート、フェニル−２−ヒドロキシ−５−メチルベンゾエート、フェニル２−ヒドロキシ−３−メトキシベンゾエート、２，４−ジ−ｔｅｒｔ−ブチルフェニル−３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンゾエート（ＴＩＮＵＶＩＮ１２０、ＢＡＳＦ社製）などが挙げられる。 Examples of salicylic acid ester compounds include phenyl-2-acryloyloxybenzoate, phenyl-2-acryloyloxy-3-methylbenzoate, phenyl-2-acryloyloxy-4-methylbenzoate, and phenyl-2-acryloyloxy-5. -Methylbenzoate, phenyl-2-acryloyloxy-3-methoxybenzoate, phenyl-2-hydroxybenzoate, phenyl-2-hydroxy-3-methylbenzoate, phenyl-2-hydroxy-4methylbenzoate, phenyl-2-hydroxy- 5-methylbenzoate, phenyl 2-hydroxy-3-methoxybenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate (TINU) IN120, manufactured by BASF), and the like.
　シアノアクリレート系化合物としては、例えば、アルキル−２−シアノアクリレート、シクロアルキル−２−シアノアクリレート、アルコキシアルキル−２−シアノアクリレート、アルケニル−２−シアノアクリレート、アルキニル−２−シアノアクリレートなどが挙げられる。 Examples of the cyanoacrylate compound include alkyl-2-cyanoacrylate, cycloalkyl-2-cyanoacrylate, alkoxyalkyl-2-cyanoacrylate, alkenyl-2-cyanoacrylate, alkynyl-2-cyanoacrylate, and the like.
　耐候剤としての酸化防止剤としては、例えば、フェノール系安定剤、リン系安定剤、チオエーテル系安定剤、アミン系安定剤から選ばれる少なくとも１種が挙げられる。耐候剤としての酸化防止剤は光安定剤とも称される。耐候剤としての酸化防止剤（光安定剤）は、１種のみを用いてもよいし、２種以上を併用してもよい。 Examples of the antioxidant as the weathering agent include at least one selected from a phenol stabilizer, a phosphorus stabilizer, a thioether stabilizer, and an amine stabilizer. Antioxidants as weathering agents are also called light stabilizers. Only one type of antioxidant (light stabilizer) as a weathering agent may be used, or two or more types may be used in combination.
　フェノール系安定剤としては、例えば、２，６−ジ−第３級ブチル−４−メチルフェノール、４−ヒドロキシメチル−２，６−ジ−第３級ブチルフェノール、２，６−ジ−第３級ブチル−４−エチルフェノール、ブチル化ヒドロキシアニソール、ｎ−オクタデシル−３−（４−ヒドロキシ−３，５−ジ−第３級ブチルフェニル）プロピオネート、ジステアリル−（４−ヒドロキシ−３−メチル−５−第３級ブチル）ベンジルマロネート、トコフェロール、２，２´−メチレンビス（４−メチル−６−第３級ブチルフェノール）、２，２´−メチレンビス（４−エチル−６−第３級ブチルフェノール）、４，４´−メチレンビス（２，６−ジ−第３級ブチルフェノール）、４，４´−ブチリデンビス（６−第３級ブチル−ｍ−クレゾール）、４，４´−チオビス（６−第３級ブチル−ｍ−クレゾール）、スチレン化フェノール、Ｎ，Ｎ´−ヘキサメチレンビス（３，５−ジ−第３級ブチル−４−ヒドロキシヒドロシンナミド、ビス（３，５−ジ−第３級ブチル−４−ヒドロキシベンジルホスホン酸エチルエステル）カルシウム、１，１，３−トリス（２−メチル−４−ヒドロキシ−５−第３級ブチルフェニル）ブタン、１，３，５−トリメチル−２，４，６−トリス（３，５−ジ−第３級ブチル−４−ヒドロキシベンジル）ベンゼン、テトラキス［３−（３，５−ジ−第３級ブチル−４−ヒドロキシフェニル）プロピオニルオキシメチル］メタン、１，６−ヘキサンジオール−ビス［３−（３，５−ジ−第３級ブチル−４−ヒドロキシフェニル）プロピオネート］、２，２´−メチレンビス（４−メチル−６−シクロヘキシルフェノール）、２，２´−メチレンビス［６−（１−メチルシクロヘキシル）−ｐクレゾール］、１，３，５−トリス（４−第３級ブチル−３−ヒドロキシ−２，６−ジメチルベンジル）イソシアヌル酸、１，３，５−トリス（３，５−ジ−第３級ブチル−４−ヒドロキシベンジル）イソシアヌル酸、トリエチレングリコール−ビス［３−（３−第３級ブチル−４−ヒドロキシ−５−メチルフェニル）プロピオネート］、２，２´−オキサミドビス［エチル３−（３，５−ジ−第３級ブチル−４−ヒドロキシフェニル）プロピオネート］、６−（４−ヒドロキシ−３，５−ジ−第３級ブチルアニリノ）−２，４−ジオクチルチオ−１，３，５−トリアジン、ビス［２−第３級ブチル−４−メチル−６−（２−ヒドロキシ−３−第３級ブチル−５−メチルベンジル）フェニル］テレフタレート、３，９−ビス｛２−［３−（３−第３級ブチル−４−ヒドロキシ−５−メチルフェニル）プロピオニルオキシ］−１，１−ジメチルエチル｝−２，４，８，１０−テトラオキサスピロ［５．５］ウンデカン、３，９−ビス｛２−［３−（３，５−ジ−第３級ブチル−４−ヒドロキシフェニル）プロピオニルオキシ］−１，１−ジメチルエチル｝−２，４，８，１０−テトラオキサスピロ［５．５］ウンデカンなどが挙げられる。 Examples of the phenol-based stabilizer include 2,6-di-tert-butyl-4-methylphenol, 4-hydroxymethyl-2,6-di-tert-butylphenol, and 2,6-di-tertiary. Butyl-4-ethylphenol, butylated hydroxyanisole, n-octadecyl-3- (4-hydroxy-3,5-di-tert-butylphenyl) propionate, distearyl- (4-hydroxy-3-methyl-5 -Tertiary butyl) benzyl malonate, tocopherol, 2,2'-methylenebis (4-methyl-6-tertiary butylphenol), 2,2'-methylenebis (4-ethyl-6-tertiary butylphenol), 4,4'-methylenebis (2,6-di-tert-butylphenol), 4,4'-butylidenebis (6-tertiarybutyl-m-cresol), 4 4'-thiobis (6-tertiarybutyl-m-cresol), styrenated phenol, N, N'-hexamethylenebis (3,5-di-tertiarybutyl-4-hydroxyhydrocinnamide, bis ( 3,5-di-tertiarybutyl-4-hydroxybenzylphosphonic acid ethyl ester) calcium, 1,1,3-tris (2-methyl-4-hydroxy-5-tertiarybutylphenyl) butane, 1, 3,5-trimethyl-2,4,6-tris (3,5-di-tertiarybutyl-4-hydroxybenzyl) benzene, tetrakis [3- (3,5-di-tertiarybutyl-4- Hydroxyphenyl) propionyloxymethyl] methane, 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2'-methylenebi (4-methyl-6-cyclohexylphenol), 2,2'-methylenebis [6- (1-methylcyclohexyl) -p-cresol], 1,3,5-tris (4-tertiarybutyl-3-hydroxy -2,6-dimethylbenzyl) isocyanuric acid, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid, triethylene glycol-bis [3- (3-tertiary Tertiary butyl-4-hydroxy-5-methylphenyl) propionate], 2,2′-oxamidobis [ethyl 3- (3,5-di-tertiary butyl-4-hydroxyphenyl) propionate], 6- (4 -Hydroxy-3,5-di-tertiary butylanilino) -2,4-dioctylthio-1,3,5-triazine, bis [2-tertiary butyl-4-methyl-6- (2 -Hydroxy-3-tertiarybutyl-5-methylbenzyl) phenyl] terephthalate, 3,9-bis {2- [3- (3-tertiarybutyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis {2- [3- (3,5-di-tert-butyl- 4-hydroxyphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5.5] undecane.
　リン系安定剤としては、例えば、トリスノニルフェニルホスファイト、トリス（２，４−ジ−第３級ブチルフェニル）ホスファイト、トリス［２−第３級ブチル−４−（３−第３級ブチル−４−ヒドロキシ−５−メチルフェニルチオ）−５−メチルフェニル］ホスファイト、トリデシルホスファイト、オクチルジフェニルホスファイト、ジ（デシル）モノフェニルホスファイト、ジ（トリデシル）ペンタエリスリトールジホスファイト、ジステアリルペンタエリスリトールジホスファイト、ジ（ノニルフェニル）ペンタエリスリトールジホスファイト、ビス（２，４−ジ−第３級ブチルフェニル）ペンタエリスリトールジホスファイト、ビス（２，６−ジ−第３級ブチル−４−メチルフェニル）ペンタエリスリトールジホスファイト、ビス（２，４，６−トリ−第３級ブチルフェニル）ペンタエリスリトールジホスファイト、テトラ（トリデシル）イソプロピリデンジフェノールジホスファイト、テトラ（トリデシル）−４，４´−ｎ−ブチリデンビス（２−第３級ブチル−５−メチルフェノール）ジホスファイト、ヘキサ（トリデシル）−１，１，３−トリス（２−メチル−４−ヒドロキシ−５−第３級ブチルフェニル）ブタントリホスファイト、テトラキス（２，４−ジ第３級ブチルフェニル）ビフェニレンジホスホナイト、９，１０−ジハイドロ−９−オキサ−１０−ホスファフェナンスレン−１０−オキサイド、トリス（２−［（２，４，８，１０−テトラキス−第３級ブチルジベンゾ［ｄ，ｆ］［１，３，２］ジオキサホスフェピン−６−イル）オキシ］エチル）アミンなどが挙げられる。 Examples of the phosphorus stabilizer include trisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris [2-tertiary butyl-4- (3-tertiary butyl). -4-hydroxy-5-methylphenylthio) -5-methylphenyl] phosphite, tridecyl phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, di (tridecyl) pentaerythritol diphosphite, di Stearyl pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl) -4-methylphenyl) pentaerythritol diphosphite, bis 2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite, tetra (tridecyl) isopropylidenediphenol diphosphite, tetra (tridecyl) -4,4′-n-butylidenebis (2-tertiary Tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butanetriphosphite, tetrakis (2,4-diphosphite) Tertiary butylphenyl) biphenylene diphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tris (2-[(2,4,8,10-tetrakis- Tertiary butyldibenzo [d, f] [1,3,2] dioxaphosphin-6-yl) oxy] ethyl) amine Etc.
　チオエーテル系安定剤としては、例えば、チオジプロピオン酸ジラウリル、ジミリスチル、ジステアリル等のジアルキルチオジプロピオネート化合物；テトラキス〔メチレン（３−ドデシルチオ）プロピオネート〕メタン等のポリオールのβ−アルキルメルカプトプロピオン酸エステル化合物；などが挙げられる。 Examples of the thioether-based stabilizer include dialkylthiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl, and distearyl; β-alkyl mercaptopropionate of polyols such as tetrakis [methylene (3-dodecylthio) propionate] methane Compound; and the like.
　アミン系安定剤としては、例えば、コハク酸ジメチルおよび４−ヒドロキシ−２，２，６，６−テトラメチル−１−ピペリジンエタノールの重合物（ＴＩＮＵＶＩＮ６２２、ＢＡＳＦ社製）、コハク酸ジメチルおよび４−ヒドロキシ−２，２，６，６−テトラメチル−１−ピペリジンエタノールの重合物とＮ，Ｎ’，Ｎ’’，Ｎ’’’−テトラキス−（４，６−ビス−（ブチル−（Ｎ−メチル−２，２，６，６−テトラメチルピペリジン−４−イル）アミノ）−トリアジン−２−イル）−４，７−ジアザデカン−１，１０−ジアミンとの１対１の反応生成物（ＴＩＮＵＶＩＮ１１９、ＢＡＳＦ社製）、ジブチルアミン・１，３−トリアジン・Ｎ、Ｎ’−ビス（２，２，６，６−テトラメチル−４−ピペリジル−１，６−ヘキサメチレンジアミンとＮ−（２，２，６，６−テトラメチル−４−ピペリジル）ブチルアミンの重縮合物（ＴＩＮＵＶＩＮ２０２０、ＢＡＳＦ社製）、ポリ［｛６−（１，１，３，３−テトラメチルブチル）アミノ−１，３，５−トリアジン−２−４−ジイル｝｛２，２，６，６−テトラメチル−４−ピペリジル｝イミノ］ヘキサメチレン｛（２，２，６，６−テトラメチル−４−ピペリジル）イミノ｝）（ＴＩＮＵＶＩＮ９４４、ＢＡＳＦ社製）、ビス（１，２，２，６，６−ペンタメチル−４−ピペリジル）セバケートおよびメチル１、２，２，６，６−ペンタメチル−４−ピペリジルセバケートの混合物（ＴＩＮＵＶＩＮ７６５、ＢＡＳＦ社製）、ビス（２，２，６，６−テトラメチル−４−ピペリジル）セバケート（ＴＩＮＵＶＩＮ７７０、ＢＡＳＦ社製）、デカン二酸ビス（２，２，６，６−テトラメチル−１−（オクチルオキシ）−４−ピペリジニル）エステル、１，１−ジメチルエチルヒドロペルオキシドとオクタンの反応生成物（ＴＩＮＵＶＩＮ１２３、ＢＡＳＦ社製）、ビス（１，２，２，６，６−ペンタメチル−４−ピペリジル）［［３，５−ビス（１，１−ジメチルエチル）−４−ヒドロキシフェニル］メチル］ブチルマロネート（ＴＩＮＵＶＩＮ１４４、ＢＡＳＦ社製）、シクロヘキサンおよび過酸化Ｎ−ブチル２，２，６，６−テトラメチル−４−ピペリジンアミン−２，４，６−トリクロロ１，３，５−トリアジンの反応生成物と２−アミノエタノールとの反応生成物（ＴＩＮＵＶＩＮ１５２、ＢＡＳＦ社製）、ビス（１，２，２，６，６ペンタメチル−４−ピペリジル）セバケートおよびメチル１，２，２，６，６−ペンタメチル−４−ピペリジルセバケートの混合物（ＴＩＮＵＶＩＮ２９２、ＢＡＳＦ社製）、１，２，３，４−ブタンテトラカルボン酸と１，２，２，６，６−ペンタメチル−４−ピペリジノールおよび３，９−ビス（２−ヒドロキシ−１，１−ジメチルエチル）−２，４，８，１０−テトラオキサスピロ［５．５］ウンデカンとの混合エステル化物（ＡＤＫ　ＳＴＡＢ　ＬＡ６３Ｐ、ＡＤＥＫＡ社製）などが挙げられる。アミン系安定剤としては、特に、ヒンダードアミン系安定剤が好ましい。 Examples of amine stabilizers include dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol polymer (TINUVIN 622, manufactured by BASF), dimethyl succinate and 4-hydroxy. Polymer of 2,2,6,6-tetramethyl-1-piperidineethanol and N, N ′, N ″, N ′ ″-tetrakis- (4,6-bis- (butyl- (N-methyl A one-to-one reaction product (TINUVIN119, with -2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine BASF), dibutylamine, 1,3-triazine, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenedia) And N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine polycondensate (TINUVIN2020, manufactured by BASF), poly [{6- (1,1,3,3-tetramethylbutyl ) Amino-1,3,5-triazine-2-4-diyl} {2,2,6,6-tetramethyl-4-piperidyl} imino] hexamethylene {(2,2,6,6-tetramethyl- 4-piperidyl) imino}) (TINUVIN 944, manufactured by BASF), bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1,2,2,6,6-pentamethyl-4- Mixture of piperidyl sebacate (TINUVIN765, manufactured by BASF), bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (TINUVIN770, BAS) ), Decanedioic acid bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester, 1,1-dimethylethyl hydroperoxide and octane reaction product (TINUVIN123, BASF), bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate ( TINUVIN 144 (manufactured by BASF), cyclohexane and N-butyl peroxide 2,2,6,6-tetramethyl-4-piperidineamine-2,4,6-trichloro 1,3,5-triazine and 2 -Reaction product with aminoethanol (TINUVIN 152, manufactured by BASF), bis (1, 2, 2, 6, 6 pentamethyl-4-piperid A) Mixture of sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate (TINUVIN292, manufactured by BASF), 1,2,3,4-butanetetracarboxylic acid and 1,2,2 , 6,6-pentamethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane mixed ester And chemicals (ADK STAB LA63P, manufactured by ADEKA). As the amine stabilizer, a hindered amine stabilizer is particularly preferable.
　易伸長性ポリマー母材における耐候剤の含有量（総量）としては、易伸長性ポリマー母材全体に対して、例えば、０．００１~１０重量％である。耐候剤の含有量（総量）の下限は、好ましくは０．０１重量％、より好ましくは０．１重量％、さらに好ましくは０．３重量％であり、上限は、好ましくは８重量％、より好ましくは６重量％、さらに好ましくは５重量％である。なお、耐候剤として紫外線吸収剤を用いる場合、その量は、易伸長性ポリマー母材２全体に対して、例えば、０．００１~１０重量％であり、下限は、好ましくは０．０１重量％、より好ましくは０．１重量％、さらに好ましくは０．３重量％であり、上限は、好ましくは５重量％、より好ましくは３重量％、さらに好ましくは２重量％である。耐候剤として酸化防止剤を用いる場合、その量は、易伸長性ポリマー母材２全体に対して、例えば、０．００１~１０重量％であり、下限は、好ましくは０．０１重量％、より好ましくは０．２重量％、さらに好ましくは０．５重量％であり、上限は、好ましくは５重量％、より好ましくは４重量％、さらに好ましくは３重量％である。 The content (total amount) of the weathering agent in the easily stretchable polymer base material is, for example, 0.001 to 10% by weight with respect to the entire easily stretchable polymer base material. The lower limit of the content (total amount) of the weathering agent is preferably 0.01% by weight, more preferably 0.1% by weight, still more preferably 0.3% by weight, and the upper limit is preferably 8% by weight. Preferably it is 6 weight%, More preferably, it is 5 weight%. When an ultraviolet absorber is used as the weathering agent, the amount thereof is, for example, 0.001 to 10% by weight with respect to the whole stretchable polymer base material 2 and the lower limit is preferably 0.01% by weight. The upper limit is preferably 5% by weight, more preferably 3% by weight, still more preferably 2% by weight. When an antioxidant is used as the weathering agent, the amount thereof is, for example, 0.001 to 10% by weight with respect to the entire stretchable polymer base material 2, and the lower limit is preferably 0.01% by weight. The upper limit is preferably 5% by weight, more preferably 4% by weight, and still more preferably 3% by weight.
　耐候剤として、前記紫外線吸収剤及び酸化防止剤（光安定剤）のうち、いずれか一方のみを用いることができ、また、両方を併用することもできる。好ましくは、両方を併用する。これにより、耐候性を著しく向上できる。 As the weathering agent, only one of the ultraviolet absorber and the antioxidant (light stabilizer) can be used, or both can be used in combination. Preferably, both are used together. Thereby, weather resistance can be remarkably improved.
　易伸長性ポリマー母材部の形成は、前記ポリマー母材（Ａ）部の形成方法に準じて行うことができる。例えば、易伸長性ポリマー母材部は、例えば支持体上に、易伸長性ポリマー母材を構成するポリマーの液状前駆体に耐候剤を添加した組成物を塗工して易伸長性ポリマー母材形成用材料層を形成し、該易伸長性ポリマー母材形成用材料層の所定部位に筒状難伸長性ポリマー部Ａの形成材料を配した後、該易伸長性ポリマー母材形成用材料層中の液状前駆体を目的のポリマーへ転化することにより形成できる。 The easily stretchable polymer base material can be formed according to the method for forming the polymer base material (A). For example, the easily stretchable polymer base material may be formed by, for example, applying a composition obtained by adding a weathering agent to a liquid precursor of a polymer constituting the easily stretchable polymer base material on a support. After forming the forming material layer and arranging the forming material of the cylindrical difficult-to-extend polymer part A at a predetermined portion of the easily-extensible polymer base material forming material layer, the easily-extensible polymer base material forming material layer It can be formed by converting the liquid precursor therein to the target polymer.
　また、易伸長性ポリマー母材部は、例えば支持体上に、易伸長性ポリマー母材を構成するポリマーと耐候剤とを含む溶液若しくは分散液を塗工して易伸長性ポリマー母材形成用材料層を形成し、該易伸長性ポリマー母材形成用材料層の所定部位に筒状難伸長性ポリマー部Ａの形成材料を配した後、該易伸長性ポリマー母材形成用材料層中の溶媒を乾燥除去することにより形成することもできる。 In addition, the easily stretchable polymer base material part is, for example, for forming an easily stretchable polymer base material by applying a solution or dispersion containing a polymer constituting the easily stretchable polymer base material and a weather resistance agent on a support. After forming the material layer and arranging the forming material of the cylindrical hardly extensible polymer portion A at a predetermined portion of the easily extensible polymer base material forming material layer, in the easily extensible polymer base material forming material layer It can also be formed by removing the solvent by drying.
　さらに、易伸長性ポリマー母材部は、例えば支持体上に、易伸長性ポリマー母材を構成するポリマー単体と耐候剤との混合物により易伸長性ポリマー母材形成用材料層を形成し、該易伸長性ポリマー母材形成用材料層の所定部位に筒状難伸長性ポリマー部Ａの形成材料を配した後、溶融・冷却処理（ホットメルト処理）を行うことにより形成することもできる。 Furthermore, the easily stretchable polymer base material part forms, on the support, for example, an easily stretchable polymer base material forming material layer by a mixture of a single polymer constituting the easily stretchable polymer base material and a weathering agent, It can also be formed by performing a melting / cooling process (hot melt process) after arranging the forming material of the cylindrical difficult-to-extend polymer part A at a predetermined portion of the easily stretchable polymer base material forming material layer.
　耐候性を有するシート状伸長性有機基材において、筒状難伸長性ポリマー部Ａ３を構成する材料は、通常、ポリマーを少なくとも含有するポリマー材料である。このポリマー材料としては、前記構造部（Ｂ）の説明箇所で述べたものと同様のものを使用できる。 In the sheet-like extensible organic base material having weather resistance, the material constituting the cylindrical difficult-to-extend polymer part A3 is usually a polymer material containing at least a polymer. As this polymer material, the same materials as those described in the explanation of the structure part (B) can be used.
　筒状難伸長性ポリマー部Ａ３には、前記易伸長性ポリマー母材部２と同様、耐候剤が含まれていてもよい。筒状難伸長性ポリマー部Ａ（難伸長部）にも耐候剤を添加することで、屋外でのシート状伸長性有機基材の劣化をより顕著に抑制することができる。該耐候剤としては前記と同様のものを使用できる。 The cylindrical difficult-to-extend polymer part A3 may contain a weathering agent in the same manner as the easily-extensible polymer base part 2. By adding a weathering agent also to the cylindrical hardly extensible polymer part A (hardly extensible part), deterioration of the sheet-like extensible organic base material outdoors can be suppressed more remarkably. The same weathering agent as described above can be used.
　筒状難伸長性ポリマー部Ａ３における耐候剤の含有量（総量）は、筒状難伸長性ポリマー部Ａ（難伸長部）３全体に対して、例えば、０．００１~１０重量％である。耐候剤の含有量（総量）の下限は、好ましくは０．０１重量％、より好ましくは０．１重量％、さらに好ましくは０．３重量％であり、上限は、好ましくは８重量％、より好ましくは６重量％、さらに好ましくは５重量％である。なお、耐候剤として紫外線吸収剤を用いる場合、その量は、筒状難伸長性ポリマー部Ａ（難伸長部）３全体に対して、例えば、０．００１~１０重量％であり、下限は、好ましくは０．０１重量％、より好ましくは０．１重量％、さらに好ましくは０．３重量％であり、上限は、好ましくは５重量％、より好ましくは３重量％、さらに好ましくは２重量％である。耐候剤として酸化防止剤を用いる場合、その量は、筒状難伸長性ポリマー部Ａ（難伸長部）３全体に対して、例えば、０．００１~１０重量％であり、下限は、好ましくは０．０１重量％、より好ましくは０．２重量％、さらに好ましくは０．５重量％であり、上限は、好ましくは５重量％、より好ましくは４重量％、さらに好ましくは３重量％である。 The content (total amount) of the weathering agent in the cylindrical difficult-to-extend polymer part A3 is, for example, 0.001 to 10% by weight with respect to the entire cylindrical difficult-to-extend polymer part A (hard extension part) 3. The lower limit of the content (total amount) of the weathering agent is preferably 0.01% by weight, more preferably 0.1% by weight, still more preferably 0.3% by weight, and the upper limit is preferably 8% by weight. Preferably it is 6 weight%, More preferably, it is 5 weight%. In the case where an ultraviolet absorber is used as the weathering agent, the amount thereof is, for example, 0.001 to 10% by weight with respect to the entire tubular hardly extensible polymer part A (hardly stretchable part) 3, and the lower limit is Preferably it is 0.01 wt%, more preferably 0.1 wt%, still more preferably 0.3 wt%, and the upper limit is preferably 5 wt%, more preferably 3 wt%, even more preferably 2 wt%. It is. When an antioxidant is used as the weathering agent, the amount thereof is, for example, 0.001 to 10% by weight with respect to the entire tubular difficult-to-extend polymer part A (hardly-extensible part) 3, and the lower limit is preferably 0.01% by weight, more preferably 0.2% by weight, still more preferably 0.5% by weight, and the upper limit is preferably 5% by weight, more preferably 4% by weight, still more preferably 3% by weight. .
　筒状難伸長性ポリマー部Ａ３における耐候剤として、前記紫外線吸収剤及び酸化防止剤（光安定剤）のうち、いずれか一方のみを用いることができ、また、両方を併用することもできる。好ましくは、両方を併用する。これにより、耐候性を著しく向上できる。 Only one of the ultraviolet absorber and the antioxidant (light stabilizer) can be used as the weathering agent in the cylindrical hardly extensible polymer part A3, or both can be used in combination. Preferably, both are used together. Thereby, weather resistance can be remarkably improved.
　耐候性を有するシート状伸長性有機基材は、例えば、耐候剤を易伸長性ポリマー母材形成用材料中に配合し、前記本発明のシート状伸長性有機基材の製造法と同様の方法により製造できる。 The sheet-like extensible organic base material having weather resistance is, for example, a method similar to the method for producing the sheet-like extensible organic base material of the present invention, in which a weathering agent is blended in an easily extensible polymer base material forming material. Can be manufactured.
　耐候性を有するシート状伸長性有機基材は、形状不変部を有する伸長性部材（又は、形状不変部を有する伸縮性部材）として、エレクトロニクス製品（トランジスタ、集積回路、コンデンサ、センサ、アクチュエータ等）用部材、オプティカル製品（ディスプレイ、照明、光導波回路等）用部材、オプトエレクトロニクス製品（発光ダイオード、フォトダイオード、太陽電池等）用部材、カーエレクトロニクス製品用部材、家電製品用部材、住宅設備用部材、建材、バンド部材、結束用部材、衛生用品、衣料品の部分、湿布剤の基布等として利用できる。 A sheet-like stretchable organic base material having weather resistance is an electronic product (a transistor, an integrated circuit, a capacitor, a sensor, an actuator, etc.) as an extensible member having a shape-invariant portion (or an elastic member having a shape-invariant portion). Materials, optical products (displays, lighting, optical waveguide circuits, etc.), optoelectronics products (light emitting diodes, photodiodes, solar cells, etc.), car electronics products, home appliances, housing equipment It can be used as building materials, band members, binding members, sanitary products, clothing parts, base fabrics for poultices, and the like.
　［不快臭防止性を有するシート状伸長性有機基材］
　不快臭防止性を有する（或いは、快い臭いを有する）シート状伸長性有機基材として、（ｉ）易伸長性ポリマー母材中に筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されている伸長性を有するシート状有機基材であって、易伸長性ポリマー母材及び／又は筒状難伸長性ポリマー部Ａが香料を含有しているシート状伸長性有機基材（「第１の態様のシート状伸長性有機基材」と称する場合がある）、（ｉｉ）易伸長性ポリマー母材中に筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されている伸長性を有するシート状有機基材の少なくとも一方の面に消臭層を有するシート状伸長性有機基材（「第２の態様のシート状伸長性有機基材」と称する場合がある）、（ｉｉｉ）易伸長性ポリマー母材中に筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されている伸長性を有するシート状有機基材を含むシート状伸長性有機基材であって、該シート状伸長性有機基材を１５０℃で３分間加熱した際に発生するモノマー量が３００ｐｐｍ以下であるシート状伸長性有機基材（「第３の態様のシート状伸長性有機基材」と称する場合がある）が挙げられる。 [Sheet-like extensible organic base material with unpleasant odor prevention]
As a sheet-like extensible organic base material having an unpleasant odor preventing property (or having a pleasant odor), (i) a cylindrical hardly extensible polymer portion A is partially and integrally in an easily extensible polymer matrix. A sheet-like organic base material having extensibility that is formed, and is a sheet-like extensible organic base material (" (Ii) the cylindrical stretchable polymer portion A is partially and integrally formed in the stretchable polymer base material (sometimes referred to as the “sheet-like stretchable organic substrate of the first aspect”). A sheet-like extensible organic substrate having a deodorizing layer on at least one surface of the extensible sheet-like organic substrate (sometimes referred to as "sheet-like extensible organic substrate of the second aspect"), (Iii) Cylindrical difficult-to-extend polymer part A in the easily-extensible polymer base material A sheet-like extensible organic substrate comprising a sheet-like organic substrate having extensibility that is partially and integrally formed, when the sheet-like extensible organic substrate is heated at 150 ° C. for 3 minutes And a sheet-like extensible organic substrate (sometimes referred to as “the sheet-like extensible organic substrate of the third embodiment”) in which the amount of monomer generated in the above is 300 ppm or less.
　このようなシート状伸長性有機基材を一方向（面方向）に伸長させると、易伸長性ポリマー母材の部位は伸長するが、部分的に形成された筒状難伸長性ポリマー部Ａは伸長しないか、又はほとんど伸長しない。このため、筒状難伸長性ポリマー部Ａに、形状が変化しないことが望まれる意匠を施したり、他の部材を固定、保持することができる。また、このシート状伸長性有機基材は、不快臭の発生が抑制されているため、例えば、該不快臭を引き起こす物質による悪影響（例えば、電子部品の汚染や腐食、作業環境への悪影響等）が抑制され、また、食品用途や医療用途等にも好ましく使用することができる。 When such a sheet-like extensible organic base material is extended in one direction (plane direction), the site of the easily extensible polymer base material is extended, but the partially formed cylindrical hardly extensible polymer portion A is Does not stretch or barely stretches. For this reason, it is possible to give the tubular hardly extensible polymer portion A a design whose shape is desired not to change, and to fix and hold other members. In addition, since the generation of unpleasant odor is suppressed in this sheet-like extensible organic base material, for example, adverse effects due to substances causing the unpleasant odor (for example, contamination and corrosion of electronic components, adverse effects on the work environment, etc.) And can be preferably used for food use, medical use, and the like.
　不快臭防止性を有するシート状伸長性有機基材の代表例として、図１８の（１）に示される多機能性シート状伸長性有機基材Ａにおいて、機能性層６が消臭層であるもの、図１８の（２）に示される多機能性シート状伸長性有機基材Ａにおいて、機能性層６が消臭層であるもの、図１８の（３）に示される多機能性シート状伸長性有機基材Ａにおいて、伸長性を有するシート状有機基材１自体において不快臭の発生が抑制されているものが挙げられる。 As a representative example of a sheet-like extensible organic base material having an unpleasant odor prevention property, the functional layer 6 is a deodorizing layer in the multifunctional sheet-like extensible organic base material A shown in (1) of FIG. In the multifunctional sheet-like extensible organic base material A shown in (2) of FIG. 18, the functional layer 6 is a deodorizing layer, and the multifunctional sheet-like shape shown in (3) of FIG. Examples of the extensible organic base material A include those in which the generation of an unpleasant odor is suppressed in the extensible sheet-like organic base material 1 itself.
　前記第１の態様のシート状伸長性有機基材は、易伸長性ポリマー母材及び／又は筒状難伸長性ポリマー部Ａ（易伸長性ポリマー母材及び筒状難伸長性ポリマー部Ａのいずれか一方又は両方）が香料を含有する。前記香料としては、公知乃至慣用の香料、例えば、天然香料、合成香料などの香気を有するものであればいずれも使用することができる。前記香料としては、易伸長性ポリマー母材の形成を阻害しないもの（例えば、重合反応を阻害しないもの）であることが好ましく、常温で液体であり、常圧下で１５０℃以上の沸点を有するものが特に好ましい。なお、香料は１種を単独で使用してもよいし、２種以上を組み合わせて使用してもよい。また、粉末状の香料については、例えば、液状の香料に混合・溶解させて使用することによって取り扱い性の向上を図ることができる。 The sheet-like extensible organic base material of the first aspect includes an easily extensible polymer base material and / or a cylindrical hardly extensible polymer portion A (any of the easily extensible polymer base material and the cylindrical hardly extensible polymer portion A). One or both) contains a fragrance. As said fragrance | flavor, all can be used if it has fragrance | flavors, such as well-known thru | or usual fragrance | flavors, for example, natural fragrance | flavor, synthetic | combination fragrance | flavor. The fragrance is preferably one that does not inhibit the formation of an easily stretchable polymer matrix (for example, one that does not inhibit the polymerization reaction), is a liquid at room temperature, and has a boiling point of 150 ° C. or higher under normal pressure. Is particularly preferred. In addition, a fragrance | flavor may be used individually by 1 type and may be used in combination of 2 or more type. Moreover, about powdery fragrance | flavor, the improvement of a handleability can be aimed at by mixing and melt | dissolving and using it for a liquid fragrance | flavor, for example.
　前記香料としては、具体的には、（１）有機鎖状低分子化合物であるアルコール類、アルデヒド類、ケトン類；（２）脂環式化合物であるアルコール類、アルデヒド類、ケトン類、エステル類、エーテル類、炭化水素類；（３）テルペン化合物であるアルコール類、アルデヒド類、ケトン類、エステル類、エーテル類；（４）芳香族化合物であるアルコール類、アルデヒド類、ケトン類、エーテル類などに分類されるものなどが挙げられる。 Specific examples of the perfume include (1) alcohols, aldehydes and ketones which are organic low-molecular-weight compounds; (2) alcohols, aldehydes, ketones and esters which are alicyclic compounds. (3) Alcohols that are terpene compounds, aldehydes, ketones, esters, ethers; (4) Alcohols that are aromatic compounds, aldehydes, ketones, ethers, etc. And the like classified into
　前記（１）に分類される香料としては、例えば、炭素数６~１２のアルコール［例えば、ｃｉｓ−３−ヘキセノール、３，３，５−トリメチルヘキサノールなど］、炭素数６~１６のアルデヒド［例えば、２，６，１０−トリメチル−９−ウンデセン−１−アールなど］、炭素数６~１２のケトン［例えば、メチルアミルケトンなど］などが挙げられる。なお、香料としての有機鎖状低分子化合物は１種を単独で使用することもできるし、２種以上を組み合わせて使用することもできる。 Examples of the fragrance classified as (1) include alcohols having 6 to 12 carbon atoms [for example, cis-3-hexenol, 3,3,5-trimethylhexanol, etc.], aldehydes having 6 to 16 carbon atoms [for example, 2,6,10-trimethyl-9-undecene-1-al, etc.], ketones having 6 to 12 carbon atoms [for example, methyl amyl ketone, etc.] and the like. In addition, the organic chain low molecular weight compound as a fragrance | flavor can also be used individually by 1 type, and can also be used in combination of 2 or more type.
　前記（２）に分類される香料としては、例えば、ｐ−ｔ−ブチルシクロヘキサノール、ｏ−ｔ−ブチルシクロヘキサノール、合成サンダル類、４−（トリシクロ［５，２，１，０２，６］−デシリデン−８）−ブタナール、２，４−ジメチルシクロヘキセ−３−エン−３−カルボアルデヒド、ｐ−ｔ−ブチルシクロヘキシルアセテート、ｏ−ｔ−ブチルシクロヘキシルアセテート、トリシクロ［５，２，１，０２，６〕−デセ−３−エン−８（または９）−イルアセテート、４−アセトキシ−３−ペンチルテトラヒドロピラン、エチレンブラシレート、ｏ−ｔ−ブチルシクロヘキサノン、ｐ−ｔ−アミルシクロヘキサノン、２−エチルヘキサナールエチレングリコールアセタールなどが挙げられる。なお、香料としての脂環式化合物は１種を単独で使用することもできるし、２種以上を組み合わせて使用することもできる。 Examples of the fragrance classified as (2) include pt-butylcyclohexanol, ot-butylcyclohexanol, synthetic sandals, 4- (tricyclo [5,2,1,02,6]- Decylidene-8) -butanal, 2,4-dimethylcyclohex-3-ene-3-carbaldehyde, pt-butylcyclohexyl acetate, ot-butylcyclohexyl acetate, tricyclo [5,2,1,0 2 , 6 ] -dec-3-en-8 (or 9) -yl acetate, 4-acetoxy-3-pentyltetrahydropyran, ethylene brushate, ot-butylcyclohexanone, pt-amylcyclohexanone, 2- Examples include ethyl hexanal ethylene glycol acetal. In addition, the alicyclic compound as a fragrance | flavor can also be used individually by 1 type, and can also be used in combination of 2 or more type.
　前記（３）に分類される香料としては、例えば、リナロール、テルピネオール、シトロネロール、ゲラニオール、ボルネオール、セドロール、ラバンジュロール、２，６−ジメチル−ヘプタン−２−オール、シトラール、シトロネラール、メトキシシトロネラール、ヒドロキシシトロネラール、ゲラノキシアセトアルデヒド、４−（４−メチル−３−ペンテニル）−シクロヘキセ−３−エン−１−カルボアルデヒド、２，４，６−トリメチルシクロヘキセ−３−エン−１−カルボアルデヒド、ｉｓｏ−ボルニルアセテート、イオノン、メチルイオノン、アセチル、セドレン、２，２，７，７−テトラメチル−２−トリシクロ［６，２，１，０３，８］−ウンデカン−４−オン、カンファー、メントン、ｄ−リモネン、ｌ−リモネン、ｐ−シメン、β−カリオフィレン、ローズオキサイド、リナロールオキサイド、ドデカヒドロ−３ａ，６，６，９ａ−テトラメチルナフト−［２，１−ｂ］−フラン、４−メチレン−１−オキサスピロ−［５，５］−ウンデカンなどが挙げられる。なお、香料としてのテルペン化合物は１種を単独で使用することもできるし、２種以上を組み合わせて使用することもできる。 Examples of the fragrance classified as (3) include linalool, terpineol, citronellol, geraniol, borneol, cedrol, lavandulol, 2,6-dimethyl-heptan-2-ol, citral, citronellal, methoxycitronellal. Hydroxycitronellal, geranoxyacetaldehyde, 4- (4-methyl-3-pentenyl) -cyclohex-3-ene-1-carbaldehyde, 2,4,6-trimethylcyclohex-3-ene-1- carbaldehyde, iso- bornyl acetate, ionone, methyl ionone, acetyl, cedrene, 2,2,7,7-tetramethyl-2-tricyclo [6,2,1,0 3,8] - undecane-4-one, Camphor, menton, d-limonene, l-limonene, p-si , Β-caryophyllene, rose oxide, linalool oxide, dodecahydro-3a, 6,6,9a-tetramethylnaphtho- [2,1-b] -furan, 4-methylene-1-oxaspiro- [5,5]- For example, undecane. In addition, the terpene compound as a fragrance | flavor can also be used individually by 1 type, and can also be used in combination of 2 or more type.
　前記（４）に分類される香料としては、例えば、フェニルエチルアルコール、アニスアルコール、フェニルエチルジメチルカルビノール、オイゲノール、ｉｓｏ−オイゲノール、シンナミックアルコール、ヘキシルシンナミックアルデヒド、ｐ−ｔｅｒｔ−ブチル−２−メチルヒドロシンナミックアルデヒド、アニスアルデヒド、クミンアルデヒド、フェノキシアセトアルデヒド、ヘリオトロピン、バニリン、ｐ−エチル−２，２−ジメチルヒドロシンナミックアルデヒド、ベンゾフェノン、ｐ−メトキシアセトフェノン、β−メチルナフィチルケトン、オーランチオール、フェニルアセトアルデヒド、ジメチルアセタール、ニトロムスク類、クマリン、イソクマロン系ムスク類、メチルアンスラニレート、ｉｓｏ−ブチルキノリン、ｐ−クレジルメチルエーテル、メチルオイゲノール、アネトールなどが挙げられる。なお、香料としての芳香族化合物は１種を単独で使用することもできるし、２種以上を組み合わせて使用することもできる。 Examples of the fragrance classified into the above (4) include phenylethyl alcohol, anis alcohol, phenylethyldimethylcarbinol, eugenol, iso-eugenol, cinnamic alcohol, hexyl cinnamaldehyde, p-tert-butyl-2- Methylhydrocinnamic aldehyde, anisaldehyde, cuminaldehyde, phenoxyacetaldehyde, heliotropin, vanillin, p-ethyl-2,2-dimethylhydrocinnamic aldehyde, benzophenone, p-methoxyacetophenone, β-methylnaphthyl ketone, auran All, phenylacetaldehyde, dimethylacetal, nitromusks, coumarins, isocoumarone musks, methylanthranilates, iso-butylquinoline, p- Registration methyl ether, methyl eugenol, and the like anethole. In addition, the aromatic compound as a fragrance | flavor can also be used individually by 1 type, and can also be used in combination of 2 or more type.
　易伸長性ポリマー母材（易伸長性ポリマー母材）中に香料が含まれる場合、該易伸長性ポリマー母材における香料の含有量（総量）は、特に限定されないが、易伸長性ポリマー母材（易伸長性ポリマー母材）を構成するポリマー１００重量部に対して、例えば、１．０×１０−５~１．０×１０−１重量部である。香料の含有量（総量）の下限は、好ましくは５．０×１０−５重量部、より好ましくは１．０×１０−４重量部である。一方、上限は、好ましくは５．０×１０−２重量部、より好ましくは１．０×１０−２重量部である。香料の含有量が１．０×１０−５重量部未満であると、不快臭のマスクが不十分となる場合があり、含有量が１．０×１０−１重量部を超えると、香料による香気が不快に感じられる場合がある。 When a fragrance is contained in the easily stretchable polymer matrix (easy stretchable polymer matrix), the content (total amount) of the fragrance in the easily stretchable polymer matrix is not particularly limited. For example, the amount is 1.0 × 10 −5 to 1.0 × 10 −1 parts by weight with respect to 100 parts by weight of the polymer constituting the (extensible polymer base material). The lower limit of the content (total amount) of the fragrance is preferably 5.0 × 10 −5 parts by weight, more preferably 1.0 × 10 −4 parts by weight. On the other hand, the upper limit is preferably 5.0 × 10 −2 parts by weight, more preferably 1.0 × 10 −2 parts by weight. If the content of the fragrance is less than 1.0 × 10 −5 parts by weight, the mask of unpleasant odor may be insufficient, and if the content exceeds 1.0 × 10 −1 parts by weight, Odor may be felt uncomfortable.
　難伸長部（筒状難伸長性ポリマー部Ａ）中に香料が含まれる場合、該難伸長部における香料の含有量（総量）は、特に限定されないが、難伸長部（筒状難伸長性ポリマー部Ａ）を構成するポリマー１００重量部に対して、例えば、１．０×１０−５~１．０×１０−１重量部である。香料の含有量（総量）の下限は、好ましくは５．０×１０−５重量部、より好ましくは１．０×１０−４重量部である。一方、上限は、好ましくは５．０×１０−２重量部、より好ましくは１．０×１０−２重量部である。香料の含有量が１．０×１０−５重量部未満であると、不快臭のマスクが不十分となる場合があり、含有量が１．０×１０−１重量部を超えると、香料による香気が不快に感じられる場合がある。 When a fragrance is contained in the difficultly stretched part (tubular hardly stretchable polymer part A), the content (total amount) of the fragrance in the difficultly stretched part is not particularly limited, but the difficultly stretched part (tubular hardly stretchable polymer) For example, 1.0 × 10 −5 to 1.0 × 10 −1 parts by weight with respect to 100 parts by weight of the polymer constituting part A). The lower limit of the content (total amount) of the fragrance is preferably 5.0 × 10 −5 parts by weight, more preferably 1.0 × 10 −4 parts by weight. On the other hand, the upper limit is preferably 5.0 × 10 −2 parts by weight, more preferably 1.0 × 10 −2 parts by weight. If the content of the fragrance is less than 1.0 × 10 −5 parts by weight, the mask of unpleasant odor may be insufficient, and if the content exceeds 1.0 × 10 −1 parts by weight, Odor may be felt uncomfortable.
　前記第１の態様のシート状伸長性有機基材は易伸長性ポリマー母材及び／又は筒状難伸長性ポリマー部Ａが香料を含有することにより、該香料の香気によって不快臭の発生が低減されている。また、前記第１の態様のシート状伸長性有機基材は、第３の態様のシート状伸長性有機基材と同様に、該シート状伸長性有機基材を１５０℃で３分間加熱した際に発生するモノマー量が３００ｐｐｍ以下であってもよい。即ち、第１の態様のシート状伸長性有機基材は、第３の態様のシート状伸長性有機基材でもあり得る。 In the sheet-like extensible organic base material of the first aspect, the easily extensible polymer base material and / or the cylindrical hardly extensible polymer portion A contains a fragrance, thereby reducing the occurrence of an unpleasant odor due to the fragrance of the fragrance. Has been. The sheet-like extensible organic base material of the first aspect is the same as the sheet-like extensible organic base material of the third aspect when the sheet-like extensible organic base material is heated at 150 ° C. for 3 minutes. The amount of monomer generated in may be 300 ppm or less. That is, the sheet-like extensible organic substrate of the first aspect can also be the sheet-like extensible organic substrate of the third aspect.
　前記第２の態様のシート状伸長性有機基材は、易伸長性ポリマー母材中に筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されている伸長性を有するシート状有機基材の少なくとも一方の面（片面側又は両面側）に消臭層を有するシート状伸長性有機基材である。 The sheet-like extensible organic base material of the second aspect is a sheet-like organic material having extensibility in which a cylindrical hardly extensible polymer portion A is partially and integrally formed in an easily extensible polymer base material. It is a sheet-like extensible organic base material having a deodorizing layer on at least one side (one side or both sides) of the base.
　前記消臭層としては、特に限定されず、消臭効果を有する任意の層を採用することができる。前記消臭層としては、具体的には、消臭剤を含有する層が挙げられる。該消臭層中の消臭剤の含有量（含有割合）は、特に限定されないが、例えば０．０１~２０重量％である。消臭剤の含有量の下限は０．１重量％が好ましく、より好ましくは０．５重量％であり、一方その上限は１５重量％が好ましく、より好ましくは１０重量％である。消臭剤の含有量を上記範囲に制御することにより、前記消臭層が非常に優れた消臭性を発現し、その結果、シート状伸長性有機基材からの不快臭の発生が効果的に抑制ないし抑止される傾向がある。なお、消臭剤は１種を単独で使用することもできるし、２種以上を組み合わせて使用することもできる。 The deodorant layer is not particularly limited, and any layer having a deodorizing effect can be adopted. Specific examples of the deodorant layer include a layer containing a deodorant. The content (content ratio) of the deodorant in the deodorant layer is not particularly limited, but is, for example, 0.01 to 20% by weight. The lower limit of the deodorant content is preferably 0.1% by weight, more preferably 0.5% by weight, while the upper limit is preferably 15% by weight, more preferably 10% by weight. By controlling the content of the deodorant within the above range, the deodorizing layer exhibits a very excellent deodorizing property, and as a result, generation of unpleasant odor from the sheet-like extensible organic base material is effective. Tend to be suppressed or deterred. In addition, a deodorizer can also be used individually by 1 type, and can also be used in combination of 2 or more type.
　前記消臭剤としては、公知乃至慣用の消臭剤を使用することができ、特に限定されないが、特に、金属成分が担持された無機粉末を好ましく使用することができる。該消臭剤（金属成分が担持された無機粉末）における金属成分の担持量は、消臭剤中の含有割合として、例えば０．１~３０重量％である。金属成分の担持量の下限は０．５重量％が好ましく、より好ましくは１重量％であり、一方その上限は２０重量％が好ましい。金属成分の担持量を上記範囲に制御することにより、前記消臭層が非常に優れた消臭性を発現し、その結果、シート状伸長性有機基材からの不快臭の発生が効果的に抑制ないし抑止される傾向がある。 As the deodorant, a known or conventional deodorant can be used, and it is not particularly limited, but in particular, an inorganic powder carrying a metal component can be preferably used. The supported amount of the metal component in the deodorant (inorganic powder on which the metal component is supported) is, for example, 0.1 to 30% by weight as the content in the deodorant. The lower limit of the metal component loading is preferably 0.5 wt%, more preferably 1 wt%, while the upper limit is preferably 20 wt%. By controlling the loading amount of the metal component within the above range, the deodorizing layer exhibits a very excellent deodorizing property, and as a result, the generation of an unpleasant odor from the sheet-like extensible organic base material is effective. There is a tendency to be suppressed or suppressed.
　前記消臭剤（金属成分が担持された無機粉末）における無機粉末としては、公知乃至慣用の無機粉末を使用することができ、特に限定されないが、例えば、ゼオライト、シリカゲル、酸化チタン、酸化アルミニウム、及び活性炭からなる群より選択された少なくとも１種の無機粉末を好ましく使用することができる。無機粉末は１種を単独で使用することもできるし、２種以上を組み合わせて使用することもできる。 As the inorganic powder in the deodorant (inorganic powder carrying a metal component), known or commonly used inorganic powder can be used, and is not particularly limited. For example, zeolite, silica gel, titanium oxide, aluminum oxide, And at least one inorganic powder selected from the group consisting of activated carbon can be preferably used. An inorganic powder can also be used individually by 1 type, and can also be used in combination of 2 or more type.
　前記消臭剤（金属成分が担持された無機粉末）における金属成分としては、公知乃至慣用の金属成分（金属）を使用することができ、特に限定されないが、例えば、銀、銅、亜鉛、錫、鉛、ビスマス、カドミウム、クロム、及び水銀からなる群より選択された少なくとも１種の金属成分を好ましく使用することができる。金属成分は１種を単独で使用することもできるし、２種以上を組み合わせて使用することもできる。 As the metal component in the deodorant (inorganic powder carrying the metal component), a known or commonly used metal component (metal) can be used, and is not particularly limited. For example, silver, copper, zinc, tin At least one metal component selected from the group consisting of lead, bismuth, cadmium, chromium, and mercury can be preferably used. A metal component can also be used individually by 1 type and can also be used in combination of 2 or more type.
　前記消臭剤としては、例えば、商品名「ケスモンＮＳ−１０」、「ケスモンＮＳ−２０」、「ケスモンＮＳ−１０Ｃ」、「ケスモンＮＳ−１０Ｎ」、「ケスモンＮＳ−７０」、「ケスモンＮＳ−８０Ｅ」、「ケスモンＮＳ−１０３」、「ケスモンＮＳ−１１０」、「ケスモンＮＳ−１２０」、「ケスモンＮＳ−１３０」（東亞合成（株）社製）、商品名「シュークレンズＫＤ−２１１」、「シュークレンズＫＤ−３１１」、「シュークレンズＫＤ−４１１」（ラサ工業（株）製）、商品名「ＦＩＮＥＸ−２５ＬＰ」（堺化学工業（株）製）などの市販品を使用することもできる。 Examples of the deodorant include trade names “Kesmon NS-10”, “Kesmon NS-20”, “Kesmon NS-10C”, “Kesmon NS-10N”, “Kesmon NS-70”, “Kesmon NS-”. 80E "," Kesmon NS-103 "," Kesmon NS-110 "," Kesmon NS-120 "," Kesmon NS-130 "(manufactured by Toagosei Co., Ltd.), trade name" Shoo Cleans KD-211 ", Commercial products such as “Shoe Cleanse KD-311”, “Shoe Cleanse KD-411” (manufactured by Lhasa Kogyo Co., Ltd.), and trade name “FINEX-25LP” (manufactured by Sakai Chemical Industry Co., Ltd.) can also be used. .
　前記消臭層は、樹脂（ポリマー）を含んでいてもよい。前記樹脂としては、公知乃至慣用の樹脂を使用することができ、特に限定されないが、例えば、フェノール系樹脂、ユリア系樹脂、メラミン系樹脂、アルキッド系樹脂、ジアリルフタレート系樹脂、エポキシ系樹脂、ポリウレタン系樹脂、ケイ素系樹脂などの熱硬化性樹脂；ポリ塩化ビニル系樹脂、ポリ塩化ビニリデン系樹脂、フッ素系樹脂、ポリフッ化ビニル系樹脂、ポリフッ化ビニリデン系樹脂、ポリ酢酸ビニル系樹脂、ポリビニルアルコール系樹脂、ポリビニルホルマール系樹脂、飽和ポリエステル系樹脂、ポリエチレン系樹脂、ポリプロピレン系樹脂、ポリスチレン系樹脂、ＡＢＳ系樹脂、アクリル系樹脂、ポリアミド系樹脂、ポリアセタール系樹脂、塩化ポリエーテル系樹脂、ポリカーボネート系樹脂、ポリアリレート系樹脂、エチルセルロース、酢酸セルロース、硝酸セルロース等の樹脂；天然ゴム、イソプレン系ゴム、アクリロニトリル系ゴム、アクリル系ゴム、ブタジエン系ゴム、ブチル系ゴム、スチレン系ゴム、クロロプレン系ゴム、クロルヒドリン系ゴム、ポリオレフィン系ゴム、ウレタン系ゴム、多硫化ゴム、シリコーン系ゴム、フッ素系ゴム、フロロシリコーン系ゴム等のエラストマーやゴム；などが挙げられる。 The deodorizing layer may contain a resin (polymer). The resin may be a known or commonly used resin, and is not particularly limited. For example, phenol resin, urea resin, melamine resin, alkyd resin, diallyl phthalate resin, epoxy resin, polyurethane Thermosetting resins such as silicon resins and silicon resins; polyvinyl chloride resins, polyvinylidene chloride resins, fluorine resins, polyvinyl fluoride resins, polyvinylidene fluoride resins, polyvinyl acetate resins, polyvinyl alcohol resins Resin, polyvinyl formal resin, saturated polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, ABS resin, acrylic resin, polyamide resin, polyacetal resin, chlorinated polyether resin, polycarbonate resin, Polyarylate resin Resins such as cellulose, cellulose acetate and cellulose nitrate; natural rubber, isoprene rubber, acrylonitrile rubber, acrylic rubber, butadiene rubber, butyl rubber, styrene rubber, chloroprene rubber, chlorohydrin rubber, polyolefin rubber And elastomers such as urethane rubber, polysulfide rubber, silicone rubber, fluorine rubber, fluorosilicone rubber, and the like.
　前記消臭層は、その他、目的に応じて任意の添加剤を含有していてもよい。該添加剤としては、例えば、光重合開始剤、シランカップリング剤、離型剤、硬化剤、硬化促進剤、希釈剤、老化防止剤、変性剤、界面活性剤、染料、顔料、変色防止剤、紫外線吸収剤、柔軟剤、安定剤、可塑剤、消泡剤などが挙げられる。なお、消臭層に含有され得る添加剤の種類、数、量は、目的に応じて適宜設定することができる。 The deodorizing layer may contain any other additive depending on the purpose. Examples of the additive include a photopolymerization initiator, a silane coupling agent, a mold release agent, a curing agent, a curing accelerator, a diluent, an anti-aging agent, a modifier, a surfactant, a dye, a pigment, and a discoloration preventing agent. UV absorbers, softeners, stabilizers, plasticizers, antifoaming agents and the like. In addition, the kind of additive which can be contained in a deodorizing layer, the number, and quantity can be suitably set according to the objective.
　前記消臭層は、単層の形態を有していてもよく、複層（積層）の形態を有していてもよい。なお、前記消臭層は、伸長性を有するシート状有機基材（シート状伸長性有機基材）１（該シート状伸長性有機基材上に後述の中間層が存在する場合は、該中間層）の表面の全体（全面）に設けてもよく、用途によっては、伸長性を有するシート状有機基材（シート状伸長性有機基材）１の表面のうち必要な箇所のみに部分的に設けてもよい。 The deodorizing layer may have a single-layer form or a multi-layer (laminated) form. In addition, the said deodorizing layer is a sheet-like organic base material (sheet-like extensible organic base material) 1 having extensibility (if the below-described intermediate layer is present on the sheet-like extensible organic base material, Layer) may be provided on the entire surface (entire surface), and depending on the application, it may be partially applied only to necessary portions of the surface of the sheet-like organic base material (sheet-like extensible organic base material) 1 having extensibility. It may be provided.
　前記消臭層の厚みは、特に限定されないが、例えば０．１~１００μｍである。厚みの下限は１μｍが好ましい。消臭層の厚みを上記範囲に制御することにより、消臭層が非常に優れた消臭性を発現し、その結果、シート状伸長性有機基材からの不快臭の発生が効果的に抑制ないし抑止される傾向がある。なお、消臭層が複層の形態を有する場合には、その合計厚みが上記範囲に制御されることが好ましい。 The thickness of the deodorant layer is not particularly limited, but is, for example, 0.1 to 100 μm. The lower limit of the thickness is preferably 1 μm. By controlling the thickness of the deodorant layer within the above range, the deodorant layer exhibits a very excellent deodorant property, and as a result, the generation of unpleasant odor from the sheet-like stretchable organic base material is effectively suppressed. There is a tendency to be deterred. In addition, when a deodorizing layer has a multilayer form, it is preferable that the total thickness is controlled by the said range.
　前記消臭層は、公知乃至慣用の方法により形成することができる。具体的には、例えば、消臭層の材料（例えば、消臭剤と樹脂とを含む樹脂組成物）を伸長性を有するシート状有機基材（該シート状伸長性有機基材上に後述の中間層が存在する場合は、該中間層）上にコーティングする方法；消臭層の材料（例えば、消臭剤）を伸長性を有するシート状有機基材（該シート状伸長性有機基材上に後述の中間層が存在する場合は、該中間層）上に蒸着（例えば、真空蒸着）する方法；消臭層を伸長性を有するシート状有機基材（該シート状伸長性有機基材上に後述の中間層が存在する場合は、該中間層）上にラミネートする方法；消臭層を適宜な支持体上に形成した後、シート状伸長性有機基材（該シート状伸長性有機基材上に後述の中間層が存在する場合は、該中間層）上に転写する方法などが挙げられる。 The deodorizing layer can be formed by a known or commonly used method. Specifically, for example, a deodorant layer material (for example, a resin composition containing a deodorant and a resin) has an extensible sheet-like organic base material (described later on the sheet-like extensible organic base material). A method of coating on the intermediate layer when an intermediate layer is present; a sheet-like organic substrate having extensible properties (for example, a deodorant) on the deodorant layer (on the sheet-like extensible organic substrate) In the case where an intermediate layer described later is present, a method of vapor-depositing (for example, vacuum vapor deposition) on the intermediate layer; a sheet-like organic substrate having extensible deodorizing layer (on the sheet-like extensible organic substrate) In the case where an intermediate layer described later is present, a method of laminating on the intermediate layer); after forming a deodorizing layer on a suitable support, a sheet-like extensible organic substrate (the sheet-like extensible organic group) In the case where an intermediate layer described later is present on the material, a method of transferring onto the intermediate layer) may be mentioned.
　伸長性を有するシート状有機基材１と消臭層６との間に、伸長性等を損なわない範囲で、必要に応じて他の層（中間層）を有していてもよい。 Between the sheet-like organic base material 1 having extensibility and the deodorizing layer 6, other layers (intermediate layers) may be provided as necessary as long as extensibility and the like are not impaired.
　前記第２の態様のシート状伸長性有機基材は前記消臭層を有することにより、不快臭の発生が低減されている。なお、前記第２の態様のシート状伸長性有機基材は、第１の態様のシート状伸長性有機基材と同様に、易伸長性ポリマー母材及び／又は筒状難伸長性ポリマー部Ａ（易伸長性ポリマー母材及び筒状難伸長性ポリマー部Ａのいずれか一方又は両方）が香料を含有していてもよい。該香料の種類や含有量は、第１の態様のシート状伸長性有機基材におけるものと同様のものが例示される。さらに、前記第２の態様のシート状伸長性有機基材は、第３の態様のシート状伸長性有機基材と同様に、該シート状伸長性有機基材を１５０℃で３分間加熱した際に発生するモノマー量が３００ｐｐｍ以下であってもよい。即ち、第２の態様のシート状伸長性有機基材は、第３の態様のシート状伸長性有機基材でもあり得る。 The occurrence of unpleasant odor is reduced by having the deodorizing layer in the sheet-like extensible organic base material of the second aspect. In addition, the sheet-like extensible organic base material of the said 2nd aspect is an easily extensible polymer base material and / or a cylindrical difficulty extensible polymer part A similarly to the sheet-like extensible organic base material of a 1st aspect. (Either one or both of the easily extensible polymer base material and the cylindrical hardly extensible polymer portion A) may contain a fragrance. The kind and content of the fragrance are exemplified by those similar to those in the sheet-like extensible organic substrate of the first aspect. Furthermore, the sheet-like extensible organic substrate of the second aspect is similar to the sheet-like extensible organic substrate of the third aspect when the sheet-like extensible organic substrate is heated at 150 ° C. for 3 minutes. The amount of monomer generated in may be 300 ppm or less. That is, the sheet-like extensible organic substrate of the second aspect may be the sheet-like extensible organic substrate of the third aspect.
　前記第３の態様のシート状伸長性有機基材は、易伸長性ポリマー母材中に筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されている伸長性を有するシート状有機基材を含むシート状伸長性有機基材であって、該シート状伸長性有機基材を１５０℃で３分間加熱した際に発生するモノマー量が３００ｐｐｍ以下である。前記第３の態様のシート状伸長性有機基材は、前記伸長性を有するシート状有機基材を含むものであればよく、例えば、前記伸長性を有するシート状有機基材であってもよいし、前記伸長性を有するシート状有機基材の少なくとも一方の面に消臭層を有するシート状伸長性有機基材であってもよい。 The sheet-like extensible organic base material according to the third aspect is a sheet-like organic material having extensibility in which a cylindrical hardly extensible polymer portion A is partially and integrally formed in an easily extensible polymer base material. A sheet-like extensible organic substrate containing a substrate, and the amount of monomer generated when the sheet-like extensible organic substrate is heated at 150 ° C. for 3 minutes is 300 ppm or less. The sheet-like extensible organic base material of the third aspect only needs to include the extensible sheet-like organic base material, and may be, for example, the extensible sheet-like organic base material. And the sheet-like extensible organic base material which has a deodorizing layer in the at least one surface of the said sheet-like organic base material which has the extendibility may be sufficient.
　前記第３の態様のシート状伸長性有機基材を１５０℃で３分間加熱した際に発生するモノマーは、主に、易伸長性ポリマー母材（伸長性ポリマー母材）を構成する伸長性を有するポリマー中に含まれる残存モノマー（残留モノマー）、筒状難伸長性ポリマー部Ａを構成するポリマー（ポリマー材料）中に含まれる残存モノマー（残留モノマー）に由来する。また、消臭層や中間層を有する場合には、これらの層を構成する樹脂中の残存モノマー（残留モノマー）に由来する場合もある。より具体的には、例えば、前記残存モノマーとしては、前述のエネルギー線硬化性基Ａ１及び反応性官能基Ｒ１を有する化合物、エネルギー線硬化性基Ａ２を有する硬化性モノマーＭ、ホモポリマーのＴｇが５℃以上であるモノマー、多官能モノマー、引張弾性率が０．１ＭＰａ以上のポリマー材料を構成するモノマーなどが挙げられる。 The monomer generated when the sheet-like extensible organic base material of the third aspect is heated at 150 ° C. for 3 minutes mainly has the extensibility constituting the easily extensible polymer matrix (extensible polymer matrix). It originates in the residual monomer (residual monomer) contained in the polymer which has, and the residual monomer (residual monomer) contained in the polymer (polymer material) which comprises the cylindrical difficulty extensible polymer part A. Moreover, when it has a deodorizing layer and an intermediate | middle layer, it may originate from the residual monomer (residual monomer) in resin which comprises these layers. More specifically, for example, as the residual monomer, the compound having the energy ray curable group A1 and the reactive functional group R1, the curable monomer M having the energy ray curable group A2, and the Tg of the homopolymer are as follows. Examples thereof include a monomer having a temperature of 5 ° C. or more, a polyfunctional monomer, and a monomer constituting a polymer material having a tensile modulus of elasticity of 0.1 MPa or more.
　前記第３の態様のシート状伸長性有機基材は、該シート状伸長性有機基材を１５０℃で３分間加熱した際に発生するモノマー量（モノマー発生量；シート状伸長性有機基材の重量に対するモノマー（発生モノマー）の量（重量）［μｇ／ｇ］）が３００ｐｐｍ以下であればよく、特に限定されないが、用途によっては２５０ｐｐｍ以下であることが好ましく、２００ｐｐｍ以下であってもよい。その下限は、特に限定されないが、０ｐｐｍが最も好ましい。前記モノマー発生量は、公知乃至慣用の方法、例えば、ガスクロマトグラフィー等を使用して測定でき、より詳しくは後述の＜モノマー発生量の測定方法＞に記載の方法に従って測定することができる。 The sheet-like extensible organic base material of the third aspect is a monomer amount generated when the sheet-like extensible organic base material is heated at 150 ° C. for 3 minutes (monomer generation amount; sheet-like extensible organic base material). The amount (weight) [μg / g]) of the monomer (generated monomer) with respect to the weight is not particularly limited as long as it is 300 ppm or less, but is preferably 250 ppm or less and may be 200 ppm or less depending on the application. The lower limit is not particularly limited, but 0 ppm is most preferable. The monomer generation amount can be measured using a known or conventional method, for example, gas chromatography or the like, and more specifically can be measured according to the method described in <Method for measuring monomer generation amount> described later.
　前記第３の態様のシート状伸長性有機基材におけるモノマー発生量を３００ｐｐｍ以下に制御する手段としては、特に限定されないが、例えば、シート状伸長性有機基材を乾燥工程において加熱処理する方法が挙げられる。前記乾燥工程の実施時期は特に限定されず、シート状伸長性有機基材の製造工程中に組み込まれて実施されるものであってもよいし（例えば、シート状伸長性有機基材の製造工程における工程Ｃの後など）、シート状伸長性有機基材を製造後、出荷する前の段階で実施されるものであってもよい。前記乾燥工程における加熱温度は、例えば５０~２００℃であり、その下限は７０℃が好ましく、より好ましくは８０℃、さらに好ましくは９０℃であり、一方その上限は１８０℃が好ましく、より好ましくは１６０℃、さらに好ましくは１４０℃である。乾燥工程における加熱温度は、該工程において常に一定であってもよいし、段階的に変更されるものであってもよい。また、前記乾燥工程における加熱時間は、例えば１分~３時間であり、その下限は１．５分が好ましく、より好ましくは２分、さらに好ましくは３分であり、一方その上限は２時間が好ましく、より好ましくは１時間、さらに好ましくは３０分である。前記乾燥工程における加熱温度、加熱時間を前記範囲に制御することで、効率良くモノマー発生量を低減できる傾向がある。前記乾燥工程における加熱処理は、公知乃至慣用の装置（例えば、各種形式のオーブン等）を用いて実施できる。また、前記乾燥工程における加熱処理は、常圧下、減圧下、加圧下のいずれにおいても実施できる。 The means for controlling the amount of monomer generated in the sheet-like extensible organic substrate of the third aspect to 300 ppm or less is not particularly limited. For example, there is a method in which the sheet-like extensible organic substrate is heat-treated in the drying step. Can be mentioned. The implementation time of the drying step is not particularly limited, and may be incorporated and implemented during the production process of the sheet-like extensible organic substrate (for example, the production process of the sheet-like extensible organic substrate) Or after step C), and after the production of the sheet-like extensible organic substrate, it may be carried out at a stage before shipment. The heating temperature in the drying step is, for example, 50 to 200 ° C., and the lower limit thereof is preferably 70 ° C., more preferably 80 ° C., further preferably 90 ° C., while the upper limit thereof is preferably 180 ° C., more preferably. It is 160 degreeC, More preferably, it is 140 degreeC. The heating temperature in the drying process may always be constant in the process, or may be changed in stages. The heating time in the drying step is, for example, 1 minute to 3 hours, and the lower limit thereof is preferably 1.5 minutes, more preferably 2 minutes, further preferably 3 minutes, while the upper limit is 2 hours. It is preferably 1 hour, more preferably 30 minutes. By controlling the heating temperature and heating time in the drying step within the above ranges, there is a tendency that the amount of monomer generation can be efficiently reduced. The heat treatment in the drying step can be carried out using a known or conventional apparatus (for example, various types of ovens). The heat treatment in the drying step can be performed under normal pressure, reduced pressure, or increased pressure.
　前記第３の態様のシート状伸長性有機基材におけるモノマー発生量を３００ｐｐｍ以下に制御する手段としては、シート状伸長性有機基材を前記乾燥工程に付すことの他、例えば、モノマー（エネルギー線硬化性モノマー等）や該モノマーの部分重合物を重合する際の条件（例えば、エネルギー線の照射条件、加熱条件など）を最適化してモノマーの反応率（重合率）を高くすること等も挙げられる。 Means for controlling the amount of monomer generated in the sheet-like extensible organic substrate of the third aspect to 300 ppm or less include, for example, monomer (energy rays) in addition to subjecting the sheet-like extensible organic substrate to the drying step. Curable monomers, etc.) and conditions for polymerizing the partially polymerized monomers (for example, energy ray irradiation conditions, heating conditions, etc.) to optimize the monomer reaction rate (polymerization rate), etc. It is done.
　前記第３の態様のシート状伸長性有機基材は、モノマー発生量が３００ｐｐｍ以下に制御されていることにより、不快臭（特に、モノマーに由来する不快臭（モノマー臭））の発生が低減されている。なお、前記第３の態様のシート状伸長性有機基材は、第１の態様のシート状伸長性有機基材と同様に、易伸長性ポリマー母材及び／又は筒状難伸長性ポリマー部Ａが香料を含有していてもよい。即ち、第３の態様のシート状伸長性有機基材は、第１の態様のシート状伸長性有機基材でもあり得る。該香料の種類や含有量は、第１の態様のシート状伸長性有機基材におけるものと同様のものが例示される。さらに、前記第３の態様のシート状伸長性有機基材は、シート状伸長性有機基材の少なくとも一方の面に消臭層を有していてもよい。即ち、第３の態様のシート状伸長性有機基材は、第２の態様のシート状伸長性有機基材でもあり得る。前記消臭層としては、第２の態様のシート状伸長性有機基材において例示したものと同様のものが例示される。 In the sheet-like extensible organic base material of the third aspect, generation of unpleasant odor (particularly, unpleasant odor derived from monomer (monomer odor)) is reduced by controlling the amount of monomer generated to 300 ppm or less. ing. In addition, the sheet-like extensible organic base material of the said 3rd aspect is an easily extensible polymer base material and / or a cylindrical difficulty extensible polymer part A similarly to the sheet-like extensible organic base material of a 1st aspect. May contain a fragrance. That is, the sheet-like extensible organic substrate of the third aspect can also be the sheet-like extensible organic substrate of the first aspect. The kind and content of the fragrance are exemplified by those similar to those in the sheet-like extensible organic substrate of the first aspect. Furthermore, the sheet-like extensible organic substrate of the third aspect may have a deodorizing layer on at least one surface of the sheet-like extensible organic substrate. That is, the sheet-like extensible organic substrate of the third aspect may be the sheet-like extensible organic substrate of the second aspect. Examples of the deodorizing layer include those similar to those exemplified in the sheet-like extensible organic substrate of the second aspect.
　不快臭防止性を有するシート状伸長性有機基材の厚みは、例えば０．０１ｍｍ以上であり、好ましくは０．０３ｍｍ以上、さらに好ましくは０．０５ｍｍ以上である。不快臭防止性を有するシート状伸長性有機基材の厚みの上限は、例えば１ｃｍであり、好ましくは５ｍｍ、さらに好ましくは２ｍｍである。 The thickness of the sheet-like extensible organic base material having an unpleasant odor preventing property is, for example, 0.01 mm or more, preferably 0.03 mm or more, and more preferably 0.05 mm or more. The upper limit of the thickness of the sheet-like extensible organic base material having an unpleasant odor preventing property is, for example, 1 cm, preferably 5 mm, and more preferably 2 mm.
　上記のシート状伸長性有機基材は、不快臭の発生が抑制され且つ形状不変部を有する伸長性部材（又は、不快臭の発生が抑制され且つ形状不変部を有する伸縮性部材）として、エレクトロニクス製品（トランジスタ、集積回路、コンデンサ、センサ、アクチュエータ等）用部材、オプティカル製品（ディスプレイ、照明、光導波回路等）用部材、オプトエレクトロニクス製品（発光ダイオード、フォトダイオード、太陽電池等）用部材、カーエレクトロニクス製品用部材、家電製品用部材、住宅設備用部材、建材、バンド部材、結束用部材、衛生用品、衣料品の部分、湿布剤の基布等として利用できる。 The sheet-like extensible organic base material is used as an extensible member that suppresses generation of unpleasant odor and has a shape-invariable portion (or an elastic member that suppresses generation of unpleasant odor and has a shape-invariable portion). Products (transistors, integrated circuits, capacitors, sensors, actuators, etc.), optical products (displays, lighting, optical waveguide circuits, etc.), optoelectronics products (light emitting diodes, photodiodes, solar cells, etc.), cars It can be used as a member for electronics products, a member for home appliances, a member for household equipment, a building material, a band member, a binding member, a sanitary article, a clothing part, a base material for a poultice.
　［着色印字性を有するシート状伸長性有機基材］
　着色印字性を有するシート状伸長性有機基材には、意匠性が付与されたシート状伸長性有機基材、意匠性の付与が容易なシート状伸長性有機基材が含まれる。着色印字性を有するシート状伸長性有機基材として、（ｉ）易伸長性ポリマー母材中に筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されている伸長性を有するシート状有機基材であって、易伸長性ポリマー母材及び／又は筒状難伸長性ポリマー部Ａ（易伸長性ポリマー母材及び筒状難伸長性ポリマー部Ａのいずれか一方又は両方）が染料若しくは顔料を含有しているシート状伸長性有機基材、（ｉｉ）易伸長性ポリマー母材中に筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されている伸長性を有するシート状有機基材の少なくとも一方の面に着色層を有するシート状伸長性有機基材、（ｉｉｉ）易伸長性ポリマー母材中に筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されている伸長性を有するシート状有機基材の少なくとも一方の面に印字層を有するシート状伸長性有機基材が挙げられる。 [Sheet-like extensible organic base material with colored printability]
The sheet-like extensible organic base material having coloring printability includes a sheet-like extensible organic base material imparted with designability and a sheet-like extensible organic base material that is easily imparted with designability. As a sheet-like extensible organic base material having colored printability, (i) a sheet having extensibility in which a cylindrical hardly extensible polymer portion A is partially and integrally formed in an easily extensible polymer base material The organic base material is an easily extensible polymer base material and / or a cylindrical hardly extensible polymer portion A (one or both of the easily extensible polymer base material and the cylindrical hard extensible polymer portion A) are dyes. Or the sheet-like extensible organic base material containing a pigment, (ii) It has the extensibility by which the cylindrical difficulty extensible polymer part A is partially and integrally formed in the easily extensible polymer base material. A sheet-like extensible organic base material having a colored layer on at least one surface of the sheet-like organic base material, and (iii) a cylindrical non-extensible polymer portion A partially and integrally in an easily extensible polymer base material Formed sheet-like organic group having extensibility Sheet elongation organic substrate having a printing layer on at least one surface of the like.
　このようなシート状伸長性有機基材を一方向（面方向）に伸長させると、易伸長性ポリマー母材の部位は伸長するが、部分的に形成された筒状難伸長性ポリマー部Ａは伸長しないか、又はほとんど伸長しない。このため、筒状難伸長性ポリマー部Ａに、形状が変化しないことが望まれる意匠を施したり、他の部材を固定、保持することができる。また、このシート状伸長性有機基材は、意匠性が付与されているが、又は、意匠性の付与が容易であるため、例えば、特に意匠性（デザイン性等）が求められる用途にも好ましく使用できる。 When such a sheet-like extensible organic base material is extended in one direction (plane direction), the site of the easily extensible polymer base material is extended, but the partially formed cylindrical hardly extensible polymer portion A is Does not stretch or barely stretches. For this reason, it is possible to give the tubular hardly extensible polymer portion A a design whose shape is desired not to change, and to fix and hold other members. Further, this sheet-like extensible organic base material is given design properties, or is easy to impart design properties, and therefore, for example, it is particularly preferable for applications requiring design properties (design properties, etc.). Can be used.
　着色印字性を有するシート状伸長性有機基材の代表例として、図１８の（１）に示される多機能性シート状伸長性有機基材Ａにおいて、機能性層６が着色層又は印字層であるもの、図１８の（２）に示される多機能性シート状伸長性有機基材Ａにおいて、機能性層６が着色層又は印字層であるもの（２つの機能性層のうち一方が着色層で、他方が印字層であってもよい）、図１８の（３）に示される多機能性シート状伸長性有機基材Ａにおいて、伸長性を有するシート状有機基材１自体（易伸長性ポリマー母材２及び／又は筒状難伸長性ポリマー部Ａ３）が着色されているものが挙げられる。 As a representative example of a sheet-like extensible organic substrate having colored printability, in the multifunctional sheet-like extensible organic substrate A shown in (1) of FIG. 18, the functional layer 6 is a colored layer or a printed layer. In the multi-functional sheet-like extensible organic base material A shown in (2) of FIG. 18, the functional layer 6 is a colored layer or a printing layer (one of the two functional layers is a colored layer) In the multifunctional sheet-like extensible organic substrate A shown in (3) of FIG. 18, the other sheet-like organic substrate 1 itself (easily extensible) Examples thereof include those in which the polymer base material 2 and / or the cylindrical hardly extensible polymer portion A3) are colored.
　上記着色印字性を有するシート状伸長性有機基材においては、本発明においては、易伸長性ポリマー母材２が染料又は顔料を含有していてもよい。なお、易伸長性ポリマー母材２は、染料と顔料の両方を含有していてもよい。これにより、易伸長性ポリマー母材が着色され、本発明のシート状伸長性有機基材には優れた意匠性が付与される。前記染料、顔料としては、公知乃至慣用のものを使用することができる。 In the sheet-like extensible organic base material having the color printing property, in the present invention, the easily extensible polymer base material 2 may contain a dye or a pigment. The easily extensible polymer base material 2 may contain both a dye and a pigment. Thereby, an easily extensible polymer base material is colored and the design property excellent in the sheet-like extensible organic base material of this invention is provided. As the dye and pigment, known or commonly used dyes can be used.
　前記染料としては、公知乃至慣用の染料を使用することができ、特に限定されないが、例えば、ニトロ染料、ニトロソ染料、スチルベン染料、ピラゾロン染料、チアゾール染料、アゾ染料、ポリアゾ染料、カルボニウム染料、キノアニル染料、インドフェノール染料、インドアニリン染料、インダミン染料、キノンイミン染料、アジン染料、酸化染料、オキサジン染料、チアジン染料、アクリジン染料、ジフェニルメタン染料、トリフェニルメタン染料、キサンテン染料、チオキサンテン染料、硫化染料、ピリジン染料、ピリドン染料、チアジアゾール染料、チオフェン染料、ベンゾイソチアゾール染料、ジシアノイミダゾール染料、ベンゾピラン染料、ベンゾジフラノン染料、キノリン染料、インジゴ染料、チオインジゴ染料、アントラキノン染料、ベンゾフェノン染料、ベンゾキノン染料、ナフトキノン染料、フタロシアニン染料、シアニン染料、メチン染料、ポリメチン染料、アゾメチン染料、縮合メチン染料、ナフタルイミド染料、ペリノン染料、トリアリールメタン染料、ザンセン染料、アミノケトン染料、オキシケトン染料、インジゴイド染料などが挙げられる。 The dye may be a known or commonly used dye, and is not particularly limited. For example, nitro dye, nitroso dye, stilbene dye, pyrazolone dye, thiazole dye, azo dye, polyazo dye, carbonium dye, quinoanyl dye , Indophenol dyes, Indoaniline dyes, Indamine dyes, Quinone imine dyes, Azine dyes, Oxidized dyes, Oxazine dyes, Thiazine dyes, Acridine dyes, Diphenylmethane dyes, Triphenylmethane dyes, Xanthene dyes, Thioxanthene dyes, Sulfurized dyes, Pyridine dyes , Pyridone dye, thiadiazole dye, thiophene dye, benzoisothiazole dye, dicyanoimidazole dye, benzopyran dye, benzodifuranone dye, quinoline dye, indigo dye, thioindigo dye, anthra Non dye, benzophenone dye, benzoquinone dye, naphthoquinone dye, phthalocyanine dye, cyanine dye, methine dye, polymethine dye, azomethine dye, condensed methine dye, naphthalimide dye, perinone dye, triarylmethane dye, xanthene dye, aminoketone dye, oxyketone And dyes and indigoid dyes.
　なお、染料は１種を単独で、又は２種以上を組み合わせて使用できる。また、染料としては、市販品を使用することもできる。また、染料は、溶液や分散液等の形態で使用することもできる。 In addition, a dye can be used individually by 1 type or in combination of 2 or more types. Moreover, as a dye, a commercial item can also be used. The dye can also be used in the form of a solution or a dispersion.
　易伸長性ポリマー母材２における染料の含有量（総量）としては、易伸長性ポリマー母材２全体に対して、例えば、０．００１~５０重量％である。染料の含有量（総量）の下限は、好ましくは０．０１重量％、より好ましくは０．１重量％、さらに好ましくは０．３重量％であり、上限は、好ましくは４５重量％、より好ましくは４０重量％、さらに好ましくは３５重量％である。含有量が０．００１重量％未満であると、用途によっては意匠性が不十分となる場合がある。一方、含有量が５０重量％を超えると、用途によっては易伸長性ポリマー母材部の機械強度が低下する場合がある。 The content (total amount) of the dye in the stretchable polymer base material 2 is, for example, 0.001 to 50% by weight with respect to the whole stretchable polymer base material 2. The lower limit of the dye content (total amount) is preferably 0.01% by weight, more preferably 0.1% by weight, still more preferably 0.3% by weight, and the upper limit is preferably 45% by weight, more preferably. Is 40% by weight, more preferably 35% by weight. If the content is less than 0.001% by weight, the design may be insufficient depending on the application. On the other hand, if the content exceeds 50% by weight, the mechanical strength of the easily extensible polymer base material may be lowered depending on the application.
　前記顔料としては、公知乃至慣用の顔料を使用することができ、特に限定されないが、例えば、酸化チタン、酸化亜鉛、タルク、シェンナ、アンバー、カオリン、炭酸カルシウム、酸化鉄、ランプブラック、ファーネスブラック、アイボリーブラック、黒鉛、フラーレン、カーボンブラック、ヴィリジアン、コバルトブルー、エメラルドグリーン、コバルトグリーン、フタロシアニングリーン、フタロシアニンブルー、ミロリブルー、ファストイエロー、ジスアゾイエロー、縮合アゾイエロー、ベンゾイミダゾロンイエロー、ジニトロアニリンオレンジ、ペンズイミダゾロンオレンジ、ペリノンオレンジ、トルイジンレッド、パーマネントカーミン、アントラキノニルレッド、パーマネントレッド、ナフトールレッド、縮合アゾレッド、ベンズイミダゾロンカーミン、ベンズイミダゾロンブラウン、アントラピリミジンイエロー、キノフタロンイエロー、コバルト紫、マンガン紫などが挙げられる。 As the pigment, known or commonly used pigments can be used, and are not particularly limited. For example, titanium oxide, zinc oxide, talc, senna, amber, kaolin, calcium carbonate, iron oxide, lamp black, furnace black, Ivory black, graphite, fullerene, carbon black, viridian, cobalt blue, emerald green, cobalt green, phthalocyanine green, phthalocyanine blue, miloli blue, fast yellow, disazo yellow, condensed azo yellow, benzimidazolone yellow, dinitroaniline orange, penzimidazo Long Orange, Perinone Orange, Toluidine Red, Permanent Carmine, Anthraquinonyl Red, Permanent Red, Naphthol Red, Condensed Azo Red, Ve 'S benzimidazolone carmine, benzimidazolone brown, anthrapyrimidine yellow, quinophthalone yellow, cobalt violet, etc. manganese violet and the like.
　なお、顔料は１種を単独で、又は２種以上を組み合わせて使用できる。また、顔料としては、市販品を使用することもできる。また、顔料は、溶液や分散液等の形態で使用することもできる。 In addition, a pigment can be used individually by 1 type or in combination of 2 or more types. Moreover, a commercial item can also be used as a pigment. The pigment can also be used in the form of a solution or a dispersion.
　易伸長性ポリマー母材２における顔料の含有量（総量）としては、易伸長性ポリマー母材２全体に対して、例えば、０．００１~５０重量％である。顔料の含有量（総量）の下限は、好ましくは０．０１重量％、より好ましくは０．１重量％、さらに好ましくは０．３重量％であり、上限は、好ましくは４５重量％、より好ましくは４０重量％、さらに好ましくは３５重量％である。含有量が０．００１重量％未満であると、用途によっては意匠性が不十分となる場合がある。一方、含有量が５０重量％を超えると、用途によっては易伸長性ポリマー母材部の機械強度が低下する場合がある。 The content (total amount) of the pigment in the stretchable polymer base material 2 is, for example, 0.001 to 50% by weight with respect to the whole stretchable polymer base material 2. The lower limit of the pigment content (total amount) is preferably 0.01% by weight, more preferably 0.1% by weight, still more preferably 0.3% by weight, and the upper limit is preferably 45% by weight, more preferably. Is 40% by weight, more preferably 35% by weight. If the content is less than 0.001% by weight, the design may be insufficient depending on the application. On the other hand, if the content exceeds 50% by weight, the mechanical strength of the easily extensible polymer base material may be lowered depending on the application.
　筒状難伸長性ポリマー部Ａ３には、前記易伸長性ポリマー母材部２と同様、染料又は顔料が含まれていてもよい。なお、筒状難伸長性ポリマー部Ａは、染料と顔料の両方を含有していてもよい。これにより、筒状難伸長性ポリマー部Ａが着色され、本発明のシート状伸長性有機基材には優れた意匠性が付与される。易伸長性ポリマー母材部と筒状難伸長性ポリマー部Ａとは同じ色であってもよいし、例えば、易伸長性ポリマー母材部と筒状難伸長性ポリマー部Ａをそれぞれ異なる色に着色したり、複数の筒状難伸長性ポリマー部Ａをそれぞれ異なる色に着色すること等によって、一層優れた意匠性を付与することも可能である。前記染料、顔料としては、公知乃至慣用のものを使用することができ、具体的には、前記と同様のものを使用できる。 The cylindrical difficult-to-extend polymer part A3 may contain a dye or a pigment, like the easily-extensible polymer base part 2. The cylindrical difficult-to-extend polymer part A may contain both a dye and a pigment. Thereby, the cylindrical difficulty extensible polymer part A is colored, and excellent designability is imparted to the sheet-like extensible organic base material of the present invention. The easily extensible polymer base material portion and the cylindrical hardly extensible polymer portion A may be the same color, for example, the easily extensible polymer base material portion and the cylindrical hardly extensible polymer portion A have different colors. It is also possible to impart more excellent design properties by coloring or coloring the plurality of cylindrical difficult-to-extend polymer parts A to different colors. As the dye and pigment, known or commonly used ones can be used, and specifically, the same ones as described above can be used.
　筒状難伸長性ポリマー部Ａ３における染料の含有量（総量）は、筒状難伸長性ポリマー部Ａ３全体に対して、例えば、０．００１~５０重量％である。染料の含有量（総量）の下限は、好ましくは０．０１重量％、より好ましくは０．１重量％、さらに好ましくは０．３重量％であり、上限は、好ましくは４５重量％、より好ましくは４０重量％、さらに好ましくは３５重量％である。含有量が０．００１重量％未満であると、用途によっては意匠性が不十分となる場合がある。一方、含有量が５０重量％を超えると、用途によっては易伸長性ポリマー母材部の機械強度が低下する場合がある。 The content (total amount) of the dye in the cylindrical difficult-to-extend polymer part A3 is, for example, 0.001 to 50% by weight with respect to the entire cylindrical difficult-to-extend polymer part A3. The lower limit of the dye content (total amount) is preferably 0.01% by weight, more preferably 0.1% by weight, still more preferably 0.3% by weight, and the upper limit is preferably 45% by weight, more preferably. Is 40% by weight, more preferably 35% by weight. If the content is less than 0.001% by weight, the design may be insufficient depending on the application. On the other hand, if the content exceeds 50% by weight, the mechanical strength of the easily extensible polymer base material may be lowered depending on the application.
　筒状難伸長性ポリマー部Ａ３における顔料の含有量（総量）は、筒状難伸長性ポリマー部Ａ３全体に対して、例えば、０．００１~５０重量％である。顔料の含有量（総量）の下限は、好ましくは０．０１重量％、より好ましくは０．１重量％、さらに好ましくは０．３重量％であり、上限は、好ましくは４５重量％、より好ましくは４０重量％、さらに好ましくは３５重量％である。含有量が０．００１重量％未満であると、用途によっては意匠性が不十分となる場合がある。一方、含有量が５０重量％を超えると、用途によっては易伸長性ポリマー母材部の機械強度が低下する場合がある。 The content (total amount) of the pigment in the cylindrical difficult-to-extend polymer part A3 is, for example, 0.001 to 50% by weight with respect to the entire cylindrical difficult-to-extend polymer part A3. The lower limit of the pigment content (total amount) is preferably 0.01% by weight, more preferably 0.1% by weight, still more preferably 0.3% by weight, and the upper limit is preferably 45% by weight, more preferably. Is 40% by weight, more preferably 35% by weight. If the content is less than 0.001% by weight, the design may be insufficient depending on the application. On the other hand, if the content exceeds 50% by weight, the mechanical strength of the easily extensible polymer base material may be lowered depending on the application.
　前記意匠性が付与されたシート状伸長性有機基材には、前記（ｉ）又は（ｉｉ）の態様がある。前記（ｉ）の態様のシート状伸長性有機基材は、易伸長性ポリマー母材及び／又は筒状難伸長性ポリマー部Ａが染料若しくは顔料を含有する。このような染料や顔料の例や、これらの含有量については、前述の通りである。なお、前記（ｉ）の態様のシート状伸長性有機基材は、例えば、伸長性を有するシート状有機基材の少なくとも一方の面に後述の印字層を有するものであってもよい。 The sheet-like extensible organic base material to which the design property is imparted has the aspect (i) or (ii). In the sheet-like extensible organic base material of the aspect (i), the easily extensible polymer base material and / or the cylindrical hardly extensible polymer portion A contains a dye or a pigment. Examples of such dyes and pigments and their contents are as described above. In addition, the sheet-like extensible organic base material of the aspect of said (i) may have a below-mentioned printing layer in the at least one surface of the sheet-like organic base material which has the extensibility, for example.
　前記（ｉｉ）の態様のシート状伸長性有機基材は、易伸長性ポリマー母材中に筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されている伸長性を有するシート状有機基材の少なくとも一方の面（片面側又は両面側）に着色層を有するシート状伸長性有機基材である。 The sheet-like extensible organic base material of the aspect of (ii) is a sheet-like form having extensibility in which a cylindrical hardly extensible polymer portion A is partially and integrally formed in an easily extensible polymer base material. It is a sheet-like extensible organic base material having a colored layer on at least one surface (one side or both sides) of the organic base.
　前記着色層としては、特に限定されず、任意の色に着色された層を採用することができる。前記着色層としては、具体的には、染料及び／又は顔料を含有する層などが挙げられる。該着色層における染料、顔料としては、前記で例示したものが使用できる。 The color layer is not particularly limited, and a layer colored in an arbitrary color can be employed. Specific examples of the colored layer include a layer containing a dye and / or a pigment. As the dye and pigment in the colored layer, those exemplified above can be used.
　前記着色層中の染料の含有量（含有割合）は、特に限定されないが、例えば０．０１~５０重量％である。染料の含有量の下限は０．１重量％が好ましく、より好ましくは０．５重量％であり、一方その上限は４０重量％が好ましく、より好ましくは３０重量％である。染料の含有量を上記範囲に制御することにより、前記着色層による優れた意匠性をシート状伸長性有機基材に対して付与できる。なお、前記着色層において染料は１種を単独で使用することもできるし、２種以上を組み合わせて使用することもできる。 The content (content ratio) of the dye in the colored layer is not particularly limited, and is, for example, 0.01 to 50% by weight. The lower limit of the dye content is preferably 0.1% by weight, more preferably 0.5% by weight, while the upper limit is preferably 40% by weight, more preferably 30% by weight. By controlling the content of the dye within the above range, excellent design properties by the colored layer can be imparted to the sheet-like extensible organic base material. In the colored layer, one type of dye can be used alone, or two or more types can be used in combination.
　前記着色層中の顔料の含有量（含有割合）は、特に限定されないが、例えば０．０１~５０重量％である。顔料の含有量の下限は０．１重量％が好ましく、より好ましくは０．５重量％であり、一方その上限は４０重量％が好ましく、より好ましくは３０重量％である。顔料の含有量を上記範囲に制御することにより、前記着色層による優れた意匠性をシート状伸長性有機基材に対して付与できる。なお、前記着色層において顔料は１種を単独で使用することもできるし、２種以上を組み合わせて使用することもできる。 The content (content ratio) of the pigment in the colored layer is not particularly limited, and is, for example, 0.01 to 50% by weight. The lower limit of the pigment content is preferably 0.1% by weight, more preferably 0.5% by weight, while the upper limit is preferably 40% by weight, more preferably 30% by weight. By controlling the content of the pigment within the above range, excellent design properties by the colored layer can be imparted to the sheet-like extensible organic base material. In addition, the pigment can be used individually by 1 type in the said colored layer, and can also be used in combination of 2 or more type.
　前記着色層は、樹脂（ポリマー）を含んでいてもよい。前記樹脂としては、公知乃至慣用の樹脂を使用することができ、特に限定されないが、例えば、フェノール系樹脂、ユリア系樹脂、メラミン系樹脂、アルキッド系樹脂、ジアリルフタレート系樹脂、エポキシ系樹脂、ポリウレタン系樹脂、ケイ素系樹脂などの熱硬化性樹脂；ポリ塩化ビニル系樹脂、ポリ塩化ビニリデン系樹脂、フッ素系樹脂、ポリフッ化ビニル系樹脂、ポリフッ化ビニリデン系樹脂、ポリ酢酸ビニル系樹脂、ポリビニルアルコール系樹脂、ポリビニルホルマール系樹脂、飽和ポリエステル系樹脂、ポリエチレン系樹脂、ポリプロピレン系樹脂、ポリスチレン系樹脂、ＡＢＳ系樹脂、アクリル系樹脂、ポリアミド系樹脂、ポリアセタール系樹脂、塩化ポリエーテル系樹脂、ポリカーボネート系樹脂、ポリアリレート系樹脂、エチルセルロース、酢酸セルロース、硝酸セルロース等の樹脂；天然ゴム、イソプレン系ゴム、アクリロニトリル系ゴム、アクリル系ゴム、ブタジエン系ゴム、ブチル系ゴム、スチレン系ゴム、クロロプレン系ゴム、クロルヒドリン系ゴム、ポリオレフィン系ゴム、ウレタン系ゴム、多硫化ゴム、シリコーン系ゴム、フッ素系ゴム、フロロシリコーン系ゴム等のエラストマーやゴム；などが挙げられる。また、前記樹脂としては、前記易伸長性ポリマー母材を構成するポリマーとして例示したポリマーを使用することもできる。 The colored layer may contain a resin (polymer). The resin may be a known or commonly used resin, and is not particularly limited. For example, phenol resin, urea resin, melamine resin, alkyd resin, diallyl phthalate resin, epoxy resin, polyurethane Thermosetting resins such as silicon resins and silicon resins; polyvinyl chloride resins, polyvinylidene chloride resins, fluorine resins, polyvinyl fluoride resins, polyvinylidene fluoride resins, polyvinyl acetate resins, polyvinyl alcohol resins Resin, polyvinyl formal resin, saturated polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, ABS resin, acrylic resin, polyamide resin, polyacetal resin, chlorinated polyether resin, polycarbonate resin, Polyarylate resin Resins such as cellulose, cellulose acetate and cellulose nitrate; natural rubber, isoprene rubber, acrylonitrile rubber, acrylic rubber, butadiene rubber, butyl rubber, styrene rubber, chloroprene rubber, chlorohydrin rubber, polyolefin rubber And elastomers such as urethane rubber, polysulfide rubber, silicone rubber, fluorine rubber, fluorosilicone rubber, and the like. Moreover, the polymer illustrated as a polymer which comprises the said easily extensible polymer base material can also be used as said resin.
　前記着色層は、その他、目的に応じて任意の添加剤を含有していてもよい。該添加剤としては、例えば、光重合開始剤、シランカップリング剤、離型剤、硬化剤、硬化促進剤、希釈剤、老化防止剤、変性剤、界面活性剤、変色防止剤、紫外線吸収剤、柔軟剤、安定剤、可塑剤、消泡剤などが挙げられる。なお、着色層に含有され得る添加剤の種類、数、量は、目的に応じて適宜設定することができる。 The colored layer may contain any other additive depending on the purpose. Examples of the additive include a photopolymerization initiator, a silane coupling agent, a release agent, a curing agent, a curing accelerator, a diluent, an anti-aging agent, a modifier, a surfactant, a discoloration preventing agent, and an ultraviolet absorber. , Softeners, stabilizers, plasticizers, antifoaming agents and the like. In addition, the kind of additive which can be contained in a colored layer, the number, and quantity can be suitably set according to the objective.
　前記着色層は、単層の形態を有していてもよく、複層（積層）の形態を有していてもよい。なお、前記着色層は、伸長性を有するシート状有機基材１（該シート状伸長性有機基材上に後述の中間層が存在する場合は、該中間層）の表面の全体（全面）に設けてもよく、用途によっては、伸長性を有するシート状有機基材１の表面のうち必要な箇所のみに部分的に設けてもよい。また、シート状伸長性有機基材（又は中間層）の一方の面において複数の異なる色の着色層を設けることもできる。 The colored layer may have a single layer form or a multi-layer form. The colored layer is formed on the entire surface (entire surface) of the sheet-like organic substrate 1 having extensibility (if the intermediate layer described later is present on the sheet-like extensible organic substrate, the intermediate layer). Depending on the application, it may be partially provided only on a necessary portion of the surface of the sheet-like organic substrate 1 having extensibility. Moreover, the colored layer of a several different color can also be provided in one surface of a sheet-like extensible organic base material (or intermediate | middle layer).
　前記着色層の厚みは、特に限定されないが、例えば０．１~１００μｍである。厚みの下限は１μｍが好ましく、より好ましくは５μｍであり、その上限は９０μｍが好ましく、より好ましくは８０μｍである。着色層の厚みを上記範囲に制御することにより、前記着色層による優れた意匠性をシート状伸長性有機基材に対して付与できる。なお、着色層が複層の形態を有する場合には、その合計厚みが上記範囲に制御されることが好ましい。 The thickness of the colored layer is not particularly limited, but is, for example, 0.1 to 100 μm. The lower limit of the thickness is preferably 1 μm, more preferably 5 μm, and the upper limit thereof is preferably 90 μm, more preferably 80 μm. By controlling the thickness of the colored layer within the above range, excellent design properties by the colored layer can be imparted to the sheet-like extensible organic base material. In addition, when a colored layer has a form of a multilayer, it is preferable that the total thickness is controlled by the said range.
　前記着色層は、公知乃至慣用の方法により形成することができる。具体的には、例えば、着色層の材料（例えば、染料及び／又は顔料と樹脂とを含む樹脂組成物）を含む溶液や分散液等を伸長性を有するシート状有機基材（該シート状伸長性有機基材上に中間層が存在する場合は、該中間層）上にコーティングする方法；着色層の材料（例えば、染料及び／又は顔料）を伸長性を有するシート状有機基材（又は中間層）上に蒸着（例えば、真空蒸着）する方法；着色層を伸長性を有するシート状有機基材（又は中間層）上にラミネートする方法；着色層を適宜な支持体上に形成した後、シート状伸長性有機基材（又は中間層）上に必要に応じて粘着層等を介して転写する方法などが挙げられる。伸長性を有するシート状有機基材の少なくとも一方の面に着色層を形成することにより、前記（ｉｉ）の態様のシート状伸長性有機基材が得られる。 The colored layer can be formed by a known or commonly used method. Specifically, for example, a sheet-like organic substrate having an extensible property (such as a resin composition containing a dye and / or a pigment and a resin) or a dispersion containing a coloring layer material (the sheet-like elongation) A method of coating on the intermediate layer when the intermediate layer is present on the extensible organic substrate; a sheet-like organic substrate (or intermediate) having a stretchable material (for example, dye and / or pigment) of the colored layer A method of depositing (for example, vacuum deposition) on the layer); a method of laminating the colored layer on the sheet-like organic substrate (or intermediate layer) having extensibility; and after forming the colored layer on an appropriate support, Examples thereof include a method of transferring onto a sheet-like extensible organic substrate (or intermediate layer) through an adhesive layer or the like as necessary. By forming the colored layer on at least one surface of the extensible sheet-like organic base material, the sheet-like extensible organic base material of the embodiment (ii) is obtained.
　意匠性が付与されたシート状伸長性有機基材は、伸長性を有するシート状有機基材１と着色層６との間に、伸長性等を損なわない範囲で、必要に応じて他の層（中間層）を有していてもよい。 The sheet-like extensible organic base material to which designability is imparted is provided as needed between the sheet-like organic base material 1 having extensibility and the colored layer 6 as long as extensibility is not impaired. (Intermediate layer) may be included.
　前記（ｉｉ）の態様のシート状伸長性有機基材は着色層を有することにより、意匠性が付与されている。なお、前記（ｉｉ）の態様のシート状伸長性有機基材は、前記（ｉ）の態様のシート状伸長性有機基材と同様に、易伸長性ポリマー母材及び／又は筒状難伸長性ポリマー部Ａが染料若しくは顔料を含有していてもよい。該染料、顔料の種類や含有量は、前記（ｉ）の態様のシート状伸長性有機基材におけるものと同様のものが例示される。また、前記（ｉｉ）の態様のシート状伸長性有機基材は、例えば、伸長性を有するシート状有機基材の着色層とは反対側の面や着色層の表面等に、さらに後述の印字層を有するものであってもよい。 The sheet-like extensible organic base material of the aspect of (ii) has a designability by having a colored layer. In addition, the sheet-like extensible organic base material of the aspect of (ii) is an easily extensible polymer base material and / or a cylindrical difficulty extensible similarly to the sheet-like extensible organic base material of the aspect of (i). The polymer part A may contain a dye or a pigment. Examples of the types and contents of the dyes and pigments are the same as those in the sheet-like extensible organic substrate of the aspect (i). In addition, the sheet-like extensible organic base material of the aspect (ii) is, for example, printed on a surface opposite to the colored layer of the extensible sheet-like organic base material or the surface of the colored layer, which will be described later. It may have a layer.
　意匠性が付与されたシート状伸長性有機基材の厚みは、例えば０．０１ｍｍ以上であり、好ましくは０．０３ｍｍ以上、さらに好ましくは０．０５ｍｍ以上である。本発明のシート状伸長性有機基材の厚みの上限は、例えば１ｃｍであり、好ましくは５ｍｍ、さらに好ましくは２ｍｍである。 The thickness of the sheet-like extensible organic base material to which designability is imparted is, for example, 0.01 mm or more, preferably 0.03 mm or more, more preferably 0.05 mm or more. The upper limit of the thickness of the sheet-like extensible organic base material of the present invention is, for example, 1 cm, preferably 5 mm, and more preferably 2 mm.
　前記意匠性の付与が容易なシート状伸長性有機基材は、伸長性（又はさらに伸縮性）を有し、しかも意匠性の付与が容易なシート状伸長性有機基材である。当該意匠性の付与が容易なシート状伸長性有機基材は、易伸長性ポリマー母材中に筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されている伸長性を有するシート状有機基材の少なくとも一方の面（片面側又は両面側）に印字層（印刷層）を有するシート状伸長性有機基材である。 The sheet-like extensible organic base material that is easily imparted with designability is a sheet-like extensible organic base material that has extensibility (or further stretchability) and that is easy to impart designability. The sheet-like extensible organic base material that is easily imparted with designability is a sheet having extensibility, in which a cylindrical hardly extensible polymer portion A is partially and integrally formed in an easily extensible polymer base material. It is a sheet-like extensible organic base material which has a printing layer (printing layer) in the at least one surface (single side | surface side or both surface side) of a glass-like organic base material.
　前記印字層としては、特に限定されず、水性インキ及び／又は油性インキによる印字（印刷）、より詳しくは公知乃至慣用のインキジェットプリンターによる印字（印刷）性に優れた表面を有する任意の層を採用することができる。前記印字層としては、具体的には、インキの吸収性に優れた層（インキ吸収層）などが挙げられる。 The printing layer is not particularly limited, and any layer having a surface excellent in printing (printing) with water-based ink and / or oil-based ink, more specifically with a known or common ink jet printer. Can be adopted. Specific examples of the print layer include a layer having excellent ink absorbability (ink absorption layer).
　前記印字層（インキ吸収層）は、水溶性樹脂を含むことが好ましい。前記水溶性樹脂としては、公知乃至慣用の水溶性樹脂を使用することができ、特に限定されないが、例えば、ポリビニルアルコール、ポリビニルピロリドン、ポリアクリル酸、ポリエチレンイミン、及びビニルピロリドンと酢酸ビニルとの共重合体からなる群より選択された少なくとも１種の水溶性樹脂が好ましい。なお、前記印字層における水溶性樹脂は１種を単独で使用することもできるし、２種以上を組み合わせて使用することもできる。 The printing layer (ink absorption layer) preferably contains a water-soluble resin. The water-soluble resin may be a known or commonly used water-soluble resin, and is not particularly limited. For example, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acid, polyethyleneimine, and a copolymer of vinyl pyrrolidone and vinyl acetate. At least one water-soluble resin selected from the group consisting of polymers is preferred. In addition, the water-soluble resin in the said printing layer can also be used individually by 1 type, and can also be used in combination of 2 or more type.
　前記印字層は、その他、目的に応じて任意の添加剤を含有していてもよい。該添加剤としては、例えば、光重合開始剤、シランカップリング剤、離型剤、硬化剤、硬化促進剤、希釈剤、老化防止剤、変性剤、界面活性剤、染料、顔料、変色防止剤、紫外線吸収剤、柔軟剤、安定剤、可塑剤、消泡剤などが挙げられる。なお、印字層に含有され得る添加剤の種類、数、量などは、目的に応じて適宜設定することができる。 The print layer may contain any other additive depending on the purpose. Examples of the additive include a photopolymerization initiator, a silane coupling agent, a mold release agent, a curing agent, a curing accelerator, a diluent, an anti-aging agent, a modifier, a surfactant, a dye, a pigment, and a discoloration preventing agent. UV absorbers, softeners, stabilizers, plasticizers, antifoaming agents and the like. The type, number, amount, and the like of additives that can be contained in the print layer can be appropriately set according to the purpose.
　前記印字層は、単層の形態を有していてもよく、複層（積層）の形態を有していてもよい。なお、前記印字層は、伸長性を有するシート状有機基材１（該シート状伸長性有機基材上に後述の中間層が存在する場合は、該中間層）の表面の全体（全面）に設けてもよく、用途によっては、伸長性を有するシート状有機基材１の表面のうち必要な箇所のみに部分的に設けてもよい。 The printing layer may have a single-layer form or a multi-layer (stacked) form. The printing layer is formed on the entire surface (entire surface) of the sheet-like organic substrate 1 having extensibility (if the intermediate layer described later is present on the sheet-like extensible organic substrate, the intermediate layer). Depending on the application, it may be partially provided only on a necessary portion of the surface of the sheet-like organic substrate 1 having extensibility.
　前記印字層の厚みは、特に限定されないが、例えば０．１~１００μｍであり、厚みの下限は１μｍが好ましい。印字層の厚みを上記範囲に制御することにより、優れた印字性をシート状伸長性有機基材に対して付与でき、その結果、意匠性の付与が容易となる。なお、印字層が複層の形態を有する場合には、その合計厚みが上記範囲に制御されることが好ましい。 The thickness of the printing layer is not particularly limited, but is, for example, 0.1 to 100 μm, and the lower limit of the thickness is preferably 1 μm. By controlling the thickness of the print layer within the above range, excellent printability can be imparted to the sheet-like extensible organic base material, and as a result, designability can be easily imparted. In addition, when a printing layer has a form of a multilayer, it is preferable that the total thickness is controlled by the said range.
　前記印字層は、公知乃至慣用の方法により形成することができる。具体的には、例えば、印字層の材料（例えば、水溶性樹脂を含む樹脂組成物）を含む溶液や分散液等を伸長性を有するシート状有機基材（該シート状伸長性有機基材上に中間層が存在する場合は、該中間層）上にコーティングする方法；印字層を伸長性を有するシート状有機基材（又は中間層）上にラミネートする方法；印字層を適宜な支持体上に形成した後、シート状伸長性有機基材（又は中間層）上に必要に応じて粘着層等を介して転写する方法などが挙げられる。 The printing layer can be formed by a known or commonly used method. Specifically, for example, a sheet-like organic substrate (such as a sheet-like extensible organic substrate) having extensibility may be used for a solution or dispersion containing a printing layer material (for example, a resin composition containing a water-soluble resin). In the case where an intermediate layer is present, a method of coating on the intermediate layer); a method of laminating the printing layer on a sheet-like organic substrate (or intermediate layer) having extensibility; and a printing layer on an appropriate support Examples of the method include a method of transferring to a sheet-like extensible organic base material (or intermediate layer) via an adhesive layer or the like, if necessary.
　意匠性の付与が容易なシート状伸長性有機基材は、伸長性を有するシート状有機基材１と印字層６との間に、伸長性等を損なわない範囲で、必要に応じて他の層（中間層）を有していてもよい。 The sheet-like extensible organic base material that is easily imparted with designability can have other extensibility between the sheet-like organic base material 1 having extensibility and the print layer 6 as long as the extensibility is not impaired. It may have a layer (intermediate layer).
　本発明のシート状伸長性有機基材は、印字層を有することにより、意匠性の付与が容易である。なお、該シート状伸長性有機基材は、前記（ｉ）の態様のシート状伸長性有機基材（意匠性が付与されたシート状伸長性有機基材）と同様に、易伸長性ポリマー母材及び／又は筒状難伸長性ポリマー部Ａが染料若しくは顔料を含有していてもよい。該染料、顔料の種類や含有量は、前記（ｉ）の態様のシート状伸長性有機基材におけるものと同様のものが例示される。また、該シート状伸長性有機基材は、例えば、伸長性を有するシート状有機基材の印字層とは反対側の面や印字層の表面等に、さらに後述の着色層を有するものであってもよい。 The sheet-like extensible organic base material of the present invention is easy to impart designability by having a printing layer. In addition, the sheet-like extensible organic base material is an easily extensible polymer matrix similar to the sheet-like extensible organic base material (sheet-like extensible organic base material to which designability is imparted) of the aspect (i). The material and / or the cylindrical hardly extensible polymer part A may contain a dye or a pigment. Examples of the types and contents of the dyes and pigments are the same as those in the sheet-like extensible organic substrate of the aspect (i). In addition, the sheet-like extensible organic substrate has, for example, a coloring layer described later on the surface opposite to the print layer of the extensible sheet-like organic substrate or the surface of the print layer. May be.
　意匠性の付与が容易なシート状伸長性有機基材の厚みは、例えば０．０１ｍｍ以上であり、好ましくは０．０３ｍｍ以上、さらに好ましくは０．０５ｍｍ以上である。本発明のシート状伸長性有機基材の厚みの上限は、例えば１ｃｍであり、好ましくは５ｍｍ、さらに好ましくは２ｍｍである。 The thickness of the sheet-like extensible organic base material to which designability is easily imparted is, for example, 0.01 mm or more, preferably 0.03 mm or more, and more preferably 0.05 mm or more. The upper limit of the thickness of the sheet-like extensible organic base material of the present invention is, for example, 1 cm, preferably 5 mm, and more preferably 2 mm.
　上記のシート状伸長性有機基材は、形状不変部を有し、且つ意匠性が付与された（若しくは意匠性の付与が容易な）伸長性部材［又は、形状不変部を有し、且つ意匠性が付与された（若しくは意匠性の付与が容易な）伸縮性部材］として、エレクトロニクス製品（トランジスタ、集積回路、コンデンサ、センサ、アクチュエータ等）用部材、オプティカル製品（ディスプレイ、照明、光導波回路等）用部材、オプトエレクトロニクス製品（発光ダイオード、フォトダイオード、太陽電池等）用部材、カーエレクトロニクス製品用部材、家電製品用部材、住宅設備用部材、建材、バンド部材、結束用部材、衛生用品、衣料品の部分、湿布剤の基布等として利用できる。 The sheet-like extensible organic base material has a shape-invariable portion and has a designability imparted (or can be easily imparted with a designability) [or a shape-invariant portion and a design. Stretchable members with added properties (or easy designability)], members for electronic products (transistors, integrated circuits, capacitors, sensors, actuators, etc.), optical products (displays, lighting, optical waveguide circuits, etc.) ) Materials, optoelectronic products (light emitting diodes, photodiodes, solar cells, etc.), car electronics products, home appliances, housing equipment, building materials, band members, binding members, sanitary goods, clothing It can be used as a product part, as a base material for poultices.
　［難燃性を有するシート状伸長性有機基材］
　難燃性を有するシート状伸長性有機基材として、易伸長性ポリマー母材中に筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されている伸長性を有するシート状有機基材であって、該シート状有機基材が難燃剤を含有している（すなわち、シート状有機基材（特に、易伸長性ポリマー母材）そのものが難燃性を有している）、及び／又は該シート状有機基材の少なくとも片面に難燃層を有しているシート状伸長性有機基材が挙げられる。 [Sheet-like extensible organic base material with flame retardancy]
As a sheet-like extensible organic base material having flame retardancy, a sheet-like organic group having extensibility, in which a cylindrical hardly extensible polymer portion A is partially and integrally formed in an easily extensible polymer base material The sheet-like organic base material contains a flame retardant (that is, the sheet-like organic base material (particularly, the easily extensible polymer base material itself) has flame retardancy), and An example is a sheet-like extensible organic base material having a flame retardant layer on at least one surface of the sheet-like organic base material.
　このようなシート状伸長性有機基材は難燃性に優れ、例えば、接炎により着火しても、炎を遠ざけると自然消火する。そのため、このシート状伸長性有機基材は、炎に接しても、自己消火若しくは遮炎により延焼を防止することができる。 Such a sheet-like extensible organic base material is excellent in flame retardancy, for example, even if ignited by flame contact, it extinguishes spontaneously when the flame is moved away. Therefore, even if this sheet-like extensible organic base material touches a flame, it can prevent fire spread by self-extinguishing or flame shielding.
　難燃性を有するシート状伸長性有機基材は、このシート状伸長性有機基材を一方向（面方向）に伸長させると、易伸長性ポリマー母材の部位は伸長するが、部分的に形成された筒状難伸長性ポリマー部Ａは伸長しないか、又はほとんど伸長しない。このため、筒状難伸長性ポリマー部Ａに、形状が変化しないことが望まれる意匠を施したり、他の部材を固定、保持することができる。 When the sheet-like extensible organic base material having flame retardancy is stretched in one direction (plane direction), the part of the easily extensible polymer base material is extended. The formed cylindrical difficult-to-extend polymer part A does not stretch or hardly stretches. For this reason, it is possible to give the tubular hardly extensible polymer portion A a design whose shape is desired not to change, and to fix and hold other members.
　難燃性を有するシート状伸長性有機基材は、易伸長性ポリマー母材中に筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されている伸長性を有するシート状有機基材であって、該シート状有機基材が難燃剤を含有しているシート状伸長性有機基材であってもよく、該シート状有機基材の少なくとも片面に難燃層を有しているシート状伸長性有機基材であってもよく、該シート状有機基材が難燃剤を含有し、且つ、該シート状有機基材の少なくとも片面に難燃層を有しているシート状伸長性有機基材であってもよい。 A sheet-like extensible organic base material having flame retardancy is a sheet-like organic group having extensibility in which a cylindrical hardly extensible polymer portion A is partially and integrally formed in an easily extensible polymer base material. The sheet-like organic substrate may be a sheet-like extensible organic substrate containing a flame retardant, and has a flame-retardant layer on at least one side of the sheet-like organic substrate. It may be a sheet-like extensible organic substrate, the sheet-like organic substrate contains a flame retardant, and the sheet-like extensibility has a flame retardant layer on at least one side of the sheet-like organic substrate. An organic base material may be sufficient.
　難燃性を有するシート状伸長性有機基材の代表例として、図１８の（１）に示される多機能性シート状伸長性有機基材Ａにおいて、機能性層６が難燃層であるもの、図１８の（２）に示される多機能性シート状伸長性有機基材Ａにおいて、機能性層６が難燃層であるもの、図１８の（３）に示される多機能性シート状伸長性有機基材Ａにおいて、伸長性を有するシート状有機基材１自体が難燃性を有しているものが挙げられる。 As a representative example of a sheet-like extensible organic substrate having flame retardancy, in the multifunctional sheet-like extensible organic substrate A shown in (1) of FIG. 18, the functional layer 6 is a flame-retardant layer. In the multifunctional sheet-like stretchable organic base material A shown in (2) of FIG. 18, the functional layer 6 is a flame retardant layer, and the multifunctional sheet-like elongation shown in (3) of FIG. Examples of the organic base material A include those in which the sheet-like organic base material 1 itself having extensibility has flame retardancy.
　（伸長性を有するシート状有機基材が難燃剤を含有する場合）
　難燃剤は、伸長性を有するシート状有機基材を構成する易伸長性ポリマー母材に含有されていてもよく、筒状難伸長性ポリマー部Ａに含有されていてもよく、易伸長性ポリマー母材と筒状難伸長性ポリマー部Ａとに含有されていてもよい。 (When the extensible sheet-like organic base material contains a flame retardant)
The flame retardant may be contained in the easily extensible polymer matrix constituting the sheet-like organic base material having extensibility, may be contained in the cylindrical hardly extensible polymer portion A, and the easily extensible polymer. It may be contained in the base material and the cylindrical hardly extensible polymer part A.
　難燃剤を含有するシード状有機基材は、上記の伸長性を有するシート状有機基剤の製造方法において、易伸長性ポリマー母材として難燃剤を含有する易伸長性ポリマー母材を使用、又は筒状難伸長性ポリマー部Ａ形成用材料として難燃剤を含有する筒状難伸長性ポリマー部Ａ形成用材料を使用、又は易伸長性ポリマー母材として難燃剤を含有する易伸長性ポリマー母材を使用し、且つ筒状難伸長性ポリマー部Ａ形成用材料として難燃剤を含有する筒状難伸長性ポリマー部Ａ形成用材料を使用することによって、製造することができる。 The seed-like organic base material containing a flame retardant uses an easily stretchable polymer base material containing a flame retardant as the easily stretchable polymer base material in the method for producing a sheet-like organic base having stretchability, or An easily extensible polymer base material containing a flame retardant as a material for forming a cylindrical hard extensible polymer portion A containing a flame retardant as a material for forming a cylindrical hard extensible polymer portion A, or containing a flame retardant as an easily extensible polymer base material And a cylindrical difficult-to-extend polymer part A forming material containing a flame retardant as the material for forming a cylindrical difficult-to-extend polymer part A can be produced.
　伸長性を有するシート状有機基材に含有する難燃剤としては、特に限定されず、公知の難燃剤を使用でき、例えば、ハロゲン系化合物、リン系化合物、アンチモン系化合物、金属水酸化物、及びその他の化合物を挙げることができる。これらは１種単独で又は２種以上を組み合わせて使用できる。 The flame retardant contained in the sheet-like organic base material having extensibility is not particularly limited, and known flame retardants can be used, for example, halogen compounds, phosphorus compounds, antimony compounds, metal hydroxides, and Other compounds can be mentioned. These can be used individually by 1 type or in combination of 2 or more types.
　前記ハロゲン系化合物には、臭素系化合物、塩素系化合物等が含まれる。前記臭素系化合物としては、例えば、デカブロモジフェニルエーテル；テトラブロモビスフェノール、テトラブロモビスフェノール・エポキシオリゴマー、テトラブロモビスフェノール・カーボネートオリゴマー、テトラブロモビスフェノール・ビス（ジブロモプロピルエーテル）、テトラブロモビスフェノール・ビス（アリールエーテル）等のテトラブロモビスフェノール誘導体；ビス（ペンタブロモフェニル）エタン、１，２−ビス（２，４，６−トリブロモフェノキシ）エタン、２，４，６−トリス（２，４，６−トリブロモフェノキシ）−１，３，５−トリアジン、２，６−ジブロモフェノール、２，４−ジブロモフェノール等の多ベンゼン環化合物；臭素化ポリスチレン、ポリ臭素化スチレン；エチレンビステトラブロモフタルイミド等のフタル酸系化合物；ヘキサボロモシクロドデカン等の環状脂肪族系化合物；ヘキサブロモベンゼン、ペンタブロモベンジルアクリレート等を挙げることができる。 The halogen compounds include bromine compounds, chlorine compounds and the like. Examples of the bromine-based compound include decabromodiphenyl ether; tetrabromobisphenol, tetrabromobisphenol / epoxy oligomer, tetrabromobisphenol / carbonate oligomer, tetrabromobisphenol / bis (dibromopropyl ether), tetrabromobisphenol / bis (aryl ether) ) Tetrabromobisphenol derivatives; bis (pentabromophenyl) ethane, 1,2-bis (2,4,6-tribromophenoxy) ethane, 2,4,6-tris (2,4,6-tribromo) Phenoxy) -1,3,5-triazine, 2,6-dibromophenol, 2,4-dibromophenol and other polybenzene ring compounds; brominated polystyrene, polybrominated styrene; ethylenebistetrabromophthaly Phthalic acid compounds such as de; hexa rag mode cyclic aliphatic compounds cyclododecane like; hexabromobenzene, it can be exemplified pentabromobenzylacrylate like.
　前記塩素系化合物としては、例えば、塩素化パラフィン、ポリ塩化ビフェニル、デクロラン、クロレンド酸、無水クロレンド酸等を挙げることができる。 Examples of the chlorinated compound include chlorinated paraffin, polychlorinated biphenyl, dechlorane, chlorendic acid, and chlorendic anhydride.
　前記リン系化合物としては、例えば、トリフェニルホスフェート、クレジルジフェニルホスフェート、トリクレジルホスフェート、トリキシレニルホスフェート、トリス（ｔ−ブチルフェニル）ホスフェート、トリス（ｉ−プロピルフェニル）ホスフェート、２−エチルヘキシルジフェニルホスフェート等の芳香族リン酸エステル類；１，３−フェニレンビス（ジフェニルホスフェート）、１，３−フェニレンビス（ジキシレニル）ホスフェート、ビスフェノールＡビス（ジフェニルホスフェート）等の芳香族縮合リン酸エステル類；トリス（ジクロロプロピル）ホスフェート、トリス（β−クロロプロピル）ホスフェート、トリス（クロロエチル）ホスフェート等の含ハロゲンリン酸エステル類；２，２−ビス（クロロメチル）トリメチレンビス（ビス（２−クロロエチル）ホスフェート）、ポリオキシアルキレンビスジクロロアルキルホスフェート等の含ハロゲンリン縮合リン酸エステル類；赤リン等の赤リン系化合物等を挙げることができる。 Examples of the phosphorus compound include triphenyl phosphate, cresyl diphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris (t-butylphenyl) phosphate, tris (i-propylphenyl) phosphate, 2-ethylhexyl diphenyl. Aromatic phosphate esters such as phosphate; aromatic condensed phosphate esters such as 1,3-phenylenebis (diphenylphosphate), 1,3-phenylenebis (dixylenyl) phosphate, bisphenol A bis (diphenylphosphate); Tris Halogen-containing phosphates such as (dichloropropyl) phosphate, tris (β-chloropropyl) phosphate, tris (chloroethyl) phosphate; 2,2-bis (chloromethyl) trimethyl Nbisu (bis (2-chloroethyl) phosphate), halogen-containing phosphoric condensed phosphate esters such as polyoxyalkylene bis-dichloro alkyl phosphates; may be mentioned red phosphorus Red phosphorus-based compounds such like.
　前記アンチモン系化合物としては、例えば、三酸化アンチモン、五酸化アンチモン、アンチモン酸ナトリウム、ジルコニウム−アンチモン複合酸化物等を挙げることができる。 Examples of the antimony compound include antimony trioxide, antimony pentoxide, sodium antimonate, zirconium-antimony composite oxide, and the like.
　金属水酸化物としては、例えば、水酸化マグネシウム、水酸化アルミニウム、水酸化カルシウム等のアルカリ金属水酸化物等を挙げることができる。 Examples of the metal hydroxide include alkali metal hydroxides such as magnesium hydroxide, aluminum hydroxide, and calcium hydroxide.
　その他、三酸化モリブデン、モリブデン酸塩等のモリブデン化合物；三酸化ビスマス、三酸化タングステン、酸化硼素、ホウ酸塩（ホウ砂を含む）、ホウ酸亜鉛、アルミン酸カルシウム、二水和石膏、メタホウ酸バリウム、カオリンクレー、硝酸ナトリウム等の硝酸塩、ジルコニウム化合物、ドーソナイト、フロゴパイト、珪素含有無機充填剤等を挙げることができる。 Other molybdenum compounds such as molybdenum trioxide and molybdate; bismuth trioxide, tungsten trioxide, boron oxide, borates (including borax), zinc borate, calcium aluminate, dihydrate gypsum, metaboric acid Examples thereof include nitrates such as barium, kaolin clay, and sodium nitrate, zirconium compounds, dawsonite, phlogopite, and silicon-containing inorganic fillers.
　易伸長性ポリマー母材に難燃剤を含有する場合、難燃剤の含有量（総量）としては、易伸長性ポリマー母材全体に対して、例えば、１~４００重量％である。難燃剤の含有量（総量）の下限は、好ましくは５重量％、より好ましくは１０重量％、さらに好ましくは２０重量％であり、上限は、好ましくは３５０重量％、より好ましくは３００重量％、さらに好ましくは２５０重量％である。 When the flame retardant is contained in the stretchable polymer base material, the content (total amount) of the flame retardant is, for example, 1 to 400% by weight with respect to the whole stretchable polymer base material. The lower limit of the content (total amount) of the flame retardant is preferably 5% by weight, more preferably 10% by weight, still more preferably 20% by weight, and the upper limit is preferably 350% by weight, more preferably 300% by weight, More preferably, it is 250 weight%.
　筒状難伸長性ポリマー部Ａに難燃剤を含有する場合、難燃剤の含有量（総量）としては、筒状難伸長性ポリマー部Ａ全体に対して、例えば、１~４００重量％である。難燃剤の含有量（総量）の下限は、好ましくは５重量％、より好ましくは１０重量％、さらに好ましくは２０重量％であり、上限は、好ましくは３５０重量％、より好ましくは３００重量％、さらに好ましくは２５０重量％である。 When the flame retardant is contained in the cylindrical hardly extensible polymer part A, the content (total amount) of the flame retardant is, for example, 1 to 400% by weight with respect to the entire cylindrical hard extensible polymer part A. The lower limit of the content (total amount) of the flame retardant is preferably 5% by weight, more preferably 10% by weight, still more preferably 20% by weight, and the upper limit is preferably 350% by weight, more preferably 300% by weight, More preferably, it is 250 weight%.
　（伸長性を有するシート状有機基材の少なくとも片面に難燃層を有している場合）
　難燃層としては、難燃剤を含有する層であってもよく、難燃性を有するポリマー（難燃性ポリマー）を含有する層であってもよい。さらに、難燃剤と難燃性ポリマーとを含有する層であってもよい。また、該難燃層は伸長性を有するシート状有機基材に接した状態で設けられていてもよく、接着剤層等を介して設けられていてもよい。更に、難燃層は、伸長性を有するシート状有機基材の表面の全体に設けてもよく、伸長性を有する伸長性を有するシート状有機基材の表面のうち必要な箇所のみに部分的に設けてもよい。更にまた、難燃層は、一層で構成されていてもよく、二層以上で構成されていてもよい。二層以上で構成される場合は、同じ組成を有する層で構成されていてもよく、異なる組成を有する層で構成されていてもよい。 (When it has a flame retardant layer on at least one side of an extensible sheet-like organic base material)
The flame retardant layer may be a layer containing a flame retardant, or may be a layer containing a flame retardant polymer (a flame retardant polymer). Further, it may be a layer containing a flame retardant and a flame retardant polymer. In addition, the flame retardant layer may be provided in contact with an extensible sheet-like organic base material, or may be provided via an adhesive layer or the like. Furthermore, the flame retardant layer may be provided on the entire surface of the sheet-like organic base material having extensibility, and is partially applied only to a necessary portion of the surface of the sheet-like organic base material having extensibility. May be provided. Furthermore, the flame retardant layer may be composed of one layer, or may be composed of two or more layers. When comprised by two or more layers, it may be comprised by the layer which has the same composition, and may be comprised by the layer which has a different composition.
　難燃層に含有する難燃剤としては、上記難燃剤を特に制限されることなく使用することができる。 As the flame retardant contained in the flame retardant layer, the above flame retardant can be used without any particular limitation.
　難燃剤を含有する難燃層には上記難燃剤以外にも、必要に応じてベースポリマーを含有してもよい。ベースポリマーとしては、易伸長性ポリマー母材２を構成するポリマーの例として挙げられているポリマーを使用することが好ましく、特に、易伸長性ポリマー母材２を構成するポリマーと同種のポリマー、或いは易伸長性ポリマー母材２を構成するポリマーが有するポリマー鎖（主鎖又は側鎖）と同種のポリマー鎖を主鎖又は側鎖に有するポリマーを選択して使用することが、伸長性を有するシート状有機基材表面への密着性に優れる難燃層を形成することができる点で好ましい。 In addition to the above flame retardant, the flame retardant layer containing a flame retardant may contain a base polymer as necessary. As the base polymer, it is preferable to use a polymer listed as an example of a polymer constituting the easily extensible polymer base material 2, and in particular, the same kind of polymer as the polymer constituting the easily extensible polymer base material 2, or A sheet having extensibility by selecting and using a polymer having a polymer chain of the same type as the polymer chain (main chain or side chain) of the polymer constituting the easily extensible polymer base material 2 in the main chain or side chain It is preferable at the point which can form the flame retardant layer which is excellent in the adhesiveness to the surface of a glassy organic base material.
　前記難燃性ポリマーとしては、例えば、ポリ塩化ビニル等を挙げることができる。難燃性ポリマーの重量平均分子量は、例えば１万~２００万、好ましくは３０万~１５０万である。 Examples of the flame retardant polymer include polyvinyl chloride. The weight average molecular weight of the flame retardant polymer is, for example, 10,000 to 2,000,000, preferably 300,000 to 1,500,000.
　難燃性ポリマーを含有する難燃層は、ベースポリマーとして難燃性ポリマーのみを含有していてもよく、難燃性ポリマーと上記難燃剤を含有する難燃層に使用することができるベースポリマーとを組み合わせて含有していてもよい。 The flame retardant layer containing the flame retardant polymer may contain only the flame retardant polymer as the base polymer, and can be used for the flame retardant layer containing the flame retardant polymer and the above flame retardant. And may be contained in combination.
　難燃層には、本発明の効果を損なわない範囲内で他の添加物を含有していてもよい。他の添加物としては、例えば、架橋剤（エポキシ系架橋剤、イソシアネート系架橋剤、メラミン系架橋剤、オキサゾリン系架橋剤、アジリジン系架橋剤、金属キレート化合物等）、架橋促進剤（架橋触媒）、粘着付与剤（例えば、ロジン誘導体樹脂、ポリテルペン樹脂、石油樹脂、油溶性フェノール樹脂など）、増粘剤、可塑剤、充填剤、発泡剤、老化防止剤、酸化防止剤、紫外線吸収剤、帯電防止剤、界面活性剤、レベリング剤、着色剤、難燃剤、シランカップリング剤等を挙げることができる。 The flame retardant layer may contain other additives as long as the effects of the present invention are not impaired. Other additives include, for example, crosslinking agents (epoxy crosslinking agents, isocyanate crosslinking agents, melamine crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, metal chelate compounds, etc.), crosslinking accelerators (crosslinking catalysts). , Tackifiers (eg, rosin derivative resins, polyterpene resins, petroleum resins, oil-soluble phenol resins, etc.), thickeners, plasticizers, fillers, foaming agents, anti-aging agents, antioxidants, UV absorbers, charging Examples thereof include an inhibitor, a surfactant, a leveling agent, a colorant, a flame retardant, and a silane coupling agent.
　難燃剤を含有する難燃層の場合、難燃層全量（１００重量％）における難燃剤の含有量（総量）としては、例えば、１~８５重量％である。難燃剤の含有量（総量）の下限は、好ましくは５重量％、より好ましくは１０重量％、さらに好ましくは２０重量％であり、上限は、好ましくは８０重量％、より好ましくは７５重量％、さらに好ましくは７０重量％である。 In the case of a flame retardant layer containing a flame retardant, the content (total amount) of the flame retardant in the total amount (100% by weight) of the flame retardant layer is, for example, 1 to 85% by weight. The lower limit of the content (total amount) of the flame retardant is preferably 5% by weight, more preferably 10% by weight, still more preferably 20% by weight, and the upper limit is preferably 80% by weight, more preferably 75% by weight, More preferably, it is 70 weight%.
　難燃層が難燃性ポリマーを含有する場合、難燃層全量（１００重量％）における難燃性ポリマーの含有量（総量）としては、例えば、１~１００重量％である。すなわち、難燃性ポリマーのみで難燃層を形成していてもよい。難燃性ポリマーの含有量（総量）の下限は、好ましくは５重量％、より好ましくは１０重量％、さらに好ましくは２０重量％であり、上限は、好ましくは９５重量％、より好ましくは９０重量％、さらに好ましくは８５重量％である。 When the flame retardant layer contains a flame retardant polymer, the content (total amount) of the flame retardant polymer in the total amount (100% by weight) of the flame retardant layer is, for example, 1 to 100% by weight. That is, the flame retardant layer may be formed of only the flame retardant polymer. The lower limit of the content (total amount) of the flame retardant polymer is preferably 5% by weight, more preferably 10% by weight, still more preferably 20% by weight, and the upper limit is preferably 95% by weight, more preferably 90% by weight. %, More preferably 85% by weight.
　難燃層が難燃性ポリマーと難燃剤とを含有する場合、難燃層全量（１００重量％）における難燃剤の含有量（総量）としては、例えば、１~８５重量％である。難燃剤の含有量（総量）の下限は、好ましくは５重量％、より好ましくは１０重量％、さらに好ましくは２０重量％であり、上限は、好ましくは８０重量％、より好ましくは７５重量％、さらに好ましくは７０重量％である。難燃層全量（１００重量％）における難燃性ポリマーの含有量（総量）としては、例えば、１重量％以上、１００重量％未満である。難燃性ポリマーの含有量（総量）の下限は、好ましくは５重量％、より好ましくは１０重量％、さらに好ましくは２０重量％であり、上限は、好ましくは９５重量％、より好ましくは９０重量％、さらに好ましくは８５重量％である。尚、難燃性ポリマーと難燃剤のみで難燃層を形成していてもよい。 When the flame retardant layer contains a flame retardant polymer and a flame retardant, the content (total amount) of the flame retardant in the total amount (100% by weight) of the flame retardant layer is, for example, 1 to 85% by weight. The lower limit of the content (total amount) of the flame retardant is preferably 5% by weight, more preferably 10% by weight, still more preferably 20% by weight, and the upper limit is preferably 80% by weight, more preferably 75% by weight, More preferably, it is 70 weight%. The content (total amount) of the flame retardant polymer in the total amount (100% by weight) of the flame retardant layer is, for example, 1% by weight or more and less than 100% by weight. The lower limit of the content (total amount) of the flame retardant polymer is preferably 5% by weight, more preferably 10% by weight, still more preferably 20% by weight, and the upper limit is preferably 95% by weight, more preferably 90% by weight. %, More preferably 85% by weight. In addition, you may form a flame-resistant layer only with a flame-retardant polymer and a flame retardant.
　難燃剤を含有する難燃層の形成方法としては、難燃剤を添加する以外は、易伸長性ポリマー母材部２の形成方法と同じ方法を採用することができる。また、難燃層は、伸長性を有するシート状有機基材表面に直接形成してもよく、適当なセパレータ（剥離紙等）上に難燃層を形成し、これを伸長性を有するシート状有機基材に転写（移着）して積層してもよい。 As a method for forming a flame retardant layer containing a flame retardant, the same method as the method for forming the easily extensible polymer base material part 2 can be adopted except that a flame retardant is added. In addition, the flame retardant layer may be formed directly on the surface of the stretchable sheet-like organic base material, and the flame retardant layer is formed on a suitable separator (release paper, etc.), and this is formed into a sheet form having the stretchability. It may be transferred (transferred) to an organic base material and laminated.
　更に、難燃剤を含有する難燃層は、難燃層の形成材（少なくとも、難燃剤とベースポリマーを含む）と、易伸長性ポリマー母材を形成する易伸長性ポリマー母材とを溶融押出して一体化させる方法でも形成することもできる。溶融押出方法としては、インフレーション法やＴダイ法等任意の公知技術を用いることができる。 Further, the flame retardant layer containing the flame retardant is obtained by melt-extruding the material for forming the flame retardant layer (including at least the flame retardant and the base polymer) and the easily stretchable polymer base material forming the easily stretchable polymer base material. It can also be formed by a method of integrating them. As the melt extrusion method, any known technique such as an inflation method or a T-die method can be used.
　難燃性ポリマーを含有する難燃層の形成方法としては、例えば、難燃性ポリマーを含む溶液又は分散液を、伸長性を有するシート状有機基材に直接塗布して難燃層を形成する方法や、適当なセパレータ（剥離紙等）上に前記難燃性ポリマーを含む溶液又は分散液を塗布して難燃層を形成し、これを伸長性を有するシート状有機基材に転写（移着）して積層する方法等が挙げられる。塗布は、コーター、押出機、印刷機等により行うことができる。 As a method for forming a flame retardant layer containing a flame retardant polymer, for example, a solution or dispersion containing a flame retardant polymer is directly applied to an extensible sheet-like organic base material to form a flame retardant layer. A flame retardant layer is formed by applying a solution or dispersion containing the flame retardant polymer on a method or an appropriate separator (such as release paper), and this is transferred (transferred) to a sheet-like organic substrate having extensibility. And a method of laminating and laminating. The application can be performed by a coater, an extruder, a printing machine or the like.
　難燃層の厚さとしては、用途等に応じて適宜選択でき、例えば、５~５００μｍであり、下限は、好ましくは１０μｍ、より好ましくは３０μｍ、さらに好ましくは５０μｍである。上限は、好ましくは４５０μｍ、より好ましくは４００μｍ、さらに好ましくは３００μｍである。 The thickness of the flame retardant layer can be appropriately selected depending on the application and the like, and is, for example, 5 to 500 μm, and the lower limit is preferably 10 μm, more preferably 30 μm, and even more preferably 50 μm. The upper limit is preferably 450 μm, more preferably 400 μm, and even more preferably 300 μm.
　粘着剤層を介して伸長性を有するシート状有機基材表面に難燃層を設ける場合、該粘着剤層を構成する粘着剤としては、特に限定されず、例えば、ゴム系粘着剤、アクリル系粘着剤、ビニルアルキルエーテル系粘着剤、シリコーン系粘着剤、ポリエステル系粘着剤、ポリアミド系粘着剤、ウレタン系粘着剤、スチレン−ジエンブロック共重合体系粘着剤、これらの粘着剤に融点が約２００℃以下の熱溶融性樹脂を配合したクリープ特性改良型粘着剤などの公知の粘着剤を１種又は２種以上組み合わせて用いることができる。粘着剤は、溶剤型、エマルジョン型、ホットメルト型、エネルギー線硬化型粘着剤、加熱剥離型等の公知のいずれの粘着剤であってもよく、用途に応じて適切なものを選択できる。また、粘着剤は、弱粘着型、強粘着型、再剥離型等の何れであってもよく、用途に応じて適宜選択できる。 In the case where a flame retardant layer is provided on the surface of a sheet-like organic substrate having extensibility via an adhesive layer, the adhesive constituting the adhesive layer is not particularly limited, and examples thereof include rubber adhesives and acrylic adhesives. Adhesives, vinyl alkyl ether adhesives, silicone adhesives, polyester adhesives, polyamide adhesives, urethane adhesives, styrene-diene block copolymer adhesives, melting point of these adhesives is about 200 ° C One or more known pressure-sensitive adhesives such as creep property-improving pressure-sensitive adhesives containing the following hot-melt resins can be used in combination. The pressure-sensitive adhesive may be any known pressure-sensitive adhesive such as a solvent type, an emulsion type, a hot-melt type, an energy ray curable pressure-sensitive adhesive, and a heat release type, and an appropriate one can be selected depending on the application. Further, the pressure-sensitive adhesive may be any of a weak pressure-sensitive adhesive type, a strong pressure-sensitive adhesive type, a re-peeling type, and the like, and can be appropriately selected according to the application.
　粘着剤層を構成する粘着剤としては、特にアクリル系ポリマー（重量平均分子量は、例えば１万~２００万、好ましくは３０万~１５０万）をベースポリマーとするアクリル系粘着剤が好ましく使用される。アクリル系ポリマーは、ランダム共重合体、ブロック共重合体、グラフト重合体等のいずれであってもよい。 As the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer, an acrylic pressure-sensitive adhesive based on an acrylic polymer (weight average molecular weight is, for example, 10,000 to 2,000,000, preferably 300,000 to 1,500,000) is preferably used. . The acrylic polymer may be any of a random copolymer, a block copolymer, a graft polymer, and the like.
　粘着剤には、ベースポリマーのほか、必要に応じて、架橋剤（エポキシ系架橋剤、イソシアネート系架橋剤、メラミン系架橋剤、オキサゾリン系架橋剤、アジリジン系架橋剤、金属キレート化合物等）、架橋促進剤（架橋触媒）、粘着付与剤（例えば、ロジン誘導体樹脂、ポリテルペン樹脂、石油樹脂、油溶性フェノール樹脂など）、増粘剤、可塑剤、充填剤、発泡剤、老化防止剤、酸化防止剤、紫外線吸収剤、帯電防止剤、界面活性剤、レベリング剤、着色剤、難燃剤、シランカップリング剤などの適宜な添加剤を含んでいてもよい。 For adhesives, in addition to the base polymer, if necessary, crosslinking agents (epoxy crosslinking agents, isocyanate crosslinking agents, melamine crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, metal chelate compounds, etc.), crosslinking Accelerator (crosslinking catalyst), tackifier (for example, rosin derivative resin, polyterpene resin, petroleum resin, oil-soluble phenol resin, etc.), thickener, plasticizer, filler, foaming agent, anti-aging agent, antioxidant And an appropriate additive such as an ultraviolet absorber, an antistatic agent, a surfactant, a leveling agent, a colorant, a flame retardant, and a silane coupling agent.
　粘着剤層の形成は公知乃至慣用の方法により行うことができる。例えば、粘着剤組成物を伸長性を有するシート状有機基材（シート状伸長性有機基材）１（該シート状伸長性有機基材上に中間層が存在する場合は、該中間層）上に塗布する方法、粘着剤組成物を適当なセパレータ上に塗布して粘着剤層を形成した後、該粘着剤層を伸長性を有するシート状有機基材１（該シート状伸長性有機基材上に中間層が存在する場合は、該中間層）上に転写（移着）する方法等が挙げられる。 The formation of the pressure-sensitive adhesive layer can be performed by a known or conventional method. For example, the pressure-sensitive adhesive composition on a sheet-like organic substrate (sheet-like extensible organic substrate) 1 having extensibility (if the intermediate layer exists on the sheet-like extensible organic substrate, the intermediate layer) After applying the pressure-sensitive adhesive composition on a suitable separator to form a pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer is formed into a sheet-like organic substrate 1 having extensibility (the sheet-like extensible organic substrate). In the case where an intermediate layer is present thereon, a method of transferring (transferring) onto the intermediate layer) may be mentioned.
　粘着剤層は、伸長性を有するシート状有機基材１の表面の全体に設けてもよく、伸長性を有するシート状有機基材１の表面のうち必要な箇所のみに部分的に設けてもよい。 The pressure-sensitive adhesive layer may be provided on the entire surface of the sheet-like organic substrate 1 having extensibility, or may be partially provided only on a necessary portion of the surface of the sheet-like organic substrate 1 having extensibility. Good.
　粘着剤層の厚さとしては、用途等に応じて適宜選択でき、例えば、５~３０００μｍであり、下限は、好ましくは１０μｍ、上限は、好ましくは５００μｍである。 The thickness of the pressure-sensitive adhesive layer can be appropriately selected according to the use and the like, and is, for example, 5 to 3000 μm, the lower limit is preferably 10 μm, and the upper limit is preferably 500 μm.
　本発明においては、伸長性を有するシート状有機基材１と難燃層６との間に、粘着剤層以外にも伸長性等を損なわない範囲で、必要に応じて他の層（中間層）を有していてもよい。また、難燃層６上には、難燃性を有するシート状伸長性有機基材Ａを使用するまでの間、表面を保護するための保護フィルムが設けられていてもよい。 In the present invention, between the sheet-like organic substrate 1 having extensibility and the flame retardant layer 6, other layers (intermediate layers) may be added as necessary as long as extensibility and the like other than the adhesive layer are not impaired. ). Further, a protective film for protecting the surface may be provided on the flame retardant layer 6 until the flame-retardant sheet-like extensible organic base material A is used.
　本発明の難燃性を有するシート状伸長性有機基材は、難燃性を有し且つ形状不変部を有する伸長性部材（又は、難燃性を有し且つ形状不変部を有する伸縮性部材）として、エレクトロニクス製品（トランジスタ、集積回路、コンデンサ、センサ、アクチュエータ等）用部材、オプティカル製品（ディスプレイ、照明、光導波回路等）用部材、オプトエレクトロニクス製品（発光ダイオード、フォトダイオード、太陽電池等）用部材、カーエレクトロニクス製品用部材、家電製品用部材、住宅設備用部材、建材、バンド部材、結束用部材、衛生用品、衣料品の部分、湿布剤の基布等として利用できる。 The sheet-like extensible organic base material having flame retardancy according to the present invention is an extensible member having flame retardancy and having a shape-invariable portion (or an elastic member having flame retardancy and having a shape-invariant portion. ), Members for electronic products (transistors, integrated circuits, capacitors, sensors, actuators, etc.), members for optical products (displays, lighting, optical waveguide circuits, etc.), optoelectronic products (light emitting diodes, photodiodes, solar cells, etc.) It can be used as a member for automobiles, a member for car electronics products, a member for household electrical appliances, a member for household equipment, a building material, a band member, a binding member, a sanitary article, a clothing part, a base cloth for a poultice.
　［熱伝導性を有するシート状伸長性有機基材］
　熱伝導性を有するシート状伸長性有機基材として、易伸長性ポリマー母材中に筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されている伸長性を有するシート状有機基材であって、該シート状有機基材が熱伝導性物質を含有している（すなわち、シート状有機基材（特に、易伸長性ポリマー母材）そのものが熱伝導性を有している）、及び／又は該シート状有機基材の少なくとも片面に熱伝導性層を有しているものが挙げられる。 [Sheet-like extensible organic base material having thermal conductivity]
As a sheet-like extensible organic base material having thermal conductivity, a sheet-like organic group having extensibility in which a cylindrical hardly extensible polymer portion A is partially and integrally formed in an easily extensible polymer base material The sheet-like organic base material contains a heat conductive substance (that is, the sheet-like organic base material (particularly, the easily extensible polymer base material itself) has a heat conductivity). And / or those having a thermally conductive layer on at least one side of the sheet-like organic substrate.
　シート状伸長性有機基材の熱伝導性としては、熱伝導率が例えば０．５Ｗ／ｍ・Ｋ以上程度、好ましくは、１．０Ｗ／ｍ・Ｋ以上である。そのため、このようなシート状伸長性有機基材は、シート状伸長性有機基材内部、及び外部で発生した熱を効率よく放熱することができる。 As the thermal conductivity of the sheet-like extensible organic base material, the thermal conductivity is, for example, about 0.5 W / m · K or more, preferably 1.0 W / m · K or more. Therefore, such a sheet-like extensible organic substrate can efficiently dissipate heat generated inside and outside the sheet-like extensible organic substrate.
　熱伝導性を有するシート状伸長性有機基材は、このシート状伸長性有機基材を一方向（面方向）に伸長させると、易伸長性ポリマー母材の部位は伸長するが、部分的に形成された筒状難伸長性ポリマー部Ａは伸長しないか、又はほとんど伸長しない。このため、筒状難伸長性ポリマー部Ａに、形状が変化しないことが望まれる意匠を施したり、他の部材を固定、保持することができる。 In the sheet-like extensible organic base material having thermal conductivity, when the sheet-like extensible organic base material is extended in one direction (plane direction), the part of the easily extensible polymer base material is extended. The formed cylindrical difficult-to-extend polymer part A does not stretch or hardly stretches. For this reason, it is possible to give the tubular hardly extensible polymer portion A a design whose shape is desired not to change, and to fix and hold other members.
　熱伝導性を有するシート状伸長性有機基材の代表例として、図１８の（１）に示される多機能性シート状伸長性有機基材Ａにおいて、機能性層６が熱伝導性層であるもの、図１８の（２）に示される多機能性シート状伸長性有機基材Ａにおいて、機能性層６が熱伝導性層であるもの、図１８の（３）に示される多機能性シート状伸長性有機基材Ａにおいて、伸長性を有するシート状有機基材１自体が熱伝導性を有しているものが挙げられる。 As a representative example of the sheet-like extensible organic base material having thermal conductivity, in the multifunctional sheet-like extensible organic base A shown in (1) of FIG. 18, the functional layer 6 is a heat conductive layer. In the multifunctional sheet-like extensible organic base material A shown in (2) of FIG. 18, the functional layer 6 is a heat conductive layer, and the multifunctional sheet shown in (3) of FIG. Examples of the stretchable organic base material A include those in which the stretchable sheet-like organic base material 1 itself has thermal conductivity.
　熱伝導性を有するシート状伸長性有機基材の熱伝導性としては、熱伝導率が例えば０．５Ｗ／ｍ・Ｋ以上程度、好ましくは、１．０Ｗ／ｍ・Ｋ以上である。そのため、このシート状伸長性有機基材は、シート状伸長性有機基材内部、及び外部で発生した熱を効率よく放熱することができる。 As the thermal conductivity of the sheet-like extensible organic base material having thermal conductivity, the thermal conductivity is, for example, about 0.5 W / m · K or more, preferably 1.0 W / m · K or more. Therefore, this sheet-like extensible organic base material can efficiently dissipate heat generated inside and outside the sheet-like extensible organic base material.
　熱伝導性を有するシート状伸長性有機基材は、このシート状伸長性有機基材を一方向（面方向）に伸長させると、易伸長性ポリマー母材の部位は伸長するが、部分的に形成された筒状難伸長性ポリマー部Ａは伸長しないか、又はほとんど伸長しない。このため、筒状難伸長性ポリマー部Ａに、形状が変化しないことが望まれる意匠を施したり、他の部材を固定、保持することができる。 In the sheet-like extensible organic base material having thermal conductivity, when the sheet-like extensible organic base material is extended in one direction (plane direction), the part of the easily extensible polymer base material is extended. The formed cylindrical difficult-to-extend polymer part A does not stretch or hardly stretches. For this reason, it is possible to give the tubular hardly extensible polymer portion A a design whose shape is desired not to change, and to fix and hold other members.
　熱伝導性を有するシート状伸長性有機基材は、易伸長性ポリマー母材中に筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されている伸長性を有するシート状有機基材であって、該シート状有機基材が熱伝導性物質を含有しているシート状伸長性有機基材であってもよく、該シート状有機基材の少なくとも片面に熱伝導性層を有しているシート状伸長性有機基材であってもよく、該シート状有機基材が熱伝導性物質を含有し、且つ、該シート状有機基材の少なくとも片面に熱伝導性層を有しているシート状伸長性有機基材であってもよい。シート状有機基材に熱伝導性物質を含有させると、面方向及び厚さ方向への熱伝導性を付与することができる。一方、シート状有機基材の少なくとも片面に熱伝導性層を設けると、面方向への熱伝導性を付与することができる。 The sheet-like extensible organic base material having thermal conductivity is a sheet-like organic group having extensibility in which a cylindrical hardly extensible polymer portion A is partially and integrally formed in an easily extensible polymer base material. The sheet-like organic base material may be a sheet-like extensible organic base material containing a heat conductive substance, and has a heat conductive layer on at least one side of the sheet-like organic base material. It may be a sheet-like extensible organic substrate, the sheet-like organic substrate contains a heat conductive substance, and has a heat conductive layer on at least one side of the sheet-like organic substrate. It may be a sheet-like extensible organic substrate. When the sheet-like organic base material contains a heat conductive substance, heat conductivity in the surface direction and the thickness direction can be imparted. On the other hand, when a heat conductive layer is provided on at least one surface of the sheet-like organic base material, heat conductivity in the surface direction can be imparted.
　（伸長性を有するシート状有機基材が熱伝導性物質を含有する場合）
　熱伝導性物質は、伸長性を有するシート状有機基材を構成する易伸長性ポリマー母材に含有されていてもよく、筒状難伸長性ポリマー部Ａに含有されていてもよく、易伸長性ポリマー母材と筒状難伸長性ポリマー部Ａとに含有されていてもよい。 (When the stretchable sheet-like organic base material contains a heat conductive substance)
The thermally conductive substance may be contained in the easily stretchable polymer base material constituting the stretchable sheet-like organic base material, or may be contained in the cylindrical difficult-to-extend polymer part A. May be contained in the porous polymer base material and the cylindrical hardly extensible polymer part A.
　熱伝導性物質を含有するシード状有機基材は、上記の伸長性を有するシート状有機基剤の製造方法において、易伸長性ポリマー母材として熱伝導性物質を含有する易伸長性ポリマー母材を使用、又は筒状難伸長性ポリマー部Ａ形成用材料として熱伝導性物質を含有する筒状難伸長性ポリマー部Ａ形成用材料を使用、又は易伸長性ポリマー母材として熱伝導性物質を含有する易伸長性ポリマー母材を使用し、且つ筒状難伸長性ポリマー部Ａ形成用材料として熱伝導性物質を含有する筒状難伸長性ポリマー部Ａ形成用材料を使用することによって、製造することができる。 A seed-like organic base material containing a thermally conductive substance is an easily stretchable polymer base material containing a thermally conductive substance as an easily stretchable polymer base material in the above-described method for producing a sheet-like organic base having stretchability. Or a cylindrical hard-to-extend polymer part A-forming material containing a heat-conducting substance as a material for forming a cylindrical hard-to-extend polymer part A, or a heat-conducting substance as an easily-extensible polymer base material. Manufactured by using a readily stretchable polymer base material containing, and using a cylindrical hardly stretchable polymer part A forming material containing a thermally conductive substance as a cylindrical hardly stretchable polymer part A forming material can do.
　伸長性を有するシート状有機基材に含有する熱伝導性物質としては、特に限定されず、公知の熱伝導性物質を使用でき、例えば、金属、金属化合物、ホウ素化合物、グラファイト、及び熱伝導性炭素繊維等を挙げることができる。これらは、単独で又は２種以上を組み合わせて使用することができる。本発明においては、なかでも、熱伝導性と共に電気絶縁性を兼ね備えることができる点で、金属化合物、ホウ素化合物を使用することが好ましい。 The heat conductive material contained in the sheet-like organic substrate having extensibility is not particularly limited, and a known heat conductive material can be used, for example, metal, metal compound, boron compound, graphite, and heat conductivity. Carbon fiber etc. can be mentioned. These can be used alone or in combination of two or more. In this invention, it is preferable to use a metal compound and a boron compound especially at the point which can combine electrical insulation with heat conductivity.
　前記金属としては、例えば、金属（例えば、金、銀、鉄、アルミニウム、銅、ニッケル、チタン）単体、またはこれらの合金等を挙げることができる。 Examples of the metal include a metal (eg, gold, silver, iron, aluminum, copper, nickel, titanium) alone, or an alloy thereof.
　前記金属化合物としては、例えば、金属酸化物（例えば、ＳｉＯ２、ＴｉＯ２、ＭｇＯ、ＮｉＯ、ＣｕＯ、Ａｌ２Ｏ３、Ｆｅ２Ｏ３）、金属窒化物（例えば、ＡｌＮ、Ｓｉ３Ｎ４）、金属水酸化物（例えば、Ｍｇ（ＯＨ）２）、金属炭酸塩（例えば、ＭｇＣＯ３）、金属ホウ化物（例えば、ＴｉＢ２）等を挙げることができる。 Examples of the metal compound include metal oxides (for example, SiO2, TiO2, MgO, NiO, CuO, Al2O3, Fe2O3), metal nitrides (for example, AlN, Si3N4), metal hydroxides (for example, Mg (OH 2), metal carbonates (for example, MgCO3), metal borides (for example, TiB2), and the like.
　前記ホウ素化合物としては、例えば、ＢＮ、Ｂ４Ｃ等を挙げることができる。 Examples of the boron compound include BN and B4C.
　これらの中でも、金属酸化物、金属窒化物、金属水酸化物、金属炭酸塩、金属ホウ化物、及びホウ素化合物は、熱伝導性と共に電気絶縁性を兼ね備えるため、好ましい。 Among these, metal oxides, metal nitrides, metal hydroxides, metal carbonates, metal borides, and boron compounds are preferable because they have both heat conductivity and electrical insulation.
　熱伝導性物質の形状は、特に限定されず、バルク、球状、針状、板状等の何れであってもよい。また、熱伝導性物質の平均粒子径（針状の場合は、長径の平均径）は、例えば、０．００１~１００μｍである。熱伝導性物質の平均粒子径（針状の場合は、長径の平均径）の上限は、好ましくは５０μｍ、さらに好ましくは２０μｍであり、下限は、好ましくは０．００５μｍ、さらに好ましくは０．０１μｍである。 The shape of the heat conductive material is not particularly limited, and may be any of a bulk shape, a spherical shape, a needle shape, a plate shape, and the like. In addition, the average particle diameter of the thermally conductive substance (in the case of needles, the average diameter of the major axis) is, for example, 0.001 to 100 μm. The upper limit of the average particle diameter of the heat conductive substance (in the case of needles, the average diameter of the major axis) is preferably 50 μm, more preferably 20 μm, and the lower limit is preferably 0.005 μm, more preferably 0.01 μm. It is.
　易伸長性ポリマー母材に熱伝導性物質を含有する場合、熱伝導性物質の含有量（総量）としては、易伸長性ポリマー母材全体に対して、例えば、１~４００重量％である。熱伝導性物質の含有量（総量）の下限は、好ましくは３重量％、より好ましくは５重量％、さらに好ましくは１０重量％であり、上限は、好ましくは３００重量％、より好ましくは２５０重量％、さらに好ましくは２００重量％である。 When the easily stretchable polymer base material contains a heat conductive substance, the content (total amount) of the heat conductive substance is, for example, 1 to 400% by weight with respect to the whole easily stretchable polymer base material. The lower limit of the content (total amount) of the heat conductive material is preferably 3% by weight, more preferably 5% by weight, still more preferably 10% by weight, and the upper limit is preferably 300% by weight, more preferably 250% by weight. %, More preferably 200% by weight.
　筒状難伸長性ポリマー部Ａに熱伝導性物質を含有する場合、熱伝導性物質の含有量（総量）としては、筒状難伸長性ポリマー部Ａ全体に対して、例えば、１~１０００重量％である。熱伝導性物質の含有量（総量）の下限は、好ましくは３重量％、より好ましくは５重量％、さらに好ましくは１０重量％であり、上限は、好ましくは８００重量％、より好ましくは５００重量％、さらに好ましくは３００重量％である。 In the case where the cylindrical hard-extensible polymer part A contains a heat conductive substance, the content (total amount) of the heat conductive substance is, for example, 1 to 1000 wt. %. The lower limit of the content (total amount) of the heat conductive material is preferably 3% by weight, more preferably 5% by weight, still more preferably 10% by weight, and the upper limit is preferably 800% by weight, more preferably 500% by weight. %, More preferably 300% by weight.
　（伸長性を有するシート状有機基材の少なくとも片面に熱伝導性層を有している場合）
　熱伝導性層は、熱伝導性物質を少なくとも含有する。また、該熱伝導性層は伸長性を有するシート状有機基材に接した状態で設けられていてもよく、接着剤層等を介して設けられていてもよい。更に、熱伝導性層は、伸長性を有するシート状有機基材の表面の全体に設けてもよく、伸長性を有するシート状有機基材の表面のうち必要な箇所のみに部分的に設けてもよい。更にまた、熱伝導性層は、一層で構成されていてもよく、二層以上で構成されていてもよい。二層以上で構成される場合は、同じ組成を有する層で構成されていてもよく、異なる組成を有する層で構成されていてもよい。 (When the heat-conductive layer is provided on at least one side of the stretchable sheet-like organic base material)
The heat conductive layer contains at least a heat conductive material. Moreover, this heat conductive layer may be provided in the state which contact | connected the sheet-like organic base material which has a stretching property, and may be provided through the adhesive bond layer etc. Further, the heat conductive layer may be provided on the entire surface of the sheet-like organic base material having extensibility, and may be provided only on necessary portions of the surface of the sheet-like organic base material having extensibility. Also good. Furthermore, the heat conductive layer may be composed of one layer or may be composed of two or more layers. When comprised by two or more layers, it may be comprised by the layer which has the same composition, and may be comprised by the layer which has a different composition.
　熱伝導性層に含有する熱伝導性物質としては、上記熱伝導性物質を特に制限されることなく使用することができる。 As the heat conductive material contained in the heat conductive layer, the above heat conductive material can be used without any particular limitation.
　熱伝導性層には上記熱伝導性物質以外にも、必要に応じてベースポリマーを含有してもよい。ベースポリマーとしては、易伸長性ポリマー母材２を構成するポリマーの例として挙げられているポリマーを使用することが好ましく、特に、易伸長性ポリマー母材２を構成するポリマーと同種のポリマー、或いは易伸長性ポリマー母材２を構成するポリマーが有するポリマー鎖（主鎖又は側鎖）と同種のポリマー鎖を主鎖又は側鎖に有するポリマーを選択して使用することが、伸長性を有するシート状有機基材表面への密着性に優れる熱伝導性層を形成することができる点で好ましい。 In addition to the above heat conductive material, the heat conductive layer may contain a base polymer as necessary. As the base polymer, it is preferable to use a polymer listed as an example of a polymer constituting the easily extensible polymer base material 2, and in particular, the same kind of polymer as the polymer constituting the easily extensible polymer base material 2, or A sheet having extensibility by selecting and using a polymer having a polymer chain of the same type as the polymer chain (main chain or side chain) of the polymer constituting the easily extensible polymer base material 2 in the main chain or side chain It is preferable at the point which can form the heat conductive layer excellent in the adhesiveness to the surface of a glassy organic base material.
　熱伝導性層には、本発明の効果を損なわない範囲内で更に他の添加物を含有していてもよい。他の添加物としては、例えば、架橋剤（エポキシ系架橋剤、イソシアネート系架橋剤、メラミン系架橋剤、オキサゾリン系架橋剤、アジリジン系架橋剤、金属キレート化合物等）、架橋促進剤（架橋触媒）、粘着付与剤（例えば、ロジン誘導体樹脂、ポリテルペン樹脂、石油樹脂、油溶性フェノール樹脂など）、増粘剤、可塑剤、充填剤、発泡剤、老化防止剤、酸化防止剤、紫外線吸収剤、帯電防止剤、界面活性剤、レベリング剤、着色剤、熱伝導性物質、シランカップリング剤等を挙げることができる。 The heat conductive layer may further contain other additives within a range not impairing the effects of the present invention. Other additives include, for example, crosslinking agents (epoxy crosslinking agents, isocyanate crosslinking agents, melamine crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, metal chelate compounds, etc.), crosslinking accelerators (crosslinking catalysts). , Tackifiers (eg, rosin derivative resins, polyterpene resins, petroleum resins, oil-soluble phenol resins, etc.), thickeners, plasticizers, fillers, foaming agents, anti-aging agents, antioxidants, UV absorbers, charging Examples thereof include an inhibitor, a surfactant, a leveling agent, a colorant, a thermally conductive substance, and a silane coupling agent.
　熱伝導性層全量（１００重量％）における熱伝導性物質の含有量（総量）としては、例えば、１~８０重量％である。熱伝導性物質の含有量（総量）の下限は、好ましくは３重量％、より好ましくは５重量％、さらに好ましくは１０重量％であり、上限は、好ましくは７５重量％、より好ましくは７０重量％、さらに好ましくは６５重量％である。 The content (total amount) of the heat conductive material in the total amount (100% by weight) of the heat conductive layer is, for example, 1 to 80% by weight. The lower limit of the content (total amount) of the heat conductive material is preferably 3% by weight, more preferably 5% by weight, still more preferably 10% by weight, and the upper limit is preferably 75% by weight, more preferably 70% by weight. %, More preferably 65% by weight.
　熱伝導性層の形成方法としては、熱伝導性物質を添加する以外は、易伸長性ポリマー母材部２の形成方法と同じ方法を採用することができる。また、熱伝導性層は、伸長性を有するシート状有機基材表面に直接形成してもよく、適当なセパレータ（剥離紙等）上に熱伝導性層を形成し、これを伸長性を有するシート状有機基材に転写（移着）して積層してもよい。 As the method for forming the heat conductive layer, the same method as the method for forming the easily stretchable polymer base material 2 can be adopted except that a heat conductive material is added. The heat conductive layer may be directly formed on the surface of the sheet-like organic base material having extensibility. The heat conductive layer is formed on an appropriate separator (such as release paper) and has the extensibility. You may transfer (transfer) and laminate | stack on a sheet-like organic base material.
　さらに、熱伝導性層は、熱伝導性層の形成材（少なくとも、熱伝導性物質とベースポリマーを含む）と、易伸長性ポリマー母材を形成する易伸長性ポリマー母材とを溶融押出して一体化させる方法でも形成することもできる。溶融押出方法としては、インフレーション法やＴダイ法等任意の公知技術を用いることができる。 Further, the heat conductive layer is obtained by melt-extruding a material for forming a heat conductive layer (including at least a heat conductive material and a base polymer) and a stretchable polymer base material that forms a stretchable polymer base material. It can also be formed by an integrated method. As the melt extrusion method, any known technique such as an inflation method or a T-die method can be used.
　熱伝導性層の厚さとしては、用途等に応じて適宜選択でき、例えば、１~５００μｍであり、下限は、好ましくは５μｍ、より好ましくは１０μｍ、さらに好ましくは２０μｍである。上限は、好ましくは４００μｍ、より好ましくは３００μｍ、さらに好ましくは２００μｍである。 The thickness of the heat conductive layer can be appropriately selected according to the use and the like, and is, for example, 1 to 500 μm, and the lower limit is preferably 5 μm, more preferably 10 μm, and still more preferably 20 μm. The upper limit is preferably 400 μm, more preferably 300 μm, and even more preferably 200 μm.
　粘着剤層を介して伸長性を有するシート状有機基材表面に熱伝導性層を設ける場合、該粘着剤層を構成する粘着剤としては、特に限定されず、例えば、ゴム系粘着剤、アクリル系粘着剤、ビニルアルキルエーテル系粘着剤、シリコーン系粘着剤、ポリエステル系粘着剤、ポリアミド系粘着剤、ウレタン系粘着剤、スチレン−ジエンブロック共重合体系粘着剤、これらの粘着剤に融点が約２００℃以下の熱溶融性樹脂を配合したクリープ特性改良型粘着剤などの公知の粘着剤を１種又は２種以上組み合わせて用いることができる。粘着剤は、溶剤型、エマルジョン型、ホットメルト型、エネルギー線硬化型粘着剤、加熱剥離型等の公知のいずれの粘着剤であってもよく、用途に応じて適切なものを選択できる。また、粘着剤は、弱粘着型、強粘着型、再剥離型等の何れであってもよく、用途に応じて適宜選択できる。 When a thermally conductive layer is provided on the surface of a sheet-like organic substrate having extensibility via an adhesive layer, the adhesive constituting the adhesive layer is not particularly limited, and examples thereof include rubber adhesives and acrylics. Adhesives, vinyl alkyl ether adhesives, silicone adhesives, polyester adhesives, polyamide adhesives, urethane adhesives, styrene-diene block copolymer adhesives, and these adhesives have a melting point of about 200 Known pressure-sensitive adhesives such as creep property-improving pressure-sensitive adhesives blended with a heat-meltable resin at a temperature of 0 ° C. or lower can be used alone or in combination of two or more. The pressure-sensitive adhesive may be any known pressure-sensitive adhesive such as a solvent type, an emulsion type, a hot-melt type, an energy ray curable pressure-sensitive adhesive, and a heat release type, and an appropriate one can be selected depending on the application. Further, the pressure-sensitive adhesive may be any of a weak pressure-sensitive adhesive type, a strong pressure-sensitive adhesive type, a re-peeling type, and the like, and can be appropriately selected according to the application.
　粘着剤層を構成する粘着剤としては、特にアクリル系ポリマー（重量平均分子量は、例えば１万~２００万、好ましくは３０万~１５０万）をベースポリマーとするアクリル系粘着剤が好ましく使用される。アクリル系ポリマーは、ランダム共重合体、ブロック共重合体、グラフト重合体等のいずれであってもよい。 As the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer, an acrylic pressure-sensitive adhesive based on an acrylic polymer (weight average molecular weight is, for example, 10,000 to 2,000,000, preferably 300,000 to 1,500,000) is preferably used. . The acrylic polymer may be any of a random copolymer, a block copolymer, a graft polymer, and the like.
　粘着剤には、ベースポリマーのほか、必要に応じて、架橋剤（エポキシ系架橋剤、イソシアネート系架橋剤、メラミン系架橋剤、オキサゾリン系架橋剤、アジリジン系架橋剤、金属キレート化合物等）、架橋促進剤（架橋触媒）、粘着付与剤（例えば、ロジン誘導体樹脂、ポリテルペン樹脂、石油樹脂、油溶性フェノール樹脂など）、増粘剤、可塑剤、充填剤、発泡剤、老化防止剤、酸化防止剤、紫外線吸収剤、帯電防止剤、界面活性剤、レベリング剤、着色剤、熱伝導性物質、シランカップリング剤などの適宜な添加剤を含んでいてもよい。 For adhesives, in addition to the base polymer, if necessary, crosslinking agents (epoxy crosslinking agents, isocyanate crosslinking agents, melamine crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, metal chelate compounds, etc.), crosslinking Accelerator (crosslinking catalyst), tackifier (for example, rosin derivative resin, polyterpene resin, petroleum resin, oil-soluble phenol resin, etc.), thickener, plasticizer, filler, foaming agent, anti-aging agent, antioxidant In addition, an appropriate additive such as an ultraviolet absorber, an antistatic agent, a surfactant, a leveling agent, a colorant, a heat conductive substance, or a silane coupling agent may be contained.
　粘着剤層の形成は公知乃至慣用の方法により行うことができる。例えば、粘着剤組成物を伸長性を有するシート状有機基材１（該シート状伸長性有機基材上に中間層が存在する場合は、該中間層）上に塗布する方法、粘着剤組成物を適当なセパレータ上に塗布して粘着剤層を形成した後、該粘着剤層を伸長性を有するシート状有機基材１（該シート状伸長性有機基材上に中間層が存在する場合は、該中間層）上に転写（移着）する方法等が挙げられる。 The formation of the pressure-sensitive adhesive layer can be performed by a known or conventional method. For example, a method of applying a pressure-sensitive adhesive composition onto a sheet-like organic substrate 1 having extensibility (or an intermediate layer when an intermediate layer is present on the sheet-like extensible organic substrate), a pressure-sensitive adhesive composition Is applied onto a suitable separator to form a pressure-sensitive adhesive layer, and then the pressure-sensitive adhesive layer is formed into a sheet-like organic substrate 1 having extensibility (if an intermediate layer is present on the sheet-like extensible organic substrate) And a method of transferring (transferring) onto the intermediate layer).
　粘着剤層は、伸長性を有するシート状有機基材１の表面の全体に設けてもよく、伸長性を有するシート状有機基材１の表面のうち必要な箇所のみに部分的に設けてもよい。 The pressure-sensitive adhesive layer may be provided on the entire surface of the sheet-like organic substrate 1 having extensibility, or may be partially provided only on a necessary portion of the surface of the sheet-like organic substrate 1 having extensibility. Good.
　粘着剤層の厚さとしては、用途等に応じて適宜選択でき、例えば、１~３０００μｍであり、下限は、好ましくは５μｍ、上限は、好ましくは５００μｍである。 The thickness of the pressure-sensitive adhesive layer can be appropriately selected according to the use and the like, and is, for example, 1 to 3000 μm, the lower limit is preferably 5 μm, and the upper limit is preferably 500 μm.
　伸長性を有するシート状有機基材１と熱伝導性層６との間に、粘着剤層以外にも伸長性等を損なわない範囲で、必要に応じて他の層（中間層）を有していてもよい。また、熱伝導性層６上には、熱伝導性を有するシート状伸長性有機基材Ａを使用するまでの間、表面を保護するための保護フィルムが設けられていてもよい。 Between the sheet-like organic substrate 1 having extensibility and the heat conductive layer 6, other layers (intermediate layers) are included as necessary within the range not impairing extensibility other than the adhesive layer. It may be. Moreover, on the heat conductive layer 6, the protective film for protecting the surface may be provided until it uses the sheet-like extensible organic base material A which has heat conductivity.
　熱伝導性を有するシート状伸長性有機基材は、熱伝導性を有し且つ形状不変部を有する伸長性部材（又は、熱伝導性を有し且つ形状不変部を有する伸縮性部材）として、エレクトロニクス製品（トランジスタ、集積回路、コンデンサ、センサ、アクチュエータ等）用部材、オプティカル製品（ディスプレイ、照明、光導波回路等）用部材、オプトエレクトロニクス製品（発光ダイオード、フォトダイオード、太陽電池等）用部材、カーエレクトロニクス製品用部材、家電製品用部材、住宅設備用部材、建材、バンド部材、結束用部材、衛生用品、衣料品の部分、湿布剤の基布等として利用できる。 The sheet-like extensible organic base material having thermal conductivity is an extensible member having thermal conductivity and having a shape-invariant portion (or a stretchable member having thermal conductivity and having a shape-invariant portion). Components for electronics products (transistors, integrated circuits, capacitors, sensors, actuators, etc.), components for optical products (displays, lighting, optical waveguide circuits, etc.), components for optoelectronic products (light emitting diodes, photodiodes, solar cells, etc.), It can be used as a member for car electronics products, a member for household electrical appliances, a member for household equipment, a building material, a band member, a binding member, a sanitary product, a clothing part, a base material for a poultice.
　［断熱性を有するシート状伸長性有機基材］
　断熱性を有するシート状伸長性有機基材として、易伸長性ポリマー母材中に筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されている伸長性を有するシート状有機基材であって、該シート状有機基材が断熱性付与剤を含有している（すなわち、シート状有機基材（特に、易伸長性ポリマー母材）そのものが断熱性を有している）、及び／又は該シート状有機基材の少なくとも片面に断熱性層を有しているものが挙げられる。 [Sheet-like extensible organic base material with heat insulation]
As a sheet-like extensible organic base material having heat insulation properties, a sheet-like organic base material having extensibility in which a cylindrical hard-extensible polymer portion A is partially and integrally formed in an easily extensible polymer base material The sheet-like organic base material contains a heat-insulating agent (that is, the sheet-like organic base material (particularly, the easily extensible polymer base material itself) has heat-insulating properties), and / Or what has a heat insulation layer in the at least single side | surface of this sheet-like organic base material is mentioned.
　断熱性を有するシート状伸長性有機基材の断熱性としては、熱伝導率が例えば０．０５Ｗ／ｍ・Ｋ以下程度、好ましくは、０．０３Ｗ／ｍ・Ｋ以下である。そのため、このようなシート状伸長性有機基材は、基材の一方の面が熱源に接しても、もう一方の面への熱伝導を抑制することができる。 As the heat insulating property of the sheet-like extensible organic base material having heat insulating property, the thermal conductivity is, for example, about 0.05 W / m · K or less, preferably 0.03 W / m · K or less. Therefore, such a sheet-like extensible organic base material can suppress heat conduction to the other surface even when one surface of the base material is in contact with a heat source.
　断熱性を有するシート状伸長性有機基材は、このシート状伸長性有機基材を一方向（面方向）に伸長させると、易伸長性ポリマー母材の部位は伸長するが、部分的に形成された筒状難伸長性ポリマー部Ａは伸長しないか、又はほとんど伸長しない。このため、筒状難伸長性ポリマー部Ａに、形状が変化しないことが望まれる意匠を施したり、他の部材を固定、保持することができる。 A sheet-like extensible organic base material having heat insulation properties, when this sheet-like extensible organic base material is extended in one direction (plane direction), the site of the easily extensible polymer base material is extended, but partially formed The formed cylindrical hardly extensible polymer part A does not stretch or hardly stretches. For this reason, it is possible to give the tubular hardly extensible polymer portion A a design whose shape is desired not to change, and to fix and hold other members.
　断熱性を有するシート状伸長性有機基材の代表例として、図１８の（１）に示される多機能性シート状伸長性有機基材Ａにおいて、機能性層６が断熱性層であるもの、図１８の（２）に示される多機能性シート状伸長性有機基材Ａにおいて、機能性層６が断熱性層であるもの、図１８の（３）に示される多機能性シート状伸長性有機基材Ａにおいて、伸長性を有するシート状有機基材１自体が断熱性を有しているものが挙げられる。 As a representative example of the sheet-like extensible organic substrate having heat insulation, in the multifunctional sheet-like extensible organic substrate A shown in (1) of FIG. 18, the functional layer 6 is a heat-insulating layer. In the multifunctional sheet-like stretchable organic substrate A shown in (2) of FIG. 18, the functional layer 6 is a heat insulating layer, and the multifunctional sheet-like stretchability shown in (3) of FIG. In the organic base material A, the sheet-like organic base material 1 itself having extensibility has a heat insulating property.
　断熱性を有するシート状伸長性有機基材は、易伸長性ポリマー母材中に筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されている伸長性を有するシート状有機基材であって、該シート状有機基材が断熱性付与剤を含有しているシート状伸長性有機基材であってもよく、該シート状有機基材の少なくとも片面に断熱性層を有しているシート状伸長性有機基材であってもよく、該シート状有機基材が断熱性付与剤を含有し、且つ、該シート状有機基材の少なくとも片面に断熱性層を有しているシート状伸長性有機基材であってもよい。本発明のシート状伸長性有機基材は断熱性を有するので、基材の一方の面が熱源に接しても、もう一方の面への熱伝導を抑制することができる。 The sheet-like extensible organic base material having heat insulation is a sheet-like organic base material having extensibility in which a cylindrical hard-extensible polymer portion A is partially and integrally formed in an easily extensible polymer base material. The sheet-like organic substrate may be a sheet-like extensible organic substrate containing a heat-insulating agent, and has a heat-insulating layer on at least one side of the sheet-like organic substrate. A sheet-like extensible organic base material, the sheet-like organic base material containing a heat-insulating agent, and having a heat-insulating layer on at least one side of the sheet-like organic base material It may be a stretchable organic substrate. Since the sheet-like extensible organic base material of the present invention has heat insulation properties, even if one surface of the base material is in contact with a heat source, heat conduction to the other surface can be suppressed.
　（伸長性を有するシート状有機基材が断熱性付与剤を含有する場合）
　断熱性付与剤は、伸長性を有するシート状有機基材を構成する易伸長性ポリマー母材に含有されていてもよく、筒状難伸長性ポリマー部Ａに含有されていてもよく、易伸長性ポリマー母材と筒状難伸長性ポリマー部Ａとに含有されていてもよい。 (When the sheet-like organic substrate having extensibility contains a heat-insulating agent)
The heat insulating property imparting agent may be contained in the easily stretchable polymer base material constituting the stretchable sheet-like organic base material, may be contained in the cylindrical hardly stretchable polymer part A, and is easily stretched. May be contained in the porous polymer base material and the cylindrical hardly extensible polymer part A.
　断熱性付与剤を含有するシード状有機基材は、上記の伸長性を有するシート状有機基剤の製造方法において、易伸長性ポリマー母材として断熱性付与剤を含有する易伸長性ポリマー母材を使用、又は筒状難伸長性ポリマー部Ａ形成用材料として断熱性付与剤を含有する筒状難伸長性ポリマー部Ａ形成用材料を使用、又は易伸長性ポリマー母材として断熱性付与剤を含有する易伸長性ポリマー母材を使用し、且つ筒状難伸長性ポリマー部Ａ形成用材料として断熱性付与剤を含有する筒状難伸長性ポリマー部Ａ形成用材料を使用することによって、製造することができる。 The seed-like organic base material containing the heat insulating property imparting agent is an easily stretchable polymer base material containing the heat insulating property imparting agent as the easily stretchable polymer base material in the above-described method for producing a sheet-like organic base having extensibility. Or a cylindrical hard-to-extend polymer part A forming material containing a heat-insulating agent as a material for forming a cylindrical hard-to-extend polymer part A, or a heat-insulating agent as an easily-extensible polymer base material. Manufactured by using an easily stretchable polymer base material containing and using a cylindrical hardly stretchable polymer part A forming material containing a heat insulating property imparting material as a cylindrical hardly stretchable polymer part A forming material can do.
　伸長性を有するシート状有機基材に含有する断熱性付与剤としては、特に限定されず、公知の断熱性付与剤を使用でき、例えば、無機中空粒子、有機中空粒子などの中空粒子を挙げることができる。これらは、単独で又は２種以上を組み合わせて使用することができる。 The heat insulating property-imparting agent contained in the sheet-like organic base material having extensibility is not particularly limited, and known heat insulating property imparting agents can be used, and examples thereof include hollow particles such as inorganic hollow particles and organic hollow particles. Can do. These can be used alone or in combination of two or more.
　前記無機中空粒子としては、例えば、ホウケイ酸ガラスを主成分とするマイクロバルーン、ナトリウムホウ素シリカを主成分とするマイクロバルーン、アルミナを主成分とするマイクロバルーン、シリカを主成分とするマイクロバルーン等を挙げることができる。 Examples of the inorganic hollow particles include a microballoon mainly composed of borosilicate glass, a microballoon mainly composed of sodium boron silica, a microballoon mainly composed of alumina, and a microballoon mainly composed of silica. Can be mentioned.
　前記有機中空粒子としては、例えば、スチレン系ポリマー、アクリル系ポリマー、塩化ビニル系ポリマー、塩化ビニリデン系ポリマーなど（単独もしくは２つ以上が共重合されたポリマー、架橋される場合もある）を主成分とするマイクロバルーン等を挙げることができる。 As the organic hollow particles, for example, a styrene polymer, an acrylic polymer, a vinyl chloride polymer, a vinylidene chloride polymer or the like (single polymer or a copolymer in which two or more are copolymerized or may be cross-linked) is a main component. And a microballoon.
　中空粒子の平均粒径は、例えば０．１~９０μｍ、好ましくは１~７５μｍ、特に好ましくは１０~６５μｍである。中空粒子の嵩比重は、例えば０．０１~０．５ｇ／ｃｍ３程度である。また、真比重は、例えば０．０１~０．７程度ある。本発明においては、例えば、商品名「Ｑ−ＣＥＬ５０２０」（ポッターズバロティーニ（株）製）、商品名「ＳＸ−８６６（Ａ）」（ＪＳＲ（株）製）、商品名「ＳＸ−８７８２（Ａ）」（ＪＳＲ（株）製）、商品名「シリナックス（登録商標）」（日鉄鉱業（株）製）、商品名「マツモトマイクロスフィアーＭ３０５」（松本油脂製薬（株）製）等の市販品を好適に使用することができる。 The average particle diameter of the hollow particles is, for example, 0.1 to 90 μm, preferably 1 to 75 μm, particularly preferably 10 to 65 μm. The bulk specific gravity of the hollow particles is, for example, about 0.01 to 0.5 g / cm 3. The true specific gravity is, for example, about 0.01 to 0.7. In the present invention, for example, the trade name “Q-CEL5020” (manufactured by Potters Barotini Co., Ltd.), the trade name “SX-866 (A)” (manufactured by JSR Corporation), and the trade name “SX-8882 ( A) "(manufactured by JSR Corporation), trade name" Sirinax (registered trademark) "(manufactured by Nittetsu Mining Co., Ltd.), trade name" Matsumoto Microsphere M305 "(manufactured by Matsumoto Yushi Seiyaku Co., Ltd.), etc. Commercially available products can be suitably used.
　易伸長性ポリマー母材に断熱性付与剤を含有する場合、断熱性付与剤の含有量（総量）としては、易伸長性ポリマー母材全体に対して、例えば、０．１~１００重量％である。断熱性付与剤の含有量（総量）の下限は、好ましくは０．５重量％、より好ましくは１重量％、さらに好ましくは２重量％であり、上限は、好ましくは９０重量％、より好ましくは８０重量％、さらに好ましくは７０重量％である。 In the case where the easily stretchable polymer base material contains a heat insulating property imparting agent, the content (total amount) of the heat insulating property imparting agent is, for example, 0.1 to 100% by weight with respect to the entire easily stretchable polymer base material. is there. The lower limit of the content (total amount) of the heat insulating agent is preferably 0.5% by weight, more preferably 1% by weight, still more preferably 2% by weight, and the upper limit is preferably 90% by weight, more preferably. 80% by weight, more preferably 70% by weight.
　筒状難伸長性ポリマー部Ａに断熱性付与剤を含有する場合、断熱性付与剤の含有量（総量）としては、筒状難伸長性ポリマー部Ａ全体に対して、例えば、０．１~１００重量％である。断熱性付与剤の含有量（総量）の下限は、好ましくは０．５重量％、より好ましくは１重量％、さらに好ましくは２重量％であり、上限は、好ましくは９０重量％、より好ましくは８０重量％、さらに好ましくは７０重量％である。 When the heat insulating property-imparting agent is contained in the cylindrical hardly extensible polymer part A, the content (total amount) of the heat insulating property imparting agent is, for example, 0.1 to 100% by weight. The lower limit of the content (total amount) of the heat insulating agent is preferably 0.5% by weight, more preferably 1% by weight, still more preferably 2% by weight, and the upper limit is preferably 90% by weight, more preferably. 80% by weight, more preferably 70% by weight.
　（伸長性を有するシート状有機基材の少なくとも片面に断熱性層を有している場合）
　断熱性層は、断熱性付与剤を少なくとも含有する層であってもよく、発泡プラスチック等の断熱材で形成された層であってもよい。また、該断熱性層は伸長性を有するシート状有機基材に接した状態で設けられていてもよく、接着剤層等を介して設けられていてもよい。更に、断熱性層は、伸長性を有するシート状有機基材の表面の全体に設けてもよく、伸長性を有する伸長性を有するシート状有機基材の表面のうち必要な箇所のみに部分的に設けてもよい。更にまた、断熱性層は、一層で構成されていてもよく、二層以上で構成されていてもよい。二層以上で構成される場合は、同じ組成を有する層で構成されていてもよく、異なる組成を有する層で構成されていてもよい。 (When a heat-insulating layer is provided on at least one side of the stretchable sheet-like organic base material)
The heat insulating layer may be a layer containing at least a heat insulating agent, or may be a layer formed of a heat insulating material such as foamed plastic. Moreover, this heat insulation layer may be provided in the state which contact | connected the sheet-like organic base material which has a stretching property, and may be provided through the adhesive bond layer etc. Furthermore, the heat insulating layer may be provided on the entire surface of the sheet-like organic base material having extensibility, and is partially applied only to a necessary portion of the surface of the sheet-like organic base material having extensibility. May be provided. Furthermore, the heat insulating layer may be composed of one layer or may be composed of two or more layers. When comprised by two or more layers, it may be comprised by the layer which has the same composition, and may be comprised by the layer which has a different composition.
　断熱性層に含有する断熱性付与剤としては、上記断熱性付与剤を特に制限されることなく使用することができる。 As the heat insulating property imparting agent contained in the heat insulating layer, the heat insulating property imparting agent can be used without any particular limitation.
　断熱性層には上記断熱性付与剤以外にも、必要に応じてベースポリマーを含有してもよい。ベースポリマーとしては、易伸長性ポリマー母材２を構成するポリマーの例として挙げられているポリマーを使用することが好ましく、特に、易伸長性ポリマー母材２を構成するポリマーと同種のポリマー、或いは易伸長性ポリマー母材２を構成するポリマーが有するポリマー鎖（主鎖又は側鎖）と同種のポリマー鎖を主鎖又は側鎖に有するポリマーを選択して使用することが、伸長性を有するシート状有機基材表面への密着性に優れる断熱性層を形成することができる点で好ましい。 In addition to the above heat-insulating agent, the heat-insulating layer may contain a base polymer as necessary. As the base polymer, it is preferable to use a polymer listed as an example of a polymer constituting the easily extensible polymer base material 2, and in particular, the same kind of polymer as the polymer constituting the easily extensible polymer base material 2, or A sheet having extensibility by selecting and using a polymer having a polymer chain of the same type as the polymer chain (main chain or side chain) of the polymer constituting the easily extensible polymer base material 2 in the main chain or side chain It is preferable at the point which can form the heat insulation layer excellent in the adhesiveness to the surface of a glassy organic base material.
　断熱性層には、本発明の効果を損なわない範囲内で更に他の添加物を含有していてもよい。他の添加物としては、例えば、架橋剤（エポキシ系架橋剤、イソシアネート系架橋剤、メラミン系架橋剤、オキサゾリン系架橋剤、アジリジン系架橋剤、金属キレート化合物等）、架橋促進剤（架橋触媒）、粘着付与剤（例えば、ロジン誘導体樹脂、ポリテルペン樹脂、石油樹脂、油溶性フェノール樹脂など）、増粘剤、可塑剤、充填剤、発泡剤、老化防止剤、酸化防止剤、紫外線吸収剤、帯電防止剤、界面活性剤、レベリング剤、着色剤、断熱性付与剤、シランカップリング剤等を挙げることができる。 The heat insulating layer may further contain other additives within a range not impairing the effects of the present invention. Other additives include, for example, crosslinking agents (epoxy crosslinking agents, isocyanate crosslinking agents, melamine crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, metal chelate compounds, etc.), crosslinking accelerators (crosslinking catalysts). , Tackifiers (eg, rosin derivative resins, polyterpene resins, petroleum resins, oil-soluble phenol resins, etc.), thickeners, plasticizers, fillers, foaming agents, anti-aging agents, antioxidants, UV absorbers, charging Examples thereof include an inhibitor, a surfactant, a leveling agent, a colorant, a heat-insulating agent, and a silane coupling agent.
　断熱性層全量（１００重量％）における断熱性付与剤の含有量（総量）としては、例えば、０．１~１００重量％である。断熱性付与剤の含有量（総量）の下限は、好ましくは０．５重量％、より好ましくは１重量％、さらに好ましくは２重量％であり、上限は、好ましくは９０重量％、より好ましくは８０重量％、さらに好ましくは７０重量％である。 The content (total amount) of the heat-insulating agent in the total amount (100% by weight) of the heat-insulating layer is, for example, 0.1 to 100% by weight. The lower limit of the content (total amount) of the heat insulating agent is preferably 0.5% by weight, more preferably 1% by weight, still more preferably 2% by weight, and the upper limit is preferably 90% by weight, more preferably. 80% by weight, more preferably 70% by weight.
　断熱性付与剤を含有する断熱性層の形成方法としては、断熱性付与剤を添加する以外は、易伸長性ポリマー母材部２の形成方法と同じ方法を採用することができる。また、断熱性層は、伸長性を有するシート状有機基材表面に直接形成してもよく、適当なセパレータ（剥離紙等）上に断熱性層を形成し、これを伸長性を有するシート状有機基材に転写（移着）して積層してもよい。 As the method for forming the heat insulating layer containing the heat insulating property imparting agent, the same method as the method for forming the easily stretchable polymer base material part 2 can be adopted except that the heat insulating property imparting agent is added. The heat insulating layer may be directly formed on the surface of the sheet-like organic base material having extensibility. The heat insulating layer is formed on an appropriate separator (such as release paper), and this is formed into a sheet form having extensibility. It may be transferred (transferred) to an organic base material and laminated.
　更に、断熱性付与剤を含有する断熱性層は、断熱性層の形成材（少なくとも、断熱性付与剤とベースポリマーを含む）と、易伸長性ポリマー母材を形成する易伸長性ポリマー母材とを溶融押出して一体化させる方法でも形成することもできる。溶融押出方法としては、インフレーション法やＴダイ法等任意の公知技術を用いることができる。 Furthermore, the heat-insulating layer containing the heat-insulating agent includes a heat-insulating layer forming material (including at least a heat-insulating agent and a base polymer) and an easily stretchable polymer base material that forms an easily stretchable polymer base material. Can also be formed by melt extrusion. As the melt extrusion method, any known technique such as an inflation method or a T-die method can be used.
　また、断熱性層が発泡プラスチックで形成された層である場合、発泡プラスチックとしては、例えば、ウレタンフォーム、発泡ポリスチレン、発泡ポリエチレン、発泡ポリプロピレン、発泡ポリエステル、発泡アクリル、ゴム発泡体（例えば、エチレンプロピレンジエンゴム（ＥＰＤＭ）発泡体等）、フェノールフォーム、シリコーンフォーム、ポリ塩化ビニルフォーム、ユリアフォーム、アクリルフォーム、ポリイミドフォーム、メラミンフォーム等を挙げることができる。 When the heat insulating layer is a layer formed of foamed plastic, examples of the foamed plastic include urethane foam, foamed polystyrene, foamed polyethylene, foamed polypropylene, foamed polyester, foamed acrylic, rubber foam (for example, ethylene propylene). Diene rubber (EPDM) foam, etc.), phenol foam, silicone foam, polyvinyl chloride foam, urea foam, acrylic foam, polyimide foam, melamine foam and the like.
　断熱性層の厚さとしては、用途等に応じて適宜選択でき、例えば、１０~１００００μｍであり、下限は、好ましくは５０μｍ、より好ましくは１００μｍ、さらに好ましくは１５０μｍである。上限は、好ましくは５０００μｍ、より好ましくは２０００μｍである。 The thickness of the heat insulating layer can be appropriately selected depending on the application and the like, and is, for example, 10 to 10,000 μm, and the lower limit is preferably 50 μm, more preferably 100 μm, and further preferably 150 μm. The upper limit is preferably 5000 μm, more preferably 2000 μm.
　粘着剤層を介して伸長性を有するシート状有機基材表面に断熱性層を設ける場合、該粘着剤層を構成する粘着剤としては、特に限定されず、例えば、ゴム系粘着剤、アクリル系粘着剤、ビニルアルキルエーテル系粘着剤、シリコーン系粘着剤、ポリエステル系粘着剤、ポリアミド系粘着剤、ウレタン系粘着剤、スチレン−ジエンブロック共重合体系粘着剤、これらの粘着剤に融点が約２００℃以下の熱溶融性樹脂を配合したクリープ特性改良型粘着剤などの公知の粘着剤を１種又は２種以上組み合わせて用いることができる。粘着剤は、溶剤型、エマルジョン型、ホットメルト型、エネルギー線硬化型粘着剤、加熱剥離型等の公知のいずれの粘着剤であってもよく、用途に応じて適切なものを選択できる。また、粘着剤は、弱粘着型、強粘着型、再剥離型等の何れであってもよく、用途に応じて適宜選択できる。 When a heat-insulating layer is provided on the surface of a sheet-like organic substrate having extensibility via an adhesive layer, the adhesive constituting the adhesive layer is not particularly limited. For example, a rubber-based adhesive, an acrylic-based adhesive Adhesives, vinyl alkyl ether adhesives, silicone adhesives, polyester adhesives, polyamide adhesives, urethane adhesives, styrene-diene block copolymer adhesives, melting point of these adhesives is about 200 ° C One or more known pressure-sensitive adhesives such as creep property-improving pressure-sensitive adhesives containing the following hot-melt resins can be used in combination. The pressure-sensitive adhesive may be any known pressure-sensitive adhesive such as a solvent type, an emulsion type, a hot-melt type, an energy ray curable pressure-sensitive adhesive, and a heat release type, and an appropriate one can be selected depending on the application. Further, the pressure-sensitive adhesive may be any of a weak pressure-sensitive adhesive type, a strong pressure-sensitive adhesive type, a re-peeling type, and the like, and can be appropriately selected according to the application.
　粘着剤層を構成する粘着剤としては、特にアクリル系ポリマー（重量平均分子量は、例えば１万~２００万、好ましくは３０万~１５０万）をベースポリマーとするアクリル系粘着剤が好ましく使用される。アクリル系ポリマーは、ランダム共重合体、ブロック共重合体、グラフト重合体等のいずれであってもよい。 As the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer, an acrylic pressure-sensitive adhesive based on an acrylic polymer (weight average molecular weight is, for example, 10,000 to 2,000,000, preferably 300,000 to 1,500,000) is preferably used. . The acrylic polymer may be any of a random copolymer, a block copolymer, a graft polymer, and the like.
　粘着剤には、ベースポリマーのほか、必要に応じて、架橋剤（エポキシ系架橋剤、イソシアネート系架橋剤、メラミン系架橋剤、オキサゾリン系架橋剤、アジリジン系架橋剤、金属キレート化合物等）、架橋促進剤（架橋触媒）、粘着付与剤（例えば、ロジン誘導体樹脂、ポリテルペン樹脂、石油樹脂、油溶性フェノール樹脂など）、増粘剤、可塑剤、充填剤、発泡剤、老化防止剤、酸化防止剤、紫外線吸収剤、帯電防止剤、界面活性剤、レベリング剤、着色剤、断熱性付与剤、シランカップリング剤などの適宜な添加剤を含んでいてもよい。 For adhesives, in addition to the base polymer, if necessary, crosslinking agents (epoxy crosslinking agents, isocyanate crosslinking agents, melamine crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, metal chelate compounds, etc.), crosslinking Accelerator (crosslinking catalyst), tackifier (for example, rosin derivative resin, polyterpene resin, petroleum resin, oil-soluble phenol resin, etc.), thickener, plasticizer, filler, foaming agent, anti-aging agent, antioxidant And an appropriate additive such as an ultraviolet absorber, an antistatic agent, a surfactant, a leveling agent, a colorant, a heat-insulating agent, and a silane coupling agent.
　粘着剤層の形成は公知乃至慣用の方法により行うことができる。例えば、粘着剤組成物を伸長性を有するシート状有機基材１（該シート状伸長性有機基材上に中間層が存在する場合は、該中間層）上に塗布する方法、粘着剤組成物を適当なセパレータ上に塗布して粘着剤層を形成した後、該粘着剤層を伸長性を有するシート状有機基材１（該シート状伸長性有機基材上に中間層が存在する場合は、該中間層）上に転写（移着）する方法等が挙げられる。 The formation of the pressure-sensitive adhesive layer can be performed by a known or conventional method. For example, a method of applying a pressure-sensitive adhesive composition onto a sheet-like organic substrate 1 having extensibility (or an intermediate layer when an intermediate layer is present on the sheet-like extensible organic substrate), a pressure-sensitive adhesive composition Is applied onto a suitable separator to form a pressure-sensitive adhesive layer, and then the pressure-sensitive adhesive layer is formed into a sheet-like organic substrate 1 having extensibility (if an intermediate layer is present on the sheet-like extensible organic substrate) And a method of transferring (transferring) onto the intermediate layer).
　粘着剤層は、伸長性を有するシート状有機基材１の表面の全体に設けてもよく、伸長性を有するシート状有機基材１の表面のうち必要な箇所のみに部分的に設けてもよい。 The pressure-sensitive adhesive layer may be provided on the entire surface of the sheet-like organic substrate 1 having extensibility, or may be partially provided only on a necessary portion of the surface of the sheet-like organic substrate 1 having extensibility. Good.
　粘着剤層の厚さとしては、用途等に応じて適宜選択でき、例えば、５~３００μｍであり、下限は、好ましくは１０μｍ、上限は、好ましくは２００μｍ、より好ましくは１００μｍ、最も好ましくは５０μｍである。 The thickness of the pressure-sensitive adhesive layer can be appropriately selected depending on the application, for example, 5 to 300 μm, the lower limit is preferably 10 μm, the upper limit is preferably 200 μm, more preferably 100 μm, and most preferably 50 μm. is there.
　伸長性を有するシート状有機基材１と断熱性層６との間に、粘着剤層以外にも伸長性等を損なわない範囲で、必要に応じて他の層（中間層）を有していてもよい。また、断熱性層６上には、断熱性を有するシート状伸長性有機基材Ａを使用するまでの間、表面を保護するための保護フィルムが設けられていてもよい。 Between the sheet-like organic substrate 1 having extensibility and the heat-insulating layer 6, other layers (intermediate layers) are included as necessary within the range not impairing extensibility other than the pressure-sensitive adhesive layer. May be. Moreover, on the heat insulation layer 6, the protective film for protecting the surface may be provided until it uses the sheet-like extensible organic base material A which has heat insulation.
　断熱性を有するシート状伸長性有機基材は、断熱性を有し且つ形状不変部を有する伸長性部材（又は、断熱性を有し且つ形状不変部を有する伸縮性部材）として、エレクトロニクス製品（トランジスタ、集積回路、コンデンサ、センサ、アクチュエータ等）用部材、オプティカル製品（ディスプレイ、照明、光導波回路等）用部材、オプトエレクトロニクス製品（発光ダイオード、フォトダイオード、太陽電池等）用部材、カーエレクトロニクス製品用部材、家電製品用部材、住宅設備用部材、建材、バンド部材、結束用部材、衛生用品、衣料品の部分、湿布剤の基布等として利用できる。 The sheet-like stretchable organic base material having heat insulation properties is an electronic product (or a stretchable member having heat insulation properties and a shape-invariable portion) (or a stretchable member having heat insulation properties and a shape-invariant portion). Transistors, integrated circuits, capacitors, sensors, actuators, etc.) members, optical products (displays, lighting, optical waveguide circuits, etc.) members, optoelectronics products (light emitting diodes, photodiodes, solar cells, etc.), car electronics products It can be used as a member for home appliances, a member for home appliances, a member for housing equipment, a building material, a band member, a member for binding, a sanitary article, a clothing part, a base cloth for a poultice.
　［耐衝撃性を有するシート状伸長性有機基材］
　耐衝撃性を有するシート状伸長性有機基材として、易伸長性ポリマー母材中に筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されている伸長性を有するシート状有機基材であって、前記易伸長性ポリマー母材が耐衝撃性付与剤を含むもの、易伸長性ポリマー母材中に筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されている伸長性を有するシート状有機基材の少なくとも一方の面に衝撃吸収層を有するものが挙げられる。 [Stretchable organic base material with impact resistance]
As a sheet-like extensible organic base material having impact resistance, a sheet-like organic group having extensibility in which a cylindrical hardly extensible polymer portion A is partially and integrally formed in an easily extensible polymer matrix. The easily stretchable polymer base material includes an impact resistance imparting agent, and the cylindrical stretchable polymer portion A is partially and integrally formed in the easily stretchable polymer base material. The thing which has an impact absorption layer in the at least one surface of the sheet-like organic base material which has a stretching property is mentioned.
　このようなシート状伸長性有機基材を一方向（面方向）に伸長させると、易伸長性ポリマー母材の部位は伸長するが、部分的に形成された筒状難伸長性ポリマー部Ａは伸長しないか、又はほとんど伸長しない。このため、筒状難伸長性ポリマー部Ａに、形状が変化しないことが望まれる意匠を施したり、他の部材を固定、保持することができる。また、優れた衝撃吸収性を有するため、例えば、衝撃が加えられた場合には当該衝撃を吸収して、被着体を保護することができ、また、シート状伸長性有機基材自身の特性を維持（保持）でき、優れた耐衝撃性を発揮できる。さらに、振動エネルギーを効率的に減衰させることができ、優れた制振性を発揮できる。 When such a sheet-like extensible organic base material is extended in one direction (plane direction), the site of the easily extensible polymer base material is extended, but the partially formed cylindrical hardly extensible polymer portion A is Does not stretch or barely stretches. For this reason, it is possible to give the tubular hardly extensible polymer portion A a design whose shape is desired not to change, and to fix and hold other members. In addition, since it has excellent impact absorbability, for example, when an impact is applied, the impact can be absorbed to protect the adherend, and the properties of the sheet-like extensible organic substrate itself Can be maintained (maintained), and excellent impact resistance can be exhibited. Furthermore, vibration energy can be attenuated efficiently, and excellent vibration damping can be exhibited.
　耐衝撃性を有するシート状伸長性有機基材の代表例として、図１８の（１）に示される多機能性シート状伸長性有機基材Ａにおいて、機能性層６が衝撃吸収層であるもの、図１８の（２）に示される多機能性シート状伸長性有機基材Ａにおいて、機能性層６が衝撃吸収層であるもの、図１８の（３）に示される多機能性シート状伸長性有機基材Ａにおいて、伸長性を有するシート状有機基材１自体が衝撃吸収性（優れた衝撃吸収性）を有しているものが挙げられる。 As a representative example of a sheet-like stretchable organic substrate having impact resistance, the functional layer 6 is a shock-absorbing layer in the multifunctional sheet-like stretchable organic substrate A shown in (1) of FIG. In the multifunctional sheet-like stretchable organic base material A shown in (2) of FIG. 18, the functional layer 6 is an impact absorbing layer, and the multifunctional sheet-like elongation shown in (3) of FIG. In the water-soluble organic base material A, the sheet-like organic base material 1 itself having extensibility has a shock absorbing property (excellent shock absorbing property).
　前記伸長性を有するシート状有機基材が衝撃吸収性を有している場合には、優れた衝撃吸収性を有するシート状伸長性有機基材として用いることができる。この場合、例えば、易伸長性ポリマー母材に衝撃吸収性を付与するための添加剤（耐衝撃性付与剤（「衝撃吸収性付与剤」ともいう））を含有させることにより、シート状伸長性有機基材に対して衝撃吸収性を付与できる。さらに、難伸長性部にも前記耐衝撃性付与剤を含有させることにより、シート状伸長性有機基材に対してより優れた衝撃吸収性を付与できる。 When the sheet-like organic substrate having extensibility has impact absorbability, it can be used as a sheet-like extensible organic substrate having excellent impact absorbability. In this case, for example, by adding an additive (impact resistance imparting agent (also referred to as “impact absorbability imparting agent”)) for imparting impact absorbability to the easily extensible polymer base material, sheet-like extensibility is obtained. Impact absorption can be imparted to the organic substrate. Furthermore, by adding the impact resistance imparting agent to the hardly extensible part, it is possible to impart more excellent impact absorbability to the sheet-like extensible organic base material.
　（耐衝撃性付与剤）
　前記耐衝撃性付与剤としては、公知乃至慣用の耐衝撃性付与剤を使用することができ、特に限定されないが、例えば、無機材料により形成された中空粒子（無機中空粒子）、有機材料により形成された中空粒子（有機中空粒子）、発泡体材料により形成された粒子（発泡体粒子）、ゴム粒子などが挙げられる。前記無機中空粒子としては、例えば、ガラス（特に、ホウケイ酸ガラス）で形成された中空バルーン（マイクロバルーン）などのガラス製の中空バルーン（ガラスバルーン）、金属化合物より形成された金属製の中空バルーン、中空セラミックバルーンなどの磁器製の中空バルーンなどが挙げられる。前記有機中空粒子としては、例えば、塩化ビニリデンバルーン、アクリルバルーンなどの樹脂製の中空バルーンなどが挙げられる。前記発泡体粒子としては、発泡ポリスチレン粒子、発泡ウレタン粒子（ウレタンフォーム粒子）、発泡ポリエチレン粒子、発泡イソプレンゴム粒子、発泡ブタジエンゴム粒子、発泡アクリルゴム粒子などの発泡プラスチック粒子などが挙げられる。前記ゴム粒子としては、天然ゴム粒子、ブタジエンゴム粒子、スチレン−ブタジエンゴム粒子、クロロプレンゴム粒子、イソプレンゴム粒子、ウレタンゴム粒子、アクリルゴム粒子、シリコーンゴム粒子などの合成ゴム粒子、コア・シェル構造を有するゴム粒子などが挙げられる。中でも、前記耐衝撃性付与剤としては、無機中空粒子、発泡プラスチック粒子が好ましい。なお、耐衝撃性付与剤は１種を単独で使用することもできるし、２種以上を組み合わせて使用することもできる。 (Impact resistance agent)
As the impact resistance imparting agent, known or commonly used impact resistance imparting agents can be used, and are not particularly limited. For example, the impact resistance imparting agent is formed of hollow particles (inorganic hollow particles) formed of an inorganic material or organic materials. And hollow particles (organic hollow particles), particles formed from a foam material (foam particles), rubber particles, and the like. Examples of the inorganic hollow particles include glass hollow balloons (glass balloons) such as hollow balloons (microballoons) formed of glass (particularly borosilicate glass), and metal hollow balloons formed of a metal compound. And porcelain hollow balloons such as hollow ceramic balloons. Examples of the organic hollow particles include resin-made hollow balloons such as vinylidene chloride balloons and acrylic balloons. Examples of the foam particles include expanded plastic particles such as expanded polystyrene particles, expanded urethane particles (urethane foam particles), expanded polyethylene particles, expanded isoprene rubber particles, expanded butadiene rubber particles, and expanded acrylic rubber particles. The rubber particles include natural rubber particles, butadiene rubber particles, styrene-butadiene rubber particles, chloroprene rubber particles, isoprene rubber particles, urethane rubber particles, acrylic rubber particles, silicone rubber particles, and other synthetic rubber particles, and a core / shell structure. And rubber particles. Among these, as the impact resistance-imparting agent, inorganic hollow particles and foamed plastic particles are preferable. In addition, the impact resistance imparting agent can be used alone or in combination of two or more.
　前記耐衝撃性付与剤の形状は、特に限定されないが、例えば、バルク、球状、針状、板状等のいずれであってもよい。 The shape of the impact resistance imparting agent is not particularly limited, and may be any of, for example, a bulk shape, a spherical shape, a needle shape, and a plate shape.
　前記耐衝撃性付与剤の粒径（平均粒子径；針状の場合は長径の平均径）は、特に限定されないが、例えば１~５００μｍが好ましい。耐衝撃性付与剤の粒径の上限は、分散性の観点で、好ましくは２００μｍ、より好ましくは１００μｍである。一方、耐衝撃性付与剤の粒径の下限は、衝撃吸収性の観点で、好ましくは５μｍ、より好ましくは１０μｍである。なお、前記平均粒子径とは、レーザー回折・散乱法により測定される粒度分布から算出される積算値５０％での粒子径（ｄ５０）を意味する。 The particle diameter (average particle diameter; in the case of needles, the average diameter of the major axis) is not particularly limited, but is preferably 1 to 500 μm, for example. The upper limit of the particle diameter of the impact resistance imparting agent is preferably 200 μm, more preferably 100 μm, from the viewpoint of dispersibility. On the other hand, the lower limit of the particle size of the impact resistance imparting agent is preferably 5 μm, more preferably 10 μm, from the viewpoint of impact absorption. The average particle diameter means a particle diameter (d50) at an integrated value of 50% calculated from a particle size distribution measured by a laser diffraction / scattering method.
　前記耐衝撃性付与剤の比重は、特に限定されないが、例えば０．０１~０．８ｇ／ｃｍ３が好ましい。耐衝撃性付与剤の比重の上限は、コスト等の観点で、０．５ｇ／ｃｍ３が好ましい。一方、耐衝撃性付与剤の比重の下限は、配合時の取り扱い性等の観点で、０．１ｇ／ｃｍ３が好ましい。 The specific gravity of the impact resistance-imparting agent is not particularly limited, but is preferably 0.01 to 0.8 g / cm 3, for example. The upper limit of the specific gravity of the impact resistance imparting agent is preferably 0.5 g / cm 3 from the viewpoint of cost and the like. On the other hand, the lower limit of the specific gravity of the impact resistance-imparting agent is preferably 0.1 g / cm 3 from the viewpoint of handleability during blending.
　易伸長性ポリマー母材における耐衝撃性付与剤の含有量（総量）は、特に限定されないが、易伸長性ポリマー母材全体に対して、例えば、１~５０重量％である。耐衝撃性付与剤の含有量（総量）の下限は、好ましくは２重量％、より好ましくは３重量％、さらに好ましくは５重量％である。一方、上限は、好ましくは４５重量％、より好ましくは４０重量％、さらに好ましくは３５重量％である。耐衝撃性付与剤の含有量が１重量％未満であると、十分な衝撃吸収性を発揮できない場合がある。一方、耐衝撃性付与剤の含有量が５０重量％を超えると、易伸長性ポリマー母材（伸長性を有する有機基材）の伸長性が低下する場合がある。 The content (total amount) of the impact resistance imparting agent in the easily stretchable polymer base material is not particularly limited, but is, for example, 1 to 50% by weight with respect to the entire easily stretchable polymer base material. The lower limit of the content (total amount) of the impact resistance imparting agent is preferably 2% by weight, more preferably 3% by weight, and still more preferably 5% by weight. On the other hand, the upper limit is preferably 45% by weight, more preferably 40% by weight, and still more preferably 35% by weight. If the content of the impact resistance-imparting agent is less than 1% by weight, sufficient impact absorbability may not be exhibited. On the other hand, when the content of the impact resistance-imparting agent exceeds 50% by weight, the extensibility of the easily extensible polymer base material (organic base material having extensibility) may be lowered.
　筒状難伸長性ポリマー部Ａが耐衝撃性付与剤を含む場合、その含有量（総量）は特に限定されないが、筒状難伸長性ポリマー部Ａ全体に対して、例えば、１~５０重量％である。耐衝撃性付与剤の含有量（総量）の下限は、好ましくは２重量％、より好ましくは３重量％、さらに好ましくは５重量％である。一方、上限は、好ましくは４５重量％、より好ましくは４０重量％、さらに好ましくは３５重量％である。耐衝撃性付与剤の含有量が１重量％未満であると、十分な衝撃吸収性を発揮できない場合がある。一方、耐衝撃性付与剤の含有量が５０重量％を超えると筒状難伸長性ポリマー部Ａの形状が変化しやすくなる場合がある。 When the cylindrical difficult-to-extend polymer part A contains an impact resistance-imparting agent, the content (total amount) is not particularly limited, but for example 1 to 50% by weight with respect to the entire cylindrical difficult-to-extend polymer part A It is. The lower limit of the content (total amount) of the impact resistance imparting agent is preferably 2% by weight, more preferably 3% by weight, and still more preferably 5% by weight. On the other hand, the upper limit is preferably 45% by weight, more preferably 40% by weight, and still more preferably 35% by weight. If the content of the impact resistance-imparting agent is less than 1% by weight, sufficient impact absorbability may not be exhibited. On the other hand, when the content of the impact resistance-imparting agent exceeds 50% by weight, the shape of the cylindrical hardly extensible polymer part A may be easily changed.
　一方、上記優れた衝撃吸収性を有するシート状伸長性有機基材が、易伸長性ポリマー母材中に筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されている伸長性を有するシート状有機基材の少なくとも一方の面に衝撃吸収層を設けた積層体として構成される場合には、当該衝撃吸収層は以下の衝撃吸収層であることが好ましい。 On the other hand, the sheet-like extensible organic base material having excellent shock absorption has an extensibility in which a cylindrical hardly extensible polymer portion A is partially and integrally formed in an easily extensible polymer base material. When configured as a laminate in which an impact absorbing layer is provided on at least one surface of the sheet-like organic base material, the impact absorbing layer is preferably the following impact absorbing layer.
　（衝撃吸収層）
　上記のシート状伸長性有機基材における衝撃吸収層６は、シート状伸長性有機基材に対して衝撃吸収性を発揮させるための層（機能層）である。前記衝撃吸収層としては、例えば、耐衝撃性付与剤を含む層（「耐衝撃性付与剤含有層」と称する場合がある）；発泡体より形成された層（「発泡体層」と称する場合がある）などが挙げられる。なお、前記衝撃吸収層は、単層の形態を有していてもよく、複層（積層）の形態を有していてもよい。なお、前記衝撃吸収層は、伸長性を有するシート状有機基材１（該シート状伸長性有機基材上に後述の中間層が存在する場合は、該中間層）の表面の全体（全面）に設けてもよく、用途によっては、伸長性を有するシート状有機基材１の表面のうち必要な箇所のみに部分的に設けてもよい。 (Shock absorbing layer)
The impact absorbing layer 6 in the sheet-like extensible organic base material is a layer (functional layer) for exerting the impact-absorbing property on the sheet-like extensible organic base material. Examples of the impact absorbing layer include a layer containing an impact resistance imparting agent (sometimes referred to as “impact resistance imparting agent-containing layer”); a layer formed from a foam (referred to as “foam layer”). There are). In addition, the said shock absorption layer may have a single layer form, and may have the form of the multilayer (lamination | stacking). In addition, the said shock absorption layer is the whole (entire surface) of the surface of the sheet-like organic base material 1 which has extensibility (this intermediate layer when the below-mentioned intermediate | middle layer exists on this sheet-like extensible organic base material). Depending on the application, it may be partially provided only at a necessary portion of the surface of the sheet-like organic substrate 1 having extensibility.
　前記耐衝撃性付与剤含有層における耐衝撃性付与剤としては、前述のものが挙げられる。中でも、前記耐衝撃性付与剤含有層が含有する耐衝撃性付与剤としては、無機中空粒子、発泡プラスチック粒子が好ましい。 Examples of the impact resistance imparting agent in the impact resistance imparting agent-containing layer include those described above. Among these, as the impact resistance imparting agent contained in the impact resistance imparting agent-containing layer, inorganic hollow particles and foamed plastic particles are preferable.
　前記耐衝撃性付与剤含有層は、特に限定されないが、耐衝撃性付与剤とポリマー（バインダーポリマー）とを含む組成物より形成された樹脂層（樹脂組成物層）であることが好ましい。前記バインダーポリマーとしては、特に限定されないが、例えば、前述の［易伸長性ポリマー母材］の項で例示した伸長性を有するポリマーを好ましく使用することができる。当該伸長性を有するポリマーをバインダーポリマーとして使用することにより、シート状伸長性有機基材の伸長性を損なうことなく、優れた衝撃吸収性を発揮させることができる。 The impact resistance-containing agent-containing layer is not particularly limited, but is preferably a resin layer (resin composition layer) formed from a composition containing an impact resistance imparting agent and a polymer (binder polymer). Although it does not specifically limit as said binder polymer, For example, the polymer which has the extendability illustrated by the term of the above-mentioned [easily stretchable polymer base material] can be used preferably. By using the polymer having the extensibility as a binder polymer, excellent impact absorbability can be exhibited without impairing the extensibility of the sheet-like extensible organic base material.
　耐衝撃性付与剤含有層における耐衝撃性付与剤の含有量（総量）は、特に限定されないが、耐衝撃性付与剤含有層全体に対して、例えば、１~５０重量％である。耐衝撃性付与剤の含有量（総量）の下限は、好ましくは２重量％、より好ましくは３重量％、さらに好ましくは５重量％である。一方、上限は、好ましくは４５重量％、より好ましくは４０重量％、さらに好ましくは３５重量％である。耐衝撃性付与剤の含有量が１重量％未満であると、十分な衝撃吸収性を発揮できない場合がある。一方、耐衝撃性付与剤の含有量が５０重量％を超えると、耐衝撃性付与剤含有層の伸長性が低下する場合がある。 The content (total amount) of the impact imparting agent in the impact imparting agent-containing layer is not particularly limited, but is, for example, 1 to 50% by weight with respect to the entire impact imparting agent-containing layer. The lower limit of the content (total amount) of the impact resistance imparting agent is preferably 2% by weight, more preferably 3% by weight, and still more preferably 5% by weight. On the other hand, the upper limit is preferably 45% by weight, more preferably 40% by weight, and still more preferably 35% by weight. If the content of the impact resistance-imparting agent is less than 1% by weight, sufficient impact absorbability may not be exhibited. On the other hand, if the content of the impact resistance-imparting agent exceeds 50% by weight, the extensibility of the impact resistance imparting agent-containing layer may be lowered.
　前記耐衝撃性付与剤含有層は、公知乃至慣用の方法により形成することができ、その形成方法は特に限定されない。具体的には、易伸長性ポリマー母材部を形成する方法と同様の方法、例えば、伸長性を有するシート状有機基材（該シート状伸長性有機基材上に後述の中間層が存在する場合には、該中間層）上に耐衝撃性付与剤を含む前記バインダーポリマーの液状前駆体を塗工して、その後、前記液状前駆体を目的のポリマー（バインダーポリマー）に転化する方法が挙げられる。前記液状前駆体としては、前記バインダーポリマーに誘導できるモノマー（エネルギー線硬化性モノマー等）、該モノマーの部分重合物、硬化又は架橋により前記バインダーポリマーに誘導できる硬化又は架橋前ポリマーなどが挙げられる。前記液状前駆体のバインダーポリマーへの転化は、例えば、重合（エネルギー線や熱による重合等）、硬化、架橋反応などにより行うことができる。また、前記耐衝撃性付与剤含有層は、例えば、伸長性を有するシート状有機基材（該シート状伸長性有機基材上に後述の中間層が存在する場合には、該中間層）上に耐衝撃性付与剤及び前記バインダーポリマーを含む溶液又は分散液を塗工して、その後、溶媒（又は分散媒）を乾燥除去する方法；伸長性を有するシート状有機基材（該シート状伸長性有機基材上に後述の中間層が存在する場合には、該中間層）上に耐衝撃性付与剤と前記バインダーポリマー単体との組成物による層を形成し、溶融・冷却処理（ホットメルト処理）を行う方法などによっても形成できる。なお、前記耐衝撃性付与剤含有層は、いったん前記耐衝撃性付与剤含有層を支持体（セパレータ等）上に形成した後、該耐衝撃性付与剤含有層を伸長性を有するシート状有機基材（該シート状伸長性有機基材上に後述の中間層が存在する場合には、該中間層）上に転写する方法等によっても形成できる。 The impact resistance-containing agent-containing layer can be formed by a known or conventional method, and the formation method is not particularly limited. Specifically, a method similar to the method for forming the easily extensible polymer base material, for example, a sheet-like organic base material having extensibility (the intermediate layer described later exists on the sheet-like extensible organic base material) In this case, the intermediate layer is coated with a liquid precursor of the binder polymer containing an impact resistance imparting agent, and then the liquid precursor is converted into a target polymer (binder polymer). It is done. Examples of the liquid precursor include a monomer that can be derived from the binder polymer (such as an energy ray-curable monomer), a partially polymerized product of the monomer, and a polymer that is precured or crosslinked that can be induced to the binder polymer by curing or crosslinking. The conversion of the liquid precursor into a binder polymer can be performed, for example, by polymerization (polymerization with energy rays or heat, etc.), curing, crosslinking reaction, or the like. Further, the impact resistance-containing agent-containing layer is formed on, for example, a sheet-like organic substrate having extensibility (if the intermediate layer described later is present on the sheet-like extensible organic substrate, the intermediate layer) Coating a solution or dispersion containing an impact resistance-imparting agent and the binder polymer, and then drying and removing the solvent (or dispersion medium); an extensible sheet-like organic substrate (the sheet-like elongation) When an intermediate layer to be described later is present on the conductive organic base material, a layer made of a composition of the impact resistance-imparting agent and the binder polymer alone is formed on the intermediate layer, and a melting / cooling process (hot melt) It can also be formed by a method of performing processing. The impact resistance-imparting agent-containing layer is formed by forming the impact resistance imparting agent-containing layer once on a support (separator or the like), and then forming the impact resistance imparting agent-containing layer into a sheet-like organic material having extensibility. It can also be formed by a method of transferring on a base material (in the case where an intermediate layer described later is present on the sheet-like extensible organic base material).
　前記発泡体層を構成する発泡体としては、公知乃至慣用の発泡体を使用することができ、特に限定されないが、特に、プラスチック発泡体を好ましく使用することができる。前記プラスチック発泡体を構成するプラスチック（プラスチック材料）としては、例えば、ポリスチレン、ウレタン（ポリウレタン）、ポリエチレン、イソプレンゴム、ブタジエンゴム、アクリルゴムなどが挙げられる。即ち、上記発泡体層としては、例えば、ポリスチレン発泡体層（発泡ポリスチレン層）、ウレタンフォーム層、ポリエチレン発泡体層（発泡ポリエチレン層）、イソプレンゴム発泡体層、ブタジエンゴム発泡体層、アクリルゴム発泡体層などが挙げられる。 As the foam constituting the foam layer, a known or conventional foam can be used, and is not particularly limited, but a plastic foam can be particularly preferably used. Examples of the plastic (plastic material) constituting the plastic foam include polystyrene, urethane (polyurethane), polyethylene, isoprene rubber, butadiene rubber, and acrylic rubber. That is, examples of the foam layer include a polystyrene foam layer (foamed polystyrene layer), a urethane foam layer, a polyethylene foam layer (foamed polyethylene layer), an isoprene rubber foam layer, a butadiene rubber foam layer, and an acrylic rubber foam. Examples include body layers.
　前記発泡体層は、公知乃至慣用の方法により形成することができ、その形成方法は特に限定されない。具体的には、例えば、周知の方法により製造したシート状の発泡体を伸長性を有するシート状有機基材１（該シート状伸長性有機基材上に後述の中間層が存在する場合には、該中間層）上に貼り合わせる方法などが挙げられる。なお、シート状の発泡体の貼り合わせには、公知乃至慣用の粘着剤（例えば、アクリル系粘着剤等）や接着剤を使用することができる。また、上記シート状の発泡体としては、市販品を使用することもできる。 The foam layer can be formed by a known or conventional method, and the formation method is not particularly limited. Specifically, for example, a sheet-like foam produced by a well-known method is made into a sheet-like organic substrate 1 having extensibility (when an intermediate layer described later is present on the sheet-like extensible organic substrate) And a method of laminating on the intermediate layer). In addition, a well-known thru | or usual adhesive (for example, acrylic adhesive etc.) and an adhesive agent can be used for bonding of a sheet-like foam. Moreover, a commercial item can also be used as said sheet-like foam.
　前記衝撃吸収層（特に、耐衝撃性付与剤含有層、発泡体層）は、その他、必要に応じて、架橋剤、架橋促進剤（架橋触媒）、粘着付与剤、増粘剤、可塑剤、充填剤、発泡剤、老化防止剤、酸化防止剤、紫外線吸収剤、帯電防止剤、界面活性剤、レベリング剤、着色剤、難燃剤、シランカップリング剤などの適宜な添加剤を含んでいてもよい。 The impact absorbing layer (in particular, the impact resistance-containing agent-containing layer and the foam layer) may be a crosslinking agent, a crosslinking accelerator (crosslinking catalyst), a tackifier, a thickener, a plasticizer, as necessary. It may contain appropriate additives such as fillers, foaming agents, anti-aging agents, antioxidants, UV absorbers, antistatic agents, surfactants, leveling agents, colorants, flame retardants, and silane coupling agents. Good.
　前記衝撃吸収層の厚さは、シート状伸長性有機基材に対して所望の衝撃吸収性を付与できるものであればよく、特に限定されないが、０．０１~１０ｍｍが好ましい。前記衝撃吸収層の厚さの下限は、例えば０．１ｍｍが好ましく、より好ましくは０．５ｍｍである。一方、前記衝撃吸収層の厚さの上限は、例えば８ｍｍが好ましく、より好ましくは５ｍｍである。 The thickness of the impact absorbing layer is not particularly limited as long as it can provide a desired impact absorbing property to the sheet-like extensible organic base material, but is preferably 0.01 to 10 mm. The lower limit of the thickness of the shock absorbing layer is, for example, preferably 0.1 mm, more preferably 0.5 mm. On the other hand, the upper limit of the thickness of the shock absorbing layer is, for example, preferably 8 mm, more preferably 5 mm.
　耐衝撃性を有するシート状伸長性有機基材の厚みは、例えば０．０１ｍｍ以上であり、好ましくは０．０３ｍｍ以上、さらに好ましくは０．０５ｍｍ以上である。耐衝撃性を有するシート状伸長性有機基材の厚みの上限は、例えば２ｃｍであり、好ましくは１ｃｍ、より好ましくは５ｍｍ、さらに好ましくは２ｍｍである。 The thickness of the sheet-like extensible organic base material having impact resistance is, for example, 0.01 mm or more, preferably 0.03 mm or more, and more preferably 0.05 mm or more. The upper limit of the thickness of the sheet-like extensible organic base material having impact resistance is, for example, 2 cm, preferably 1 cm, more preferably 5 mm, and further preferably 2 mm.
　伸長性を有するシート状有機基材１と衝撃吸収層６との間に、伸長性等を損なわない範囲で、必要に応じて他の層（中間層）を有していてもよい。 Between the sheet-like organic base material 1 having extensibility and the shock absorbing layer 6, other layers (intermediate layers) may be provided as necessary within a range not impairing extensibility.
　上記のシート状伸長性有機基材は、優れた衝撃吸収性を有し且つ形状不変部を有する伸長性部材（又は、優れた衝撃吸収性を有し且つ形状不変部を有する伸縮性部材）として、エレクトロニクス製品（トランジスタ、集積回路、コンデンサ、センサ、アクチュエータ等）用部材、オプティカル製品（ディスプレイ、照明、光導波回路等）用部材、オプトエレクトロニクス製品（発光ダイオード、フォトダイオード、太陽電池等）用部材、カーエレクトロニクス製品用部材、家電製品用部材、住宅設備用部材、建材、バンド部材、結束用部材、衛生用品、衣料品の部分、湿布剤の基布等として利用できる。 The sheet-like extensible organic base material has an excellent impact absorbability and an extensible member having a shape invariable portion (or an elastic member having an excellent impact absorbability and having a shape invariable portion). , Materials for electronics products (transistors, integrated circuits, capacitors, sensors, actuators, etc.), materials for optical products (displays, lighting, optical waveguide circuits, etc.), materials for optoelectronic products (light emitting diodes, photodiodes, solar cells, etc.) It can be used as a member for car electronics products, a member for household electrical appliances, a member for household equipment, a building material, a band member, a binding member, a sanitary article, a clothing part, a base cloth for a poultice.
　［ガスバリア性を有するシート状伸長性有機基材］
　ガスバリア性を有するシート状伸長性有機基材としては、易伸長性ポリマー母材中に筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されている伸長性を有するシート状有機基材の少なくとも一方の面にガスバリア層を有しており、下記［ｉ］及び［ｉｉ］のいずれか一方又は両方を満たすシート状伸長性有機基材が挙げられる。
［ｉ］ＪＩＳ　Ｋ７１２６−２法に準じて２０℃、７０％ＲＨ条件下で測定される厚さ１００μｍ相当の酸素透過率（酸素透過度）が１０ｍＬ／ｍ２／０．１ＭＰａ／ｄａｙ［ｍＬ／（ｍ２・０．１ＭＰａ・ｄａｙ）］以下である
［ｉｉ］ＪＩＳ　Ｋ７１２９Ｂ法に準じて４０℃、９０％ＲＨ条件下で測定される厚さ１００μｍ相当の水蒸気透過率（水蒸気透過度）が１０ｇ／ｍ２／０．１ＭＰａ／ｄａｙ［ｇ／（ｍ２・０．１ＭＰａ・ｄａｙ）］以下である [Sheet-like extensible organic base material having gas barrier properties]
As a sheet-like extensible organic base material having gas barrier properties, an extensible sheet-like organic group in which a cylindrical hardly extensible polymer portion A is partially and integrally formed in an easily extensible polymer base material Examples include a sheet-like extensible organic base material having a gas barrier layer on at least one surface of the material and satisfying one or both of the following [i] and [ii].
[I] Oxygen permeability (oxygen permeability) corresponding to a thickness of 100 μm measured under the conditions of 20 ° C. and 70% RH according to JIS K7126-2 method is 10 mL / m 2 /0.1 MPa / day [mL / ( mii · 0.1 MPa · day)] or less. [ii] The water vapor permeability (water vapor permeability) corresponding to a thickness of 100 μm measured at 40 ° C. and 90% RH according to JIS K7129B method is 10 g / m 2. /0.1 MPa / day [g / (m 2 · 0.1 MPa · day)] or less
　他のガスバリア性を有するシート状伸長性有機基材として、易伸長性ポリマー母材中に筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されている伸長性を有するシート状有機基材であって、該シート状伸長性有機基材が下記［ｉ］及び［ｉｉ］のいずれか一方又は両方を満たすシート状伸長性有機基材が挙げられる。
［ｉ］ＪＩＳ　Ｋ７１２６−２法に準じて２０℃、７０％ＲＨ条件下で測定される厚さ１００μｍ相当の酸素透過率が１０ｍＬ／ｍ２／０．１ＭＰａ／ｄａｙ以下である
［ｉｉ］ＪＩＳ　Ｋ７１２９Ｂ法に準じて４０℃、９０％ＲＨ条件下で測定される厚さ１００μｍ相当の水蒸気透過率が１０ｇ／ｍ２／０．１ＭＰａ／ｄａｙ以下である As a sheet-like extensible organic base material having other gas barrier properties, an extensible sheet-like organic material in which a cylindrical hardly extensible polymer portion A is partially and integrally formed in an easily extensible polymer base material Examples of the base material include a sheet-like extensible organic base material that satisfies any one or both of the following [i] and [ii].
[I] The oxygen permeability corresponding to a thickness of 100 μm measured under the conditions of 20 ° C. and 70% RH according to JIS K7126-2 method is 10 mL / m 2 /0.1 MPa / day or less. [Ii] JIS K7129B method The water vapor permeability corresponding to a thickness of 100 μm measured under the conditions of 40 ° C. and 90% RH is 10 g / m 2 /0.1 MPa / day or less
　このようなシート状伸長性有機基材を一方向（面方向）に伸長させると、易伸長性ポリマー母材の部位は伸長するが、部分的に形成された筒状難伸長性ポリマー部Ａは伸長しないか、又はほとんど伸長しない。このため、筒状難伸長性ポリマー部Ａに、形状が変化しないことが望まれる意匠を施したり、他の部材を固定、保持することができる。また、このシート状伸長性有機基材はガスバリア性（優れたガスバリア性）を有するので、例えば、酸素や水蒸気などのガスによる材料の劣化（例えば、金属の劣化など）を抑制することができる。 When such a sheet-like extensible organic base material is extended in one direction (plane direction), the site of the easily extensible polymer base material is extended, but the partially formed cylindrical hardly extensible polymer portion A is Does not stretch or barely stretches. For this reason, it is possible to give the tubular hardly extensible polymer portion A a design whose shape is desired not to change, and to fix and hold other members. Moreover, since this sheet-like extensible organic base material has gas barrier properties (excellent gas barrier properties), for example, deterioration of materials (for example, deterioration of metals) due to gas such as oxygen or water vapor can be suppressed.
　なお、本明細書における「ガスバリア性」とは、ガスの透過を抑制ないし抑止する特性（性質）を意味し、例えば、上記［ｉ］及び［ｉｉ］のいずれか一方又は両方を満たす特性を意味する場合がある。 In addition, the “gas barrier property” in the present specification means a characteristic (property) that suppresses or suppresses the permeation of gas, for example, a characteristic that satisfies one or both of the above [i] and [ii]. There is a case.
　ガスバリア性を有するシート状伸長性有機基材の代表例として、図１８の（１）に示される多機能性シート状伸長性有機基材Ａにおいて、機能性層６がガスバリア層であるもの、図１８の（２）に示される多機能性シート状伸長性有機基材Ａにおいて、機能性層６がガスバリア層であるもの、図１８の（３）に示される多機能性シート状伸長性有機基材Ａにおいて、伸長性を有するシート状有機基材１自体がガスバリア性を有しているものが挙げられる。 As a representative example of a sheet-like extensible organic substrate having gas barrier properties, in the multifunctional sheet-like extensible organic substrate A shown in (1) of FIG. 18, the functional layer 6 is a gas barrier layer. In the multifunctional sheet-like extensible organic base material A shown in 18 (2), the functional layer 6 is a gas barrier layer, and the multifunctional sheet-like extensible organic group shown in (3) of FIG. Examples of the material A include those in which the stretchable sheet-like organic substrate 1 itself has gas barrier properties.
　前記伸長性を有するシート状有機基材がガスバリア性（特に、酸素バリア性及び／又は水蒸気バリア性）を有している場合には、そのままガスバリア性を有するシート状伸長性有機基材として用いることができる。この場合、例えば、易伸長性ポリマー母材を、ガスバリア性を有する材料で構成することによりガスバリア性を付与できる。また、この場合、該シート状伸長性有機基材は、下記［ｉ］及び［ｉｉ］のいずれか一方又は両方を満たす。
［ｉ］ＪＩＳ　Ｋ７１２６−２法に準じて２０℃、７０％ＲＨ条件下で測定される厚さ１００μｍ相当の酸素透過率が１０ｍＬ／ｍ２／０．１ＭＰａ／ｄａｙ以下である
［ｉｉ］ＪＩＳ　Ｋ７１２９Ｂ法に準じて４０℃、９０％ＲＨ条件下で測定される厚さ１００μｍ相当の水蒸気透過率が１０ｇ／ｍ２／０．１ＭＰａ／ｄａｙ以下である When the sheet-like organic substrate having extensibility has a gas barrier property (particularly oxygen barrier property and / or water vapor barrier property), it is used as it is as a sheet-like extensible organic substrate having gas barrier property. Can do. In this case, for example, gas barrier properties can be imparted by configuring the easily stretchable polymer base material with a material having gas barrier properties. In this case, the sheet-like extensible organic base material satisfies either one or both of the following [i] and [ii].
[I] The oxygen permeability corresponding to a thickness of 100 μm measured under the conditions of 20 ° C. and 70% RH according to JIS K7126-2 method is 10 mL / m 2 /0.1 MPa / day or less. [Ii] JIS K7129B method The water vapor permeability corresponding to a thickness of 100 μm measured under the conditions of 40 ° C. and 90% RH is 10 g / m 2 /0.1 MPa / day or less
　前記シート状伸長性有機基材の酸素透過率は、好ましくは９ｍＬ／ｍ２／０．１ＭＰａ／ｄａｙ以下であり、用途によっては８ｍＬ／ｍ２／０．１ＭＰａ／ｄａｙ以下、あるいは７ｍＬ／ｍ２／０．１ＭＰａ／ｄａｙ以下であってもよい。また、前記シート状伸長性有機基材の水蒸気透過率は、好ましくは９ｇ／ｍ２／０．１ＭＰａ／ｄａｙ以下であり、用途によっては８ｇ／ｍ２／０．１ＭＰａ／ｄａｙ以下、あるいは７ｇ／ｍ２／０．１ＭＰａ／ｄａｙ以下であってもよい。 The oxygen permeability of the sheet-like extensible organic base material is preferably 9 mL / m 2 /0.1 MPa / day or less, and depending on the application, it is 8 mL / m 2 /0.1 MPa / day or less, or 7 mL / m 2/0. It may be 1 MPa / day or less. Further, the water vapor permeability of the sheet-like extensible organic base material is preferably 9 g / m 2 /0.1 MPa / day or less, and depending on the application, it is 8 g / m 2 /0.1 MPa / day or less, or 7 g / m 2 / It may be 0.1 MPa / day or less.
　前記ガスバリア性を有する材料としては、例えば、ポリ塩化ビニリデン、塩化ビニリデン共重合体（例えば、塩化ビニル、アクリロニトリルなどとの共重合体）などのポリ塩化ビニリデン系ポリマー；ポリアクリロニトリル、アクリロニトリル共重合体などのポリアクリロニトリル系ポリマー；ポリビニルアルコール、ポリビニルアルコールの部分ケン化物、エチレン−ビニルアルコール共重合体などのポリビニルアルコール系ポリマー；ポリ塩化ビニル系ポリマー；ポリオレフィン系ポリマー（例えば高密度ポリエチレン、ポリプロピレンなど）；ポリアミド系ポリマー（例えばナイロン６、ナイロン６６など）；ポリエステル系ポリマー（例えばポリエチレンテレフタレート、ポリエチレンナフタレートなど）；ガスバリア性物質（ガスバリア性を付与するための物質）と各種ポリマーとを含む樹脂組成物（例えば、ポリマー中にガスバリア性物質が分散した樹脂組成物）などが挙げられる。 Examples of the material having gas barrier properties include polyvinylidene chloride polymers such as polyvinylidene chloride and vinylidene chloride copolymers (for example, copolymers with vinyl chloride, acrylonitrile, etc.); polyacrylonitrile, acrylonitrile copolymers, etc. Polyacrylonitrile polymers such as: polyvinyl alcohol, polyvinyl alcohol polymers such as polyvinyl alcohol, partially saponified polyvinyl alcohol, and ethylene-vinyl alcohol copolymers; polyvinyl chloride polymers; polyolefin polymers (eg, high density polyethylene, polypropylene, etc.); polyamides Polymer (eg nylon 6, nylon 66 etc.); polyester polymer (eg polyethylene terephthalate, polyethylene naphthalate etc.); gas barrier material (gas Resin composition comprising the various polymers and materials) for imparting barrier properties (e.g., a resin composition which gas barrier material is dispersed in the polymer) and the like.
　前記樹脂組成物におけるポリマーとしては、例えば、前記［易伸長性ポリマー母材］の項で伸長性を有するポリマーとして例示したポリマーなどが挙げられる。前記ガスバリア性物質としては、例えば、シリカ、炭酸カルシウム、クレー、酸化チタン、タルク、層状ケイ酸塩、粘土鉱物（例えば、層状粘度鉱物など）、金属粉、ガラス、ガラスビーズ、ガラスバルーン、アルミナバルーン、セラミックバルーン、チタン白、カーボンブラックなどの粒子（微粒子、微粒子粉末）などが挙げられる。前記粒子は、中実体、中空体（バルーン）のいずれであってもよい。また、前記層状粘度鉱物としては、例えば、モンモリロナイト、バイデライト、ヘクトライト、サポナイト、ノントロナイト、スチーブンサイト等のスメクタイト；バーミキュライト；ベントナイト；カネマイト、ケニアナイト、マカナイト等の層状ケイ酸ナトリウム等が挙げられる。なお、ガスバリア性物質は１種のみを用いてもよいし、２種以上を併用してもよい。 Examples of the polymer in the resin composition include the polymers exemplified as the polymer having extensibility in the section of [Easily extensible polymer base material]. Examples of the gas barrier substance include silica, calcium carbonate, clay, titanium oxide, talc, layered silicate, clay mineral (for example, layered viscosity mineral), metal powder, glass, glass beads, glass balloon, and alumina balloon. And particles (fine particles, fine particle powder) of ceramic balloon, titanium white, carbon black and the like. The particles may be solid or hollow (balloon). Examples of the layered viscosity mineral include smectites such as montmorillonite, beidellite, hectorite, saponite, nontronite, and stevensite; vermiculite; bentonite; layered sodium silicate such as kanemite, kenyaite, and macanite. . In addition, only 1 type may be used for a gas barrier substance and it may use 2 or more types together.
　前記易伸長性ポリマー母材がガスバリア性物質と各種ポリマーとを含む樹脂組成物で構成される場合、該易伸長性ポリマー母材におけるガスバリア性物質の含有量は、特に限定されないが、易伸長性ポリマー母材を構成するポリマー１００重量部に対して、例えば０．１~４００重量部が好ましい。 When the easily extensible polymer matrix is composed of a resin composition containing a gas barrier substance and various polymers, the content of the gas barrier substance in the easily extensible polymer matrix is not particularly limited, For example, 0.1 to 400 parts by weight is preferable with respect to 100 parts by weight of the polymer constituting the polymer base material.
　一方、ガスバリア性を有するシート状伸長性有機基材が、易伸長性ポリマー母材中に筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されている伸長性を有するシート状有機基材の少なくとも一方の面にガスバリア層を設けた積層体として構成される場合には、該シート状伸長性有機基材（積層体）が下記［ｉ］及び［ｉｉ］のいずれか一方又は両方を満たす。
［ｉ］ＪＩＳ　Ｋ７１２６−２法に準じて２０℃、７０％ＲＨ条件下で測定される厚さ１００μｍ相当の酸素透過率が１０ｍＬ／ｍ２／０．１ＭＰａ／ｄａｙ以下である
［ｉｉ］ＪＩＳ　Ｋ７１２９Ｂ法に準じて４０℃、９０％ＲＨ条件下で測定される厚さ１００μｍ相当の水蒸気透過率が１０ｇ／ｍ２／０．１ＭＰａ／ｄａｙ以下である On the other hand, the sheet-like extensible organic base material having gas barrier properties is an extensible sheet-like organic material in which the cylindrical hardly extensible polymer portion A is partially and integrally formed in the easily extensible polymer base material. When configured as a laminate in which a gas barrier layer is provided on at least one surface of the substrate, the sheet-like extensible organic substrate (laminate) is either or both of the following [i] and [ii]: Meet.
[I] The oxygen permeability corresponding to a thickness of 100 μm measured under the conditions of 20 ° C. and 70% RH according to JIS K7126-2 method is 10 mL / m 2 /0.1 MPa / day or less. [Ii] JIS K7129B method The water vapor permeability corresponding to a thickness of 100 μm measured under the conditions of 40 ° C. and 90% RH is 10 g / m 2 /0.1 MPa / day or less
　前記シート状伸長性有機基材（積層体）の酸素透過率は、好ましくは９ｍＬ／ｍ２／０．１ＭＰａ／ｄａｙ以下であり、用途によっては８ｍＬ／ｍ２／０．１ＭＰａ／ｄａｙ以下、あるいは７ｍＬ／ｍ２／０．１ＭＰａ／ｄａｙ以下であってもよい。また、前記シート状伸長性有機基材（積層体）の水蒸気透過率は、好ましくは９ｇ／ｍ２／０．１ＭＰａ／ｄａｙ以下であり、用途によっては８ｇ／ｍ２／０．１ＭＰａ／ｄａｙ以下、あるいは７ｇ／ｍ２／０．１ＭＰａ／ｄａｙ以下であってもよい。 The oxygen permeability of the sheet-like extensible organic base material (laminate) is preferably 9 mL / m 2 /0.1 MPa / day or less, depending on the application, or 8 mL / m 2 /0.1 MPa / day or less, or 7 mL / It may be less than m2 / 0.1 MPa / day. Further, the water vapor permeability of the sheet-like extensible organic base material (laminate) is preferably 9 g / m 2 /0.1 MPa / day or less, depending on the application, or 8 g / m 2 /0.1 MPa / day or less, or It may be 7 g / m2 / 0.1 MPa / day or less.
　ガスバリア性を有するシート状伸長性有機基材の厚みは、例えば０．０１ｍｍ以上であり、好ましくは０．０３ｍｍ以上、さらに好ましくは０．０５ｍｍ以上である。ガスバリア性を有するシート状伸長性有機基材の厚みの上限は、例えば１ｃｍであり、好ましくは５ｍｍ、さらに好ましくは２ｍｍである。 The thickness of the sheet-like extensible organic base material having gas barrier properties is, for example, 0.01 mm or more, preferably 0.03 mm or more, and more preferably 0.05 mm or more. The upper limit of the thickness of the sheet-like extensible organic base material having gas barrier properties is, for example, 1 cm, preferably 5 mm, and more preferably 2 mm.
　［ガスバリア層］
　前記ガスバリア層６は、本発明のシート状伸長性有機基材に対してガスバリア性を付与するための層（機能層）である。前記ガスバリア層としては、特に、本発明のシート状伸長性有機基材に対して酸素バリア性及び／又は水蒸気バリア性を付与するガスバリア層が好ましい。なお、前記「酸素バリア性」とは、酸素の透過を抑制ないし抑止する特性（性質）を意味し、例えば、ＪＩＳ　Ｋ７１２６−２法に準じて２０℃、７０％ＲＨ条件下で測定される厚さ（シート状伸長性有機基材の厚さ）１００μｍ相当の酸素透過率が１０ｍＬ／ｍ２／０．１ＭＰａ／ｄａｙ以下である特性であってもよい。また、前記「水蒸気バリア性」とは、水蒸気の透過を抑制ないし抑止する特性（性質）を意味し、例えば、ＪＩＳ　Ｋ７１２９Ｂ法に準じて４０℃、９０％ＲＨ条件下で測定される厚さ（シート状伸長性有機基材の厚さ）１００μｍ相当の水蒸気透過率が１０ｇ／ｍ２／０．１ＭＰａ／ｄａｙ以下である特性であってもよい。特に、前記ガスバリア層は、本発明のシート状伸長性有機基材に対して酸素バリア性及び水蒸気バリア性を付与するガスバリア層であることが好ましい。 [Gas barrier layer]
The gas barrier layer 6 is a layer (functional layer) for imparting gas barrier properties to the sheet-like extensible organic substrate of the present invention. As the gas barrier layer, a gas barrier layer that imparts oxygen barrier properties and / or water vapor barrier properties to the sheet-like extensible organic substrate of the present invention is particularly preferable. The “oxygen barrier property” means a property (property) that suppresses or inhibits the permeation of oxygen. The thickness (thickness of the sheet-like extensible organic base material) may be such that the oxygen permeability corresponding to 100 μm is 10 mL / m 2 /0.1 MPa / day or less. The “water vapor barrier property” means a property (property) that suppresses or inhibits the permeation of water vapor. (Thickness of sheet-like extensible organic substrate) The water vapor transmission rate corresponding to 100 μm may be 10 g / m 2 /0.1 MPa / day or less. In particular, the gas barrier layer is preferably a gas barrier layer that imparts oxygen barrier properties and water vapor barrier properties to the sheet-like extensible organic substrate of the present invention.
　前記ガスバリア層は、単層の形態を有していてもよく、複層（積層）の形態を有していてもよい。また、前記ガスバリア層は、伸長性を有するシート状有機基材１（該シート状伸長性有機基材上に後述の中間層が存在する場合は、該中間層）の表面の全体に設けてもよく、用途によっては、伸長性を有するシート状有機基材１の表面のうち必要な箇所のみに部分的に設けてもよい。 The gas barrier layer may have a single-layer form or a multi-layer (stacked) form. Further, the gas barrier layer may be provided on the entire surface of the sheet-like organic base material 1 having extensibility (if the below-described intermediate layer is present on the sheet-like extensible organic base material, the intermediate layer). Well, depending on the application, it may be partially provided only on the necessary portion of the surface of the sheet-like organic substrate 1 having extensibility.
　前記ガスバリア層としては、特に限定されないが、例えば、有機ガスバリア層、無機ガスバリア層などが挙げられる。 The gas barrier layer is not particularly limited, and examples thereof include an organic gas barrier layer and an inorganic gas barrier layer.
　前記有機ガスバリア層を形成するための材料（有機材料）としては、特に限定されないが、例えば、ポリ塩化ビニリデン、塩化ビニリデン共重合体などのポリ塩化ビニリデン系ポリマー；ポリアクリロニトリル、アクリロニトリル共重合体などのポリアクリロニトリル系ポリマー；ポリビニルアルコール、ポリビニルアルコールの部分ケン化物、エチレン−ビニルアルコール共重合体などのビニルアルコール系ポリマー；ポリ塩化ビニル、ポリ塩化ビニル共重合体などのポリ塩化ビニル系ポリマー；高密度ポリエチレン、ポリプロピレンなどのポリオレフィン系ポリマー；ナイロン６、ナイロン６６などのポリアミド系ポリマー；ポリエチレンテレフタレート、ポリエチレンナフタレートなどのポリエステル系ポリマーなどの酸素透過率や水蒸気透過率が小さい材料が挙げられる。中でも、酸素透過率と水蒸気透過率の両方が小さい点で、ポリ塩化ビニリデン系ポリマーが好ましい。なお、前記有機材料は１種のみを用いてもよいし、２種以上を併用してもよい。 The material (organic material) for forming the organic gas barrier layer is not particularly limited. For example, polyvinylidene chloride polymers such as polyvinylidene chloride and vinylidene chloride copolymers; polyacrylonitrile, acrylonitrile copolymers, and the like. Polyacrylonitrile polymer; polyvinyl alcohol, partially saponified polyvinyl alcohol, vinyl alcohol polymer such as ethylene-vinyl alcohol copolymer; polyvinyl chloride polymer such as polyvinyl chloride and polyvinyl chloride copolymer; high density polyethylene Polyolefin polymers such as polypropylene; polyamide polymers such as nylon 6 and nylon 66; oxygen permeability such as polyester polymers such as polyethylene terephthalate and polyethylene naphthalate Material vapor permeability is small and the like. Among these, a polyvinylidene chloride polymer is preferable in that both oxygen permeability and water vapor permeability are small. In addition, the said organic material may use only 1 type and may use 2 or more types together.
　前記有機ガスバリア層は、公知乃至慣用の方法により形成することができ、その形成方法は特に限定されない。具体的には、例えば、前記有機材料（例えば、前記有機材料を含む溶液又は分散液など）を伸長性を有するシート状有機基材１（該シート状伸長性有機基材上に後述の中間層が存在する場合には、該中間層）上に塗布し、必要に応じて乾燥させる方法などが挙げられる。なお、塗工液の塗布は、一般に用いられるコーター、押出機、印刷機などを用いて行うことができる。 The organic gas barrier layer can be formed by a known or conventional method, and the formation method is not particularly limited. Specifically, for example, the organic material (for example, a solution or dispersion containing the organic material) is a sheet-like organic substrate 1 having extensibility (an intermediate layer described later on the sheet-like extensible organic substrate). In the case where there is, a method of coating on the intermediate layer) and drying as necessary is mentioned. In addition, application | coating of a coating liquid can be performed using a coater, an extruder, a printing machine, etc. which are generally used.
　前記有機ガスバリア層の厚さは、シート状伸長性有機基材に対して所望のガスバリア性を付与できるものであればよく、特に限定されないが、０．０１~１０００μｍが好ましい。前記有機ガスバリア層の厚さの下限は、例えば０．１μｍが好ましく、より好ましくは１μｍである。一方、前記有機ガスバリア層の厚さの上限は、例えば８００μｍが好ましく、より好ましくは５００μｍである。 The thickness of the organic gas barrier layer is not particularly limited as long as the desired gas barrier property can be imparted to the sheet-like extensible organic base material, but is preferably 0.01 to 1000 μm. The lower limit of the thickness of the organic gas barrier layer is, for example, preferably 0.1 μm, more preferably 1 μm. On the other hand, the upper limit of the thickness of the organic gas barrier layer is preferably, for example, 800 μm, and more preferably 500 μm.
　前記無機ガスバリア層を形成するための材料（無機材料）としては、特に限定されないが、例えば、ケイ素酸化物、マグネシウム酸化物、アルミニウム酸化物、亜鉛酸化物、層状ケイ酸塩などの材料が挙げられる。なお、前記無機材料は１種のみを用いてもよいし、２種以上を併用してもよい。 The material (inorganic material) for forming the inorganic gas barrier layer is not particularly limited, and examples thereof include materials such as silicon oxide, magnesium oxide, aluminum oxide, zinc oxide, and layered silicate. . In addition, the said inorganic material may use only 1 type and may use 2 or more types together.
　前記無機ガスバリア層は、公知乃至慣用の方法により形成することができ、その形成方法は特に限定されない。具体的には、例えば、伸長性を有するシート状有機基材１（該シート状伸長性有機基材上に後述の中間層が存在する場合には、該中間層）上に、前記無機材料を含む塗工液を塗布し、乾燥させて前記無機材料による層（無機ガスバリア層）を形成する方法や、スパッタ法により前記無機材料による層（無機ガスバリア層）を形成する方法などが挙げられる。 The inorganic gas barrier layer can be formed by a known or conventional method, and the formation method is not particularly limited. Specifically, for example, the inorganic material is placed on the sheet-like organic substrate 1 having extensibility (if the intermediate layer described later is present on the sheet-like extensible organic substrate, the intermediate layer). Examples thereof include a method in which a coating liquid containing the coating liquid is applied and dried to form a layer made of the inorganic material (inorganic gas barrier layer), and a method in which the layer made of the inorganic material (inorganic gas barrier layer) is formed by a sputtering method.
　前記無機ガスバリア層の厚さは、シート状伸長性有機基材に対して所望のガスバリア性を付与できるものであればよく、特に限定されないが、１~５０００ｎｍが好ましい。前記無機ガスバリア層の厚さの下限は、例えば５ｎｍが好ましく、より好ましくは１０ｎｍである。一方、前記無機ガスバリア層の厚さの上限は、例えば４０００ｎｍが好ましく、より好ましくは３０００ｎｍである。 The thickness of the inorganic gas barrier layer is not particularly limited as long as it can provide a desired gas barrier property to the sheet-like extensible organic base material, but is preferably 1 to 5000 nm. The lower limit of the thickness of the inorganic gas barrier layer is, for example, preferably 5 nm, more preferably 10 nm. On the other hand, the upper limit of the thickness of the inorganic gas barrier layer is preferably, for example, 4000 nm, and more preferably 3000 nm.
　前記ガスバリア層としては、上述の有機ガスバリア層、無機ガスバリア層の他、例えば、前述のガスバリア性を有する材料として例示したガスバリア性物質と各種ポリマーとを含む樹脂組成物などで構成されたガスバリア層、有機−無機ハイブリッド材料で構成されたガスバリア層なども使用することができる。これらのガスバリア層は、公知乃至慣用の方法により形成できる。これらのガスバリア層の厚さは、シート状伸長性有機基材に対して所望のガスバリア性を付与できるものであればよく、特に限定されないが、０．０１~１０００μｍが好ましい。なお、これらのガスバリア層の厚さの下限は、例えば０．１μｍが好ましく、より好ましくは１μｍである。一方、これらのガスバリア層の厚さの上限は、例えば８００μｍが好ましく、より好ましくは５００μｍである。 As the gas barrier layer, in addition to the organic gas barrier layer and the inorganic gas barrier layer described above, for example, a gas barrier layer composed of a resin composition containing a gas barrier substance exemplified as the material having the gas barrier property and various polymers, and the like, A gas barrier layer composed of an organic-inorganic hybrid material can also be used. These gas barrier layers can be formed by a known or conventional method. The thickness of these gas barrier layers is not particularly limited as long as the desired gas barrier property can be imparted to the sheet-like extensible organic base material, but is preferably 0.01 to 1000 μm. In addition, the minimum of the thickness of these gas barrier layers is 0.1 micrometer, for example, More preferably, it is 1 micrometer. On the other hand, the upper limit of the thickness of these gas barrier layers is, for example, preferably 800 μm, and more preferably 500 μm.
　前記ガスバリア層は、その他、必要に応じて、架橋剤、架橋促進剤（架橋触媒）、粘着付与剤、増粘剤、可塑剤、充填剤、発泡剤、老化防止剤、酸化防止剤、紫外線吸収剤、帯電防止剤、界面活性剤、レベリング剤、着色剤、難燃剤、シランカップリング剤などの適宜な添加剤を含んでいてもよい。 In addition, the gas barrier layer is optionally provided with a crosslinking agent, a crosslinking accelerator (crosslinking catalyst), a tackifier, a thickener, a plasticizer, a filler, a foaming agent, an anti-aging agent, an antioxidant, and an ultraviolet absorber. An appropriate additive such as an agent, an antistatic agent, a surfactant, a leveling agent, a colorant, a flame retardant, and a silane coupling agent may be included.
　中でも、前記ガスバリア層としては、シート状伸長性有機基材を十分に伸長させることができ、伸長させた際にもガスバリア層の破壊等の不具合を生じにくい点で、有機ガスバリア層、ガスバリア性物質と各種ポリマーとを含む樹脂組成物などで構成されたガスバリア層、有機−無機ハイブリッド材料で構成されたガスバリア層が好ましい。 Among them, as the gas barrier layer, an organic gas barrier layer, a gas barrier substance can be sufficiently stretched in a sheet-like extensible organic base material, and even when stretched, the gas barrier layer is not easily damaged. A gas barrier layer composed of a resin composition containing a polymer and various polymers and a gas barrier layer composed of an organic-inorganic hybrid material are preferred.
　伸長性を有するシート状有機基材１とガスバリア層６との間に、伸長性等を損なわない範囲で、必要に応じて他の層（中間層）を有していてもよい。 Between the sheet-like organic base material 1 having extensibility and the gas barrier layer 6, other layers (intermediate layers) may be provided as necessary as long as extensibility and the like are not impaired.
　上記のシート状伸長性有機基材は、ガスバリア性（優れたガスバリア性）を有し且つ形状不変部を有する伸長性部材（又は、ガスバリア性を有し且つ形状不変部を有する伸縮性部材）として、エレクトロニクス製品（トランジスタ、集積回路、コンデンサ、センサ、アクチュエータ等）用部材、オプティカル製品（ディスプレイ、照明、光導波回路等）用部材、オプトエレクトロニクス製品（発光ダイオード、フォトダイオード、太陽電池等）用部材、カーエレクトロニクス製品用部材、家電製品用部材、住宅設備用部材、建材、バンド部材、結束用部材、衛生用品、衣料品の部分、湿布剤の基布等として利用できる。 The sheet-like extensible organic base material has a gas barrier property (excellent gas barrier property) and an extensible member having a shape-invariable portion (or an elastic member having a gas barrier property and having a shape-invariant portion). , Materials for electronics products (transistors, integrated circuits, capacitors, sensors, actuators, etc.), materials for optical products (displays, lighting, optical waveguide circuits, etc.), materials for optoelectronic products (light emitting diodes, photodiodes, solar cells, etc.) It can be used as a member for car electronics products, a member for household electrical appliances, a member for household equipment, a building material, a band member, a binding member, a sanitary article, a clothing part, a base cloth for a poultice.
　［透湿性を有するシート状伸長性有機基材］
　透湿性を有するシート状伸長性有機基材として、易伸長性ポリマー母材中に筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されているシート状伸長性有機基材であって、ＪＩＳ　Ｋ７１２９Ａ法に準じて４０℃、９０％ＲＨ条件下で測定される厚さ４０μｍ相当の水蒸気透過率（水蒸気透過度）が１００ｇ／ｍ２／０．１ＭＰａ／ｄａｙ以上であるシート状伸長性有機基材が挙げられる。前記水蒸気透過率は、好ましくは３００ｇ／ｍ２／０．１ＭＰａ／ｄａｙ以上、用途によっては５００ｇ／ｍ２／０．１ＭＰａ／ｄａｙ以上、１０００ｇ／ｍ２／０．１ＭＰａ／ｄａｙ以上であってもよい。 [Sheet-like extensible organic base material having moisture permeability]
As a sheet-like extensible organic base material having moisture permeability, a sheet-like extensible organic base material in which a cylindrical hard-extensible polymer portion A is partially and integrally formed in an easily extensible polymer base material. The sheet-like extensibility having a water vapor transmission rate (water vapor transmission rate) equivalent to a thickness of 40 μm measured at 40 ° C. and 90% RH according to JIS K7129A method is 100 g / m 2 /0.1 MPa / day or more. An organic base material is mentioned. The water vapor transmission rate is preferably 300 g / m2 / 0.1 MPa / day or more, and may be 500 g / m2 / 0.1 MPa / day or more, or 1000 g / m2 / 0.1 MPa / day or more depending on the application.
　このようなシート状伸長性有機基材を一方向（面方向）に伸長させると、易伸長性ポリマー母材の部位は伸長するが、部分的に形成された筒状難伸長性ポリマー部Ａは伸長しないか、又はほとんど伸長しない。このため、筒状難伸長性ポリマー部Ａに、形状が変化しないことが望まれる意匠を施したり、他の部材を固定、保持することができる。また、このシート状伸長性有機基材は高い透湿性を有するため、例えば、皮膚などへ貼り付けた場合の蒸れを抑制することができる。当該シート状伸長性有機基材は、多項構造（多孔質構造）とすることなく（即ち、非多孔性基材の態様で）高い透湿性を発揮できる点でも有用である。但し、このシート状伸長性有機基材は多孔性基材であってもよい。 When such a sheet-like extensible organic base material is extended in one direction (plane direction), the site of the easily extensible polymer base material is extended, but the partially formed cylindrical hardly extensible polymer portion A is Does not stretch or barely stretches. For this reason, it is possible to give the tubular hardly extensible polymer portion A a design whose shape is desired not to change, and to fix and hold other members. Moreover, since this sheet-like extensible organic base material has high moisture permeability, for example, it is possible to suppress stuffiness when pasted on the skin or the like. The sheet-like extensible organic base material is also useful in that it can exhibit high moisture permeability without a multi-dimensional structure (porous structure) (that is, in the form of a non-porous base material). However, the sheet-like extensible organic substrate may be a porous substrate.
　特に、伸長性（又はさらに伸縮性）を有し、なおかつ高い透湿性を有するポリマーにより伸長性母材を構成すると、下記の透湿性付与剤を使用しない又はその使用量を低く抑えた場合であっても、伸長性母材の水蒸気透過率を高くすることができ、ひいては伸長性有機基材の水蒸気透過率を１００ｇ／ｍ２／０．１ＭＰａ／ｄａｙ以上に制御し得る。前記伸長性（又はさらに伸縮性）を有し、なおかつ高い透湿性を有するポリマーとして、例えば、ポリウレタン系ポリマー、ポリウレア系ポリマー、ポリウレタンウレア系ポリマー、シリコーン系ポリマー、ポリエステル系ポリマー、ポリエーテル系ポリマー、ポリアミド系ポリマー、ガラス転移温度（Ｔｇ）の低いアクリル系ポリマー（Ｔｇが、例えば５℃未満、好ましくは０℃以下、さらに好ましくは−５℃以下のアクリル系ポリマー）などが挙げられる。 In particular, when the extensible base material is composed of a polymer having extensibility (or further stretchability) and high moisture permeability, the following moisture permeability imparting agent is not used or the amount used is kept low. However, the water vapor transmission rate of the extensible base material can be increased, and as a result, the water vapor transmission rate of the extensible organic base material can be controlled to 100 g / m 2 /0.1 MPa / day or more. Examples of the polymer having the stretchability (or further stretchability) and having high moisture permeability include, for example, a polyurethane polymer, a polyurea polymer, a polyurethane urea polymer, a silicone polymer, a polyester polymer, a polyether polymer, Examples thereof include polyamide polymers and acrylic polymers having a low glass transition temperature (Tg) (Tg is less than 5 ° C., preferably 0 ° C. or less, more preferably −5 ° C. or less).
　本発明においては、易伸長性ポリマー母材２が透湿性付与剤を含有していてもよい。この場合、本発明のシート状伸長性有機基材は、特に高い透湿性を発揮することができる。透湿性付与剤としては、特に限定されず、易伸長性ポリマー母材の透湿性（水蒸気透過率）を向上させることができる公知乃至慣用の添加剤を使用できる。前記透湿性付与剤としては、公知乃至慣用の親水性材料、具体的には、例えば、界面活性剤、親水性化合物、親水性ポリマーなどが挙げられる。 In the present invention, the easily extensible polymer base material 2 may contain a moisture permeability imparting agent. In this case, the sheet-like extensible organic base material of the present invention can exhibit particularly high moisture permeability. The moisture permeability imparting agent is not particularly limited, and a known or commonly used additive that can improve the moisture permeability (water vapor permeability) of the easily stretchable polymer base material can be used. Examples of the moisture permeability imparting agent include known or commonly used hydrophilic materials, specifically, surfactants, hydrophilic compounds, hydrophilic polymers, and the like.
　前記界面活性剤としては、ノニオン性界面活性剤（非イオン性界面活性剤）、カチオン性界面活性剤、アニオン性界面活性剤、両性界面活性剤のいずれも用いることができる。前記ノニオン性界面活性剤としては、例えば、ポリオキシエチレンアルキルフェニルエーテル［例えば、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンドデシルフェニルエーテルなど］、ポリオキシエチレンアルキルアリルエーテル、ポリオキシエチレンアルキルエーテル［例えば、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンラウリルエーテルなど］、ポリオキシエチレンポリオキシプロピレンブロックポリマー等のエーテル型ノニオン性界面活性剤；ポリエチレングリコール脂肪酸エステル［例えば、ポリエチレングリコールオレイン酸エステルなど］、ポリオキシエチレンソルビタン脂肪酸エステル［例えば、ポリオキシエチレンソルビタンモノパルミチン酸エステルなど］等のエステルエーテル型ノニオン性界面活性剤；グリセリン脂肪酸エステル［例えば、グリセリンモノステアリン酸エステルなど］、ソルビタン脂肪酸エステル［例えば、ソルビタンモノステアリン酸エステルなど］、ショ糖脂肪酸エステル［例えば、ショ糖ステアリン酸エステルなど］等のエステル型ノニオン性界面活性剤；脂肪酸アルカノールアミド［例えば、ラウリン酸ジエタノールアミドなど］等のアルカノールアミド型ノニオン性界面活性剤などが挙げられる。 As the surfactant, any of nonionic surfactants (nonionic surfactants), cationic surfactants, anionic surfactants, and amphoteric surfactants can be used. Examples of the nonionic surfactant include polyoxyethylene alkyl phenyl ether [eg, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene dodecyl phenyl ether, etc.], polyoxyethylene alkyl allyl ether, Polyoxyethylene alkyl ethers [for example, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, etc.], ether-type nonionic surfactants such as polyoxyethylene polyoxypropylene block polymers; polyethylene glycol fatty acid esters [for example, polyethylene glycol olein Acid ester, etc.], polyoxyethylene sorbitan fatty acid ester [for example, polyoxyethylene sorbitan monopal Ester ether type nonionic surfactants such as tinic acid ester, etc .; glycerin fatty acid ester [eg glycerin monostearate etc.], sorbitan fatty acid ester [eg sorbitan monostearate etc.], sucrose fatty acid ester [eg And ester type nonionic surfactants such as sucrose stearate], and alkanolamide type nonionic surfactants such as fatty acid alkanolamides [for example, lauric acid diethanolamide and the like].
　前記カチオン性界面活性剤としては、例えば、アミン塩系カチオン性界面活性剤、第四級アンモニウム塩系カチオン性界面活性剤［例えば、ラウリルトリメチルアンモニウム塩、ステアリルトリメチルアンモニウム塩、トリオクチルアンモニウム塩、ジステアリルジメチルアンモニウム塩などの脂肪族四級アンモニウム塩、ジステアリルジベンジルアンモニウム塩などの芳香族四級アンモニウム塩など］、第四級ホスホニウム塩系カチオン性界面活性剤［例えば、ドデシルトリフェニルホスホニウム塩、メチルトリフェニルホスホニウム塩、ラウリルトリメチルホスホニウム塩、ステアリルトリメチルホスホニウム塩、ジステアリルジメチルホスホニウム塩、ジステアリルジベンジルホスホニウム塩など］などが挙げられる。 Examples of the cationic surfactant include amine salt-based cationic surfactants, quaternary ammonium salt-based cationic surfactants [for example, lauryltrimethylammonium salt, stearyltrimethylammonium salt, trioctylammonium salt, dioctylamine. Aliphatic quaternary ammonium salts such as stearyldimethylammonium salt, aromatic quaternary ammonium salts such as distearyl dibenzylammonium salt], quaternary phosphonium salt-based cationic surfactants [eg, dodecyltriphenylphosphonium salt, Methyltriphenylphosphonium salt, lauryltrimethylphosphonium salt, stearyltrimethylphosphonium salt, distearyldimethylphosphonium salt, distearyldibenzylphosphonium salt, etc.].
　前記アニオン性界面活性剤としては、例えば、硫酸エステル系アニオン性界面活性剤［例えば、ポリオキシエチレンアルキルエーテル硫酸塩、ポリオキシエチレンスチレン化フェニルエーテル硫酸塩、アルキル硫酸塩など］；リン酸エステル系アニオン性界面活性剤［例えば、アルキルリン酸塩、ポリオキシエチレンアルキルエーテルリン酸塩など］；スルホン酸系アニオン性界面活性剤［例えば、スルホン酸塩、スルホコハク酸塩など］；カルボン酸系アニオン性界面活性剤［例えば、脂肪酸塩、ポリオキシエチレンアルキルエーテル酢酸塩、ポリオキシエチレンアルキルスルホコハク酸塩など］などが挙げられる。 Examples of the anionic surfactant include sulfate ester anionic surfactants [for example, polyoxyethylene alkyl ether sulfate, polyoxyethylene styrenated phenyl ether sulfate, alkyl sulfate, etc.]; Anionic surfactants [for example, alkyl phosphates, polyoxyethylene alkyl ether phosphates, etc.]; sulfonic acid-based anionic surfactants [for example, sulfonates, sulfosuccinates, etc.]; Carboxylic acid-based anionic properties Surfactant [For example, fatty acid salt, polyoxyethylene alkyl ether acetate, polyoxyethylene alkyl sulfosuccinate, etc.] etc. are mentioned.
　前記両性界面活性剤としては、例えば、ベタイン系両性界面活性剤［例えば、アルキルベタイン、アミドベタインなど］、グリシン系両性界面活性剤などが挙げられる。 Examples of the amphoteric surfactants include betaine-based amphoteric surfactants [for example, alkyl betaines, amide betaines, etc.] and glycine-based amphoteric surfactants.
　また、前記界面活性剤としては、分子内に反応性基（例えば、（メタ）アクリロイル基、ビニル基、アリル基などの炭素−炭素不飽和結合を含む基、特に、活性エネルギー線硬化性基）を有する界面活性剤を使用することもできる。 The surfactant is a reactive group in the molecule (for example, a group containing a carbon-carbon unsaturated bond such as a (meth) acryloyl group, a vinyl group or an allyl group, particularly an active energy ray-curable group). Surfactants having can also be used.
　前記親水性化合物としては、例えば、グリコール化合物［例えば、エチレングリコール、プロピレングリコール、ブチレングリコール、ヘキシレングリコール、ジエチレングリコール、ジプロピレングリコール、トリエチレングリコール、トリプロピレングリコールなど］；グリセリン；グリセリン誘導体［例えば、ジグリセリンなど］；エチレングリコールモノエーテル化合物［例えば、エチレングリコールモノアリルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールイソブチルエーテル、エチレングリコールモノフェニルエーテル、エチレングリコールモノヘキシルエーテル、エチレングリコールモノ２−エチルヘキシルエーテルなど］；ジエチレングリコールモノエーテル化合物［例えば、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノプロピルエーテル、ジエチレングリコールモノブチルエーテル、ジエチレングリコールモノヘキシルエーテル、ジエチレングリコールモノ−２−エチルヘキシルエーテルなど］；ジプロピレングリコールモノエーテル化合物［例えば、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノプロピルエーテル、ジプロピレングリコールモノブチルエーテルなど］；ポリアルキレングリコールエーテル化合物［例えば、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノブチルエーテル、トリエチレングリコールジメチルエーテル、トリプロピレングリコールモノメチルエーテル、トリプロピレングリコールモノブチルエーテル、テトラエチレングリコールジメチルエーテル、テトラエチレングリコールモノブチルエーテルなど］などが挙げられる。 Examples of the hydrophilic compound include glycol compounds [eg, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, etc.]; glycerin; glycerin derivatives [eg, Diglycerin, etc.]; ethylene glycol monoether compounds [eg, ethylene glycol monoallyl ether, ethylene glycol monobutyl ether, ethylene glycol isobutyl ether, ethylene glycol monophenyl ether, ethylene glycol monohexyl ether, ethylene glycol mono 2-ethylhexyl ether, etc.] Diethylene glycol monoether compounds [for example, diethylene glycol Monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol mono-2-ethylhexyl ether, etc.]; dipropylene glycol monoether compounds [for example, dipropylene glycol monomethyl ether, dipropylene Glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, etc.]; polyalkylene glycol ether compounds [for example, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, triethylene glycol dimethyl ether, tripropylene glycol Monomethyl ether, tripropylene glycol monobutyl ether, tetraethylene glycol dimethyl ether, etc. tetraethylene glycol monobutyl ether], and the like.
　前記親水性ポリマーとしては、アクリル系ポリマー［例えば、ポリアクリル酸ナトリウム、ポリアクリル酸アンモニウム、ポリアクリル酸など］；ポリアミド系ポリマー；ポリアルキレンオキシド系ポリマー［例えば、ポリエチレンオキシドなど］；ポリビニルアルコール系ポリマー；ポリエーテルグリコール系ポリマー；アルギン酸類［例えば、アルギン酸ナトリウム、アルギン酸アンモニウム、アルギン酸プロピレングリコールエステルなど］；ゼラチン類；セルロース誘導体［例えば、カルボキシメチルセルロース、ヒドロキシエチルセルロースなど］；ポリビニルピロリドン系ポリマー［例えば、ポリビニルピロリドン、ビニルピロリドンと酢酸ビニル等との共重合体など］；無水マレイン酸共重合体又はその塩［例えば、イソブチレン−無水マレイン酸共重合体、メチルビニルエーテル−無水マレイン酸共重合体、スチレン−無水マレイン酸共重合体、又はこれらの塩など］；キトサン；キチン；デンプンなどが挙げられる。 Examples of the hydrophilic polymer include acrylic polymers [for example, sodium polyacrylate, ammonium polyacrylate, polyacrylic acid and the like]; polyamide-based polymers; polyalkylene oxide-based polymers [for example, polyethylene oxide and the like]; Polyether glycol-based polymers; alginic acids [for example, sodium alginate, ammonium alginate, propylene glycol ester of alginate]; gelatins; cellulose derivatives [for example, carboxymethylcellulose, hydroxyethylcellulose, etc.]; polyvinylpyrrolidone-based polymers [for example, polyvinylpyrrolidone , Copolymers of vinyl pyrrolidone and vinyl acetate, etc.]; maleic anhydride copolymers or salts thereof [for example, isobutene Len - maleic anhydride copolymer, methyl vinyl ether - maleic anhydride copolymer, styrene - maleic anhydride copolymer, or the like salts thereof]; chitosan; chitin; starch and the like.
　なお、透湿性付与剤は１種を単独で、又は２種以上を組み合わせて使用できる。また、透湿性付与剤としては、市販品を使用することもできる。 In addition, a moisture permeability imparting agent can be used alone or in combination of two or more. Moreover, a commercial item can also be used as a moisture permeability imparting agent.
　上記透湿性付与剤は、特に限定されないが、易伸長性ポリマー母材部の形成が容易となる点で、前記硬化性モノマーＭ（エネルギー線硬化性基Ａ２を有する硬化性モノマーＭ）や有機溶剤に溶解するものが好ましい。但し、易伸長性ポリマー母材部をポリマーを含む水分散液より形成する場合には、水溶性を有するものであってもよい。 The moisture permeability imparting agent is not particularly limited. However, the curable monomer M (the curable monomer M having an energy ray curable group A2) or an organic solvent is used in that the easily stretchable polymer base material can be easily formed. Those which are soluble in are preferable. However, when the easily extensible polymer base material is formed from an aqueous dispersion containing a polymer, it may be water-soluble.
　前記透湿性付与剤の添加によりシート状伸長性有機基材の透湿性が向上するのは、該透湿性付与剤の添加によってシート状伸長性有機基材の吸水性が向上し、その結果、シート状伸長性有機基材に吸収された水（水分）の移動が容易となることによるものと推測される。 The moisture permeability of the sheet-like extensible organic base material is improved by the addition of the moisture permeability-imparting agent. The water-absorbing property of the sheet-like extensible organic base material is improved by the addition of the moisture-permeability imparting agent. It is presumed that the movement of water (moisture) absorbed by the stretchable organic base material becomes easy.
　易伸長性ポリマー母材２における透湿性付与剤の含有量（総量）としては、易伸長性ポリマー母材２全体に対して、例えば、０．０１~８０重量％である。透湿性付与剤の含有量（総量）の下限は、好ましくは０．１重量％、より好ましくは０．５重量％、さらに好ましくは１．０重量％であり、上限は、好ましくは７０重量％、より好ましくは６０重量％、さらに好ましくは５０重量％である。含有量が０．０１重量％未満であると、用途によっては透湿性が不十分となる場合がある。一方、含有量が８０重量％を超えると、易伸長性ポリマー母材部の機械強度が低下する場合がある。 The content (total amount) of the moisture permeability imparting agent in the easily stretchable polymer base material 2 is, for example, 0.01 to 80% by weight with respect to the entire easily stretchable polymer base material 2. The lower limit of the content (total amount) of the moisture permeability imparting agent is preferably 0.1% by weight, more preferably 0.5% by weight, still more preferably 1.0% by weight, and the upper limit is preferably 70% by weight. More preferably, it is 60% by weight, and further preferably 50% by weight. If the content is less than 0.01% by weight, moisture permeability may be insufficient depending on the application. On the other hand, if the content exceeds 80% by weight, the mechanical strength of the easily extensible polymer base material portion may be lowered.
　易伸長性ポリマー母材部の形成は、前記ポリマー母材（Ａ）部の形成方法に準じて行うことができる。例えば、易伸長性ポリマー母材部２は、例えば支持体上に、易伸長性ポリマー母材を構成するポリマーの液状前駆体に必要に応じて透湿性付与剤を添加した組成物を塗工して易伸長性ポリマー母材形成用材料層を形成し、該易伸長性ポリマー母材形成用材料層の所定部位に筒状難伸長性ポリマー部Ａの形成材料を配した後、該易伸長性ポリマー母材形成用材料層中の液状前駆体を目的のポリマーへ転化することにより形成できる。 The easily stretchable polymer base material can be formed according to the method for forming the polymer base material (A). For example, the stretchable polymer base material part 2 is formed by applying a composition in which a moisture permeability imparting agent is added to a liquid precursor of a polymer constituting the stretchable polymer base material, if necessary, on a support. And forming an easily stretchable polymer base material forming material layer, and disposing the forming material of the cylindrical hardly stretchable polymer portion A at a predetermined portion of the easily stretchable polymer base material forming material layer, It can be formed by converting the liquid precursor in the polymer base material forming material layer into a target polymer.
　また、易伸長性ポリマー母材部２は、例えば支持体上に、易伸長性ポリマー母材を構成するポリマーと必要に応じて配合される透湿性付与剤とを含む溶液若しくは分散液を塗工して易伸長性ポリマー母材形成用材料層を形成し、該易伸長性ポリマー母材形成用材料層の所定部位に筒状難伸長性ポリマー部Ａの形成材料を配した後、該易伸長性ポリマー母材形成用材料層中の溶媒を乾燥除去することにより形成することもできる。 In addition, the easily stretchable polymer base 2 is coated on a support with a solution or dispersion containing a polymer constituting the easily stretchable polymer base and a moisture permeability imparting agent blended as necessary. After forming the easily stretchable polymer base material forming material layer, and arranging the forming material of the cylindrical hardly stretchable polymer portion A at a predetermined portion of the easily stretchable polymer base material forming material layer, the easy stretch It can also be formed by removing the solvent in the conductive polymer base material forming material layer by drying.
　さらに、易伸長性ポリマー母材部２は、例えば支持体上に、易伸長性ポリマー母材を構成するポリマー単体（又は前記ポリマー単体と透湿性付与剤との混合物）により易伸長性ポリマー母材形成用材料層を形成し、該易伸長性ポリマー母材形成用材料層の所定部位に筒状難伸長性ポリマー部Ａの形成材料を配した後、溶融・冷却処理（ホットメルト処理）を行うことにより形成することもできる。 Furthermore, the easily extensible polymer base material portion 2 is formed by, for example, a polymer simple substance (or a mixture of the polymer simple substance and the moisture permeability imparting agent) constituting the easily extensible polymer base material on the support. After forming the forming material layer and arranging the forming material of the cylindrical hardly extensible polymer portion A at a predetermined portion of the easily extensible polymer base material forming material layer, a melting / cooling process (hot melt process) is performed. It can also be formed.
　筒状難伸長性ポリマー部Ａ３には、前記易伸長性ポリマー母材部２と同様、透湿性付与剤が含まれていてもよい。筒状難伸長性ポリマー部Ａに透湿性付与剤を添加することで、シート状伸長性有機基材の透湿性を顕著に向上させることができる。該透湿性付与剤としては前記と同様のものを使用できる。 The cylindrical difficult-to-extend polymer part A3 may contain a moisture permeability imparting agent, like the easily-extensible polymer base part 2. The moisture permeability of the sheet-like extensible organic base material can be remarkably improved by adding a moisture permeability imparting agent to the cylindrical hardly extensible polymer portion A. As the moisture permeability imparting agent, the same ones as described above can be used.
　筒状難伸長性ポリマー部Ａ３における透湿性付与剤の含有量（総量）は、筒状難伸長性ポリマー部Ａ３全体に対して、例えば、０．０１~８０重量％である。透湿性付与剤の含有量（総量）の下限は、好ましくは０．１重量％、より好ましくは０．５重量％、さらに好ましくは１．０重量％であり、上限は、好ましくは７０重量％、より好ましくは６０重量％、さらに好ましくは５０重量％である。含有量が０．０１重量％未満であると、用途によっては透湿性が不十分となる場合がある。一方、含有量が８０重量％を超えると、筒状難伸長性ポリマー部Ａの機械強度が低下したり、伸長し易くなってしまう場合がある。 The content (total amount) of the moisture permeability imparting agent in the cylindrical difficult-to-extend polymer part A3 is, for example, 0.01 to 80% by weight with respect to the entire cylindrical difficult-to-extend polymer part A3. The lower limit of the content (total amount) of the moisture permeability imparting agent is preferably 0.1% by weight, more preferably 0.5% by weight, still more preferably 1.0% by weight, and the upper limit is preferably 70% by weight. More preferably, it is 60% by weight, and further preferably 50% by weight. If the content is less than 0.01% by weight, moisture permeability may be insufficient depending on the application. On the other hand, if the content exceeds 80% by weight, the mechanical strength of the cylindrical difficult-to-extend polymer part A may be reduced or the film may be easily stretched.
　透湿性を有するシート状伸長性有機基材は、例えば、透湿性付与剤を易伸長性ポリマー母材形成用材料中に配合し、前記本発明のシート状伸長性有機基材の製造法と同様の方法により製造できる。 The sheet-like extensible organic base material having moisture permeability is, for example, blended with a moisture-permeability imparting agent in the material for forming an easily extensible polymer base material, and is the same as the method for producing the sheet-like extensible organic base material of the present invention. It can manufacture by the method of.
　上記のシート状伸長性有機基材１は、形状不変部を有する伸長性部材（又は、形状不変部を有する伸縮性部材）として、エレクトロニクス製品（トランジスタ、集積回路、コンデンサ、センサ、アクチュエータ等）用部材、オプティカル製品（ディスプレイ、照明、光導波回路等）用部材、オプトエレクトロニクス製品（発光ダイオード、フォトダイオード、太陽電池等）用部材、カーエレクトロニクス製品用部材、家電製品用部材、住宅設備用部材、建材、バンド部材、結束用部材、衛生用品、衣料品の部分、湿布剤の基布等として利用できる。 The sheet-like extensible organic substrate 1 is used for an electronic product (a transistor, an integrated circuit, a capacitor, a sensor, an actuator, etc.) as an extensible member having a shape-invariant portion (or an elastic member having a shape-invariant portion). Parts, members for optical products (displays, lighting, optical waveguide circuits, etc.), members for optoelectronic products (light emitting diodes, photodiodes, solar cells, etc.), members for car electronics products, members for home appliances, members for housing equipment, It can be used as building materials, band members, binding members, sanitary products, clothing parts, base fabrics for poultices, and the like.
　［導電性を有するシート状伸長性有機基材］
　導電性を有するシート状伸長性有機基材として、易伸長性ポリマー母材中に筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されている伸長性を有するシート状有機基材であって、該シート状有機基材が導電性物質を含有している（すなわち、シート状有機基材（特に、易伸長性ポリマー母材）そのものが導電性を有している）、及び／又は該シート状有機基材の少なくとも片面に導電性層を有しているシート状伸長性有機基材が挙げられる。 [Conductive sheet-like extensible organic base material]
As a sheet-like stretchable organic base material having conductivity, a sheet-like organic base material having extensibility in which a cylindrical difficult-to-extend polymer part A is partially and integrally formed in an easily extensible polymer base material. The sheet-like organic base material contains a conductive substance (that is, the sheet-like organic base material (particularly, the easily extensible polymer base material itself) has conductivity), and / or Or the sheet-like extensible organic base material which has an electroconductive layer on the at least single side | surface of this sheet-like organic base material is mentioned.
　導電性を有するシート状伸長性有機基材の導電性としては、表面抵抗率が、例えば１０１２Ω／□以下程度、特に好ましくは１０６Ω／□未満である。そのため、このシート状伸長性有機基材は、表面に電流を流すことができる。また、シート状伸長性有機基材への帯電を抑制することができ、電子部材周辺に使用する際に、静電気による電子部材へのダメージを低減することもできる。さらにまた、この導電性を有するシート状伸長性有機基材は、含有する導電性物質が到来電磁波を反射する性質を有することから、電磁波シールド性も発揮することができる。 As the conductivity of the sheet-like extensible organic base material having conductivity, the surface resistivity is, for example, about 1012 Ω / □ or less, and particularly preferably less than 106 Ω / □. Therefore, this sheet-like extensible organic base material can flow an electric current on the surface. In addition, charging of the sheet-like extensible organic base material can be suppressed, and damage to the electronic member due to static electricity can be reduced when used around the electronic member. Furthermore, since this conductive sheet-like extensible organic base material has a property that the conductive material contained reflects incoming electromagnetic waves, it can also exhibit electromagnetic shielding properties.
　導電性を有するシート状伸長性有機基材は、このシート状伸長性有機基材を一方向（面方向）に伸長させると、易伸長性ポリマー母材の部位は伸長するが、部分的に形成された筒状難伸長性ポリマー部Ａは伸長しないか、又はほとんど伸長しない。このため、筒状難伸長性ポリマー部Ａに、形状が変化しないことが望まれる意匠を施したり、他の部材を固定、保持することができる。 The electrically conductive sheet-like extensible organic base material is partially formed when the sheet-like extensible organic base material is stretched in one direction (plane direction), but the part of the easily extensible polymer base material is elongated. The formed cylindrical hardly extensible polymer part A does not stretch or hardly stretches. For this reason, it is possible to give the tubular hardly extensible polymer portion A a design whose shape is desired not to change, and to fix and hold other members.
　導電性を有するシート状伸長性有機基材の代表例として、図１８の（１）に示される多機能性シート状伸長性有機基材Ａにおいて、機能性層６が導電性層であるもの、図１８の（２）に示される多機能性シート状伸長性有機基材Ａにおいて、機能性層６が導電性層であるもの、図１８の（３）に示される多機能性シート状伸長性有機基材Ａにおいて、伸長性を有するシート状有機基材１自体が導電性を有しているものが挙げられる。 As a representative example of the sheet-like extensible organic substrate having conductivity, in the multifunctional sheet-like extensible organic substrate A shown in (1) of FIG. 18, the functional layer 6 is a conductive layer. In the multifunctional sheet-like stretchable organic substrate A shown in (2) of FIG. 18, the functional layer 6 is a conductive layer, and the multifunctional sheet-like stretchability shown in (3) of FIG. In the organic base material A, the sheet-like organic base material 1 itself having extensibility has a conductive property.
　導電性を有するシート状伸長性有機基材は、易伸長性ポリマー母材中に筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されている伸長性を有するシート状有機基材であって、該シート状有機基材が導電性物質を含有しているシート状伸長性有機基材であってもよく、該シート状有機基材の少なくとも片面に導電性層を有しているシート状伸長性有機基材であってもよく、該シート状有機基材が導電性物質を含有し、且つ、該シート状有機基材の少なくとも片面に導電性層を有しているシート状伸長性有機基材であってもよい。シート状有機基材に導電性物質を含有させると、面方向及び厚さ方向への導電性を付与することができる。一方、シート状有機基材の少なくとも片面に導電性層を設けると、面方向への導電性を付与することができる。更に、帯電を抑制することができ、電子部材周辺に使用する際に、静電気による電子部材へのダメージを低減することができる。更にまた、電磁波シールド性も発揮することができる。 The sheet-like extensible organic base material having conductivity is a sheet-like organic base material having extensibility in which a cylindrical hardly extensible polymer portion A is partially and integrally formed in an easily extensible polymer base material. The sheet-like organic base material may be a sheet-like extensible organic base material containing a conductive substance, and has a conductive layer on at least one side of the sheet-like organic base material. It may be a sheet-like extensible organic substrate, and the sheet-like organic substrate contains a conductive substance, and has a conductive layer on at least one side of the sheet-like organic substrate. An organic base material may be used. When a sheet-like organic base material contains a conductive substance, conductivity in the surface direction and the thickness direction can be imparted. On the other hand, when a conductive layer is provided on at least one surface of the sheet-like organic base material, conductivity in the surface direction can be imparted. Further, charging can be suppressed, and damage to the electronic member due to static electricity can be reduced when used around the electronic member. Furthermore, electromagnetic wave shielding properties can also be exhibited.
　（伸長性を有するシート状有機基材が導電性物質を含有する場合）
　導電性物質は、伸長性を有するシート状有機基材を構成する易伸長性ポリマー母材に含有されていてもよく、筒状難伸長性ポリマー部Ａに含有されていてもよく、易伸長性ポリマー母材と筒状難伸長性ポリマー部Ａとに含有されていてもよい。 (When the sheet-like organic substrate having extensibility contains a conductive substance)
The conductive substance may be contained in the easily extensible polymer base material constituting the sheet-like organic base material having extensibility, or may be contained in the cylindrical hardly extensible polymer portion A. It may be contained in the polymer base material and the cylindrical hardly extensible polymer part A.
　導電性物質を含有するシード状有機基材は、上記の伸長性を有するシート状有機基剤の製造方法において、易伸長性ポリマー母材として導電性物質を含有する易伸長性ポリマー母材を使用、又は筒状難伸長性ポリマー部Ａ形成用材料として導電性物質を含有する筒状難伸長性ポリマー部Ａ形成用材料を使用、又は易伸長性ポリマー母材として導電性物質を含有する易伸長性ポリマー母材を使用し、且つ筒状難伸長性ポリマー部Ａ形成用材料として導電性物質を含有する筒状難伸長性ポリマー部Ａ形成用材料を使用することによって、製造することができる。 The seed-like organic base material containing a conductive substance uses an easily stretchable polymer base material containing a conductive substance as the easily stretchable polymer base material in the above-described method for producing a stretchable sheet-like organic base. , Or a cylindrical difficult-to-extend polymer part A forming material containing a conductive substance is used as a material for forming a cylindrical difficult-to-extend polymer part A, or an easy extension containing a conductive substance as an easily-extensible polymer base material It can manufacture by using the cylindrical difficult-to-extend polymer part A forming material containing an electroconductive substance as a cylindrical difficult-to-extend polymer part A forming material.
　伸長性を有するシート状有機基材に含有する導電性物質としては、例えば、導電性フィラー、導電性ポリマー、界面活性剤、親水性化合物、親水性ポリマー、イオン性液体等を挙げることができる。前記導電性フィラーには、カーボン系導電性フィラー、金属系導電性フィラー等が含まれる。これらは、分散性を向上させるために、シラン系カップリング剤等で表面処理されたものでもよい。また、これらは、単独で又は２種以上を組み合わせて使用することができる。 Examples of the conductive substance contained in the sheet-like organic substrate having extensibility include a conductive filler, a conductive polymer, a surfactant, a hydrophilic compound, a hydrophilic polymer, and an ionic liquid. Examples of the conductive filler include a carbon-based conductive filler and a metal-based conductive filler. These may be surface-treated with a silane coupling agent or the like in order to improve dispersibility. Moreover, these can be used individually or in combination of 2 or more types.
　前記カーボン系導電性フィラーを形成するカーボンとしては、例えば、ケッチェンブラック、アセチレンブラック、サーマルブラック、ファーネスブラック等のカーボンブラック等を挙げることができる。これらは、単独で又は２種以上を組み合わせて使用することができる。 Examples of carbon forming the carbon-based conductive filler include carbon black such as ketjen black, acetylene black, thermal black, and furnace black. These can be used alone or in combination of two or more.
　前記金属系導電性フィラーを形成する金属としては、例えば、ニッケル、鉄、クロム、コバルト、アルミニウム、アンチモン、モリブデン、銅、銀、白金、金などの金属、及びこれらの合金、若しくは酸化物（例えば、酸化チタン、酸化錫、酸化亜鉛、酸化アンチモン、酸化インジウム、チタン酸カリウム、及びこれらの複合酸化物等）を挙げることができる。これらは、単独で、または２種以上を組み合わせて使用することができる。 Examples of the metal forming the metal conductive filler include metals such as nickel, iron, chromium, cobalt, aluminum, antimony, molybdenum, copper, silver, platinum, and gold, and alloys or oxides thereof (for example, , Titanium oxide, tin oxide, zinc oxide, antimony oxide, indium oxide, potassium titanate, and complex oxides thereof). These can be used alone or in combination of two or more.
　前記導電性フィラーの形状は、特に制限されることなく、例えば、球状、スパイク状、フィラメント状、フレーク状や樹枝状等を挙げることができる。また、導電性フィラーの平均粒子径は、例えば０．１~１００μｍである。導電性フィラーの平均粒子径の上限は、好ましくは８０μｍ、さらに好ましくは６０μｍであり、下限は、好ましくは０．５μｍ、さらに好ましくは１μｍである。 The shape of the conductive filler is not particularly limited, and examples thereof include a spherical shape, a spike shape, a filament shape, a flake shape, and a dendritic shape. The average particle diameter of the conductive filler is, for example, 0.1 to 100 μm. The upper limit of the average particle diameter of the conductive filler is preferably 80 μm, more preferably 60 μm, and the lower limit is preferably 0.5 μm, more preferably 1 μm.
　導電性ポリマーとしては、例えば、ポリアニリン、ポリピロール、ポリチオフェン、またはこれらの誘導体が挙げられる。これらは、単独で、または２種以上を組み合わせて使用することができる。 Examples of the conductive polymer include polyaniline, polypyrrole, polythiophene, and derivatives thereof. These can be used alone or in combination of two or more.
　導電性ポリマーとして、例えば、商品名「ＰＰＹ−１２」（丸菱油化工業（株）製、ポリピロール系水分散体）、商品名「Ｄｅｎａｔｒｏｎ　Ｐ−５０２Ｓ」（ナガセケムテックス（株）製、ポリチオフェン系水分散体）、商品名「ａｑｕａＰＡＳＳ−０１」（三菱レーヨン（株）製、ポリアニリンスルホン酸系水分散体）等の市販品を好適に使用することができる。 As the conductive polymer, for example, trade name “PPY-12” (manufactured by Maruhishi Oil Chemical Co., Ltd., polypyrrole aqueous dispersion), trade name “Denatron P-502S” (manufactured by Nagase ChemteX Corporation, polythiophene) Commercially available products such as a water-based dispersion) and a trade name “aquaPASS-01” (manufactured by Mitsubishi Rayon Co., Ltd., polyaniline sulfonic acid-based water dispersion) can be suitably used.
　前記界面活性剤としては、ノニオン性界面活性剤（非イオン性界面活性剤）、カチオン性界面活性剤、アニオン性界面活性剤、両性界面活性剤等を挙げることができる。これらは、単独で、または２種以上を組み合わせて使用することができる。 Examples of the surfactant include nonionic surfactants (nonionic surfactants), cationic surfactants, anionic surfactants, and amphoteric surfactants. These can be used alone or in combination of two or more.
　前記ノニオン性界面活性剤としては、例えば、ポリオキシエチレンアルキルフェニルエーテル［例えば、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンドデシルフェニルエーテルなど］、ポリオキシエチレンアルキルアリルエーテル、ポリオキシエチレンアルキルエーテル［例えば、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンラウリルエーテルなど］、ポリオキシエチレンポリオキシプロピレンブロックポリマー等のエーテル型ノニオン性界面活性剤；ポリエチレングリコール脂肪酸エステル［例えば、ポリエチレングリコールオレイン酸エステルなど］、ポリオキシエチレンソルビタン脂肪酸エステル［例えば、ポリオキシエチレンソルビタンモノパルミチン酸エステルなど］等のエステルエーテル型ノニオン性界面活性剤；グリセリン脂肪酸エステル［例えば、グリセリンモノステアリン酸エステルなど］、ソルビタン脂肪酸エステル［例えば、ソルビタンモノステアリン酸エステルなど］、ショ糖脂肪酸エステル［例えば、ショ糖ステアリン酸エステルなど］等のエステル型ノニオン性界面活性剤；脂肪酸アルカノールアミド［例えば、ラウリン酸ジエタノールアミドなど］等のアルカノールアミド型ノニオン性界面活性剤等を挙げることができる。 Examples of the nonionic surfactant include polyoxyethylene alkyl phenyl ether [eg, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene dodecyl phenyl ether, etc.], polyoxyethylene alkyl allyl ether, Polyoxyethylene alkyl ethers [for example, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, etc.], ether-type nonionic surfactants such as polyoxyethylene polyoxypropylene block polymers; polyethylene glycol fatty acid esters [for example, polyethylene glycol olein Acid ester, etc.], polyoxyethylene sorbitan fatty acid ester [for example, polyoxyethylene sorbitan monopa Ester ether type nonionic surfactants such as mitinate ester, etc .; glycerin fatty acid ester [eg glycerin monostearate etc.], sorbitan fatty acid ester [eg sorbitan monostearate etc.], sucrose fatty acid ester [eg And ester type nonionic surfactants such as sucrose stearate] and the like; and alkanolamide type nonionic surfactants such as fatty acid alkanolamides [for example, lauric acid diethanolamide and the like].
　前記カチオン性界面活性剤としては、例えば、アミン塩系カチオン性界面活性剤、第四級アンモニウム塩系カチオン性界面活性剤［例えば、ラウリルトリメチルアンモニウム塩、ステアリルトリメチルアンモニウム塩、トリオクチルアンモニウム塩、ジステアリルジメチルアンモニウム塩などの脂肪族四級アンモニウム塩、ジステアリルジベンジルアンモニウム塩などの芳香族四級アンモニウム塩など］、第四級ホスホニウム塩系カチオン性界面活性剤［例えば、ドデシルトリフェニルホスホニウム塩、メチルトリフェニルホスホニウム塩、ラウリルトリメチルホスホニウム塩、ステアリルトリメチルホスホニウム塩、ジステアリルジメチルホスホニウム塩、ジステアリルジベンジルホスホニウム塩など］等を挙げることができる。 Examples of the cationic surfactant include amine salt-based cationic surfactants, quaternary ammonium salt-based cationic surfactants [for example, lauryltrimethylammonium salt, stearyltrimethylammonium salt, trioctylammonium salt, dioctylamine. Aliphatic quaternary ammonium salts such as stearyldimethylammonium salt, aromatic quaternary ammonium salts such as distearyl dibenzylammonium salt], quaternary phosphonium salt-based cationic surfactants [eg, dodecyltriphenylphosphonium salt, Methyltriphenylphosphonium salt, lauryltrimethylphosphonium salt, stearyltrimethylphosphonium salt, distearyldimethylphosphonium salt, distearyldibenzylphosphonium salt, etc.].
　前記アニオン性界面活性剤としては、例えば、硫酸エステル系アニオン性界面活性剤［例えば、ポリオキシエチレンアルキルエーテル硫酸塩、ポリオキシエチレンスチレン化フェニルエーテル硫酸塩、アルキル硫酸塩など］；リン酸エステル系アニオン性界面活性剤［例えば、アルキルリン酸塩、ポリオキシエチレンアルキルエーテルリン酸塩など］；スルホン酸系アニオン性界面活性剤［例えば、スルホン酸塩、スルホコハク酸塩など］；カルボン酸系アニオン性界面活性剤［例えば、脂肪酸塩、ポリオキシエチレンアルキルエーテル酢酸塩、ポリオキシエチレンアルキルスルホコハク酸塩など］等を挙げることができる。 Examples of the anionic surfactant include sulfate ester anionic surfactants [for example, polyoxyethylene alkyl ether sulfate, polyoxyethylene styrenated phenyl ether sulfate, alkyl sulfate, etc.]; Anionic surfactants [for example, alkyl phosphates, polyoxyethylene alkyl ether phosphates, etc.]; sulfonic acid-based anionic surfactants [for example, sulfonates, sulfosuccinates, etc.]; Carboxylic acid-based anionic properties Surfactant [For example, fatty acid salt, polyoxyethylene alkyl ether acetate, polyoxyethylene alkyl sulfosuccinate, etc.] etc. can be mentioned.
　前記両性界面活性剤としては、例えば、ベタイン系両性界面活性剤［例えば、アルキルベタイン、アミドベタインなど］、グリシン系両性界面活性剤等を挙げることができる。 Examples of the amphoteric surfactant include betaine-based amphoteric surfactants [for example, alkyl betaines, amide betaines, etc.], glycine-based amphoteric surfactants, and the like.
　また、前記界面活性剤としては、分子内に反応性基（例えば、（メタ）アクリロイル基、ビニル基、アリル基などの炭素−炭素不飽和結合を含む基、特に、活性エネルギー線硬化性基）を有する界面活性剤を使用することもできる。 The surfactant is a reactive group in the molecule (for example, a group containing a carbon-carbon unsaturated bond such as a (meth) acryloyl group, a vinyl group or an allyl group, particularly an active energy ray-curable group). Surfactants having can also be used.
　界面活性剤として、例えば、商品名「ハイテノールＬＡ−１６」（第一工業製薬（株）製、硫酸エステル系アニオン性界面活性剤）、商品名「カチオーゲンＴＭＬ」（第一工業製薬（株）製、第四級アンモニウム塩系カチオン性界面活性剤）等の市販品を好適に使用することができる。 Examples of the surfactant include, for example, trade name “Hytenol LA-16” (Daiichi Kogyo Seiyaku Co., Ltd., sulfate ester anionic surfactant), trade name “Katiogen TML” (Daiichi Kogyo Seiyaku Co., Ltd.) Commercially available products such as manufactured and quaternary ammonium salt cationic surfactants) can be suitably used.
　前記親水性化合物としては、例えば、グリコール化合物［例えば、エチレングリコール、プロピレングリコール、ブチレングリコール、ヘキシレングリコール、ジエチレングリコール、ジプロピレングリコール、トリエチレングリコール、トリプロピレングリコールなど］；グリセリン；グリセリン誘導体［例えば、ジグリセリンなど］；エチレングリコールモノエーテル化合物［例えば、エチレングリコールモノアリルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールイソブチルエーテル、エチレングリコールモノフェニルエーテル、エチレングリコールモノヘキシルエーテル、エチレングリコールモノ２−エチルヘキシルエーテルなど］；ジエチレングリコールモノエーテル化合物［例えば、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノプロピルエーテル、ジエチレングリコールモノブチルエーテル、ジエチレングリコールモノヘキシルエーテル、ジエチレングリコールモノ−２−エチルヘキシルエーテルなど］；ジプロピレングリコールモノエーテル化合物［例えば、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノプロピルエーテル、ジプロピレングリコールモノブチルエーテルなど］；ポリアルキレングリコールエーテル化合物［例えば、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノブチルエーテル、トリエチレングリコールジメチルエーテル、トリプロピレングリコールモノメチルエーテル、トリプロピレングリコールモノブチルエーテル、テトラエチレングリコールジメチルエーテル、テトラエチレングリコールモノブチルエーテルなど］等を挙げることができる。 Examples of the hydrophilic compound include glycol compounds [eg, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, etc.]; glycerin; glycerin derivatives [eg, Diglycerin, etc.]; ethylene glycol monoether compounds [eg, ethylene glycol monoallyl ether, ethylene glycol monobutyl ether, ethylene glycol isobutyl ether, ethylene glycol monophenyl ether, ethylene glycol monohexyl ether, ethylene glycol mono 2-ethylhexyl ether, etc.] Diethylene glycol monoether compounds [for example, diethylene glycol Monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol mono-2-ethylhexyl ether, etc.]; dipropylene glycol monoether compounds [for example, dipropylene glycol monomethyl ether, dipropylene Glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, etc.]; polyalkylene glycol ether compounds [for example, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, triethylene glycol dimethyl ether, tripropylene glycol Monomethyl ether, tripropylene glycol monobutyl ether, tetraethylene glycol dimethyl ether, etc. tetraethylene glycol monobutyl ether], and the like.
　前記親水性ポリマーとしては、アクリル系ポリマー［例えば、ポリアクリル酸ナトリウム、ポリアクリル酸アンモニウム、ポリアクリル酸など］；ポリアミド系ポリマー；ポリアルキレンオキシド系ポリマー［例えば、ポリエチレンオキシドなど］；ポリビニルアルコール系ポリマー；ポリエーテルグリコール系ポリマー；アルギン酸類［例えば、アルギン酸ナトリウム、アルギン酸アンモニウム、アルギン酸プロピレングリコールエステルなど］；ゼラチン類；セルロース誘導体［例えば、カルボキシメチルセルロース、ヒドロキシエチルセルロースなど］；ポリビニルピロリドン系ポリマー［例えば、ポリビニルピロリドン、ビニルピロリドンと酢酸ビニル等との共重合体など］；無水マレイン酸共重合体又はその塩［例えば、イソブチレン−無水マレイン酸共重合体、メチルビニルエーテル−無水マレイン酸共重合体、スチレン−無水マレイン酸共重合体、又はこれらの塩など］；キトサン；キチン；デンプン等を挙げることができる。 Examples of the hydrophilic polymer include acrylic polymers [for example, sodium polyacrylate, ammonium polyacrylate, polyacrylic acid and the like]; polyamide-based polymers; polyalkylene oxide-based polymers [for example, polyethylene oxide and the like]; Polyether glycol-based polymers; alginic acids [for example, sodium alginate, ammonium alginate, propylene glycol ester of alginate]; gelatins; cellulose derivatives [for example, carboxymethylcellulose, hydroxyethylcellulose, etc.]; polyvinylpyrrolidone-based polymers [for example, polyvinylpyrrolidone , Copolymers of vinyl pyrrolidone and vinyl acetate, etc.]; maleic anhydride copolymers or salts thereof [for example, isobutene Len - maleic anhydride copolymer, methyl vinyl ether - maleic anhydride copolymer, styrene - maleic anhydride copolymer, or the like salts thereof]; chitosan; can be mentioned starch and the like; chitin.
　前記イオン性液体としては、含窒素オニウム塩、含硫黄オニウム塩、または含リンオニウム塩等の各種オニウム塩等を用いることができる。 As the ionic liquid, various onium salts such as a nitrogen-containing onium salt, a sulfur-containing onium salt, or a phosphorus-containing onium salt can be used.
　導電性物質として界面活性剤、親水性化合物、親水性ポリマーを使用することにより、帯電を抑制できるレベルの導電性を付与することができる。 By using a surfactant, a hydrophilic compound, or a hydrophilic polymer as the conductive substance, a level of conductivity that can suppress charging can be imparted.
　易伸長性ポリマー母材に導電性物質を含有する場合、導電性物質の含有量（総量）としては、易伸長性ポリマー母材全体に対して、例えば、０．１~８０重量％である。導電性物質の含有量（総量）の下限は、好ましくは０．５重量％、より好ましくは１重量％、さらに好ましくは２重量％であり、上限は、好ましくは７０重量％、より好ましくは６０重量％、さらに好ましくは５０重量％である。 When the easily extensible polymer base material contains a conductive substance, the content (total amount) of the conductive substance is, for example, 0.1 to 80% by weight with respect to the whole easily extensible polymer base material. The lower limit of the content (total amount) of the conductive material is preferably 0.5% by weight, more preferably 1% by weight, still more preferably 2% by weight, and the upper limit is preferably 70% by weight, more preferably 60% by weight. % By weight, more preferably 50% by weight.
　筒状難伸長性ポリマー部Ａに導電性物質を含有する場合、導電性物質の含有量（総量）としては、筒状難伸長性ポリマー部Ａ全体に対して、例えば、０．１~１００重量％である。導電性物質の含有量（総量）の下限は、好ましくは０．５重量％、より好ましくは１重量％、さらに好ましくは２重量％である。また、筒状難伸長性ポリマー部Ａは導電性材料のみで形成してもよいが、上限は、好ましくは９５重量％、より好ましくは９０重量％、さらに好ましくは８５重量％である。 When the cylindrical hardly extensible polymer part A contains a conductive substance, the content (total amount) of the conductive substance is, for example, 0.1 to 100 wt. %. The lower limit of the content (total amount) of the conductive material is preferably 0.5% by weight, more preferably 1% by weight, and still more preferably 2% by weight. Moreover, although the cylindrical hardly extensible polymer part A may be formed of only a conductive material, the upper limit is preferably 95% by weight, more preferably 90% by weight, and still more preferably 85% by weight.
　（伸長性を有するシート状有機基材の少なくとも片面に導電性層を有している場合）
　導電性層は、導電性物質を少なくとも含有する。また、該導電性層は伸長性を有するシート状有機基材に接した状態で設けられていてもよく、接着剤層等を介して設けられていてもよい。更に、導電性層は、伸長性を有するシート状有機基材の表面の全体に設けてもよく、伸長性を有する伸長性を有するシート状有機基材の表面のうち必要な箇所のみに部分的に設けてもよい。更にまた、導電性層は、一層で構成されていてもよく、二層以上で構成されていてもよい。二層以上で構成される場合は、同じ組成を有する層で構成されていてもよく、異なる組成を有する層で構成されていてもよい。 (When a conductive layer is provided on at least one side of an extensible sheet-like organic base material)
The conductive layer contains at least a conductive substance. Moreover, this electroconductive layer may be provided in the state which contact | connected the sheet-like organic base material which has a stretching property, and may be provided through the adhesive bond layer etc. Furthermore, the conductive layer may be provided on the entire surface of the sheet-like organic base material having extensibility, and is partially applied only to a necessary portion of the surface of the sheet-like organic base material having extensibility. May be provided. Furthermore, the conductive layer may be composed of one layer or may be composed of two or more layers. When comprised by two or more layers, it may be comprised by the layer which has the same composition, and may be comprised by the layer which has a different composition.
　導電性層に含有する導電性物質としては、上記導電性物質を特に制限されることなく使用することができる。 As the conductive substance contained in the conductive layer, the conductive substance can be used without any particular limitation.
　導電性層には上記導電性物質以外にも、必要に応じてベースポリマーを含有してもよい。ベースポリマーとしては、ベースポリマーとしては、易伸長性ポリマー母材２を構成するポリマーの例として挙げられているポリマーを使用することが好ましく、特に、易伸長性ポリマー母材２を構成するポリマーと同種のポリマー、或いは易伸長性ポリマー母材２を構成するポリマーが有するポリマー鎖（主鎖又は側鎖）と同種のポリマー鎖を主鎖又は側鎖に有するポリマーを選択して使用することが、伸長性を有するシート状有機基材表面への密着性に優れる導電性層を形成することができる点で好ましい。 In addition to the conductive material, the conductive layer may contain a base polymer as necessary. As the base polymer, it is preferable to use a polymer listed as an example of a polymer constituting the easily extensible polymer base material 2 as the base polymer, and in particular, a polymer constituting the easily extensible polymer base material 2 It is possible to select and use the same kind of polymer or the polymer having the same kind of polymer chain in the main chain or side chain as the polymer chain (main chain or side chain) of the polymer constituting the stretchable polymer base material 2, It is preferable at the point which can form the electroconductive layer which is excellent in the adhesiveness to the sheet-like organic base material surface which has an extendibility.
　導電性層には、本発明の効果を損なわない範囲内で更に他の添加物を含有していてもよい。他の添加物としては、例えば、架橋剤（エポキシ系架橋剤、イソシアネート系架橋剤、メラミン系架橋剤、オキサゾリン系架橋剤、アジリジン系架橋剤、金属キレート化合物等）、架橋促進剤（架橋触媒）、粘着付与剤（例えば、ロジン誘導体樹脂、ポリテルペン樹脂、石油樹脂、油溶性フェノール樹脂など）、増粘剤、可塑剤、充填剤、発泡剤、老化防止剤、酸化防止剤、紫外線吸収剤、帯電防止剤、界面活性剤、レベリング剤、着色剤、導電性物質、シランカップリング剤等を挙げることができる。 The conductive layer may further contain other additives as long as the effects of the present invention are not impaired. Other additives include, for example, crosslinking agents (epoxy crosslinking agents, isocyanate crosslinking agents, melamine crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, metal chelate compounds, etc.), crosslinking accelerators (crosslinking catalysts). , Tackifiers (eg, rosin derivative resins, polyterpene resins, petroleum resins, oil-soluble phenol resins, etc.), thickeners, plasticizers, fillers, foaming agents, anti-aging agents, antioxidants, UV absorbers, charging Examples thereof include an inhibitor, a surfactant, a leveling agent, a colorant, a conductive substance, and a silane coupling agent.
　導電性層全量（１００重量％）における導電性物質の含有量（総量）としては、例えば、０．１~１００重量％である。導電性物質の含有量（総量）の下限は、好ましくは０．５重量％、より好ましくは１重量％、さらに好ましくは２重量％である。また、導電性層は導電性材料のみで形成してもよいが、上限は、好ましくは９５重量％、より好ましくは９０重量％、さらに好ましくは８５重量％である。 The content (total amount) of the conductive material in the total amount (100% by weight) of the conductive layer is, for example, 0.1 to 100% by weight. The lower limit of the content (total amount) of the conductive material is preferably 0.5% by weight, more preferably 1% by weight, and still more preferably 2% by weight. The conductive layer may be formed of only a conductive material, but the upper limit is preferably 95% by weight, more preferably 90% by weight, and still more preferably 85% by weight.
　導電性層の形成方法としては、導電性物質を添加する以外は、易伸長性ポリマー母材部２の形成方法と同じ方法を採用することができる。また、導電性層は、伸長性を有するシート状有機基材表面に直接形成してもよく、適当なセパレータ（剥離紙等）上に導電性層を形成し、これを伸長性を有するシート状有機基材に転写（移着）して積層してもよい。 As a method for forming the conductive layer, the same method as the method for forming the easily stretchable polymer base material 2 can be adopted except that a conductive substance is added. In addition, the conductive layer may be directly formed on the surface of the sheet-like organic base material having extensibility. The conductive layer is formed on an appropriate separator (such as release paper), and this is formed into a sheet-like form having extensibility. It may be transferred (transferred) to an organic base material and laminated.
　さらに、導電性層は、導電性層の形成材（少なくとも、導電性物質とベースポリマーを含む）と、易伸長性ポリマー母材を形成する易伸長性ポリマー母材とを溶融押出して一体化させる方法でも形成することもできる。溶融押出方法としては、インフレーション法やＴダイ法等任意の公知技術を用いることができる。 Furthermore, the conductive layer is formed by melt-extrusion of the material for forming the conductive layer (including at least the conductive material and the base polymer) and the easily stretchable polymer base material forming the easily stretchable polymer base material. It can also be formed by a method. As the melt extrusion method, any known technique such as an inflation method or a T-die method can be used.
　導電性層の厚さとしては、用途等に応じて適宜選択でき、例えば、０．１~５００μｍであり、下限は、好ましくは０．２μｍ、より好ましくは０．５μｍ、さらに好ましくは１μｍである。上限は、好ましくは４００μｍ、より好ましくは３００μｍ、さらに好ましくは２００μｍである。 The thickness of the conductive layer can be appropriately selected depending on the application, for example, 0.1 to 500 μm, and the lower limit is preferably 0.2 μm, more preferably 0.5 μm, and even more preferably 1 μm. . The upper limit is preferably 400 μm, more preferably 300 μm, and even more preferably 200 μm.
　粘着剤層を介して伸長性を有するシート状有機基材表面に導電性層を設ける場合、該粘着剤層を構成する粘着剤としては、特に限定されず、例えば、ゴム系粘着剤、アクリル系粘着剤、ビニルアルキルエーテル系粘着剤、シリコーン系粘着剤、ポリエステル系粘着剤、ポリアミド系粘着剤、ウレタン系粘着剤、スチレン−ジエンブロック共重合体系粘着剤、これらの粘着剤に融点が約２００℃以下の熱溶融性樹脂を配合したクリープ特性改良型粘着剤などの公知の粘着剤を１種又は２種以上組み合わせて用いることができる。粘着剤は、溶剤型、エマルジョン型、ホットメルト型、エネルギー線硬化型粘着剤、加熱剥離型等の公知のいずれの粘着剤であってもよく、用途に応じて適切なものを選択できる。また、粘着剤は、弱粘着型、強粘着型、再剥離型等の何れであってもよく、用途に応じて適宜選択できる。 When the conductive layer is provided on the surface of the sheet-like organic substrate having extensibility via the pressure-sensitive adhesive layer, the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is not particularly limited, and examples thereof include rubber-based pressure-sensitive adhesives and acrylic-based layers. Adhesives, vinyl alkyl ether adhesives, silicone adhesives, polyester adhesives, polyamide adhesives, urethane adhesives, styrene-diene block copolymer adhesives, melting point of these adhesives is about 200 ° C One or more known pressure-sensitive adhesives such as creep property-improving pressure-sensitive adhesives containing the following hot-melt resins can be used in combination. The pressure-sensitive adhesive may be any known pressure-sensitive adhesive such as a solvent type, an emulsion type, a hot-melt type, an energy ray curable pressure-sensitive adhesive, and a heat release type, and an appropriate one can be selected depending on the application. Further, the pressure-sensitive adhesive may be any of a weak pressure-sensitive adhesive type, a strong pressure-sensitive adhesive type, a re-peeling type, and the like, and can be appropriately selected according to the application.
　粘着剤層を構成する粘着剤としては、特にアクリル系ポリマー（重量平均分子量は、例えば１万~２００万、好ましくは３０万~１５０万）をベースポリマーとするアクリル系粘着剤が好ましく使用される。アクリル系ポリマーは、ランダム共重合体、ブロック共重合体、グラフト重合体等のいずれであってもよい。 As the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer, an acrylic pressure-sensitive adhesive based on an acrylic polymer (weight average molecular weight is, for example, 10,000 to 2,000,000, preferably 300,000 to 1,500,000) is preferably used. . The acrylic polymer may be any of a random copolymer, a block copolymer, a graft polymer, and the like.
　粘着剤には、ベースポリマーのほか、必要に応じて、架橋剤（エポキシ系架橋剤、イソシアネート系架橋剤、メラミン系架橋剤、オキサゾリン系架橋剤、アジリジン系架橋剤、金属キレート化合物等）、架橋促進剤（架橋触媒）、粘着付与剤（例えば、ロジン誘導体樹脂、ポリテルペン樹脂、石油樹脂、油溶性フェノール樹脂など）、増粘剤、可塑剤、充填剤、発泡剤、老化防止剤、酸化防止剤、紫外線吸収剤、帯電防止剤、界面活性剤、レベリング剤、着色剤、導電性物質、シランカップリング剤などの適宜な添加剤を含んでいてもよい。 For adhesives, in addition to the base polymer, if necessary, crosslinking agents (epoxy crosslinking agents, isocyanate crosslinking agents, melamine crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, metal chelate compounds, etc.), crosslinking Accelerator (crosslinking catalyst), tackifier (for example, rosin derivative resin, polyterpene resin, petroleum resin, oil-soluble phenol resin, etc.), thickener, plasticizer, filler, foaming agent, anti-aging agent, antioxidant In addition, an appropriate additive such as an ultraviolet absorber, an antistatic agent, a surfactant, a leveling agent, a colorant, a conductive substance, or a silane coupling agent may be contained.
　粘着剤層の形成は公知乃至慣用の方法により行うことができる。例えば、粘着剤組成物を伸長性を有するシート状有機基材１（該シート状伸長性有機基材上に中間層が存在する場合は、該中間層）上に塗布する方法、粘着剤組成物を適当なセパレータ上に塗布して粘着剤層を形成した後、該粘着剤層を伸長性を有するシート状有機基材１（該シート状伸長性有機基材上に中間層が存在する場合は、該中間層）上に転写（移着）する方法等が挙げられる。 The formation of the pressure-sensitive adhesive layer can be performed by a known or conventional method. For example, a method of applying a pressure-sensitive adhesive composition onto a sheet-like organic substrate 1 having extensibility (or an intermediate layer when an intermediate layer is present on the sheet-like extensible organic substrate), a pressure-sensitive adhesive composition Is applied onto a suitable separator to form a pressure-sensitive adhesive layer, and then the pressure-sensitive adhesive layer is formed into a sheet-like organic substrate 1 having extensibility (if an intermediate layer is present on the sheet-like extensible organic substrate) And a method of transferring (transferring) onto the intermediate layer).
　粘着剤層は、伸長性を有するシート状有機基材１の表面の全体に設けてもよく、伸長性を有するシート状有機基材１の表面のうち必要な箇所のみに部分的に設けてもよい。 The pressure-sensitive adhesive layer may be provided on the entire surface of the sheet-like organic substrate 1 having extensibility, or may be partially provided only on a necessary portion of the surface of the sheet-like organic substrate 1 having extensibility. Good.
　粘着剤層の厚さとしては、用途等に応じて適宜選択でき、例えば、１~３０００μｍであり、下限は、好ましくは５μｍ、上限は、好ましくは５００μｍである。 The thickness of the pressure-sensitive adhesive layer can be appropriately selected according to the use and the like, and is, for example, 1 to 3000 μm, the lower limit is preferably 5 μm, and the upper limit is preferably 500 μm.
　伸長性を有するシート状有機基材１と導電性層６との間に、粘着剤層以外にも伸長性等を損なわない範囲で、必要に応じて他の層（中間層）を有していてもよい。また、導電性層６上には、導電性を有するシート状伸長性有機基材Ａを使用するまでの間、表面を保護するための保護フィルムが設けられていてもよい。 Between the sheet-like organic base material 1 having extensibility and the conductive layer 6, other layers (intermediate layers) are included as needed as long as extensibility and the like are not impaired in addition to the pressure-sensitive adhesive layer. May be. Further, a protective film for protecting the surface may be provided on the conductive layer 6 until the conductive sheet-like extensible organic base material A is used.
　導電性を有するシート状伸長性有機基材は、導電性を有し且つ形状不変部を有する伸長性部材（又は、導電性を有し且つ形状不変部を有する伸縮性部材）として、エレクトロニクス製品（トランジスタ、集積回路、コンデンサ、センサ、アクチュエータ等）用部材、オプティカル製品（ディスプレイ、照明、光導波回路等）用部材、オプトエレクトロニクス製品（発光ダイオード、フォトダイオード、太陽電池等）用部材、カーエレクトロニクス製品用部材、家電製品用部材、住宅設備用部材、建材、バンド部材、結束用部材、衛生用品、衣料品の部分、湿布剤の基布等として利用できる。 The sheet-like extensible organic base material having conductivity is an electronic product (or a stretchable member having conductivity and having a shape-invariable portion) (or an elastic member having conductivity and having a shape-invariant portion). Transistors, integrated circuits, capacitors, sensors, actuators, etc.) members, optical products (displays, lighting, optical waveguide circuits, etc.) members, optoelectronics products (light emitting diodes, photodiodes, solar cells, etc.), car electronics products It can be used as a member for home appliances, a member for home appliances, a member for housing equipment, a building material, a band member, a member for binding, a sanitary article, a clothing part, a base cloth for a poultice.
　［表面層を有するシート状伸長性有機基材］
　表面層を有するシート状伸長性有機基材として、易伸長性ポリマー母材中に筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されている伸長性を有するシート状有機基材の少なくとも一方の面に、フッ素系化合物による表面層を有するシート状伸長性有機基材が挙げられる。なお、本明細書では「フッ素系化合物による表面層」を「フッ素系表面層」や「表面層」と称する場合がある。 [Sheet-like extensible organic base material having a surface layer]
As a sheet-like extensible organic base material having a surface layer, a sheet-like organic base material having extensibility in which a cylindrical hardly extensible polymer portion A is partially and integrally formed in an easily extensible polymer base material The sheet-like extensible organic base material which has the surface layer by a fluorine-type compound is mentioned on the at least one surface of these. In the present specification, the “surface layer made of a fluorine-based compound” may be referred to as “fluorine-based surface layer” or “surface layer”.
　表面層を有するシート状伸長性有機基材は、このシート状伸長性有機基材を一方向（面方向）に伸長させると、易伸長性ポリマー母材の部位は伸長するが、部分的に形成された筒状難伸長性ポリマー部Ａは伸長しないか、又はほとんど伸長しない。このため、筒状難伸長性ポリマー部Ａに、形状が変化しないことが望まれる意匠を施したり、他の部材を固定、保持することができる。また、このシート状伸長性有機基材はフッ素系表面層が付与されているので、耐擦過性、防汚性、撥水性、反射防止性などの特性を持つ。 When the sheet-like extensible organic base material having a surface layer is stretched in one direction (plane direction), the part of the easily extensible polymer base material is elongated, but partially formed. The formed cylindrical hardly extensible polymer part A does not stretch or hardly stretches. For this reason, it is possible to give the tubular hardly extensible polymer portion A a design whose shape is desired not to change, and to fix and hold other members. Moreover, since this sheet-like extensible organic base material is provided with a fluorine-based surface layer, it has characteristics such as scratch resistance, antifouling properties, water repellency, and antireflection properties.
　表面層を有するシート状伸長性有機基材の代表例として、図１８の（１）に示される多機能性シート状伸長性有機基材Ａにおいて、機能性層６が表面層であるもの、図１８の（２）に示される多機能性シート状伸長性有機基材Ａにおいて、機能性層６が表面層であるものが挙げられる。 As a representative example of a sheet-like extensible organic substrate having a surface layer, in the multifunctional sheet-like extensible organic substrate A shown in (1) of FIG. 18, the functional layer 6 is a surface layer. In the multifunctional sheet-like extensible organic base material A shown in 18 (2), the functional layer 6 is a surface layer.
　［表面層（フッ素化合物による表面層、フッ素系表面層）］
　本発明において、表面層６を構成するフッ素系化合物は、少なくとも１つのフッ素原子を分子中に有する化合物である。なお、フッ素系化合物は１種単独で又は２種以上を組み合わせて使用できる。 [Surface layer (surface layer with fluorine compound, fluorine-based surface layer)]
In the present invention, the fluorine compound constituting the surface layer 6 is a compound having at least one fluorine atom in the molecule. In addition, a fluorine-type compound can be used individually by 1 type or in combination of 2 or more types.
　前記フッ素系化合物としては、特に限定されないが、例えば、フルオロエチレンビニルエーテル共重合体、フルオロエチレンビニルエステル共重合体、フルオロエチレンアクリル共重合体、フッ化ビニリデン、クロロトリフルオロエチレン、テトラフルオロエチレン、ヘキサフルオロプロピレン等が好ましく挙げられる。この中でも特にフルオロエチレンビニルエーテル共重合体が好ましい。 The fluorine compound is not particularly limited. For example, fluoroethylene vinyl ether copolymer, fluoroethylene vinyl ester copolymer, fluoroethylene acrylic copolymer, vinylidene fluoride, chlorotrifluoroethylene, tetrafluoroethylene, hexa Preferred examples include fluoropropylene. Among these, a fluoroethylene vinyl ether copolymer is particularly preferable.
　前記フルオロエチレンビニルエーテル共重合体は、フルオロエチレン単位とビニルエーテル単位とを交互に有する共重合体が好ましい。前記フルオロエチレンビニルエーテル共重合体としては、下記式（１）で示される化合物がより好ましく挙げられる。
Figure JPOXMLDOC01-appb-C000001
 　式（１）中、Ｘはフッ素原子、塩素原子または臭素原子を表し、Ｒａは水素原子または炭素数１~１０のアルキル基を表し、Ｒｂは炭素数１~１６のアルキル基を表し、Ｒｃは炭素数１~１６のアルキレン基を表す。なお、ｍおよびｎはそれぞれ整数である。 The fluoroethylene vinyl ether copolymer is preferably a copolymer having fluoroethylene units and vinyl ether units alternately. As the fluoroethylene vinyl ether copolymer, a compound represented by the following formula (1) is more preferable.
Figure JPOXMLDOC01-appb-C000001
 In the formula (1), X represents a fluorine atom, a chlorine atom or a bromine atom, Ra represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, Rb represents an alkyl group having 1 to 16 carbon atoms, and Rc represents Represents an alkylene group having 1 to 16 carbon atoms. Note that m and n are integers.
　前記フルオロエチレンビニルエーテル交互共重合体の重量平均分子量は、特に限定されないが、１，０００~２，０００，０００であることが好ましく、より好ましくは５，０００~１，０００，０００であり、さらに好ましくは１０，０００~５００，０００である。本発明において、式（１）中のｍおよびｎは、フルオロエチレンビニルエーテル交互共重合体の重量平均分子量が前記範囲となるように選択されることが好ましい。 The weight average molecular weight of the fluoroethylene vinyl ether alternating copolymer is not particularly limited, but is preferably 1,000 to 2,000,000, more preferably 5,000 to 1,000,000, Preferably, it is 10,000 to 500,000. In the present invention, m and n in the formula (1) are preferably selected so that the weight average molecular weight of the fluoroethylene vinyl ether alternating copolymer falls within the above range.
　さらに、前記フッ素系化合物としては、フッ素基を含有する樹脂系材料、フッ素基を含有するハイブリッド系材料（フッ素基を含有する樹脂及び粒子を少なくとも含む材料）、フッ素基を含有するゾル系−ゲル系材料なども挙げられる。前記樹脂系材料としては、特に限定されないが、例えば、フッ素系樹脂の他にも、フッ素基を含有するポリウレタン、フッ素基を含有するポリエステル、フッ素基を含有するシリコーン（シリコーン樹脂）、フッ素基を含有するエポキシ樹脂、フッ素基を含有する紫外線硬化型のアクリル系樹脂などのフッ素基を含有するアクリル系樹脂が挙げられる。前記ハイブリッド系材料としては、特に限定されないが、例えば、樹脂（例えば、フッ素基を含有するポリウレタン、フッ素基を含有するポリエステル、フッ素基を含有するシリコーン（シリコーン樹脂）、フッ素基を含有するエポキシ樹脂、フッ素基を含有するアクリル系樹脂、フッ素系樹脂など）中にコロイダルシリカ等の無機微粒子を分散させたものが挙げられる。前記ゾル系−ゲル系材料としては、特に限定されないが、例えば、テトラエトキシシラン、チタンテトラエトキシド等の金属アルコキシを用いた材料が挙げられる。これらの材料は、耐擦過性を向上させるために、無機成分含有量の大きいものが好ましい。このような無機成分含有量の多き形成材料としては、前記ゾル系−ゲル系材料が挙げられる。前記ゾル系−ゲル系材料は、部分縮合されていてもよい。これらの中では、特に、前記のフッ素基を含有するハイブリッド系材料が好ましい。 Furthermore, as the fluorine-based compound, a fluorine-containing resin-based material, a fluorine-containing hybrid material (a material containing at least a fluorine-containing resin and particles), a fluorine-containing sol-gel Examples include system materials. The resin material is not particularly limited. For example, in addition to a fluorine resin, a fluorine group-containing polyurethane, a fluorine group-containing polyester, a fluorine group-containing silicone (silicone resin), and a fluorine group. Examples thereof include an acrylic resin containing a fluorine group, such as an epoxy resin containing, an ultraviolet curable acrylic resin containing a fluorine group. Although it does not specifically limit as said hybrid material, For example, resin (For example, the polyurethane containing a fluorine group, the polyester containing a fluorine group, the silicone (silicone resin) containing a fluorine group, the epoxy resin containing a fluorine group) And acrylic fine particles containing fluorine groups, fluorine resins, etc.) in which inorganic fine particles such as colloidal silica are dispersed. Although it does not specifically limit as said sol-gel type material, For example, the material using metal alkoxy, such as tetraethoxysilane and titanium tetraethoxide, is mentioned. These materials are preferably those having a high inorganic component content in order to improve the scratch resistance. Examples of the forming material having a large inorganic component content include the sol-gel based materials. The sol-gel material may be partially condensed. Among these, the above-described hybrid material containing a fluorine group is particularly preferable.
　他にも、耐擦傷性と低反射の両立の点より、エチレングリコール換算数平均分子量５００~１００００の範囲のシロキサンオリゴマーと、ポリスチレン換算数平均分子量５０００以上であって、フルオロアルキル構造およびポリシロキサン構造を有するフッ素化合物とを含有する材料（特開２００４−１６７８２７号公報に記載の材料）も挙げられる。 In addition, from the viewpoint of both scratch resistance and low reflection, a siloxane oligomer having a number average molecular weight in the range of ethylene glycol equivalent of 500 to 10,000, a polystyrene equivalent number average molecular weight of 5000 or more, a fluoroalkyl structure and a polysiloxane structure The material (The material as described in Unexamined-Japanese-Patent No. 2004-167827) containing the fluorine compound which has this is also mentioned.
　前記表面層６は、強度を向上させる点より、架橋構造を有していてもよい。前記架橋構造を形成する架橋剤としては、特に限定されないが、イソシアネート系架橋剤が好ましく挙げられる。なお、架橋剤は１種単独で又は２種以上を組み合わせて使用できる。 The surface layer 6 may have a crosslinked structure from the viewpoint of improving strength. Although it does not specifically limit as a crosslinking agent which forms the said crosslinked structure, An isocyanate type crosslinking agent is mentioned preferably. In addition, a crosslinking agent can be used individually by 1 type or in combination of 2 or more types.
　前記イソシアネート系架橋剤は、イソシアネート基を分子内に２個以上有する化合物である。前記イソシアネート系架橋剤としては、特に限定されないが、例えば、水添キシリレンジイソシアネート、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、水添ジフェニルメタンジイシシアネート、エチレンジイソシアネート、１，４−テトラメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、ノルボルネンジイソシアネート等の２官能イソシアネート、デスモジュールＮ３２００（住化バイエルウレタン（株）製）、コロネートＬ，ＨＬ，ＨＸ（日本ポリウレタン（株）製）、タケネートＤ−１４０Ｎ，Ｄ−１２７，Ｄ−１１０Ｎ（三井化学ポリウレタン（株）製）等の３官能イソシアネートなどが挙げられる。 The isocyanate-based crosslinking agent is a compound having two or more isocyanate groups in the molecule. The isocyanate-based crosslinking agent is not particularly limited. For example, hydrogenated xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, ethylene diisocyanate, 1,4-tetramethylene diisocyanate, trimethylhexamethylene diisocyanate. , Bifunctional isocyanates such as norbornene diisocyanate, Desmodur N3200 (manufactured by Sumika Bayer Urethane Co., Ltd.), Coronate L, HL, HX (manufactured by Nippon Polyurethane Co., Ltd.), Takenate D-140N, D-127, D-110N Trifunctional isocyanates such as (Mitsui Chemicals Polyurethane Co., Ltd.) are listed.
　前記イソシアネート系架橋剤の使用量は、特に限定されないが、例えば、前記式（１）で示される化合物に前記イソシアネート系架橋剤を使用する場合、式（１）で示される化合物１００重量部に対して、０．０１~２０重量部が好ましく、より好ましくは０．０５~１５重量部であり、さらに好ましくは０．１~１０重量部である。 Although the usage-amount of the said isocyanate type crosslinking agent is not specifically limited, For example, when using the said isocyanate type crosslinking agent for the compound shown by said Formula (1), with respect to 100 weight part of compounds shown by Formula (1). The content is preferably 0.01 to 20 parts by weight, more preferably 0.05 to 15 parts by weight, and still more preferably 0.1 to 10 parts by weight.
　なお、前記表面層６には、必要に応じて、本発明の効果を損なわない範囲で添加剤が含まれていてもよい。このような添加剤としては、例えば、エポキシ系架橋剤、メラミン系架橋剤、過酸化物系架橋剤、尿素系架橋剤、金属アルコキシド系架橋剤、金属キレート系架橋剤、金属塩系架橋剤、カルボジイミド系架橋剤、オキサゾリン系架橋剤、アジリジン系架橋剤、アミン系架橋剤などの前記イソシアネート系架橋剤以外の架橋剤、架橋促進剤、シランカップリング剤、粘着付与樹脂（ロジン誘導体、ポリテルペン樹脂、石油樹脂、油溶性フェノールなど）、老化防止剤、充填剤、着色剤（顔料や染料など）、紫外線吸収剤、酸化防止剤、可塑剤、軟化剤、界面活性剤、帯電防止剤などが挙げられる。 In addition, the surface layer 6 may contain an additive as long as it does not impair the effects of the present invention. Such additives include, for example, epoxy crosslinking agents, melamine crosslinking agents, peroxide crosslinking agents, urea crosslinking agents, metal alkoxide crosslinking agents, metal chelate crosslinking agents, metal salt crosslinking agents, Crosslinking agents other than the isocyanate crosslinking agents such as carbodiimide crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, amine crosslinking agents, crosslinking accelerators, silane coupling agents, tackifying resins (rosin derivatives, polyterpene resins, Petroleum resins, oil-soluble phenols, etc.), anti-aging agents, fillers, colorants (pigments, dyes, etc.), UV absorbers, antioxidants, plasticizers, softeners, surfactants, antistatic agents, etc. .
　前記表面層６の形成は公知乃至慣用の方法により行うことができる。例えば、前記フルオロエチレンビニルエーテル共重合体、架橋剤（特に前記イソシアネート系架橋剤）及び有機溶媒（例えば、キシレン、トルエン、酢酸ブチル、酢酸エチル及び前記溶媒の混合溶媒など）を混合することにより表面層形成組成物を得て、該表面層形成組成物を乾燥及び硬化させることにより表面層を形成することができる。乾燥及び硬化により、架橋構造が形成される。なお、表面層形成組成物には、触媒（例えば、ジブチル錫ラウリン酸など）が含まれていてもよい。 The surface layer 6 can be formed by a known or conventional method. For example, the surface layer is prepared by mixing the fluoroethylene vinyl ether copolymer, a crosslinking agent (particularly the isocyanate-based crosslinking agent) and an organic solvent (for example, a mixed solvent of xylene, toluene, butyl acetate, ethyl acetate and the solvent). A surface layer can be formed by obtaining a forming composition and drying and curing the surface layer forming composition. A crosslinked structure is formed by drying and curing. In addition, the catalyst (for example, dibutyltin lauric acid etc.) may be contained in the surface layer forming composition.
　前記の表面層を形成する際の乾燥及び硬化としては、特に限定されないが、例えば、４０~１８０℃の温度で１~３０分間の加熱が挙げられる。 The drying and curing at the time of forming the surface layer are not particularly limited, and examples thereof include heating at a temperature of 40 to 180 ° C. for 1 to 30 minutes.
　前記表面層６は、伸長性を有するシート状有機基材１の表面の全体に設けてもよく、用途によっては、伸長性を有するシート状有機基材１の表面のうち必要な箇所にのみ部分的に設けてもよい。 The surface layer 6 may be provided on the entire surface of the sheet-like organic substrate 1 having extensibility. Depending on the application, the surface layer 6 is only part of the surface of the sheet-like organic substrate 1 having extensibility. It may be provided.
　前記表面層６の厚みは、特に限定されないが、２~５０μｍが好ましく、より好ましくは５~４０μｍである。厚みが２μｍ未満であると、強度の点で問題を生じる場合があり、またピンホールなどの表面層が形成されない欠陥部位が発生しやすく、さらに表面層による特性が十分に発揮できない場合がある。また、厚みが５０μｍを超えると、本発明のシート状伸長性有機基材の伸長性に悪影響を及ぼすおそれがある。なお、前記表面層は、単層構造であってもよいし、２層以上の層を有する積層構造であってもよい。 The thickness of the surface layer 6 is not particularly limited, but is preferably 2 to 50 μm, more preferably 5 to 40 μm. If the thickness is less than 2 μm, there may be a problem in strength, a defect site where a surface layer such as a pinhole is not formed is likely to occur, and the characteristics of the surface layer may not be fully exhibited. Moreover, when thickness exceeds 50 micrometers, there exists a possibility of having a bad influence on the extensibility of the sheet-like extensible organic base material of this invention. The surface layer may have a single layer structure or a laminated structure having two or more layers.
［中間層］
　表面層を有する伸長性基材は、伸長性を有するシート状基材１と表面層６との間に、伸長性等を損なわない範囲で、必要に応じて他の層（中間層）を有していてもよい。 [Middle layer]
The extensible substrate having a surface layer has another layer (intermediate layer) between the sheet-like substrate 1 having extensibility and the surface layer 6 as needed, as long as the extensibility is not impaired. You may do it.
　前記中間層としては、特に限定されないが、例えば、伸長性を有するシート状基材１と表面層６との固定に用いられる粘着剤層が挙げられる。前記粘着剤層は、特に限定されないが、公知乃至慣用の粘着剤層であってもよく、例えば、ウレタン系粘着剤層、アクリル系粘着剤層、ゴム系粘着剤層、シリコーン系粘着剤層、ポリエステル系粘着剤層、ポリアミド系粘着剤層、エポキシ系粘着剤層、ビニルアルキルエーテル系粘着剤層、フッ素系粘着剤層などが挙げられる。中でも、前記粘着剤層としては、アクリル系粘着剤層が好ましい。なお、前記粘着剤層は公知乃至慣用の方法により形成される。 The intermediate layer is not particularly limited, and examples thereof include a pressure-sensitive adhesive layer used for fixing the sheet-like substrate 1 having extensibility and the surface layer 6. The pressure-sensitive adhesive layer is not particularly limited, but may be a known or commonly used pressure-sensitive adhesive layer. For example, a urethane-based pressure-sensitive adhesive layer, an acrylic pressure-sensitive adhesive layer, a rubber-based pressure-sensitive adhesive layer, a silicone-based pressure-sensitive adhesive layer, Examples thereof include a polyester-based pressure-sensitive adhesive layer, a polyamide-based pressure-sensitive adhesive layer, an epoxy-based pressure-sensitive adhesive layer, a vinyl alkyl ether-based pressure-sensitive adhesive layer, and a fluorine-based pressure-sensitive adhesive layer. Among these, an acrylic pressure-sensitive adhesive layer is preferable as the pressure-sensitive adhesive layer. The pressure-sensitive adhesive layer is formed by a known or conventional method.
　前記粘着剤層の厚みは、特に限定されないが、１~１００μｍが好ましく、より好ましくは５~８０μｍである。 The thickness of the pressure-sensitive adhesive layer is not particularly limited, but is preferably 1 to 100 μm, more preferably 5 to 80 μm.
　表面層を有する伸長性基材は、公知乃至慣用の方法を利用して作製されてもよい。例えば、前記表面層形成組成物を伸長性を有するシート状有機基材１（該シート状有基材上に中間層が存在する場合には、該中間層）上に塗布して、加熱し、表面層形成組成物を乾燥硬化させて表面層を形成することにより、作製されてもよい。また、前記表面層形成組成物を適当なセパレータ上に塗布して、加熱し、表面層形成組成物を乾燥硬化させて表面層を形成した後、該表面層を伸長性を有するシート状有機基材１（該シート状有基材上に中間層が存在する場合には、該中間層）上に転写（移着）することにより、作製されてもよい。さらに、中間層としての粘着剤層を有する場合には、まず、前記表面層形成組成物を適当なセパレータ上に塗布して、加熱し、表面層形成組成物を乾燥硬化させて表面層を形成した後、該表面層に粘着剤層を設けて粘着剤層付き表面層を得て、次に、該粘着剤層付き表面層を粘着剤層により伸長性を有するシート状有機基材１に貼り合わせることにより、作製されてもよい。なお、塗布は、一般に用いられるコーター、押出機、印刷機などにより行うことができる。 The extensible substrate having a surface layer may be produced using a known or conventional method. For example, the surface layer forming composition is applied onto a sheet-like organic substrate 1 having extensibility (if an intermediate layer is present on the sheet-like substrate, the intermediate layer), and heated. It may be produced by drying and curing the surface layer forming composition to form a surface layer. In addition, the surface layer forming composition is applied onto a suitable separator, heated, and the surface layer forming composition is dried and cured to form a surface layer, and then the surface layer is formed into a sheet-like organic group having extensibility. It may be produced by transferring (transferring) onto the material 1 (in the case where an intermediate layer is present on the sheet-like base material, this intermediate layer). Further, in the case of having an adhesive layer as an intermediate layer, first, the surface layer forming composition is applied on a suitable separator, heated, and the surface layer forming composition is dried and cured to form a surface layer. After that, a pressure-sensitive adhesive layer is provided on the surface layer to obtain a surface layer with a pressure-sensitive adhesive layer, and then the surface layer with the pressure-sensitive adhesive layer is attached to the sheet-like organic substrate 1 having extensibility by the pressure-sensitive adhesive layer. It may be produced by combining them. In addition, application | coating can be performed with the coater, extruder, printer, etc. which are generally used.
　表面層を有するシート状伸長性有機基材は、表面層を有し且つ形状不変部を有する伸長性部材（又は、表面層を有し且つ形状不変部を有する伸縮性部材）として、エレクトロニクス製品（トランジスタ、集積回路、コンデンサ、センサ、アクチュエータ等）用部材、オプティカル製品（ディスプレイ、照明、光導波回路等）用部材、オプトエレクトロニクス製品（発光ダイオード、フォトダイオード、太陽電池等）用部材、カーエレクトロニクス製品用部材、家電製品用部材、住宅設備用部材、建材、バンド部材、結束用部材、衛生用品、衣料品の部分、湿布剤の基布等として利用できる。 A sheet-like extensible organic base material having a surface layer is an electronic product (or a stretchable member having a surface layer and having a shape-invariable portion) (or an elastic member having a surface layer and having a shape-invariant portion). Transistors, integrated circuits, capacitors, sensors, actuators, etc.) members, optical products (displays, lighting, optical waveguide circuits, etc.) members, optoelectronics products (light emitting diodes, photodiodes, solar cells, etc.), car electronics products It can be used as a member for home appliances, a member for home appliances, a member for housing equipment, a building material, a band member, a member for binding, a sanitary article, a clothing part, a base cloth for a poultice.
　［反射防止性を有するシート状伸長性有機基材］
　反射防止性を有するシート状伸長性有機基材として、易伸長性ポリマー母材中に筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されている伸長性を有するシート状有機基材の少なくとも一方の面に反射防止層を有するシート状伸長性有機基材が挙げられる。 [Sheet-like extensible organic base material having antireflection properties]
As a sheet-like extensible organic base material having antireflective properties, a sheet-like organic group having extensibility, in which a cylindrical hardly extensible polymer portion A is partially and integrally formed in an easily extensible polymer base material Examples thereof include a sheet-like extensible organic base material having an antireflection layer on at least one surface of the material.
　反射防止性を有するシート状伸長性有機基材は、このシート状伸長性有機基材を一方向（面方向）に伸長させると、易伸長性ポリマー母材の部位は伸長するが、部分的に形成された筒状難伸長性ポリマー部Ａは伸長しないか、又はほとんど伸長しない。このため、筒状難伸長性ポリマー部Ａに、形状が変化しないことが望まれる意匠を施したり、他の部材を固定、保持することができる。また、このシート状伸長性有機基材は反射防止層を有するので、反射防止性を有する。このため、例えば、このシート状伸長性有機基材を表示装置などに貼り付けた場合などに、外部からの映り込みを低減することができる。 In the sheet-like extensible organic base material having antireflection properties, when this sheet-like extensible organic base material is stretched in one direction (plane direction), the part of the easily stretchable polymer base material is stretched. The formed cylindrical difficult-to-extend polymer part A does not stretch or hardly stretches. For this reason, it is possible to give the tubular hardly extensible polymer portion A a design whose shape is desired not to change, and to fix and hold other members. Moreover, since this sheet-like extensible organic base material has an antireflection layer, it has antireflection properties. For this reason, for example, when this sheet-like extensible organic base material is attached to a display device or the like, reflection from the outside can be reduced.
　反射防止性を有するシート状伸長性有機基材の代表例として、図１８の（１）に示される多機能性シート状伸長性有機基材Ａにおいて、機能性層６が反射防止層であるもの、図１８の（２）に示される多機能性シート状伸長性有機基材Ａにおいて、機能性層６が反射防止層であるものが挙げられる。 As a representative example of a sheet-like extensible organic substrate having antireflection properties, in the multifunctional sheet-like extensible organic substrate A shown in (1) of FIG. 18, the functional layer 6 is an antireflection layer. In the multifunctional sheet-like extensible organic base material A shown in (2) of FIG. 18, the functional layer 6 is an antireflection layer.
　反射防止層６としては、反射防止効果が得られる限り、特に限定されない。例えば、公知の反射防止層など、任意の適切な層を採用してもよい。なお、反射防止層６は、１層のみからなる単層であってもよいし、２層以上からなる複数層であってもよい。また、反射防止層６は、１層のみの形成材料からなる層であってもよいし、２種以上の形成材料からなる層であってもよい。 The antireflection layer 6 is not particularly limited as long as an antireflection effect is obtained. For example, any appropriate layer such as a known antireflection layer may be adopted. The antireflection layer 6 may be a single layer consisting of only one layer or a plurality of layers consisting of two or more layers. The antireflection layer 6 may be a layer made of only one layer or may be a layer made of two or more kinds of forming materials.
　反射防止層６の形成材料としては、特に限定されないが、例えば、紫外線硬化型アクリル樹脂等のアクリル系樹脂、ポリウレタン、ポリエステル、シリコーン（シリコーン樹脂）、ポリアミド、エポキシ樹脂などの樹脂系材料；樹脂（例えば、前記樹脂系材料における樹脂、特にアクリル系樹脂、ポリウレタンなど）中にコロイダルシリカ等の無機微粒子を分散させたハイブリッド系材料；テトラエトキシラン、チタンテトラエトキシド等の金属アルコキシを用いたゾル−ゲル系材料などが挙げられる。これらの形成材料は、耐擦傷性を向上させるために、無機成分含有量が多い形成材料が好ましい。このような無機成分含有量の多い形成材料としては、上記ゾル−ゲル系材料が挙げられる。上記ゾル−ゲル系材料は、部分縮合されていてもよい。これらの中でも、ハイブリッド系材料（樹脂及び粒子を少なくとも含む材料）が好ましい。 The material for forming the antireflection layer 6 is not particularly limited. For example, an acrylic resin such as an ultraviolet curable acrylic resin, a resin material such as polyurethane, polyester, silicone (silicone resin), polyamide, and epoxy resin; For example, a hybrid material in which inorganic fine particles such as colloidal silica are dispersed in a resin in the resin material (especially acrylic resin, polyurethane, etc.); a sol using a metal alkoxy such as tetraethoxylane or titanium tetraethoxide Examples thereof include gel materials. These forming materials are preferably formed materials having a high content of inorganic components in order to improve the scratch resistance. Examples of the forming material having a large inorganic component content include the sol-gel materials. The sol-gel material may be partially condensed. Among these, a hybrid material (a material containing at least a resin and particles) is preferable.
　耐擦傷性と低反射が両立できる反射防止層６としては、例えば、エチレングリコール換算数平均分子量５００~１００００の範囲のシロキサンオリゴマーと、ポリスチレン換算数平均分子量５０００以上であって、フルオロアルキル構造およびポリシロキサン構造を有するフッ素化合物とを含有する材料（特開２００４−１６７８２７号公報に記載の材料）から形成された反射防止層も挙げられる。 Examples of the antireflection layer 6 capable of achieving both scratch resistance and low reflection include, for example, a siloxane oligomer having a number average molecular weight of 500 to 10,000 in terms of ethylene glycol, a polystyrene equivalent number average molecular weight of 5000 or more, An antireflection layer formed from a material containing a fluorine compound having a siloxane structure (a material described in JP-A No. 2004-167827) is also included.
　反射防止層６の形成材料としては、無機ゾルも挙げられる。無機ゾルとしては、例えば、シリカ、アルミナ、フッ化マグネシウムなどが挙げられる。 As a material for forming the antireflection layer 6, an inorganic sol can also be mentioned. Examples of the inorganic sol include silica, alumina, and magnesium fluoride.
　反射防止層６の形成材料には、中空で球状の酸化ケイ素微粒子が含有されていてもよい。このような中空で球状の酸化ケイ素微粒子としては、例えば、特開２００１−２３３６１１号公報に開示されたシリカ系微粒子が挙げられる。 The forming material of the antireflection layer 6 may contain hollow spherical silicon oxide fine particles. Examples of such hollow spherical silicon oxide fine particles include silica-based fine particles disclosed in JP-A-2001-233611.
　反射防止層６が２層以上からなる複数層の場合、例えば、屈折率の高い酸化チタン層（屈折率：約１．８）の上に屈折率の低い酸化ケイ素層（屈折率：約１．４５）を積層した二層構造のものが好ましい。 When the antireflection layer 6 is composed of two or more layers, for example, a silicon oxide layer having a low refractive index (refractive index: about 1.) is formed on a titanium oxide layer having a high refractive index (refractive index: about 1.8). 45) is preferred.
　反射防止層６は、目的に応じて任意の適切な添加剤をさらに含有していてもよい。前記添加剤としては、例えば、光重合開始剤、シランカップリング剤、離型剤、硬化剤、硬化促進剤、希釈剤、老化防止剤、変成剤、界面活性剤、染料、顔料、変色防止剤、紫外線吸収剤、柔軟剤、安定剤、可塑剤、消泡剤等が挙げられる。前記反射防止層に含有される添加剤の種類、数、および量は、目的に応じて適切に設定される。 The antireflection layer 6 may further contain any appropriate additive depending on the purpose. Examples of the additive include a photopolymerization initiator, a silane coupling agent, a release agent, a curing agent, a curing accelerator, a diluent, an anti-aging agent, a denaturing agent, a surfactant, a dye, a pigment, and a discoloration preventing agent. UV absorbers, softeners, stabilizers, plasticizers, antifoaming agents and the like. The kind, number, and amount of additives contained in the antireflection layer are appropriately set according to the purpose.
　反射防止層６の形成は公知乃至慣用の方法により行うことができる。例えば、前記の形成材料等を混合することにより反射防止層形成組成物（反射防止層形成材料）を得て、この反射防止層形成組成物を乾燥及び硬化することにより、反射防止層を形成することができる。なお、反射防止層６を形成する際の乾燥及び硬化の温度としては、任意の適切な温度を採用できる。また、反射防止層形成組成物には、酢酸ブチルなどの有機溶剤が含まれていてよい。 The formation of the antireflection layer 6 can be performed by a known or common method. For example, an antireflection layer forming composition (antireflection layer forming material) is obtained by mixing the above-described forming materials, and the antireflection layer is formed by drying and curing the antireflection layer forming composition. be able to. In addition, arbitrary appropriate temperature can be employ | adopted as the temperature of drying and hardening at the time of forming the antireflection layer 6. FIG. The antireflection layer forming composition may contain an organic solvent such as butyl acetate.
　反射防止層を形成する際の乾燥及び硬化としては、特に限定されないが、例えば、６０~１６０℃の温度で１~３０分間の加熱が挙げられる。 Drying and curing when forming the antireflection layer are not particularly limited, and examples thereof include heating at a temperature of 60 to 160 ° C. for 1 to 30 minutes.
　前記反射防止層６は、伸長性を有するシート状有機基材１の表面の全体に設けてもよく、用途によっては、伸長性を有するシート状有機基材１の表面のうち必要な箇所にのみ部分的に設けてもよい。 The antireflection layer 6 may be provided on the entire surface of the sheet-like organic substrate 1 having extensibility. Depending on the application, the antireflection layer 6 may be provided only on a necessary portion of the surface of the extensible sheet-like organic substrate 1. It may be provided partially.
　前記反射防止層の屈折率は、特に限定されないが、本発明において良好な反射防止性を得る点より、１．３０~１．６０が好ましく、より好ましくは１．３５~１．５０である。 The refractive index of the antireflection layer is not particularly limited, but is preferably from 1.30 to 1.60, more preferably from 1.35 to 1.50 from the viewpoint of obtaining good antireflection properties in the present invention.
　前記反射防止層の厚みは、特に限定されないが、本発明において良好な反射防止性を得る点より、０．００５~３０μｍが好ましく、より好ましくは０．０１~２５μｍであり、さらに好ましくは０．０１~２０μｍである。 The thickness of the antireflection layer is not particularly limited, but is preferably from 0.005 to 30 μm, more preferably from 0.01 to 25 μm, still more preferably from the viewpoint of obtaining good antireflection properties in the present invention. 01 to 20 μm.
　反射防止性を有する伸長性基材は、伸長性を有するシート状基材１と反射防止層６との間に、伸長性等を損なわない範囲で、必要に応じて他の層（中間層）を有していてもよい。 The extensible base material having antireflective property is another layer (intermediate layer) as required between the sheet-like base material 1 having extensibility and the antireflective layer 6 as long as the extensibility and the like are not impaired. You may have.
　反射防止性を有する伸長性基材は、公知乃至慣用の方法を利用して作製されてもよい。例えば、前記反射防止層形成組成物を伸長性を有するシート状有機基材１（該シート状有基材上に中間層が存在する場合には、該中間層）上に塗布して、加熱し、反射防止層形成組成物を乾燥硬化させて反射防止層を形成することにより、作製されてもよい。また、前記反射防止層形成組成物を適当なセパレータ上に塗布して、加熱し、反射防止層形成組成物を乾燥硬化させて反射防止層を形成した後、該反射防止層を伸長性を有するシート状有機基材１（該シート状有基材上に中間層が存在する場合には、該中間層）上に転写（移着）することにより、作製されてもよい。なお、塗布は、一般に用いられるコーター、押出機、印刷機などにより行うことができる。 The extensible base material having antireflection properties may be produced using a known or conventional method. For example, the antireflective layer-forming composition is applied onto a stretchable sheet-like organic substrate 1 (or an intermediate layer when an intermediate layer is present on the sheet-like substrate) and heated. The antireflection layer-forming composition may be dried and cured to form an antireflection layer. Further, the antireflection layer-forming composition is applied on a suitable separator, heated, and the antireflection layer-forming composition is dried and cured to form an antireflection layer. It may be produced by transferring (transferring) onto the sheet-like organic base material 1 (in the case where an intermediate layer is present on the sheet-like base material, this intermediate layer). In addition, application | coating can be performed with the coater, extruder, printer, etc. which are generally used.
　反射防止性を有するシート状伸長性有機基材は、反射防止性を有し且つ形状不変部を有する伸長性部材（又は、反射防止性を有し且つ形状不変部を有する伸縮性部材）として、エレクトロニクス製品（トランジスタ、集積回路、コンデンサ、センサ、アクチュエータ等）用部材、オプティカル製品（ディスプレイ、照明、光導波回路等）用部材、オプトエレクトロニクス製品（発光ダイオード、フォトダイオード、太陽電池等）用部材、カーエレクトロニクス製品用部材、家電製品用部材、住宅設備用部材、建材、バンド部材、結束用部材、衛生用品、衣料品の部分、湿布剤の基布等として利用できる。 The sheet-like stretchable organic base material having antireflection properties is an extensible member having antireflection properties and having a shape-invariable portion (or an elastic member having antireflection properties and having a shape-invariant portion). Components for electronics products (transistors, integrated circuits, capacitors, sensors, actuators, etc.), components for optical products (displays, lighting, optical waveguide circuits, etc.), components for optoelectronic products (light emitting diodes, photodiodes, solar cells, etc.), It can be used as a member for car electronics products, a member for household electrical appliances, a member for household equipment, a building material, a band member, a binding member, a sanitary product, a clothing part, a base material for a poultice.
　以下、本発明について実施例及び比較例を挙げてさらに具体的に説明するが、本発明はこれらにより何ら限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these.
　製造例１（母材シロップの製造）
　冷却管、温度計、および撹拌装置を備えた反応容器に、（メタ）アクリル系モノマーとして、イソボルニルアクリレート（商品名「ＩＢＸＡ」、大阪有機化学工業（株）製）を７１重量部、ｎ−ブチルアクリレート（ＢＡ、東亜合成（株）製）を１９重量部、アクリル酸（ＡＡ）を１０重量部、ポリオールとして、数平均分子量６５０のポリ（オキシテトラメチレン）グリコール（ＰＴＭＧ６５０、三菱化学（株）製）を６８．４重量部、触媒としてジラウリン酸ジブチルスズ（ＤＢＴＬ）０．０１重量部を投入し、撹拌しながら、水添キシリレンジイソシアネート（ＨＸＤＩ、三井化学ポリウレタン（株）製）を２５．５重量部滴下し、６５℃で５時間反応させ、ウレタンポリマー−アクリル系モノマー混合物を得た。その後、さらにヒドロキシエチルアクリレート（商品名「アクリックス　ＨＥＡ」、東亜合成（株）製）６．１重量部を投入し、６５℃で１時間反応することでアクリロイル基末端ウレタンポリマー−アクリル系モノマー混合物を得た。その後、光重合開始剤としてビス（２，４，６−トリメチルベンゾイル）フェニル−フォスフィンオキシド（商品名「イルガキュア８１９」、ＢＡＳＦ社製）を０．１５重量部添加した。なお、イソシアネート基含有成分およびポリオール（ヒドロキシル基含有成分）のＮＣＯ／ＯＨ（官能基の当量比）は１．２５、ポリマー濃度は５０ｗｔ％であった。得られたシロップ（母材シロップ）の粘度（２５℃）は８Ｐａ・ｓであった。 Production Example 1 (Manufacture of base material syrup)
In a reaction vessel equipped with a condenser, a thermometer, and a stirrer, 71 parts by weight of isobornyl acrylate (trade name “IBXA”, manufactured by Osaka Organic Chemical Industry Co., Ltd.) as a (meth) acrylic monomer, n -19 parts by weight of butyl acrylate (BA, manufactured by Toa Gosei Co., Ltd.), 10 parts by weight of acrylic acid (AA), and poly (oxytetramethylene) glycol (PTMG650, Mitsubishi Chemical Corporation) having a number average molecular weight of 650 as a polyol 68.4 parts by weight) and 0.01 part by weight of dibutyltin dilaurate (DBTL) as a catalyst, and with stirring, hydrogenated xylylene diisocyanate (HXDI, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.) 25. 5 parts by weight was dropped and reacted at 65 ° C. for 5 hours to obtain a urethane polymer-acrylic monomer mixture. Thereafter, 6.1 parts by weight of hydroxyethyl acrylate (trade name “Acrix HEA”, manufactured by Toa Gosei Co., Ltd.) was added, and reacted at 65 ° C. for 1 hour, whereby an acryloyl group-terminated urethane polymer-acrylic monomer mixture. Got. Thereafter, 0.15 parts by weight of bis (2,4,6-trimethylbenzoyl) phenyl-phosphine oxide (trade name “Irgacure 819”, manufactured by BASF) was added as a photopolymerization initiator. The isocyanate group-containing component and polyol (hydroxyl group-containing component) had an NCO / OH (functional group equivalent ratio) of 1.25 and a polymer concentration of 50 wt%. The viscosity (25 ° C.) of the obtained syrup (base material syrup) was 8 Pa · s.
　製造例２（筒状難伸長性ポリマー部Ａ形成用シロップの製造）
　冷却管、温度計、および撹拌装置を備えた反応容器に、ポリオールとして、数平均分子量６５０のポリ（オキシテトラメチレン）グリコール（ＰＴＭＧ６５０、三菱化学（株）製）を５１．２重量部、触媒としてジラウリン酸ジブチルスズ（ＤＢＴＬ）０．０１重量部を投入し、撹拌しながら、水添キシリレンジイソシアネート（ＨＸＤＩ、三井化学ポリウレタン（株）製）を３０．６重量部滴下し、６５℃で５時間反応させ、ウレタンポリマーを得た。その後、さらにヒドロキシエチルアクリレート（商品名「アクリックス　ＨＥＡ」、東亜合成（株）製）１８．３重量部を投入し、６５℃で１時間反応することでアクリロイル基末端ウレタンポリマーを得た。このアクリロイル基末端ウレタンポリマーの重量平均分子量は５４００であった。
　その後、アクリロイル基末端ウレタンポリマー１００重量部に対し、トリメチロールプロパンＥＯ付加トリアクリレート（商品名「ビスコート＃３６０」、大阪有機化学工業（株）製）を４２．９重量部、赤色インキ（商品名「シャチハタスタンプ台専用スタンプインキ　ＳＧＮ−４０赤」、シャチハタ（株）製）４．７重量部および光重合開始剤としてビス（２，４，６−トリメチルベンゾイル）フェニル−フォスフィンオキシド（商品名「イルガキュア８１９」、ＢＡＳＦ社製）を０．０４重量部添加することによりアクリロイル基末端ウレタンポリマーを７０重量％含有するアクリル系モノマー混合物（筒状難伸長性ポリマー部形成用シロップ）を得た。 Production Example 2 (Manufacture of Syrup for Forming Cylindrical Difficulty Polymer Part A)
In a reaction vessel equipped with a condenser, a thermometer, and a stirrer, 51.2 parts by weight of poly (oxytetramethylene) glycol (PTMG650, manufactured by Mitsubishi Chemical Corporation) having a number average molecular weight of 650 as a polyol as a polyol, as a catalyst Add 0.01 parts by weight of dibutyltin dilaurate (DBTL), add 30.6 parts by weight of hydrogenated xylylene diisocyanate (HXDI, manufactured by Mitsui Chemicals Polyurethanes Co., Ltd.) while stirring, and react at 65 ° C. for 5 hours. To obtain a urethane polymer. Thereafter, 18.3 parts by weight of hydroxyethyl acrylate (trade name “Acrix HEA”, manufactured by Toa Gosei Co., Ltd.) was added and reacted at 65 ° C. for 1 hour to obtain an acryloyl group-terminated urethane polymer. The weight average molecular weight of this acryloyl group-terminated urethane polymer was 5400.
Thereafter, 42.9 parts by weight of trimethylolpropane EO-added triacrylate (trade name “Biscoat # 360”, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and red ink (trade name) are added to 100 parts by weight of the acryloyl group-terminated urethane polymer. "Shachihata Stamp Stand Dedicated Stamp Ink SGN-40 Red" (manufactured by Shachihata Co., Ltd.) 4.7 parts by weight and bis (2,4,6-trimethylbenzoyl) phenyl-phosphine oxide (trade name " By adding 0.04 part by weight of “Irgacure 819” (manufactured by BASF), an acrylic monomer mixture (syrup for forming a cylindrical hardly stretchable polymer part) containing 70% by weight of an acryloyl group-terminated urethane polymer was obtained.
　実施例１~４
　セパレータ（商品名「ＭＲＦ３８」、三菱樹脂（株）製、厚み３８μｍ）の表面に、製造例１で得られた母材シロップをアプリケータにて塗工し、厚み３００μｍの母材シロップ層を形成した。この母材シロップ層の所定部位にディスペンサー（商品名「ＳＭ３００ＤＳ−Ｓ、ＭＰＰ−１」、武蔵エンジニアリング（株）製）を用いて、上から、製造例２で得られた筒状難伸長性ポリマー部形成用シロップを滴下していき、表１の寸法に従い、図８に示すようなパターン（所定の幅を有する環状の矩形（正方形又は長方形）が横方向及び縦方向にそれぞれ等間隔に配列されたパターン；行列型）を形成した。パターン形成後、即座に、上から、紫外線ランプ（ＢＬタイプ）により紫外線を照射し（紫外線照度：３．４ｍＷ／ｃｍ２、積算照射量：１００ｍＪ／ｃｍ２）、母材シロップ及び筒状難伸長性ポリマー部形成用シロップを半硬化させた後、半硬化したシロップ上にカバーセパレータ（商品名「ＭＲＦ３８」、三菱樹脂（株）製、厚み３８μｍ）をハンドローラーにて貼り合わせ、さらに紫外線ランプ（ＢＬタイプ）により紫外線を照射し（紫外線照度：３．４ｍＷ／ｃｍ２、積算照射量：２０００ｍＪ／ｃｍ２）、母材シロップの硬化物（＝易伸長性ポリマー母材）中に筒状難伸長性ポリマー部形成用シロップ硬化部（＝筒状難伸長性ポリマー部；筒状難伸長部）が配置されたシート状伸長性有機基材（厚み：３００μｍ）を得た。断面の顕微鏡観察の結果、得られたシート状伸長性有機基材において、筒状難伸長性ポリマー部はシート状伸長性有機基材の一方の表面から２／３以上の深さまで連続して形成されていたが、他方の面に至るまでは形成されていなかった（埋込型）。表１、図８において、Ｘは筒状難伸長性ポリマー部形成用シロップ部の表面形状である矩形環（外周）の横の長さ（ｍｍ）、Ｙは筒状難伸長性ポリマー部形成用シロップ部の表面形状である矩形環（外周）の縦の長さ（ｍｍ）、Ｌｘは横方向に隣接する筒状難伸長性ポリマー部形成用シロップ部の中心間距離（ｍｍ）、Ｌｙは縦方向に隣接する筒状難伸長性ポリマー部形成用シロップ部の中心間距離（ｍｍ）、Ｗは環の幅（ｍｍ）を示す。 Examples 1-4
The base material syrup obtained in Production Example 1 is coated with an applicator on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 μm) to form a base material syrup layer having a thickness of 300 μm. did. Using a dispenser (trade name “SM300DS-S, MPP-1”, manufactured by Musashi Engineering Co., Ltd.) at a predetermined portion of the base material syrup layer, the cylindrical hardly extensible polymer obtained in Production Example 2 from above. Part formation syrup is dropped, and according to the dimensions shown in Table 1, a pattern as shown in FIG. 8 (annular rectangles having a predetermined width (square or rectangle) are arranged at equal intervals in the horizontal and vertical directions, respectively. Pattern; matrix type). Immediately after pattern formation, ultraviolet rays are irradiated from above by an ultraviolet lamp (BL type) (ultraviolet illuminance: 3.4 mW / cm 2 , integrated irradiation amount: 100 mJ / cm 2 ), and the base material syrup and cylindrical difficulty elongation After semi-curing the syrup for forming the polymer part, a cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 μm) is pasted onto the semi-cured syrup with a hand roller, and an ultraviolet lamp ( BL type) (ultraviolet light illuminance: 3.4 mW / cm 2 , cumulative irradiation amount: 2000 mJ / cm 2 ), and difficult to stretch cylindrically in a cured base material (= extensible polymer base material) A sheet-like extensible organic base material (thickness: 300 μm) in which a syrup cured part for forming a polymerizable polymer part (= cylinder difficult extensible polymer part; cylindrical hard extensible part) was obtained. As a result of microscopic observation of the cross section, in the obtained sheet-like extensible organic base material, the cylindrical hardly extensible polymer portion is continuously formed from one surface of the sheet-like extensible organic base material to a depth of 2/3 or more. However, it was not formed up to the other surface (embedded type). In Table 1 and FIG. 8, X is the lateral length (mm) of the rectangular ring (outer periphery) which is the surface shape of the cylindrical refractory polymer portion forming syrup portion, and Y is for forming the cylindrical hardly extensible polymer portion. The vertical length (mm) of the rectangular ring (outer periphery) which is the surface shape of the syrup part, Lx is the distance (mm) between the centers of the syrup parts for forming the cylindrical hardly extensible polymer part adjacent in the horizontal direction, Ly is the vertical The center-to-center distance (mm) of the syrup portion for forming a cylindrical difficult-to-extend polymer portion adjacent in the direction, and W represents the width (mm) of the ring.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　実施例５~８
　セパレータ（商品名「ＭＲＦ３８」、三菱樹脂（株）製、厚み３８μｍ）の表面に、製造例１で得られた母材シロップをアプリケータにて塗工し、厚み３００μｍの母材シロップ層を形成した。この母材シロップ層の所定部位にディスペンサー（商品名「ＳＭ３００ＤＳ−Ｓ、ＭＰＰ−１」、武蔵エンジニアリング（株）製）を用いて、上から、製造例２で得られた筒状難伸長性ポリマー部形成用シロップを滴下していき、表２の寸法に従い、図９に示すようなパターン（所定の幅を有する環状の矩形（正方形又は長方形）が横方向及び縦方向にそれぞれ等間隔に配列されたパターン；最密充填型）を形成した。パターン形成後、即座に、上から、紫外線ランプ（ＢＬタイプ）により紫外線を照射し（紫外線照度：３．４ｍＷ／ｃｍ２、積算照射量：１００ｍＪ／ｃｍ２）、母材シロップ及び筒状難伸長性ポリマー部形成用シロップを半硬化させた後、半硬化したシロップ上にカバーセパレータ（商品名「ＭＲＦ３８」、三菱樹脂（株）製、厚み３８μｍ）をハンドローラーにて貼り合わせ、さらに紫外線ランプ（ＢＬタイプ）により紫外線を照射し（紫外線照度：３．４ｍＷ／ｃｍ２、積算照射量：２０００ｍＪ／ｃｍ２）、母材シロップの硬化物（＝易伸長性ポリマー母材）中に筒状難伸長性ポリマー部形成用シロップ硬化部（＝筒状難伸長性ポリマー部；筒状難伸長部）が配置されたシート状伸長性有機基材（厚み：３００μｍ）を得た。断面の顕微鏡観察の結果、得られたシート状伸長性有機基材において、筒状難伸長性ポリマー部はシート状伸長性有機基材の一方の表面から２／３以上の深さまで連続して形成されていたが、他方の面に至るまでは形成されていなかった（埋込型）。表２、図９において、Ｘは筒状難伸長性ポリマー部形成用シロップ部の表面形状である矩形環（外周）の横の長さ（ｍｍ）、Ｙは筒状難伸長性ポリマー部形成用シロップ部の表面形状である矩形環（外周）の縦の長さ（ｍｍ）、Ｌｘは横方向に隣接する筒状難伸長性ポリマー部形成用シロップ部の中心間距離（ｍｍ）、Ｌｙは斜め方向に隣接する筒状難伸長性ポリマー部形成用シロップ部の中心間距離（ｍｍ）、Ｗは環の幅（ｍｍ）を示す。 Examples 5-8
The base material syrup obtained in Production Example 1 is coated with an applicator on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 μm) to form a base material syrup layer having a thickness of 300 μm. did. Using a dispenser (trade name “SM300DS-S, MPP-1”, manufactured by Musashi Engineering Co., Ltd.) at a predetermined portion of the base material syrup layer, the cylindrical hardly extensible polymer obtained in Production Example 2 from above. The part forming syrup is dropped, and according to the dimensions in Table 2, a pattern as shown in FIG. 9 (annular rectangles (squares or rectangles) having a predetermined width are arranged at equal intervals in the horizontal and vertical directions, respectively. Pattern; closest packing type). Immediately after pattern formation, ultraviolet rays are irradiated from above by an ultraviolet lamp (BL type) (ultraviolet illuminance: 3.4 mW / cm 2 , integrated irradiation amount: 100 mJ / cm 2 ), and the base material syrup and cylindrical difficulty elongation After semi-curing the syrup for forming the polymer part, a cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 μm) is pasted onto the semi-cured syrup with a hand roller, and an ultraviolet lamp ( BL type) (ultraviolet light illuminance: 3.4 mW / cm 2 , cumulative irradiation amount: 2000 mJ / cm 2 ), and difficult to stretch cylindrically in a cured base material (= extensible polymer base material) A sheet-like extensible organic base material (thickness: 300 μm) in which a syrup cured part for forming a polymerizable polymer part (= cylinder difficult extensible polymer part; cylindrical hard extensible part) was obtained. As a result of microscopic observation of the cross section, in the obtained sheet-like extensible organic base material, the cylindrical hardly extensible polymer portion is continuously formed from one surface of the sheet-like extensible organic base material to a depth of 2/3 or more. However, it was not formed up to the other surface (embedded type). In Table 2 and FIG. 9, X is the horizontal length (mm) of the rectangular ring (outer periphery) which is the surface shape of the cylindrical refractory polymer portion forming syrup portion, and Y is for forming the cylindrical hardly extensible polymer portion. The vertical length (mm) of the rectangular ring (outer periphery) that is the surface shape of the syrup part, Lx is the distance (mm) between the centers of the syrup parts for forming the cylindrical hardly extensible polymer part adjacent in the horizontal direction, and Ly is diagonal The center-to-center distance (mm) of the syrup portion for forming a cylindrical difficult-to-extend polymer portion adjacent in the direction, and W represents the width (mm) of the ring.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　実施例９~１２
　セパレータ（商品名「ＭＲＦ３８」、三菱樹脂（株）製、厚み３８μｍ）の表面に、製造例１で得られた母材シロップをアプリケータにて塗工し、厚み３００μｍの母材シロップ層を形成した。この母材シロップ層の所定部位にディスペンサー（商品名「ＳＭ３００ＤＳ−Ｓ、ＭＰＰ−１」、武蔵エンジニアリング（株）製）を用いて、上から、製造例２で得られた筒状難伸長性ポリマー部形成用シロップを滴下していき、表３の寸法に従い、図１０に示すようなパターン（所定の幅を有する環状の円形（真円又は楕円）が横方向及び縦方向にそれぞれ等間隔に配列されたパターン；行列型）を形成した。パターン形成後、即座に、上から、紫外線ランプ（ＢＬタイプ）により紫外線を照射し（紫外線照度：３．４ｍＷ／ｃｍ２、積算照射量：１００ｍＪ／ｃｍ２）、母材シロップ及び筒状難伸長性ポリマー部形成用シロップを半硬化させた後、半硬化したシロップ上にカバーセパレータ（商品名「ＭＲＦ３８」、三菱樹脂（株）製、厚み３８μｍ）をハンドローラーにて貼り合わせ、さらに紫外線ランプ（ＢＬタイプ）により紫外線を照射し（紫外線照度：３．４ｍＷ／ｃｍ２、積算照射量：２０００ｍＪ／ｃｍ２）、母材シロップの硬化物（＝易伸長性ポリマー母材）中に筒状難伸長性ポリマー部形成用シロップ硬化部（＝筒状難伸長性ポリマー部；筒状難伸長部）が配置されたシート状伸長性有機基材（厚み：３００μｍ）を得た。断面の顕微鏡観察の結果、得られたシート状伸長性有機基材において、筒状難伸長性ポリマー部はシート状伸長性有機基材の一方の表面から２／３以上の深さまで連続して形成されていたが、他方の面に至るまでは形成されていなかった（埋込型）。表３、図１０において、Ｄｘは筒状難伸長性ポリマー部形成用シロップ部の表面形状である円環（外周）の直径（又は楕円環の短径）（ｍｍ）、Ｄｙは筒状難伸長性ポリマー部形成用シロップ部の表面形状である円環（外周）の直径（又は楕円環の長径）（ｍｍ）、Ｌｘは横方向に隣接する筒状難伸長性ポリマー部形成用シロップ部の中心間距離（ｍｍ）、Ｌｙは縦方向に隣接する筒状難伸長性ポリマー部形成用シロップ部の中心間距離（ｍｍ）、Ｗは環の幅（ｍｍ）を示す。 Examples 9-12
The base material syrup obtained in Production Example 1 is coated with an applicator on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 μm) to form a base material syrup layer having a thickness of 300 μm. did. Using a dispenser (trade name “SM300DS-S, MPP-1”, manufactured by Musashi Engineering Co., Ltd.) at a predetermined portion of the base material syrup layer, the cylindrical hardly extensible polymer obtained in Production Example 2 from above. Part formation syrup is dropped, and according to the dimensions in Table 3, a pattern as shown in FIG. 10 (annular circles (perfect circles or ellipses) having a predetermined width are arranged at equal intervals in the horizontal and vertical directions, respectively. Pattern; matrix type). Immediately after pattern formation, ultraviolet rays are irradiated from above by an ultraviolet lamp (BL type) (ultraviolet illuminance: 3.4 mW / cm 2 , integrated irradiation amount: 100 mJ / cm 2 ), and the base material syrup and cylindrical difficulty elongation After semi-curing the syrup for forming the polymer part, a cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 μm) is pasted onto the semi-cured syrup with a hand roller, and an ultraviolet lamp ( BL type) (ultraviolet light illuminance: 3.4 mW / cm 2 , cumulative irradiation amount: 2000 mJ / cm 2 ), and difficult to stretch cylindrically in a cured base material (= extensible polymer base material) A sheet-like extensible organic base material (thickness: 300 μm) in which a syrup cured part for forming a polymerizable polymer part (= cylinder difficult extensible polymer part; cylindrical hard extensible part) was obtained. As a result of microscopic observation of the cross section, in the obtained sheet-like extensible organic base material, the cylindrical hardly extensible polymer portion is continuously formed from one surface of the sheet-like extensible organic base material to a depth of 2/3 or more. However, it was not formed up to the other surface (embedded type). In Table 3 and FIG. 10, Dx is the diameter of the ring (outer periphery) (or the minor axis of the elliptical ring) (mm), which is the surface shape of the syrup part for forming the cylindrical difficult-to-extend polymer part, and Dy is the difficult cylindrical extension. The diameter of the ring (outer periphery) (or the major axis of the elliptical ring) (mm), which is the surface shape of the syrup part for forming the polymer part, Lx is the center of the syrup part for forming the cylindrical difficult-to-extend polymer part adjacent in the horizontal direction The distance between the centers (mm), Ly is the distance between the centers (mm) of the cylindrically stretchable polymer part-forming syrups adjacent in the longitudinal direction, and W is the width (mm) of the ring.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　実施例１３~１６
　セパレータ（商品名「ＭＲＦ３８」、三菱樹脂（株）製、厚み３８μｍ）の表面に、製造例１で得られた母材シロップをアプリケータにて塗工し、厚み３００μｍの母材シロップ層を形成した。この母材シロップ層の所定部位にディスペンサー（商品名「ＳＭ３００ＤＳ−Ｓ、ＭＰＰ−１」、武蔵エンジニアリング（株）製）を用いて、上から、製造例２で得られた筒状難伸長性ポリマー部形成用シロップを滴下していき、表４の寸法に従い、図１１に示すようなパターン（所定の幅を有する環状の円形（真円又は楕円）が横方向及び縦方向にそれぞれ等間隔に配列されたパターン；最密充填型）を形成した。パターン形成後、即座に、上から、紫外線ランプ（ＢＬタイプ）により紫外線を照射し（紫外線照度：３．４ｍＷ／ｃｍ２、積算照射量：１００ｍＪ／ｃｍ２）、母材シロップ及び筒状難伸長性ポリマー部形成用シロップを半硬化させた後、半硬化したシロップ上にカバーセパレータ（商品名「ＭＲＦ３８」、三菱樹脂（株）製、厚み３８μｍ）をハンドローラーにて貼り合わせ、さらに紫外線ランプ（ＢＬタイプ）により紫外線を照射し（紫外線照度：３．４ｍＷ／ｃｍ２、積算照射量：２０００ｍＪ／ｃｍ２）、母材シロップの硬化物（＝易伸長性ポリマー母材）中に筒状難伸長性ポリマー部形成用シロップ硬化部（＝筒状難伸長性ポリマー部；筒状難伸長部）が配置されたシート状伸長性有機基材（厚み：３００μｍ）を得た。断面の顕微鏡観察の結果、得られたシート状伸長性有機基材において、筒状難伸長性ポリマー部はシート状伸長性有機基材の一方の表面から２／３以上の深さまで連続して形成されていたが、他方の面に至るまでは形成されていなかった（埋込型）。表４、図１１において、Ｄｘは筒状難伸長性ポリマー部形成用シロップ部の表面形状である円環（外周）の直径（又は楕円環の短径）（ｍｍ）、Ｄｙは筒状難伸長性ポリマー部形成用シロップ部の表面形状である円環（外周）の直径（又は楕円環の長径）（ｍｍ）、Ｌｘは横方向に隣接する筒状難伸長性ポリマー部形成用シロップ部の中心間距離（ｍｍ）、Ｌｙは斜め方向に隣接する筒状難伸長性ポリマー部形成用シロップ部の中心間距離（ｍｍ）、Ｗは環の幅（ｍｍ）を示す。 Examples 13 to 16
The base material syrup obtained in Production Example 1 is coated with an applicator on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 μm) to form a base material syrup layer having a thickness of 300 μm. did. Using a dispenser (trade name “SM300DS-S, MPP-1”, manufactured by Musashi Engineering Co., Ltd.) at a predetermined portion of the base material syrup layer, the cylindrical hardly extensible polymer obtained in Production Example 2 from above. The part forming syrup is dropped, and according to the dimensions in Table 4, a pattern as shown in FIG. 11 (annular circles (perfect circles or ellipses) having a predetermined width are arranged at equal intervals in the horizontal and vertical directions, respectively. Pattern; close-packed mold). Immediately after pattern formation, ultraviolet rays are irradiated from above by an ultraviolet lamp (BL type) (ultraviolet illuminance: 3.4 mW / cm 2 , integrated irradiation amount: 100 mJ / cm 2 ), and the base material syrup and cylindrical difficulty elongation After semi-curing the syrup for forming the polymer part, a cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 μm) is pasted onto the semi-cured syrup with a hand roller, and an ultraviolet lamp ( BL type) (ultraviolet light illuminance: 3.4 mW / cm 2 , cumulative irradiation amount: 2000 mJ / cm 2 ), and difficult to stretch cylindrically in a cured base material (= extensible polymer base material) A sheet-like extensible organic base material (thickness: 300 μm) in which a syrup cured part for forming a polymerizable polymer part (= cylinder difficult extensible polymer part; cylindrical hard extensible part) was obtained. As a result of microscopic observation of the cross section, in the obtained sheet-like extensible organic base material, the cylindrical hardly extensible polymer portion is continuously formed from one surface of the sheet-like extensible organic base material to a depth of 2/3 or more. However, it was not formed up to the other surface (embedded type). In Table 4 and FIG. 11, Dx is the diameter of the ring (outer periphery) (or the minor axis of the elliptical ring) (mm), which is the surface shape of the syrup portion for forming the cylindrical hardly extensible polymer portion, and Dy is the hard cylindrical shape. The diameter of the ring (outer circumference) (or the major axis of the elliptical ring) (mm), which is the surface shape of the syrup part for forming the polymer part, and Lx is the center of the syrup part for forming the cylindrical difficult-to-extend polymer part adjacent in the horizontal direction The distance (mm), Ly is the distance (mm) between the centers of the cylindrical refractory polymer part-forming syrup parts adjacent in the oblique direction, and W is the ring width (mm).
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　実施例１７~２０
　セパレータ（商品名「ＭＲＦ３８」、三菱樹脂（株）製、厚み３８μｍ）の表面に、製造例１で得られた母材シロップをアプリケータにて塗工し、厚み３００μｍの母材シロップ層を形成した。この母材シロップ層の所定部位にディスペンサー（商品名「ＳＭ３００ＤＳ−Ｓ、ＭＰＰ−１」、武蔵エンジニアリング（株）製）を用いて、上から、製造例２で得られた筒状難伸長性ポリマー部形成用シロップを滴下していき、表５の寸法に従い、図１２に示すようなパターン（所定の幅を有する環状の十字形が横方向及び縦方向にそれぞれ等間隔に配列されたパターン；行列型）を形成した。パターン形成後、即座に、上から、紫外線ランプ（ＢＬタイプ）により紫外線を照射し（紫外線照度：３．４ｍＷ／ｃｍ２、積算照射量：１００ｍＪ／ｃｍ２）、母材シロップ及び筒状難伸長性ポリマー部形成用シロップを半硬化させた後、半硬化したシロップ上にカバーセパレータ（商品名「ＭＲＦ３８」、三菱樹脂（株）製、厚み３８μｍ）をハンドローラーにて貼り合わせ、さらに紫外線ランプ（ＢＬタイプ）により紫外線を照射し（紫外線照度：３．４ｍＷ／ｃｍ２、積算照射量：２０００ｍＪ／ｃｍ２）、母材シロップの硬化物（＝易伸長性ポリマー母材）中に筒状難伸長性ポリマー部形成用シロップ硬化部（＝筒状難伸長性ポリマー部；筒状難伸長部）が配置されたシート状伸長性有機基材（厚み：３００μｍ）を得た。断面の顕微鏡観察の結果、得られたシート状伸長性有機基材において、筒状難伸長性ポリマー部はシート状伸長性有機基材の一方の表面から２／３以上の深さまで連続して形成されていたが、他方の面に至るまでは形成されていなかった（埋込型）。表５、図１２において、Ｘは筒状難伸長性ポリマー部形成用シロップ部の表面形状である十字形環（外周）の横（最長部）の長さ（ｍｍ）、Ｙは筒状難伸長性ポリマー部形成用シロップ部の表面形状である十字形環（外周）の縦（最長部）の長さ（ｍｍ）、Ｌｘは横方向に隣接する筒状難伸長性ポリマー部形成用シロップ部の中心間距離（ｍｍ）、Ｌｙは縦方向に隣接する筒状難伸長性ポリマー部形成用シロップ部の中心間距離（ｍｍ）、Ｗは環の幅（ｍｍ）を示す。 Examples 17-20
The base material syrup obtained in Production Example 1 is coated with an applicator on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 μm) to form a base material syrup layer having a thickness of 300 μm. did. Using a dispenser (trade name “SM300DS-S, MPP-1”, manufactured by Musashi Engineering Co., Ltd.) at a predetermined portion of the base material syrup layer, the cylindrical hardly extensible polymer obtained in Production Example 2 from above. The part forming syrup is dropped, and according to the dimensions shown in Table 5, a pattern as shown in FIG. 12 (a pattern in which annular crosses having a predetermined width are arranged at equal intervals in the horizontal and vertical directions; matrix Mold). Immediately after pattern formation, ultraviolet rays are irradiated from above by an ultraviolet lamp (BL type) (ultraviolet illuminance: 3.4 mW / cm 2 , integrated irradiation amount: 100 mJ / cm 2 ), and the base material syrup and cylindrical difficulty elongation After semi-curing the syrup for forming the polymer part, a cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 μm) is pasted onto the semi-cured syrup with a hand roller, and an ultraviolet lamp ( BL type) (ultraviolet light illuminance: 3.4 mW / cm 2 , cumulative irradiation amount: 2000 mJ / cm 2 ), and difficult to stretch cylindrically in a cured base material (= extensible polymer base material) A sheet-like extensible organic base material (thickness: 300 μm) in which a syrup cured part for forming a polymerizable polymer part (= cylinder difficult extensible polymer part; cylindrical hard extensible part) was obtained. As a result of microscopic observation of the cross section, in the obtained sheet-like extensible organic base material, the cylindrical hardly extensible polymer portion is continuously formed from one surface of the sheet-like extensible organic base material to a depth of 2/3 or more. However, it was not formed up to the other surface (embedded type). In Table 5 and FIG. 12, X is the length (mm) of the side (longest part) of the cruciform ring (outer periphery) which is the surface shape of the cylindrically difficult-to-extend polymer part forming syrup part, and Y is the cylindrical difficultly extended part. The length (mm) of the longitudinal (longest part) of the cruciform ring (outer circumference), which is the surface shape of the syrup part for forming the polymer part, Lx is the syrup part for forming the cylindrical difficult-to-extend polymer part adjacent in the horizontal direction The center-to-center distance (mm), Ly represents the center-to-center distance (mm) of the cylindrically stretchable polymer part-forming syrup part adjacent in the longitudinal direction, and W represents the ring width (mm).
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
　実施例２１~２４
　セパレータ（商品名「ＭＲＦ３８」、三菱樹脂（株）製、厚み３８μｍ）の表面に、製造例１で得られた母材シロップをアプリケータにて塗工し、厚み３００μｍの母材シロップ層を形成した。この母材シロップ層の所定部位にディスペンサー（商品名「ＳＭ３００ＤＳ−Ｓ、ＭＰＰ−１」、武蔵エンジニアリング（株）製）を用いて、上から、製造例２で得られた筒状難伸長性ポリマー部形成用シロップを滴下していき、表６の寸法に従い、図１３に示すようなパターン（所定の幅を有する環状の十字形が最密充填となるように配列されたパターン；最密充填型）を形成した。パターン形成後、即座に、上から、紫外線ランプ（ＢＬタイプ）により紫外線を照射し（紫外線照度：３．４ｍＷ／ｃｍ２、積算照射量：１００ｍＪ／ｃｍ２）、母材シロップ及び筒状難伸長性ポリマー部形成用シロップを半硬化させた後、半硬化したシロップ上にカバーセパレータ（商品名「ＭＲＦ３８」、三菱樹脂（株）製、厚み３８μｍ）をハンドローラーにて貼り合わせ、さらに紫外線ランプ（ＢＬタイプ）により紫外線を照射し（紫外線照度：３．４ｍＷ／ｃｍ２、積算照射量：２０００ｍＪ／ｃｍ２）、母材シロップの硬化物（＝易伸長性ポリマー母材）中に筒状難伸長性ポリマー部形成用シロップ硬化部（＝筒状難伸長性ポリマー部；筒状難伸長部）が配置されたシート状伸長性有機基材（厚み：３００μｍ）を得た。断面の顕微鏡観察の結果、得られたシート状伸長性有機基材において、筒状難伸長性ポリマー部はシート状伸長性有機基材の一方の表面から２／３以上の深さまで連続して形成されていたが、他方の面に至るまでは形成されていなかった（埋込型）。表６、図１３において、Ｘは筒状難伸長性ポリマー部形成用シロップ部の表面形状である十字形環（外周）の横（最長部）の長さ（ｍｍ）、Ｙは筒状難伸長性ポリマー部形成用シロップ部の表面形状である十字形環（外周）の縦（最長部）の長さ（ｍｍ）、Ｌｘは横方向に隣接する筒状難伸長性ポリマー部形成用シロップ部の中心間距離（ｍｍ）、Ｌｙは斜め方向に隣接する筒状難伸長性ポリマー部形成用シロップ部の中心間距離（ｍｍ）、Ｗは環の幅（ｍｍ）を示す。 Examples 21-24
The base material syrup obtained in Production Example 1 is coated with an applicator on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 μm) to form a base material syrup layer having a thickness of 300 μm. did. Using a dispenser (trade name “SM300DS-S, MPP-1”, manufactured by Musashi Engineering Co., Ltd.) at a predetermined portion of the base material syrup layer, the cylindrical hardly extensible polymer obtained in Production Example 2 from above. Part formation syrup is dropped, and according to the dimensions shown in Table 6, a pattern as shown in FIG. 13 (a pattern in which circular crosses having a predetermined width are arranged so as to be closest packed; closest packed type ) Was formed. Immediately after pattern formation, ultraviolet rays are irradiated from above by an ultraviolet lamp (BL type) (ultraviolet illuminance: 3.4 mW / cm 2 , integrated irradiation amount: 100 mJ / cm 2 ), and the base material syrup and cylindrical difficulty elongation After semi-curing the syrup for forming the polymer part, a cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 μm) is pasted onto the semi-cured syrup with a hand roller, and an ultraviolet lamp ( BL type) (ultraviolet light illuminance: 3.4 mW / cm 2 , cumulative irradiation amount: 2000 mJ / cm 2 ), and difficult to stretch cylindrically in a cured base material (= extensible polymer base material) A sheet-like extensible organic base material (thickness: 300 μm) in which a syrup cured part for forming a polymerizable polymer part (= cylinder difficult extensible polymer part; cylindrical hard extensible part) was obtained. As a result of microscopic observation of the cross section, in the obtained sheet-like extensible organic base material, the cylindrical hardly extensible polymer portion is continuously formed from one surface of the sheet-like extensible organic base material to a depth of 2/3 or more. However, it was not formed up to the other surface (embedded type). In Table 6 and FIG. 13, X is the length (mm) of the side (longest part) of the cruciform ring (outer periphery) which is the surface shape of the cylindrically difficult-to-extend polymer part syrup part, and Y is the cylindrically difficult-to-extend The length (mm) of the longitudinal (longest part) of the cruciform ring (outer circumference), which is the surface shape of the syrup part for forming the polymer part, Lx is the syrup part for forming the cylindrical difficult-to-extend polymer part adjacent in the horizontal direction The center-to-center distance (mm), Ly is the center-to-center distance (mm) of the cylindrically stretchable polymer part-forming syrup part adjacent in the oblique direction, and W is the ring width (mm).
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
　実施例２５~２８
　セパレータ（商品名「ＭＲＦ３８」、三菱樹脂（株）製、厚み３８μｍ）の表面に、製造例１で得られた母材シロップをアプリケータにて塗工し、厚み３００μｍの母材シロップ層を形成した。この母材シロップ層の所定部位にディスペンサー（商品名「ＳＭ３００ＤＳ−Ｓ、ＭＰＰ−１」、武蔵エンジニアリング（株）製）を用いて、上から、製造例２で得られた筒状難伸長性ポリマー部形成用シロップを滴下していき、表７の寸法に従い、図１４に示すようなパターン（所定の幅を有する環状の円が多重に形成されたパターン）を形成した。パターン形成後、即座に、上から、紫外線ランプ（ＢＬタイプ）により紫外線を照射し（紫外線照度：３．４ｍＷ／ｃｍ２、積算照射量：１００ｍＪ／ｃｍ２）、母材シロップ及び筒状難伸長性ポリマー部形成用シロップを半硬化させた後、半硬化したシロップ上にカバーセパレータ（商品名「ＭＲＦ３８」、三菱樹脂（株）製、厚み３８μｍ）をハンドローラーにて貼り合わせ、さらに紫外線ランプ（ＢＬタイプ）により紫外線を照射し（紫外線照度：３．４ｍＷ／ｃｍ２、積算照射量：２０００ｍＪ／ｃｍ２）、母材シロップの硬化物（＝易伸長性ポリマー母材）中に筒状難伸長性ポリマー部形成用シロップ硬化部（＝筒状難伸長性ポリマー部；筒状難伸長部）が配置されたシート状伸長性有機基材（厚み：３００μｍ）を得た。断面の顕微鏡観察の結果、得られたシート状伸長性有機基材において、筒状難伸長性ポリマー部はシート状伸長性有機基材の一方の表面から２／３以上の深さまで連続して形成されていたが、他方の面に至るまでは形成されていなかった（埋込型）。表７、図１４において、Ｒ１は筒状難伸長性ポリマー部形成用シロップ部の表面形状である一番外側の円環（外周）の直径（ｍｍ）、Ｒ２は筒状難伸長性ポリマー部形成用シロップ部の表面形状である外側から二番目の円環（外周）の直径（ｍｍ）、Ｒ３は筒状難伸長性ポリマー部形成用シロップ部の表面形状である外側から三番目の円環（外周）の直径（ｍｍ）、Ｌ１，２は筒状難伸長性ポリマー部形成用シロップ部の表面形状である一番外側の円環と外側から二番目の円環の中心間距離（ｍｍ）、Ｌ１，３は筒状難伸長性ポリマー部形成用シロップ部の表面形状である一番外側の円環と外側から三番目の円環の中心間距離（ｍｍ）、Ｗは各環の幅（ｍｍ）を示す。 Examples 25-28
The base material syrup obtained in Production Example 1 is coated with an applicator on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 μm) to form a base material syrup layer having a thickness of 300 μm. did. Using a dispenser (trade name “SM300DS-S, MPP-1”, manufactured by Musashi Engineering Co., Ltd.) at a predetermined portion of the base material syrup layer, the cylindrical hardly extensible polymer obtained in Production Example 2 from above. Part formation syrup was dropped to form a pattern as shown in FIG. 14 (a pattern in which annular circles having a predetermined width were formed in multiple layers) according to the dimensions in Table 7. Immediately after pattern formation, ultraviolet rays are irradiated from above by an ultraviolet lamp (BL type) (ultraviolet illuminance: 3.4 mW / cm 2 , integrated irradiation amount: 100 mJ / cm 2 ), and the base material syrup and cylindrical difficulty elongation After semi-curing the syrup for forming the polymer part, a cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 μm) is pasted onto the semi-cured syrup with a hand roller, and an ultraviolet lamp ( BL type) (ultraviolet light illuminance: 3.4 mW / cm 2 , cumulative irradiation amount: 2000 mJ / cm 2 ), and difficult to stretch cylindrically in a cured base material (= extensible polymer base material) A sheet-like extensible organic base material (thickness: 300 μm) in which a syrup cured part for forming a polymerizable polymer part (= cylinder difficult extensible polymer part; cylindrical hard extensible part) was obtained. As a result of microscopic observation of the cross section, in the obtained sheet-like extensible organic base material, the cylindrical hardly extensible polymer portion is continuously formed from one surface of the sheet-like extensible organic base material to a depth of 2/3 or more. However, it was not formed up to the other surface (embedded type). In Table 7 and FIG. 14, R1 is the diameter (mm) of the outermost ring (outer periphery) which is the surface shape of the cylindrical refractory polymer portion forming syrup portion, and R2 is the cylindrical hardly extensible polymer portion formation. The diameter (mm) of the second annular ring (outer periphery) from the outside, which is the surface shape of the syrup part, and R3 is the third annular ring from the outside, which is the surface form of the cylindrical refractory polymer part syrup part Diameter (mm) of the outer circumference), L 1 and 2 are the distances between the centers of the outermost ring and the second ring from the outside (mm), which are the surface shapes of the cylindrical refractory polymer part forming syrup part , L 1 and 3 are distances (mm) between the centers of the outermost annular ring and the third annular ring from the outside, which are the surface shapes of the cylindrical refractory polymer part forming syrup part, and W is the width of each ring (Mm) is shown.
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
　実施例２９~３０
　セパレータ（商品名「ＭＲＦ３８」、三菱樹脂（株）製、厚み３８μｍ）の表面に、製造例１で得られた母材シロップをアプリケータにて塗工し、厚み３００μｍの母材シロップ層を形成した。この母材シロップ層の所定部位にディスペンサー（商品名「ＳＭ３００ＤＳ−Ｓ、ＭＰＰ−１」、武蔵エンジニアリング（株）製）を用いて、上から、製造例２で得られた筒状難伸長性ポリマー部形成用シロップを滴下していき、表８の寸法に従い、図１５に示すようなパターン（所定の幅の輪郭を有する文字、数字、図形を表す形状が規則的に配列されたパターン；行列型）を形成した。パターン形成後、即座に、上から、紫外線ランプ（ＢＬタイプ）により紫外線を照射し（紫外線照度：３．４ｍＷ／ｃｍ２、積算照射量：１００ｍＪ／ｃｍ２）、母材シロップ及び筒状難伸長性ポリマー部形成用シロップを半硬化させた後、半硬化したシロップ上にカバーセパレータ（商品名「ＭＲＦ３８」、三菱樹脂（株）製、厚み３８μｍ）をハンドローラーにて貼り合わせ、さらに紫外線ランプ（ＢＬタイプ）により紫外線を照射し（紫外線照度：３．４ｍＷ／ｃｍ２、積算照射量：２０００ｍＪ／ｃｍ２）、母材シロップの硬化物（＝易伸長性ポリマー母材）中に筒状難伸長性ポリマー部形成用シロップ硬化部（＝筒状難伸長性ポリマー部；筒状難伸長部）が配置されたシート状伸長性有機基材（厚み：３００μｍ）を得た。断面の顕微鏡観察の結果、得られたシート状伸長性有機基材において、筒状難伸長性ポリマー部はシート状伸長性有機基材の一方の表面から２／３以上の深さまで連続して形成されていたが、他方の面に至るまでは形成されていなかった（埋込型）。表８、図１５において、Ｗは各環の幅（ｍｍ）を示す。 Examples 29-30
The base material syrup obtained in Production Example 1 is coated with an applicator on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 μm) to form a base material syrup layer having a thickness of 300 μm. did. Using a dispenser (trade name “SM300DS-S, MPP-1”, manufactured by Musashi Engineering Co., Ltd.) at a predetermined portion of the base material syrup layer, the cylindrical hardly extensible polymer obtained in Production Example 2 from above. A portion forming syrup is dropped, and according to the dimensions in Table 8, a pattern as shown in FIG. 15 (a pattern in which letters, numbers, and figures having contours with a predetermined width are regularly arranged; matrix type ) Was formed. Immediately after pattern formation, ultraviolet rays are irradiated from above by an ultraviolet lamp (BL type) (ultraviolet illuminance: 3.4 mW / cm 2 , integrated irradiation amount: 100 mJ / cm 2 ), and the base material syrup and cylindrical difficulty elongation After semi-curing the syrup for forming the polymer part, a cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 μm) is pasted onto the semi-cured syrup with a hand roller, and an ultraviolet lamp ( BL type) (ultraviolet light illuminance: 3.4 mW / cm 2 , cumulative irradiation amount: 2000 mJ / cm 2 ), and difficult to stretch cylindrically in a cured base material (= extensible polymer base material) A sheet-like extensible organic base material (thickness: 300 μm) in which a syrup cured part for forming a polymerizable polymer part (= cylinder difficult extensible polymer part; cylindrical hard extensible part) was obtained. As a result of microscopic observation of the cross section, in the obtained sheet-like extensible organic base material, the cylindrical hardly extensible polymer portion is continuously formed from one surface of the sheet-like extensible organic base material to a depth of 2/3 or more. However, it was not formed up to the other surface (embedded type). In Table 8 and FIG. 15, W represents the width (mm) of each ring.
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
　実施例３１
　セパレータ（商品名「ＭＲＦ３８」、三菱樹脂（株）製、厚み３８μｍ）の表面に、製造例１で得られた母材シロップをアプリケータにて塗工し、厚み３００μｍの母材シロップ層を形成した。この母材シロップ層の所定部位にディスペンサー（商品名「ＳＭ３００ＤＳ−Ｓ、ＭＰＰ−１」、武蔵エンジニアリング（株）製）を用いて、上から、製造例２で得られた筒状難伸長性ポリマー部形成用シロップを滴下していき、図１６に示すようなパターン（所定の幅の輪郭を有する図形の組み合わせからなる絵）を形成した。パターン形成後、即座に、上から、紫外線ランプ（ＢＬタイプ）により紫外線を照射し（紫外線照度：３．４ｍＷ／ｃｍ２、積算照射量：１００ｍＪ／ｃｍ２）、母材シロップ及び筒状難伸長性ポリマー部形成用シロップを半硬化させた後、半硬化したシロップ上にカバーセパレータ（商品名「ＭＲＦ３８」、三菱樹脂（株）製、厚み３８μｍ）をハンドローラーにて貼り合わせ、さらに紫外線ランプ（ＢＬタイプ）により紫外線を照射し（紫外線照度：３．４ｍＷ／ｃｍ２、積算照射量：２０００ｍＪ／ｃｍ２）、母材シロップの硬化物（＝易伸長性ポリマー母材）中に筒状難伸長性ポリマー部形成用シロップ硬化部（＝筒状難伸長性ポリマー部；筒状難伸長部）が配置されたシート状伸長性有機基材（筒状難伸長性ポリマー部Ａの筒の空洞部に相当する領域内にさらに筒状の柱状難伸長性ポリマー部Ｂを有する）（厚み：３００μｍ）を得た。断面の顕微鏡観察の結果、得られたシート状伸長性有機基材において、筒状難伸長性ポリマー部はシート状伸長性有機基材の一方の表面から２／３以上の深さまで連続して形成されていたが、他方の面に至るまでは形成されていなかった（埋込型）。 Example 31
The base material syrup obtained in Production Example 1 is coated with an applicator on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 μm) to form a base material syrup layer having a thickness of 300 μm. did. Using a dispenser (trade name “SM300DS-S, MPP-1”, manufactured by Musashi Engineering Co., Ltd.) at a predetermined portion of the base material syrup layer, the cylindrical hardly extensible polymer obtained in Production Example 2 from above. The part forming syrup was dropped to form a pattern as shown in FIG. 16 (a picture composed of a combination of figures having an outline with a predetermined width). Immediately after pattern formation, ultraviolet rays are irradiated from above by an ultraviolet lamp (BL type) (ultraviolet illuminance: 3.4 mW / cm 2 , integrated irradiation amount: 100 mJ / cm 2 ), and the base material syrup and cylindrical difficulty elongation After semi-curing the syrup for forming the functional polymer part, a cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 μm) is bonded to the semi-cured syrup with a hand roller, and an ultraviolet lamp ( BL type) (ultraviolet light illuminance: 3.4 mW / cm 2 , integrated irradiation amount: 2000 mJ / cm 2 ), and difficult to stretch cylindrically in a cured base material syrup (= extensible polymer base material) Sheet-like extensible organic base material (cylindrical difficult-to-extend polymer part A cylinder) in which a syrup hardened part (= cylindrical difficult-to-extend polymer part; cylindrical difficult-to-extend part) is disposed In the region corresponding to the hollow portion of the above, a cylindrical columnar hardly extensible polymer portion B is further provided (thickness: 300 μm). As a result of microscopic observation of the cross section, in the obtained sheet-like extensible organic base material, the cylindrical hardly extensible polymer portion is continuously formed from one surface of the sheet-like extensible organic base material to a depth of 2/3 or more. However, it was not formed up to the other surface (embedded type).
　実施例３２
　セパレータ（商品名「ＭＲＦ３８」、三菱樹脂（株）製、厚み３８μｍ）の表面に、製造例１で得られた母材シロップをアプリケータにて塗工し、厚み３００μｍの母材シロップ層を形成した。この母材シロップ層の所定部位にディスペンサー（商品名「ＳＭ３００ＤＳ−Ｓ、ＭＰＰ−１」、武蔵エンジニアリング（株）製）を用いて、上から、製造例２で得られた筒状難伸長性ポリマー部形成用シロップを滴下していき、図１７に示すようなパターン（所定の幅の輪郭を有する図形、文字の組み合わせからなるパターン；複合型）を形成した。パターン形成後、即座に、上から、紫外線ランプ（ＢＬタイプ）により紫外線を照射し（紫外線照度：３．４ｍＷ／ｃｍ２、積算照射量：１００ｍＪ／ｃｍ２）、母材シロップ及び筒状難伸長性ポリマー部形成用シロップを半硬化させた後、半硬化したシロップ上にカバーセパレータ（商品名「ＭＲＦ３８」、三菱樹脂（株）製、厚み３８μｍ）をハンドローラーにて貼り合わせ、さらに紫外線ランプ（ＢＬタイプ）により紫外線を照射し（紫外線照度：３．４ｍＷ／ｃｍ２、積算照射量：２０００ｍＪ／ｃｍ２）、母材シロップの硬化物（＝易伸長性ポリマー母材）中に筒状難伸長性ポリマー部形成用シロップ硬化部（＝筒状難伸長性ポリマー部；筒状難伸長部）が配置されたシート状伸長性有機基材（筒状難伸長性ポリマー部Ａの筒の空洞部に相当する領域内にさらに筒状及び中実の柱状難伸長性ポリマー部Ｂを有する）（厚み：３００μｍ）を得た。断面の顕微鏡観察の結果、得られたシート状伸長性有機基材において、筒状難伸長性ポリマー部はシート状伸長性有機基材の一方の表面から２／３以上の深さまで連続して形成されていたが、他方の面に至るまでは形成されていなかった（埋込型）。 Example 32
The base material syrup obtained in Production Example 1 is coated with an applicator on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 μm) to form a base material syrup layer having a thickness of 300 μm. did. Using a dispenser (trade name “SM300DS-S, MPP-1”, manufactured by Musashi Engineering Co., Ltd.) at a predetermined portion of the base material syrup layer, the cylindrical hardly extensible polymer obtained in Production Example 2 from above. The part forming syrup was dropped to form a pattern as shown in FIG. 17 (a pattern composed of a combination of figures and characters having an outline with a predetermined width; a composite type). Immediately after pattern formation, ultraviolet rays are irradiated from above by an ultraviolet lamp (BL type) (ultraviolet illuminance: 3.4 mW / cm 2 , integrated irradiation amount: 100 mJ / cm 2 ), and the base material syrup and cylindrical difficulty elongation After semi-curing the syrup for forming the functional polymer part, a cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 μm) is bonded to the semi-cured syrup with a hand roller, and an ultraviolet lamp ( BL type) (ultraviolet light illuminance: 3.4 mW / cm 2 , integrated irradiation amount: 2000 mJ / cm 2 ), and difficult to stretch cylindrically in a cured base material syrup (= extensible polymer base material) Sheet-like extensible organic base material (cylindrical difficult-to-extend polymer part A cylinder) in which a syrup hardened part (= cylindrical difficult-to-extend polymer part; cylindrical difficult-to-extend part) is disposed In addition, a cylindrical and solid columnar difficult-to-extend polymer part B is further provided in the region corresponding to the hollow part (thickness: 300 μm). As a result of microscopic observation of the cross section, in the obtained sheet-like extensible organic base material, the cylindrical hardly extensible polymer portion is continuously formed from one surface of the sheet-like extensible organic base material to a depth of 2/3 or more. However, it was not formed up to the other surface (embedded type).
　評価試験（伸び量の測定）
　実施例４で得られたシート状伸長性有機基材のサンプル［環状の矩形難伸長性ポリマー部（難伸長部）が幅中央となるように幅３０ｍｍで切り出した試料］を、環状の矩形難伸長性ポリマー部（難伸長部）がチャック間（５０ｍｍ）の中央となるように設置して、引張試験機（商品名「Ａｕｔｏｇｒａｐｈ　ＡＧ−Ｘ　２００Ｎ」、（株）島津製作所製）により引張試験（温度：２５℃、引張速度：２００ｍｍ／ｍｉｎ）を行い、５０％伸長時（元の長さの１５０％）における環状の矩形難伸長性ポリマー部の伸長方向の伸長率Ｓ１（％）（平均値）と、環状の矩形難伸長性ポリマー部の外側の部位［易伸長性ポリマー母材部（＝易伸長部）］の伸長方向の伸長率Ｓ２（％）（平均値）を計測し、それらの比（Ｓ２／Ｓ１）及び差（Ｓ２−Ｓ１）（％）を計算で求めた（図７参照）。
　伸長率Ｓ１（％）は、環状の矩形難伸長性ポリマー部の伸長方向の幅（基材表面の矩形の線幅）を伸長の前後で測定し、式：｛（伸長後の長さ−伸長前の長さ）／（伸長前の長さ）｝×１００）により計算で求めた。
　伸長率Ｓ２（％）は、環状の矩形難伸長性ポリマー部の外側の部位（易伸長性ポリマー母材部）の伸長方向に６箇所印を付けておき、隣り合う印の間の長さを伸長の前後で測定し、式：｛（伸長後の長さ−伸長前の長さ）／（伸長前の長さ）｝×１００）により計算で求めた。
　その結果、Ｓ１（％）＝５、Ｓ２（％）＝８０、（Ｓ２／Ｓ１）＝１６、（Ｓ２−Ｓ１）（％）＝７５であった。
　なお、実施例４で得られたシート状伸長性有機基材は伸縮性をも有していた。 Evaluation test (measurement of elongation)
The sample of the sheet-like extensible organic base material obtained in Example 4 [the sample cut out with a width of 30 mm so that the annular rectangular difficult-to-extend polymer part (hard extension part) becomes the center of the width] was obtained. Installed so that the extensible polymer part (hardly stretched part) is in the center of the chuck (50 mm), and a tensile test (trade name “Autograph AG-X 200N”, manufactured by Shimadzu Corp.) Elongation rate S 1 (%) in the direction of elongation of the annular rectangular hardly extensible polymer portion at 50% elongation (150% of the original length) at a temperature of 25 ° C. and a tensile speed of 200 mm / min) Value) and the elongation ratio S 2 (%) (average value) in the extension direction of the site [easily extensible polymer base material portion (= easily elongate portion)] of the annular rectangular difficult extensible polymer portion, their ratio (S 2 / S 1) and difference (S 2 S 1) (%) was determined by calculation (see FIG. 7).
Elongation rate S 1 (%) is determined by measuring the width in the direction of elongation of the ring-shaped rectangular difficult-to-extend polymer part (rectangular line width of the substrate surface) before and after stretching, and the formula: {(length after stretching− Length before stretching) / (Length before stretching)} × 100).
Elongation rate S 2 (%) is the length between adjacent marks by marking 6 points in the extending direction of the outer part (easily extensible polymer base material part) of the annular rectangular hardly extensible polymer part. Was measured before and after stretching, and calculated by the formula: {(length after stretching−length before stretching) / (length before stretching)} × 100).
As a result, S 1 (%) = 5, S 2 (%) = 80, (S 2 / S 1 ) = 16, and (S 2 −S 1 ) (%) = 75.
In addition, the sheet-like extensible organic base material obtained in Example 4 also had stretchability.
　本発明のシート状伸長性有機基材によれば、該基材をある一方向（面方向）に伸長させても、筒状難伸長性ポリマー部の形状がほとんど変化しないので、伸長性部材としての機能を有しつつ、その形状不変部に所望の意匠を施したり、他の部材を適宜な固定手段を用いて保持、固定することができる。また、筒状難伸長性ポリマー部の筒状の空洞部に当たる領域は易伸長性ポリマー材料で構成されるので、該領域においては厚み方向に伸長可能である。そのため、当該シート状伸長性有機基材を被装着物に装着する際、該被装着物の形状に良好に追従させることができ、優れた装着性を発揮する。このため、本発明のシート状伸長性有機基材は、例えば、バンド部材、結束用部材、衛生用品、衣料品の部分、湿布剤の基布のほか、エレクトロニクス部材、オプティカル部材、オプトエレクトロニクス部材、カーエレクトロニクス部材、家電製品用部材、住宅設備用部材、建材などにも利用できる。 According to the sheet-like extensible organic base material of the present invention, the shape of the cylindrical difficult-to-extend polymer part hardly changes even when the base material is extended in one direction (plane direction). While having this function, a desired design can be applied to the shape invariant portion, and other members can be held and fixed using appropriate fixing means. Moreover, since the area | region which hits the cylindrical cavity part of a cylindrical difficulty extensible polymer part is comprised with an easily extensible polymer material, it can extend | expand in the thickness direction in this area | region. For this reason, when the sheet-like extensible organic base material is attached to an object to be attached, the shape of the object to be attached can be satisfactorily followed, and excellent wearability is exhibited. Therefore, the sheet-like extensible organic base material of the present invention includes, for example, a band member, a binding member, a sanitary article, a clothing part, a base material for a poultice, an electronic member, an optical member, an optoelectronic member, It can also be used for car electronics members, household appliance members, housing equipment members, building materials, and the like.
　１　　　シート状伸長性有機基材
　２　　　易伸長性ポリマー母材（易伸長性ポリマー母材部）
　２０　　ポリマー母材形成用材料層（易伸長性ポリマー母材形成用エネルギー線硬化性組成物層）
　２１　　ポリマー母材形成用材料層
　２２　　ポリマー母材形成用材料層
　２００　部分硬化した易伸長性ポリマー母材形成用エネルギー線硬化性組成物層
　３　　　筒状難伸長性ポリマー部Ａ
　３ａ　　筒状の空洞部に当たる領域
　３０　　筒状難伸長性ポリマー部形成用材料（筒状難伸長性ポリマー部形成用エネルギー線硬化性組成物）
　３１　　筒状難伸長性ポリマー部形成用材料
　３２　　筒状難伸長性ポリマー部形成用材料
　３００　部分硬化した筒状難伸長性ポリマー部形成用エネルギー線硬化性組成物
　４　　　支持体
　５　　　カバーフィルム
　Ａ　　　多機能性シート状伸長性有機基材（粘着性を有するシート状伸長性有機基材等）
　６　　　機能性層（粘着剤層等） 1 Sheet-like extensible organic base material 2 Easily extensible polymer base material (Easily extensible polymer base part)
20 Material layer for polymer matrix formation (energy ray curable composition layer for easily stretchable polymer matrix formation)
21 Polymer Base Material Forming Material Layer 22 Polymer Base Material Forming Material Layer 200 Partially Cured Easy Stretchable Polymer Base Material Forming Energy Beam Curable Composition Layer 3 Tubular Difficult Stretchable Polymer Part A
3a Region corresponding to a cylindrical cavity 30 Material for forming a cylindrical hardly stretchable polymer part (energy ray curable composition for forming a cylindrical difficult stretchable polymer part)
31 Cylindrical Difficult-to-Extend Polymer Part Forming Material 32 Cylindrical Difficult-to-Extend Polymer Part Forming Material 300 Partially Cured Cylindrical Difficult-to-Extend Polymer Part Forming Energy Beam Curing Composition 4 Support 5 Cover Film A Multifunctional Sheet-like extensible organic substrate (such as adhesive sheet-like extensible organic substrate)
6 Functional layers (such as adhesive layers)

Claims (12)

  1. 　易伸長性ポリマー母材中に、表面形状又はシート状伸長性有機基材表面を投影面としたときの投影形状が輪帯状である筒状難伸長性ポリマー部Ａが部分的に且つ一体的に形成されているシート状伸長性有機基材。 In the easily stretchable polymer base material, a cylindrical hardly stretchable polymer portion A whose projection shape is a ring zone when the surface shape or sheet-like stretchable organic substrate surface is a projection surface is partially and integrally formed. The formed sheet-like extensible organic base material.
  2. 　前記筒状難伸長性ポリマー部Ａの前記表面形状又は投影形状における輪帯の外周形状が、略円形、略多角形、無定形、又は文字、記号若しくは数字を表す形状である請求項１記載のシート状伸長性有機基材。 2. The outer peripheral shape of the annular zone in the surface shape or projected shape of the cylindrical hardly extensible polymer portion A is a substantially circular shape, a substantially polygonal shape, an amorphous shape, or a shape representing a character, a symbol, or a number. Sheet-like extensible organic base material.
  3. 　前記筒状難伸長性ポリマー部Ａの前記表面形状又は投影形状における輪帯の外周形状が略多角形であり、且つ該略多角形の内角が９０度以下又は９０度を超える角度である請求項２記載のシート状伸長性有機基材。 The outer peripheral shape of the annular zone in the surface shape or projected shape of the cylindrical hardly stretchable polymer portion A is a substantially polygon, and the inner angle of the substantially polygon is an angle of 90 degrees or less or more than 90 degrees. 2. The sheet-like extensible organic base material according to 2.
  4. 　複数の筒状難伸長性ポリマー部Ａが規則的パターンで形成されている請求項１~３のいずれか一項に記載のシート状伸長性有機基材。 The sheet-like extensible organic base material according to any one of claims 1 to 3, wherein the plurality of cylindrical hardly extensible polymer portions A are formed in a regular pattern.
  5. 　隣接する筒状難伸長性ポリマー部Ａ間の距離が０．０５ｍｍ~５０ｃｍである請求項４記載のシート状伸長性有機基材。 The sheet-like extensible organic base material according to claim 4, wherein the distance between adjacent cylindrical difficult-to-extend polymer parts A is 0.05 mm to 50 cm.
  6. 　隣接する筒状難伸長性ポリマー部Ａの中心間の距離が５ｍｍ~８０ｃｍである請求項４又は５記載のシート状伸長性有機基材。 The sheet-like extensible organic base material according to claim 4 or 5, wherein the distance between the centers of adjacent cylindrical hardly extensible polymer portions A is 5 mm to 80 cm.
  7. 　筒状難伸長性ポリマー部Ａの筒状の空洞部に当たる易伸長性ポリマー材料からなる領域内に、さらに、表面形状又はシート状伸長性有機基材表面を投影面としたときの投影形状が、略円形、略多角形、無定形、又は文字、記号若しくは数字を表す形状、輪帯状、又は線状である難伸長性ポリマー部Ｂを１又は２以上有する請求項１~６のいずれか一項に記載のシート状伸長性有機基材。 In the region made of the easily extensible polymer material that hits the cylindrical cavity of the cylindrical hardly extensible polymer portion A, the projection shape when the surface shape or the sheet-like extensible organic base material surface is the projection surface, 7. One or more hardly extensible polymer portions B that are substantially circular, substantially polygonal, amorphous, or have a shape representing a character, symbol, or number, a ring shape, or a linear shape. The sheet-like extensible organic base material as described in 1.
  8. 　厚みが０．０１ｍｍ~１ｃｍである請求項１~７のいずれか一項に記載のシート状伸長性有機基材。 The sheet-like extensible organic substrate according to any one of claims 1 to 7, having a thickness of 0.01 mm to 1 cm.
  9. 　筒状難伸長性ポリマー部Ａの厚み方向の長さがシート状伸長性有機基材の厚みの少なくとも１／５０である請求項１~８のいずれか一項に記載のシート状伸長性有機基材。 The sheet-like extensible organic group according to any one of claims 1 to 8, wherein the length in the thickness direction of the cylindrical hardly extensible polymer portion A is at least 1/50 of the thickness of the sheet-like extensible organic base material. Wood.
  10. 　筒状難伸長性ポリマー部Ａが、シート状伸長性有機基材の一方の表面から他方の表面に至るまで連続して形成されている請求項１~９のいずれか一項に記載のシート状伸長性有機基材。 The sheet form according to any one of claims 1 to 9, wherein the cylindrical hardly extensible polymer part A is continuously formed from one surface of the sheet-like extensible organic base material to the other surface. Stretchable organic base material.
  11. 　筒状難伸長性ポリマー部Ａと易伸長性ポリマー母材の界面近傍において、伸び特性がグラデーションをなしている請求項１~１０のいずれか一項に記載のシート状伸長性有機基材。 11. The sheet-like extensible organic base material according to any one of claims 1 to 10, wherein the elongation characteristic forms a gradation in the vicinity of the interface between the cylindrical hardly extensible polymer portion A and the easily extensible polymer base material.
  12. 　さらに伸縮性を有する請求項１~１１のいずれか一項に記載のシート状伸長性有機基材。 The sheet-like extensible organic substrate according to any one of claims 1 to 11, which further has stretchability.
PCT/JP2012/058496 2011-03-30 2012-03-23 Sheet-elongatable organic base material WO2012133721A1 (en)

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JP2011-075980 2011-03-30
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JP2012-015392 2012-01-27
JP2012015388A JP5876309B2 (en) 2011-03-30 2012-01-27 Stretchable organic substrate
JP2012015387A JP5876308B2 (en) 2011-03-30 2012-01-27 Sheet organic substrate
JP2012015384A JP5876306B2 (en) 2011-03-30 2012-01-27 Stretchable organic substrate
JP2012-015389 2012-01-27
JP2012015393A JP2013155121A (en) 2012-01-27 2012-01-27 Elongatable organic base material
JP2012015389A JP2013155241A (en) 2012-01-27 2012-01-27 Sheet-like elongatable organic base material
JP2012-015388 2012-01-27
JP2012-015386 2012-01-27
JP2012-015387 2012-01-27
JP2012015386A JP2012214015A (en) 2011-03-30 2012-01-27 Method of manufacturing sheet like organic base material
JP2012-015393 2012-01-27
JP2012015392A JP5956171B2 (en) 2012-01-27 2012-01-27 Stretchable organic substrate with adhesiveness
JP2012-015385 2012-01-27
JP2012-015384 2012-01-27
JP2012015385A JP5876307B2 (en) 2011-03-30 2012-01-27 Stretchable organic substrate
JP2012030137A JP2013166280A (en) 2012-02-15 2012-02-15 Stretchable organic base material with antireflection property
JP2012-030090 2012-02-15
JP2012030088A JP2013166279A (en) 2012-02-15 2012-02-15 Stretchable organic base material
JP2012-030042 2012-02-15
JP2012-030040 2012-02-15
JP2012-030041 2012-02-15
JP2012030086A JP2013166278A (en) 2012-02-15 2012-02-15 Stretchable organic base material
JP2012-030086 2012-02-15
JP2012030041A JP2013166276A (en) 2012-02-15 2012-02-15 Extensibility organic base material having flame retardancy
JP2012030087A JP2013166836A (en) 2012-02-15 2012-02-15 Stretchable organic base material
JP2012-030039 2012-02-15
JP2012030138A JP2013166281A (en) 2012-02-15 2012-02-15 Extensibility organic base material having surface layer
JP2012030089A JP2013166837A (en) 2012-02-15 2012-02-15 Extensible organic base material
JP2012-030089 2012-02-15
JP2012030040A JP2013168258A (en) 2012-02-15 2012-02-15 Extensible organic substrate with conductivity
JP2012030090A JP2013166838A (en) 2012-02-15 2012-02-15 Extensibility organic base material
JP2012030039A JP2013166275A (en) 2012-02-15 2012-02-15 Extensibility organic base material having thermal insulating properties
JP2012-030087 2012-02-15
JP2012030042A JP2013166277A (en) 2012-02-15 2012-02-15 Stretchable organic base material with thermal conductivity
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