WO2012133722A1

WO2012133722A1 - Sheet-form stretchable organic base material

Info

Publication number: WO2012133722A1
Application number: PCT/JP2012/058497
Authority: WO
Inventors: 内藤　友也; 達也北原; 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: 2011-03-30
Filing date: 2012-03-23
Publication date: 2012-10-04

Abstract

This sheet-form stretchable organic base material is a sheet-form stretchable organic base material in which a poorly stretchable polymer section is formed partially and integrally in an easily stretchable polymer matrix, the sheet-form stretchable organic base material being characterized in that the superficial shape of the poorly stretchable polymer section, or the projected shape of the poorly stretchable polymer section when the surface of the sheet-form stretchable organic base material is employed as the surface of projection, is linear. The width of the line in the superficial shape or the projected shape of the poorly stretchable polymer section is, for example, from 0.01 mm to 5 cm. The superficial shape or the projected shape of the poorly stretchable polymer section is, for example, a straight line, a zigzag line, a wavy line, an arc-shaped line, or a formless line. This sheet-form stretchable organic base material is stretchable in the surface direction, has a poorly stretchable section less prone to deformation even when stretched, and can be prevented from stretching in a specific direction and can be provided with strength in a specific direction.

Description

Sheet-like extensible organic substrate

In the present invention, a sheet-like extensible organic base material, more specifically, a hard-extensible polymer portion whose surface shape or projected shape onto the substrate surface is linear is integrally formed in an easily extensible polymer base material. It is related with the sheet-like extensible organic base material (especially elastic organic base material). 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 the sheet-like extensible organic base material is stretched in the plane direction, the whole base material is stretched. Designs such as characters can be applied to the polymer part, and other members can be held and fixed. Furthermore, since the hardly extensible polymer portion has a shape extending linearly when viewed from the substrate surface, it is possible to suppress the elongation in a specific direction and to impart strength in the specific direction. 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 | extends, it is difficult to hold | maintain and fix this other member reliably.

JP 2003-342169 A

The object of the present invention is to have a stretchable portion in the surface direction and a difficultly stretchable portion that does not easily change its shape even when stretched. The object is to provide a sheet-like extensible substrate.
Another object of the present invention is that it has stretchability in the surface direction and has a difficult-to-change part that does not easily change its shape even if it is stretched. An object of the present invention is to provide a sheet-like extensible substrate that can be used.

As a result of intensive studies to achieve the above object, the present inventors have found that the above object can be achieved by integrally forming a hardly extensible polymer part having a specific shape in an easily extensible polymer matrix. The headline and the present invention were completed.

That is, the present invention is a sheet-like extensible organic base material in which a hardly extensible polymer portion is partially and integrally formed in an easily extensible polymer matrix, and the surface of the hardly extensible polymer portion Provided is a sheet-like extensible organic substrate whose shape or projection shape when the surface of the sheet-like extensible organic substrate of the hardly extensible polymer portion is a projection surface.

The line width of the surface shape or projected shape of the hardly extensible polymer portion is, for example, 0.01 mm to 5 cm.

The surface shape or projected shape of the hardly extensible polymer portion may be any of a straight line, a polygonal line, a wavy line, an arc line, or an amorphous line.

In addition, the surface shape or the projected shape has a plurality of hardly extensible polymer portions, and the plurality of hardly extensible polymer portions are parallel, intersect, or twisted. May be.

A plurality of hardly extensible polymer portions may be formed in a regular pattern.

The center lines of the surface shape or projected shape of the plurality of hardly extensible polymer portions may be parallel.

The distance between the center lines of the surface shape or projection shape of the adjacent hardly extensible polymer portions is, for example, 0.01 mm to 50 cm.

The thickness of the sheet-like extensible organic base material is, for example, 0.01 mm to 1 cm.

The length in the thickness direction of the hardly extensible polymer portion is preferably at least 1/50 of the thickness of the sheet-like extensible organic base material. In addition, the hardly extensible polymer portion may be continuously formed from one surface of the sheet-like extensible organic base material to the other surface.

In the vicinity of the interface between the hardly extensible polymer portion and the easily extensible polymer base material, the elongation characteristic may have a gradation.

The sheet-like extensible organic base material may further have stretchability.

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] A sheet-like organic base material having extensibility in which a hardly extensible polymer portion is partially and integrally formed in an easily extensible polymer matrix, and the hardly extensible polymer portion A pressure-sensitive adhesive layer is provided on at least one surface of the sheet-like organic substrate having a linear shape when the surface shape or the surface of the sheet-like organic substrate of the hardly extensible polymer portion is the projection surface. The pressure-sensitive adhesive layer has a pressure-sensitive adhesive strength (temperature 23 ° C., humidity 65% RH, tensile speed 300 mm / min, peel angle 180 °, SUS304) of 0.1 N / 20 mm or more. Stretchable organic base material.

[1-2] A sheet-like organic base material having extensibility, in which the hardly extensible polymer portion is partially and integrally formed in the easily extensible polymer matrix, and the hardly extensible polymer portion Adhesive force (temperature: 23 ° C., at least one surface of a sheet-shaped organic substrate having a linear shape when the surface shape or the surface of the sheet-shaped organic substrate of the hardly extensible polymer portion is a projection surface. A multifunctional sheet-like extensible organic base material having adhesiveness with a humidity of 65% RH, a tensile speed of 300 mm / min, a peeling angle of 180 °, and a SUS304 ratio of 0.1 N / 20 mm or more.

[2-1] A sheet-like organic base material having extensibility, in which a hardly extensible polymer portion is partially and integrally formed in an easily extensible polymer base material, and the hardly extensible polymer portion A surface shape or a sheet-like organic substrate having a projection shape when the surface of the sheet-like organic substrate of the hardly extensible polymer portion is a projection surface, wherein the easily extensible polymer matrix is weather resistant Multifunctional sheet-like extensible organic base material containing an agent.

[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] A sheet-like organic base material having extensibility, in which the hardly extensible polymer portion is partially and integrally formed in the easily extensible polymer base material, and the hardly extensible polymer portion The surface shape or a sheet-like organic base material having a projection shape when the surface of the sheet-like organic base material of the hardly extensible polymer portion is a projection surface, and an easily extensible polymer base material and / or A multifunctional sheet-like extensible organic base material in which the hardly extensible polymer portion contains a fragrance.

[3-2] A sheet-like organic base material having extensibility, in which the hardly extensible polymer portion is partially and integrally formed in the easily extensible polymer matrix, and the hardly extensible polymer portion Multifunctional having a deodorizing layer on at least one surface of a surface shape or a sheet-like organic substrate whose projection shape is linear when the surface of the sheet-like organic substrate of the hardly extensible polymer portion is a projection surface Sheet-like extensible organic base material.

[3-3] A stretchable sheet-like organic base material having a stretchable polymer portion partially and integrally formed in a stretchable polymer base material, and the stretchable polymer portion A sheet-like extensible organic base material comprising a sheet-like organic base material whose projection shape when the surface shape or the sheet-like organic base material surface of the hardly extensible polymer part is a projection surface, A multifunctional sheet-like extensible organic base material in which the amount of monomer generated when the sheet-like extensible organic base material is heated at 150 ° C. for 3 minutes is 300 ppm or less.

[4-1] A sheet-like organic base material having extensibility in which a hardly extensible polymer portion is partially and integrally formed in an easily extensible polymer base material, and the hardly extensible polymer portion The surface shape or a sheet-like organic base material having a projection shape when the surface of the sheet-like organic base material of the hardly extensible polymer portion is a projection surface, and an easily extensible polymer base material and / or A multifunctional sheet-like extensible organic base material in which the hardly extensible polymer portion contains a dye or a pigment.

[4-2] A sheet-like organic base material having extensibility, in which the hardly extensible polymer portion is partially and integrally formed in the easily extensible polymer matrix, and the hardly extensible polymer portion Multi-functionality having a colored layer on at least one surface of a surface shape or a sheet-like organic substrate having a linear projection shape when the surface of the sheet-like organic substrate of the hardly extensible polymer portion is a projection surface Sheet-like extensible organic base material.

[4-3] A sheet-like organic base material having extensibility in which the hardly extensible polymer portion is partially and integrally formed in the easily extensible polymer matrix, and the hardly extensible polymer portion Multi-functionality having a printing layer on at least one surface of a surface shape or a sheet-like organic substrate whose projection shape is linear when the surface of the sheet-like organic substrate of the hardly extensible polymer portion is a projection surface Sheet-like extensible organic base material.

[5-1] A sheet-like organic base material having extensibility in which a hardly extensible polymer portion is partially and integrally formed in an easily extensible polymer matrix, and the hardly extensible polymer portion A surface shape or a sheet-like organic substrate having a projection shape when the projection-like surface of the sheet-like organic substrate surface of the hardly extensible polymer portion is a projection surface, and the sheet-like organic substrate is a flame retardant And / or a flame-retardant multifunctional sheet-like extensible organic substrate having a flame-retardant layer on at least one side of the sheet-like organic substrate.

[5-2] Multifunctionality having flame retardancy according to the above [5-1], wherein the flame retardant is at least one selected from halogen compounds, phosphorus compounds, antimony compounds, and metal hydroxides. Sheet-like extensible organic base material.

[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] A sheet-like organic base material having extensibility, in which a hardly extensible polymer portion is partially and integrally formed in an easily extensible polymer matrix, and the hardly extensible polymer portion A sheet-like organic substrate having a surface shape or a projected shape when the surface of the sheet-like organic substrate of the hardly extensible polymer portion is a projection surface, and the sheet-like organic substrate is thermally conductive A multifunctional sheet-like extensible organic base material having thermal conductivity, containing a conductive material and / or having a thermal conductive layer on at least one side of the sheet-like extensible organic base material.

[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] 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] A sheet-like organic base material having extensibility, in which a hardly extensible polymer portion is partially and integrally formed in an easily extensible polymer base material, and the hardly extensible polymer portion The surface shape or the sheet-like organic base material having a projection shape when the surface of the sheet-like organic base material of the hardly extensible polymer portion is a projection surface, and the sheet-like organic base material is heat insulating. A multifunctional sheet-like extensible organic base material having a heat insulating property containing an imparting agent and / or having a heat insulating layer on at least one side of the sheet-like extensible organic base material.

[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.

[8-1] A stretchable sheet-like organic base material in which a hardly extensible polymer portion is partially and integrally formed in an easily extensible polymer matrix, and the hardly extensible polymer portion The surface shape or a sheet-like organic substrate having a projected shape when the surface of the sheet-like organic substrate of the hardly extensible polymer portion is a projection surface, wherein the easily extensible polymer matrix is resistant to A multifunctional sheet-like extensible organic base material containing an impact imparting agent.

[8-2] A sheet-like organic base material having extensibility, in which the hardly extensible polymer portion is partially and integrally formed in the easily extensible polymer base material, and the hardly extensible polymer portion Multifunctional having a shock absorbing layer on at least one surface of a surface shape or a sheet-like organic substrate whose projection shape is linear when the surface of the sheet-like organic substrate of the hardly extensible polymer portion is a projection surface Sheet-like extensible organic base material.

[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] 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] A sheet-like organic base material having extensibility, in which the hardly extensible polymer portion is partially and integrally formed in the easily extensible polymer base material, and the hardly extensible polymer portion It has a gas barrier layer on at least one surface of the surface shape or the sheet-like organic base material in which the projection shape when the surface of the sheet-like organic base material of the hardly extensible polymer part is a projection surface is linear A multifunctional sheet-like extensible organic base material that satisfies 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

[9-2] A sheet-like organic base material having extensibility, in which the hardly extensible polymer portion is partially and integrally formed in the easily extensible polymer base material, and the hardly extensible polymer portion The surface shape or a sheet-like organic substrate having a projection shape when the projection-like surface of the sheet-like organic substrate surface of the hardly extensible polymer portion is a projection surface, A multifunctional sheet-like extensible organic base material that satisfies one or both of 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

[10-1] A sheet-like organic base material having extensibility, in which the hardly extensible polymer portion is partially and integrally formed in the easily extensible polymer base material, and the hardly extensible polymer portion The surface shape, or a sheet-like organic substrate having a projection shape when the surface of the sheet-like organic substrate of the hardly extensible polymer portion is a projection surface, is 40 ° C. according to JIS K7129A method, A multifunctional sheet-like extensible organic base material having a water vapor transmission rate corresponding to a thickness of 40 μm measured under a 90% RH condition of 100 g / m 2 /0.1 MPa / day or more.

[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] A sheet-like organic base material having extensibility, in which the hardly extensible polymer portion is partially and integrally formed in the easily extensible polymer base material, and the hardly extensible polymer portion A surface shape or a sheet-like organic substrate having a linear projection shape when the surface of the sheet-like organic substrate of the hardly extensible polymer portion is a projection surface, and the sheet-like organic substrate is conductive. A multifunctional sheet-like extensible organic base material having conductivity and / or having a conductive layer on at least one side of the sheet-like organic base material.

[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] 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] A sheet-like organic base material having extensibility, in which the hardly extensible polymer portion is partially and integrally formed in the easily extensible polymer matrix, and the hardly extensible polymer portion A surface layer of a fluorine-based compound is formed on at least one surface of the surface shape or the sheet-like organic substrate having a linear projection when the surface of the sheet-like organic substrate of the hardly extensible polymer portion is a projection surface. A multifunctional sheet-like extensible organic base material having a surface layer.

[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] A sheet-like organic base material having extensibility, in which the hardly extensible polymer portion is partially and integrally formed in the easily extensible polymer matrix, and the hardly extensible polymer portion An antireflection layer having an antireflection layer on at least one surface of the surface shape or a sheet-like organic substrate in which the projection shape when the surface of the sheet-like organic substrate of the hardly extensible polymer portion is a projection surface Multifunctional sheet-like extensible organic base material having properties.

[13-2] The multifunctional 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] In the easily stretchable polymer base material, the hardly stretchable polymer portion is partially formed in a state where it is exposed or not exposed on at least one surface of the sheet-like organic base material. [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] to [13-1] [13-2] The multifunctional sheet-like extensible organic substrate according to any one of [13-2].

[14-2] The surface shape of the hardly extensible polymer portion or the projection shape when the surface of the sheet-like organic base material of the hardly extensible polymer portion is a projection surface is substantially circular, substantially polygonal, amorphous, or text The multi-functional sheet-like extensible organic base material according to [14-1], which has a shape representing a symbol or a number, a ring-shaped shape, or a linear shape.

[14-3] [1-1] to [1-2], [2-1] to [2-2] wherein the length of the long axis in the surface direction of the hardly extensible polymer portion is 0.05 mm to 10 cm. ], [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 [14-2] Multifunctional sheet-like extensible organic base material.

[14-4] [1-1] to [1-2], [2-1] to [2] in which a plurality of hardly extensible polymer portions are formed in a regular pattern in the easily extensible polymer matrix. -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], or [14-1] to [14-3] The multifunctional sheet-like extensible organic base material as described in 1.

[14-5] The multifunctional sheet-like extensible organic base material according to the above [14-4], wherein the distance between adjacent hardly extensible polymer portions is 0.05 mm to 50 cm.

[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] The above [1-1] to [1-2], [2-1] to which the length direction of the hardly extensible polymer portion is at least 1/50 of the thickness of the sheet-like organic 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 [14-6]. The multifunctional sheet-like extensible organic base material in any one.

[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] 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] [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].

According to the sheet-like extensible organic base material of the present invention, the shape of the hardly extensible polymer portion hardly changes even when the base material is extended in a certain direction, so that it has a function as an extensible member. A desired design can be given to the shape invariant portion, and other members can be held and fixed. In addition, the projection shape when the surface shape of the hardly extensible polymer part or the sheet-like extensible organic substrate surface of the hardly extensible polymer part is the projection surface is linear, and the hardly extensible polymer part is the sheet-like extensibility. Since it has a shape extending linearly when viewed from the organic substrate surface side, it is possible to suppress elongation in a specific direction or to impart strength in a specific direction.
Furthermore, according to the stretchable sheet-like stretchable organic base material, the shape of the hardly stretchable polymer portion hardly changes even when the base material is stretched, while having a function as a stretchable member. It is possible to give a desired design to the shape-invariant portion and hold and fix other members. In addition, since the hardly extensible polymer portion has a shape extending linearly when viewed from the surface side of the sheet-like extensible organic base material, it suppresses expansion and contraction in a specific direction or imparts strength in a specific direction. be able to.

It is a schematic perspective view which shows an example (part) of the sheet-like extensible organic base material of this invention. It is a figure which shows the example of the pattern shape of a hardly extensible polymer part when it sees from the surface side of the sheet-like extensible organic base material of this invention. Sectional drawing which shows the example of the sheet-like extensible organic base material of this invention (In the projection shape when the surface shape of a hardly extensible polymer part or the sheet-like extensible organic base material surface of a hardly extensible polymer part is used as a projection surface) It is sectional drawing when cut | disconnecting by a surface perpendicular | vertical with respect to the extending direction of a certain line. 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. 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. 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. 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. FIG. 5 is a schematic view showing a pattern shape of a hardly extensible polymer portion on the surface of the sheet-like extensible organic base material obtained in Examples 1 to 5. FIG. 3 is a schematic diagram showing a pattern shape of a hardly extensible polymer portion on the surface of a sheet-like extensible organic substrate obtained in Examples 6 to 12. FIG. 3 is a schematic view showing a pattern shape of a hardly extensible polymer portion on the surface of a sheet-like extensible organic base material obtained in Examples 13 to 14. It is the schematic which shows the pattern shape of the hardly extensible polymer part in the surface of the sheet-like extensible organic base material obtained in Example 15. It is the schematic which shows the pattern shape of the hardly extensible polymer part in the surface of the sheet-like extensible organic base material obtained in Example 16. FIG. 3 is a schematic view showing the shape of a hardly extensible polymer portion on the surface of a sheet-like extensible organic base material obtained in Examples 17 to 19. It is the schematic which shows the shape of the hardly extensible polymer part A in the surface of the sheet-like extensible organic base material obtained in Example 20. FIG. 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. In Example 21, it is the schematic which shows the grid | lattice pattern of 1 mm of line | wire widths and 1 mm of line | wire width intervals formed with the syrup for hardly extensible polymer part formation. In Example 22, it is the schematic which shows the grid | lattice pattern of 1 mm of line | wire widths and 1 mm of line | wire width intervals formed with the electroconductive water dispersion.

[Sheet-like extensible organic substrate]
In the sheet-like extensible organic base material of the present invention, the hardly extensible polymer portion is partially and integrally formed in the easily extensible polymer base material. Then, the surface shape of the hardly extensible polymer portion, or the projected shape when viewed from the surface of the sheet extensible organic substrate surface of the hardly extensible polymer portion (viewed from the surface side of the sheet extensible organic substrate). (Hereinafter sometimes referred to as “base surface projection shape”) is linear. When this organic base material is stretched in one direction (plane direction), the portion of the easily stretchable polymer base material is stretched, but the partially formed linear stretchable polymer portion is not stretched, or Hardly stretches. For this reason, the design in which a shape is desired not to change can be given to a hardly extensible polymer part, or another member can be fixed and hold | maintained. Moreover, an extension direction can be controlled or intensity | strength can be provided to a specific direction with the hardly extensible polymer part which has a shape extended linearly seeing from the surface side of a sheet-like extensible organic base material.

FIG. 1 is a schematic perspective view showing an example (part) of a sheet-like extensible organic base material of the present invention. In FIG. 1, a sheet-like extensible organic substrate 1 is easily 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 extensible polymer part 3. FIG.

The hardly extensible polymer portion 3 only needs to be integrally formed in the easily extensible polymer base material 2, for example, may be formed only at one place, and is formed discontinuously at a plurality of places. Alternatively, a plurality of hardly extensible polymer portions may intersect.

The surface shape of the hardly extensible polymer portion 3 or the projected shape of the substrate surface is linear, and the “line” has a predetermined width. The linear type is not particularly limited, and may be any of a straight line, a polygonal line, a curved line such as a wavy line and an arc line, and an amorphous line. In addition, when the surface shape or the substrate surface projection shape has a plurality of hardly extensible polymer portions, the plurality of hardly extensible polymer portions may be parallel or crossed. It may be in a twisted position.

The width (line width) of the line which is the surface shape of the hardly extensible polymer part 3 or the projected surface of the base material can be appropriately set according to the purpose and application, and is, for example, 0.01 mm to 5 cm. The lower limit of the line width (line width) which is the surface shape of the hardly extensible polymer part 3 or the projected surface of the base material is preferably 0.05 mm, more preferably 0.1 mm. The upper limit of the line width (line width) which is the surface shape of the hardly extensible polymer part 3 or the projected surface of the substrate surface is preferably 2 cm, more preferably 1 cm. The length of the line that is the surface shape of the hardly extensible polymer portion 3 or the projected shape of the substrate surface can be appropriately set according to the purpose and application, and is, for example, 0.5 mm to 10 m. The lower limit of the length of the line that is the surface shape of the hardly extensible polymer portion 3 or the projected shape of the substrate surface is preferably 5 mm, more preferably 1 cm. The upper limit of the length of the line which is the surface shape of the hardly extensible polymer portion 3 or the projected shape of the substrate surface is preferably 5 m, and more preferably 1 m. The ratio of the line length to the line width (line length / line width) which is the surface shape of the hardly extensible polymer part 3 or the substrate surface projected shape (line length / line width) is, for example, 3 or more, preferably 5 or more, more preferably It is 10 or more, more preferably 50 or more, and particularly preferably 100 or more.

In the vicinity of the interface (boundary portion) between the hardly extensible polymer portion 3 and the easily extensible polymer base material portion 2, there is a gradation (gradient) in which the composition and / or physical properties (elongation characteristics, hardness, etc.) gradually change. Also good. 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 hardly extensible polymer portion 3 and the easily extensible polymer base material portion 2 is, for example, the sheet shape. When the extensible organic base material 1 is extended, it has a characteristic that it is difficult to break at the interface between the hardly extensible polymer portion 3 and the easily extensible polymer base material portion 2. In addition to the vicinity of the interface (boundary portion) between the hardly extensible polymer portion 3 and the easily extensible polymer base material portion 2, many portions of the hardly extensible polymer portion 3 and / or the easily extensible polymer base material portion 2 or A gradation may be exhibited throughout. In the sheet-like extensible organic base material having a gradation portion, the boundary between the hardly extensible polymer portion 3 and the easily extensible polymer base portion 2 is the hardness of the non-gradient portion of the easily extensible polymer base portion 2 [easy extension. In the case where 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 hardly stretchable polymer portion 3 [overall stretchable polymer portion 3 In the case where gradation is exhibited, it can be determined by a line connecting the average values of the hardness of the highest hardness portion].

In the present invention, the hardly extensible polymer portion 3 may be formed at any site in the easily extensible polymer base material 2. For example, the hardly extensible polymer portion 3 may be formed in a state where it is exposed on at least one surface of the sheet-like extensible organic substrate 1, or is exposed on the surface of the sheet-like extensible organic substrate 1. It may be formed in the state without. When the hardly extensible polymer part 3 is formed in a state where it is exposed on at least one surface of the sheet-like extensible organic substrate 1, the surface shape of the hardly extensible polymer part 3 and the projected surface shape of the substrate are: Or the size may be different (for example, when there is a bulge inside). When the hardly extensible polymer part 3 is formed in a state where it is not exposed on the surface of the sheet-like extensible organic substrate 1, the surface of the sheet-like extensible organic substrate 1 of the hardly extensible polymer part 3 ( The projected shape (the shape seen from the surface side of the sheet-like extensible organic base material 1) when the projection surface is at least one surface) is linear.

From the viewpoint that the hardly extensible polymer portion 3 can be effectively used, the hardly extensible polymer portion 3 is preferably formed in a state of being exposed on at least one surface of the sheet-like extensible organic substrate 1. Moreover, in order to ensure smooth extensibility of the sheet-like extensible organic base material 1, the hardly extensible polymer portion 3 is formed at a place other than the end portion in the surface direction of the easily extensible polymer base material 2. Is preferred. That is, it is preferable that the hardly extensible polymer part 3 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 of the stretchable polymer base material 2 in the plane direction, the hardly stretchable polymer portion 3 is formed at the end, or the end of the hardly stretchable polymer portion 3 is easily stretched depending on the application. May reach the edge of the surface direction of the conductive polymer base material 2.

When a plurality of hardly extensible polymer portions 3 are formed in the easily extensible polymer base material 2, the plurality of hardly extensible polymer portions 3 may be randomly formed and formed in a regular pattern. May be. If the hardly extensible polymer portions 3 are formed in a regular pattern in advance, a large number of sheet-like extensible organic base materials 1 can be efficiently produced by cutting. When a plurality of the hardly extensible polymer portions 3 are formed, the shapes and sizes of the plurality of hardly extensible polymer portions 3 may be the same or different. When the plurality of hardly extensible polymer portions 3 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.

When the plurality of hardly extensible polymer portions 3 are formed in a regular pattern, the center lines in the surface shape or the substrate surface projected shape of the plurality of hardly extensible polymer portions 3 may be parallel or intersect. You may do it.

When the center line in the said surface shape or base-material surface projection shape of the some non-extensible polymer part 3 is parallel, between the center lines in the said surface shape or base-material surface projection shape of an adjacent difficult-extension polymer part 3 The distance (the distance between the center lines on the sheet-like extensible organic substrate surface or the sheet-like extensible organic substrate projection surface) is, for example, 0.01 mm to 50 cm. The lower limit of the distance between the center lines of the surface shape or the substrate surface projected shape of the adjacent hardly extensible polymer portion 3 is preferably 0.1 mm, more preferably 1 mm. The upper limit of the distance between the center lines of the surface shape or the substrate surface projected shape of the adjacent hardly extensible polymer part 3 is preferably 20 cm, more preferably 10 cm, and particularly preferably 5 cm. In addition, when the center lines of the surface shape or the substrate surface projection shape of the plurality of hardly extensible polymer portions 3 are parallel, the distance between the adjacent hardly extensible polymer portions 3 (sheet-like extensible organic substrate surface or The distance on the projection surface of the sheet-like extensible organic base material is, for example, 0.01 mm to 50 cm, and the upper limit of the distance is preferably 30 cm, more preferably 20 cm, still more preferably 15 cm, particularly preferably 10 cm. is there. The lower limit of the distance is preferably 0.1 mm, more preferably 1 mm, and still more preferably 3 mm. Furthermore, when the center line of the surface shape or the substrate surface projection shape of the plurality of hardly extensible polymer portions 3 is parallel, the line width in the surface shape or the substrate surface projection shape of the hardly extensible polymer portion 3 and the The ratio of the distance between adjacent hardly extensible polymer portions 3 is, for example, the former / the latter = 0.01-100. The upper limit of this ratio is preferably 80, more preferably 50, and the lower limit is preferably 0.1, more preferably 1.

FIG. 2 shows an example of the pattern shape (surface shape or substrate surface projected shape) of the hardly extensible polymer portion when viewed from the surface side of the sheet-like extensible organic substrate of the present invention. In each figure, the rectangular outer frame does not necessarily indicate the contour shape of the sheet-like extensible organic base material. The upper right diagram in FIG. 2 is an example in which a plurality of hardly extensible polymer portions having a linear surface shape or substrate surface projection shape are formed in parallel at equal intervals. In this example, the hardly extensible polymer portion is formed at right angles to the length direction of the sheet, but may be formed parallel or oblique to the length direction of the sheet. The lower right figure of FIG. 2 is an example in which a plurality of hardly extensible polymer portions having a polygonal line shape on the surface shape or substrate surface projection shape are formed at equal intervals. In this example, the center lines of the surface shape or the substrate surface projection shape of the plurality of hardly extensible polymer portions are parallel to each other. In this example, the center line of the surface shape or base surface projection shape of the hardly extensible polymer portion extends at right angles to the length direction of the sheet, but is parallel to the length direction of the sheet. Or you may extend diagonally. The upper left figure in FIG. 2 shows a plurality of equally-spaced hardly extensible polymer portions having the surface shape or the substrate surface projection shape extending obliquely with respect to the linear sheet length direction, and the surface shape or substrate. This is an example in which the surface projection shape intersects each other with a plurality of equally-spaced hardly extensible polymer portions extending obliquely with respect to the linear sheet length direction, thereby exhibiting a mesh shape. 2 shows a plurality of equally-spaced hardly extensible polymer part groups extending in parallel with the sheet length direction of the surface shape or the substrate surface projected shape, and the surface shape or base. In this example, the material surface projection shape intersects each other with a plurality of equally-spaced hardly extensible polymer portions extending perpendicularly to the linear sheet length direction. The lower left figure in FIG. 2 shows a plurality of equally spaced hardly extensible polymer portions extending in the sheet width direction in which the surface shape or the substrate surface projection shape is a polygonal line, and the surface shape or the substrate surface projection shape is a polygonal line. This is an example in which a plurality of equally-spaced hardly extensible polymer portions extending in the sheet length direction intersect each other to form a complex mesh shape.

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 hardly extensible polymer portion 3 may be continuously formed from one surface of the sheet-like extensible organic substrate 1 to a predetermined depth, and from one surface of the sheet-like extensible organic substrate 1 to the other. It may be formed continuously up to the surface. The hardly extensible polymer portion 3 may be formed by being embedded in the sheet-like extensible organic base material 1. The length (thickness) in the thickness direction of the hardly extensible polymer portion 3 is preferably at least 1/50 of the thickness of the sheet-like extensible organic substrate 1 in any of the above cases from the viewpoint of usefulness, etc. Preferably it is at least 1/20, more preferably at least 1/10, particularly preferably at least 1/4. In addition, from the viewpoint of retention of other members, for example, when the hardly extensible polymer portion 3 is continuously formed from one surface of the sheet-like extensible organic base material 1, The length (thickness) in the thickness direction of the conductive polymer part 3 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 substrate 1. desirable.

(1) to (7) in FIG. 3 are sectional views showing examples of the sheet-like extensible organic substrate 1 of the present invention (the surface shape of the hardly extensible polymer portion 3 or the substrate surface projected shape), respectively. It is sectional drawing when cut | disconnecting in a surface perpendicular | vertical with respect to the direction where a line is extended. As shown in this figure, the cross-sectional shape of the hardly extensible polymer portion 3 can take various shapes such as a rectangle, a hoof, an arc, a semicircle, a circle, an ellipse, and a dumbbell. The cross-sectional shape of the hardly extensible polymer part 3 is the kind, composition, viscosity of the easily extensible polymer base material forming material and the hardly extensible polymer part forming material; the easily extensible polymer of the hardly extensible polymer part forming material. It can be adjusted by the application method (dropping, pouring, etc.) to the base material forming material layer, the application location, the application amount; the conditions for forming the easily extensible polymer base material and the hardly extensible polymer portion. After applying the coating solution for forming the hardly extensible polymer part to the material layer for forming the easily extensible polymer base material, if the time until the hardly extensible polymer part is formed by curing or the like is long, A dumbbell-shaped hardly extensible polymer portion as shown in FIG. 3 (7) may be formed by diffusing in the lateral direction.

The elongation (breaking elongation) of the sheet-like extensible organic base material of the present invention in a tensile test (test piece width 20 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.

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 hardly extensible polymer portion 3 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 extensible organic base material that does not stretch up to 1.5 times, when stretched up to 1.25 times or about a sheet-like organic base material that does not stretch up to 1.25 times) , When stretched to 1.1 times), the elongation rate S ₁ (%) (ratio of the stretched length to the original length) of the hardly extensible polymer portion 3 is preferably 49% or less, more preferably It is 40% or less, more preferably 25% or less, and particularly preferably 10% or less.

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 extensible organic base material that does not extend up to 1.5 times, when it is extended up to 1.25 times, it does not extend up to 1.25 times) , When stretched up 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 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 easily extensible polymer base material portion 2 is extended, the hardly extensible polymer portion 3 is difficult to extend, Since it is difficult to change, it is possible to apply a desired design to the hardly extensible polymer part 3 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).

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 extensible organic base material that does not extend up to 1.5 times, when it is extended up to 1.25 times, it does not extend up to 1.25 times) for, when was stretched 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 flame stretch polymer portion 3 _(%) [S ₂ (%)-S ₁ (%)] is preferably 20% or more, and more preferably 40% or more.

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.

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 20 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).

Moreover, in the sheet-like extensible organic base material of this invention, the easily extensible polymer base material 2 is usually soft, and the hardly extensible polymer part 3 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 flame stretch polymer unit 3 as determined by the temperature of _{25 ℃) (H 1 / H} 2) is greater than 1 More preferably, it is 1.01 or more, More preferably, it is 1.10 or more, Most preferably, it is 1.20 or more.

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 hardly extensible polymer part 3. 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 distortion: 0.2% measurement time: 120 sec, number of measurements: 10 times) tensile modulus of poorly extensible polymer portion 3 as measured by E _'1 (Pa) and tensile modulus of the easily extensible polymer matrix 2 The ratio of E ′ ₂ (Pa) (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.

Furthermore, the load in the nanoindentation measurement can be used as a measure of the hardness of the easily extensible polymer base material 2 and the hardly extensible polymer portion 3. In the sheet-like extensible organic base material, the load P ₁ of the hardly extensible polymer portion 3 and the easily extensible polymer matrix in nanoindentation measurement (indentation depth 4 μm, indentation speed 1.5 μm / second, temperature 25 ° C.). The ratio (P ₁ / P ₂ ) of the material 2 to the load 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.

The surface roughness Ra of the surface (at least one surface) of the easily extensible polymer base part 2 and the surface (at least one surface) of the formation site of the hardly extensible polymer part 3 is preferably 100 nm or less, 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).

[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.

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).

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 material for forming the hardly extensible polymer portion is disposed 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 converted into a target polymer. Can be formed. 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.

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. Forming and arranging the forming material of the hardly extensible polymer portion at a predetermined portion of the easily extensible polymer base material forming material layer, and then drying and removing the solvent in the easily extensible polymer base material forming material layer 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).

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 hardly extensible 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.

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.

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.

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.

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 in the molecule with respect to the reactive functional group R ₁ . And at least one selected from the group consisting of polyurethane chain, polyurea chain, polyurethane urea chain, polyolefin chain (particularly polydiene chain), silicone chain, polyester chain, polyether chain, polyamide chain and 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 of a product 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 A combination with a group having a heavy bond is exemplified.

Polymer and having a polyurethane chain having a reactive functional group R ₂ is a polyisocyanate compound, a long chain polyol compound (a long-chain polyol) and a chain extender used according to need and with other isocyanate-reactive compounds Can be obtained by a conventional method.

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.

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.

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.

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.

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.

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. .

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 (meth) acrylate, (meth) acrylic acid alkyl ester [for example, (meth) acrylic acid C _1-20 alkyl ester, etc.] is preferably used.

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.

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.

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.

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 .

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, (meth) acryloyloxyethyl isocyanate or the like can be used as the compound having the energy ray-curable group A ₁ and the reactive functional group R ₁ .

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.

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.

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.

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.

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 Multifunctional 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 It is also possible to use functional monomers). “EO” represents ethylene oxide, and “PO” represents propylene oxide.

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.

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 hardly extensible polymer portion 3, the same kind of monomer as the polymer constituting the hardly extensible polymer portion as the curable monomer M (particularly, It is also preferable to use the same monomer).

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, 10% by weight or more (10 to 100% by weight), preferably 40% by weight or more (40 to 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). In addition, (meth) acrylic acid C _1-20 alkyl ester as curable monomer M, (meth) acrylic acid ester having an alicyclic group such as isobornyl (meth) acrylic acid, carboxyl group such as (meth) acrylic acid Alternatively, an acid anhydride group-containing monomer or a hydroxyl group-containing monomer such as 2-hydroxyethyl (meth) acrylate may be used. In this case, the amount of (meth) acrylic acid ester having a cycloaliphatic group such as isobornyl (meth) acrylate, a carboxyl group or acid anhydride group-containing monomer, and a hydroxyl group-containing monomer is used with respect to the entire curable monomer. These can be selected, for example, from the range of 0 to 90% by weight (0.1 to 90% by weight), preferably 0 to 50% by weight (about 0.1 to 50% by weight), and 1 to 45% by weight. A degree may be used.

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.

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 system photopolymerization initiator or the like is used.

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.

In the case where the energy beam curable groups A ₁ and A ₂ are cationic polymerizable groups, a known or commonly used 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.

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.

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.

[Refractory polymer part]
In the present invention, the material constituting the hardly extensible polymer portion 3 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.

As the hardly extensible polymer part 3, for example, (i) a monomer having a Tg of homopolymer of 5 ° C. or higher (more preferably 15 ° C. or higher, more preferably 50 ° C. or higher) [particularly, (meth) acrylic monomer] A polymer containing 50% by weight or more (more preferably 60% by weight or more, and still more preferably 80% by weight or more) based on the total structural unit of the polymer [for example, Tg is 5 ° C. or more, preferably Polymer material containing polymer of 15 ° C. or higher (particularly acrylic polymer)], (ii) Configuration derived from polyfunctional monomer having two or more curable groups (radical polymerizable group, cationic polymerizable group) in the molecule A polymer containing 50% by weight or more (more preferably 60% by weight or more, and still more preferably 80% by weight or more) of the unit with respect to all structural units of the polymer In particular, the structural unit derived from a polyfunctional monomer having 2 or more radically polymerizable groups in the molecule (particularly an acrylic polyfunctional monomer) is 50% by weight or more (more preferably) based on the total structural unit of the polymer. 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.

In the case of (i), the polymer material constituting the hardly extensible polymer part of the polymer containing 50% by weight or more of the structural unit derived from the monomer whose Tg of the homopolymer is 5 ° C. or higher with respect to all the structural units of the polymer The ratio to the whole 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), it constitutes a hardly extensible polymer portion 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 with respect to all the structural units of the polymer. The proportion of 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 (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.

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.

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 the hardly extensible polymer portion 3 can be imparted with difficulty extensibility and hardness, 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 column 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.

The “polymer” in the filler-containing polymer material is not particularly limited, and the polymer exemplified as the polymer constituting the easily extensible polymer matrix and the (i) homopolymer exemplified as the polymer constituting the hardly extensible polymer portion 3. (Ii) Curability exemplified as a polymer comprising 50% by weight or more of a structural unit derived from a monomer having a polymer Tg of 5 ° C. or higher, and a polymer constituting the hardly extensible polymer part 3 (Iv) Tensile, which will be described later, as a polymer comprising 50% by weight or more of a structural unit derived from a polyfunctional monomer having two or more groups in the molecule with respect to all the structural units of the polymer, and a polymer constituting the hardly extensible polymer part 3 Any of polymers having an elastic modulus of 0.1 MPa or more may be used. The polymer may be an energy ray curable polymer.

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.

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.

The hardly extensible polymer part 3 includes a polymer part formed by converting a precursor of a polymer material constituting the hardly extensible polymer part 3 into the polymer material, and a solvent in the solution or dispersion containing the polymer material. Any of a polymer part formed by drying and removing, a polymer part formed by melting and cooling the polymer material, and the like may be used.

The hardly extensible polymer portion 3 is composed of a polymer material containing a polymer containing (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. In this case, for example, after arranging a monomer component containing 50% by weight or more of the monomer having a Tg of 5 ° C. or more of the homopolymer at a predetermined portion of the easily extensible polymer base material forming material layer, energy rays Can be formed by 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.

A polymer material containing a polymer containing 50% by weight or more of a structural unit derived from a polyfunctional monomer having (ii) two or more curable groups in the molecule, based on the total structural unit of the polymer. For example, after arranging a monomer component containing the polyfunctional monomer in an amount of 50% by weight or more of the entire monomer at a predetermined portion of the easily stretchable polymer base material forming material layer, irradiation with energy rays and 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.

When forming the hardly extensible polymer part 3, 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.

When the hardly extensible polymer part 3 is composed of the above-mentioned (iii) filler-containing polymer, a dispersion containing a filler (an aqueous dispersion, an organic solvent) at a predetermined portion of the easily extensible polymer base material forming material layer After the dispersion or the like is disposed, the hardly extensible polymer portion 3 can be formed by drying and removing the solvent in the dispersion. In this case, the hardly extensible polymer portion 3 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 filler and a monomer (such as an energy ray-curable monomer) that can be derived into a polymer that should form a hardly extensible polymer portion or a partial polymer thereof are necessary at a predetermined portion of the easily extensible polymer base material forming material layer. The hard-to-extend polymer part 3 can be formed by polymerizing the monomer or a partial polymer thereof after arranging a mixed solution containing a solvent according to the above. Furthermore, after arranging a mixed liquid containing a filler, a pre-crosslinking polymer that can be induced by crosslinking to a polymer that should constitute a hardly extensible polymer portion, and a crosslinking agent at a predetermined portion of the material layer for forming an easily stretchable polymer base material A hardly extensible polymer part can be formed by crosslinking the polymer before crosslinking. 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. Thus, a hardly extensible polymer portion can be formed at the same time. In this case, the hardly extensible polymer portion 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 difficulty extensible polymer part to form, the intensity | strength of the difficult extensible polymer part desired, etc. For example, the filler content in the hardly extensible polymer part 3 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 80% by weight. The lower limit is preferably 1% by weight, more preferably 5% by weight, and particularly preferably 10% by weight.

When the hardly extensible polymer part 3 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 polymer thereof is used. The hardly extensible polymer portion 3 can be formed by polymerizing, or by curing or cross-linking a polymer that can be induced by curing or cross-linking to the polymer, or a polymer before cross-linking.

For the hardly extensible polymer part 3, 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, a metal alkoxide is used as necessary. 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, tackifying resin (Rosin derivatives, polyterpene resins, petroleum resins, oil-soluble phenols, etc.), anti-aging agents, fillers, colorants (pigments and dyes, etc.), UV absorbers, antioxidants, plasticizers, softeners, surfactants, Additives such as antistatic agents may be included within the range not impairing the properties of the present invention.

Of the materials constituting the hardly extensible polymer part, the polymer is the same as the polymer constituting the easily extensible polymer matrix from the viewpoint of the integrity and adhesion of the easily extensible polymer matrix and the hardly extensible polymer member. Or 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 stretchable polymer matrix in the main chain or side chain.

More specifically, as a preferred combination of the polymer constituting the easily extensible polymer matrix and the polymer constituting the hardly extensible polymer portion, a combination of polyurethane polymers, a combination of polyurea polymers, a polyurethane urea polymer 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 polymers The combination of these is 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.

Among these, as a preferable combination of the polymer constituting the easily extensible polymer matrix and the polymer constituting the hardly extensible polymer portion, a combination of polyurethane polymers, a combination of polymers having a polyurethane chain, and a combination of polystyrene polymers A combination, 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.

[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: Step of Disposing a Non-Extensible Polymer Portion Forming Material to a Predetermined Part of the Highly Stretchable Polymer Base Material Forming Material Layer Step C: Forming a Stretchable Polymer Portion The stretchable polymer base material forming material layer in which the material for the material is arranged 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, and is easily stretchable. Process for obtaining a sheet-like extensible organic base material in which a hardly extensible polymer portion is partially and integrally formed in a polymer base material

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.

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.

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.

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.

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.

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.

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.

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.

Next, in Step B, a hardly extensible polymer part forming material is disposed at a predetermined portion of the easily extensible polymer base material forming material layer. The material for forming a hardly extensible polymer portion may be any of solid, liquid, gas, solution, dispersion and the like. As the material for forming the hardly extensible polymer part, a material (polymer material) (b) precursor constituting the hardly extensible polymer part (for example, an energy ray curable composition), a material constituting the hardly extensible polymer part (Polymer material) (b) itself may be a solution or dispersion containing the material (polymer material) (b) constituting the hardly extensible polymer part.

In step B, as the material for forming the hardly extensible polymer part, the hardly extensible polymer part is composed of the structural unit derived from the monomer (i) whose Tg of the homopolymer is 5 ° C. or more with respect to all the structural units of the polymer. The monomer component containing 50% by weight or more of the monomer having a Tg of 5 ° C. or higher, or a partial polymer thereof. A curable composition (such as an energy beam curable composition) can be used. This curable composition usually contains a polymerization initiator.

(Ii) a polymer material containing a polymer containing (ii) 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 constituting, a curable composition containing a monomer component containing 50% by weight or more of a polyfunctional monomer having two or more of the curable groups in the molecule, or a partially polymerized product thereof as a material for forming a hardly extensible polymer part A thing (energy beam curable composition etc.) can be used. This curable composition usually contains a polymerization initiator.

When the hardly extensible polymer part is composed of the above (iii) filler-containing polymer material, as the hardly extensible polymer part forming material, a dispersion containing a filler (an aqueous dispersion, an organic solvent dispersion, etc.), A curable composition comprising the filler and a monomer (such as an energy ray-curable monomer) that can be derived into a polymer that should constitute the hardly extensible polymer part or a partial polymer thereof, and a filler and the hardly extensible polymer part A mixed liquid of a polymer before curing or crosslinking that can be induced by curing or crosslinking and a crosslinking agent, or a filler alone (powder) can be used.

In the case where the hardly extensible polymer part is composed of (iv) a polymer material having a tensile elastic modulus of 0.1 MPa or more, the polymer having the tensile elastic modulus of 0.1 MPa or more is used as the hardly extensible polymer part forming material. A curable composition containing an inducible monomer (such as an energy beam curable monomer) or a partial polymer thereof (such as an energy beam curable composition) can be used.

A method (means) for disposing the hardly extensible polymer part forming material at a predetermined portion of the easily extensible polymer base material forming material layer is not particularly limited. For example, (1) forming the hardly extensible polymer part Coating, dripping, placing, driving or placing the material on the predetermined portion of the easily stretchable polymer base material forming material layer so that the cross-sectional shape of the difficultly stretchable polymer portion becomes a desired shape from above. A method of printing, (2) the cross-sectional shape of the hardly extensible polymer portion is a desired shape in a predetermined position of the easily extensible polymer base material forming material layer in a liquid form with the material for forming the hardly extensible polymer portion (3) On the support different from the support on which the material layer for forming the easily stretchable polymer base material is formed, the material for forming the hardly stretchable polymer portion is made difficult to stretch. Coating, so that the cross-sectional shape of the polymer part is the desired shape Lower, placing 置又 prints, and a method of transferring it to the easily extensible polymer matrix forming material layer.

When the hardly stretchable polymer part forming material 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, a predetermined temperature within the range of 10 to 40 ° C. In particular, at 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. s. If this viscosity is too low, it will be difficult to obtain a difficult-to-extend polymer part having a desired shape. Conversely, if it is too high, the coating workability will tend to deteriorate.

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.

By selecting and adjusting the kind, amount of use, viscosity, etc. of the material for forming the hardly extensible polymer portion to be arranged at a predetermined portion of the easily extensible polymer base material forming material layer, the size of the hardly extensible polymer portion ( The size and height in the surface direction can be controlled. In the case of forming a plurality of hardly extensible polymer parts, the hardly extensible polymer part forming material is applied at an appropriate interval. In addition, the shape of a hardly extensible polymer part is controllable by using the means which regulates the dripping and injection | pouring location of the material for forming a hardly extensible polymer part. The drop method is often used when the size of the hardly extensible polymer portion is relatively large, and the injection method is often used when the size of the hardly extensible polymer portion 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 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.

In addition, when using the energy-beam curable composition which is a precursor of the material (b) which comprises a difficult-to-extend polymer part as a material for forming a hardly-extensible polymer part, this energy-ray-curable composition (application | coating) Liquid) at the predetermined site of the easily stretchable polymer base material forming material layer, the energy ray curable composition (coating liquid) diffuses to the periphery (the easily stretchable polymer base material forming material layer). In order to suppress, it is preferable to contain a polymer in the energy beam curable composition. In particular, when a large number of hardly extensible polymer parts 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 material layer, energy rays are applied. When moving to the irradiation process, the coating solution diffuses to the peripheral part (bleeds) over time at the place where the coating solution is initially placed, and cures in that state, and is difficult to stretch in the desired shape and size. A polymer part may not be obtained, or the outline of a hardly extensible polymer part may become unclear. 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). ), And even when a large number of hardly extensible polymer portions are formed, it is possible to form a hardly extensible polymer portion having a uniform shape and size and having a clear outline. 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. 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.

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 hardly extensible polymer portion, and constitutes the easily extensible polymer base material. Any of the polymer exemplified as the polymer and the polymer exemplified as the polymer constituting the hardly extensible polymer portion may be used, but the integrity of the easily extensible polymer base material and the hardly extensible polymer portion, adhesion, etc. From the viewpoint, the same type of polymer as the polymer constituting the easily stretchable polymer matrix, or the same polymer chain as the polymer chain (main chain or side chain) of the polymer constituting the easily stretchable polymer matrix A polymer having a chain is preferred.

As the energy ray curable composition (coating liquid), the stretchable polymer 60 seconds after dropping the coating liquid onto the material layer for forming an easily stretchable polymer base material (drop amount: about 0.03 μL). The coating liquid on the base material forming material layer preferably has a diameter of 1.2 times or less, more preferably 1.15 times or less of the diameter of the coating liquid immediately after dropping. In addition, the diameter of the coating solution on the easily stretchable polymer base material forming material layer 120 seconds after the coating solution is dropped onto the easily stretchable polymer base material forming material layer (drop amount: about 0.03 μL). However, what becomes 1.4 times or less with respect to the diameter of the coating liquid immediately after dripping is preferable, and what becomes 1.3 times or less is more preferable. 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 number of hardly extensible polymer portions are formed (for example, formed in a regular pattern) may not be obtained.

After coating, dripping, placing, driving in, printing, pouring or transferring of the hardly stretchable polymer part forming material, if necessary, the hardly stretchable polymer part forming material is easily stretchable polymer base material forming material. Let stand until it penetrates, migrates and settles to the desired depth of the layer.

Then, in step C, reaction, solvent removal treatment, and melting / cooling treatment (hot melt) are performed on the easily stretchable polymer base material forming material layer in which the hardly stretchable polymer portion forming material is arranged at a predetermined site. The sheet-like extensible organic base material in which the hardly extensible polymer portion is partially and integrally formed in the easily extensible polymer base material is obtained by performing at least one treatment selected from (treatment).

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 hardly stretchable polymer part forming material are melted.

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 hardly stretchable polymer part forming material used in step B is not particularly limited and can be arbitrarily combined. . 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 a case of using a hot-melt material [polymer (a) alone], the hardly extensible polymer part forming material may be a solvent. Materials (polymer solutions), dispersion materials (polymer emulsions, etc.), energy ray curable materials [polymeric liquid precursors (syrups, etc.)], solids [hot melt materials (polymer alone), fillers (powder) Etc.] can be used. More specifically, the form of the easily stretchable polymer base material and the hardly stretchable polymer part forming material is a combination of energy ray curable materials (energy ray curable syrups, etc.), solvent-based materials Combinations of (solutions), dispersion materials (emulsions, etc.), hot melt materials, and combinations of solvent materials (solutions) and dispersion materials (emulsions, etc.) (in no particular order) ), Combinations of hot-melt materials and solvent-based materials (solutions) (in no particular order), combinations of hot-melt materials and dispersion-based materials (emulsions, etc.) (in no particular order), solvent-based materials (solutions) and fillers Any of a combination of (powder), a dispersion material (emulsion, etc.) and a filler (powder), a hot melt material and a filler (powder), etc. may be used. In step C, a sheet-like extensible organic base material in which a hardly extensible polymer portion is partially and integrally formed in an easily extensible polymer base material by performing a treatment suitable for the form of each material. Obtainable.

In addition, in the vicinity of the interface between the hardly extensible polymer portion and the easily extensible polymer base material portion, a sheet-like extensible organic base material having gradation regarding composition and / or physical properties (elongation characteristics, hardness, etc.) Use materials that are common or similar to each other (solvents, monomers, etc.) or materials that are compatible with each other (solvents, monomers, etc.) as materials for forming extensible polymer base materials and materials for forming difficult-to-extend polymer parts. Can be manufactured. Specifically, for example, by forming both the easily stretchable polymer base material forming material and the hardly stretchable polymer part forming material with a material (such as a polymer liquid precursor) containing an acrylic monomer, A 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 forming material of each part [hardly extensible polymer part, easily extensible polymer base material part]. The degree of gradation (width) can be adjusted by the type and amount of the easily stretchable polymer base material forming material and the hardly stretchable polymer part forming material (solvent, monomer, etc.). Further, as described above, in the case of using an energy ray curable composition as the material for forming a hardly extensible polymer part, when a polymer is blended in the energy ray curable composition, the type and amount of the polymer The gradation level (width) can be adjusted by the weight average molecular weight or the like.

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) 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 hardly extensible polymer portion is disposed at a predetermined portion of the extensible polymer base material forming material layer, and in step C, the material (b) The energy beam curable composition, which is a precursor of the above, is irradiated to the easily stretchable polymer base material forming material layer arranged at a predetermined site, and the two energy beam curable compositions are cured to easily stretch. Of obtaining a sheet-like extensible organic base material in which a hardly extensible polymer portion is partially and integrally formed in an extensible polymer base material.

(II) In step A, an easily extensible polymer matrix-forming material layer is formed on the support using a solution or dispersion containing the polymer (a). In step B, the easily extensible polymer matrix is formed. The material (b) [for example, polymer, filler (powder), etc.] constituting the hardly extensible polymer portion or a solution or dispersion containing the material (b) is disposed at a predetermined part of the material layer for use, and the process C In the above, a dry removal treatment of the solvent on the material layer for forming an easily stretchable polymer base material in which the material (b) constituting the hardly stretchable polymer portion or a solution or dispersion containing the material (b) is disposed at a predetermined site To obtain a sheet-like extensible organic base material in which a hardly extensible polymer portion is partially and integrally formed in an easily extensible polymer base material.

(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 predetermined layer of the easily stretchable polymer base material forming material layer is determined. The material (b) [for example, polymer, filler (powder), etc.] constituting the hardly extensible polymer part is arranged in the part, and in step C, the material (b) constituting the hardly extensible polymer part is set to a predetermined part. The material layer for forming an easily stretchable polymer matrix disposed on the substrate is subjected to a melting / cooling process (hot melt treatment), and the hardly stretchable polymer part is partially in the easily stretchable polymer matrix (A). A method for obtaining an integrally formed sheet-like extensible organic substrate.

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, Step of disposing (containing) an energy ray-curable composition for forming a hardly extensible polymer portion so that the cross-sectional shape of the hardly extensible polymer portion becomes a desired shape Step C1: For forming the hardly extensible polymer portion An energy beam curable composition for forming a hardly extensible polymer part and an easily extensible material are formed by irradiating the energy ray curable composition layer for forming an easily extensible polymer base material provided with the energy ray curable composition with energy rays. An energy ray-curable composition layer for forming a polymer matrix is cured to form a sheet-like material having extensibility in which a hardly extensible polymer portion is partially and integrally formed in an easily extensible polymer matrix. Obtaining a substrate

This method is a specific example of the above aspect (I), and FIG. 4 is a schematic explanatory view (cross-sectional view) thereof. 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.

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.

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.

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.

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.

The thickness of the energy-beam curable composition layer 20 for forming the easily stretchable polymer base material is the same as described above.

In Step B1, the energy beam curable composition 30 for forming a hardly extensible polymer part is disposed (included) in the energy beam curable composition layer 20 for forming an easily extensible polymer base material.

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.

The energy ray-curable composition 30 for forming a hardly extensible polymer part is preferably syrup-like. From the viewpoint of workability and the like, the viscosity of the energy beam curable composition 30 for forming a hardly extensible polymer part is determined at a coating temperature (for example, a predetermined temperature within a range of 10 to 40 ° C., particularly 25 ° C.). For example, the upper limit is preferably 10 to 50000 mPa · s, and 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 hardly extensible 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 hardly extensible polymer portion is not particularly limited. For example, a method using an intaglio coating machine such as a gravure coater, energy ray curable for forming a hardly extensible polymer portion. The support etc. which apply | coated and dripped the composition 30 and the method of bonding the energy-beam curable composition layer 20 for extensible polymer base material formation etc. can be used.

By adjusting the amount and viscosity of the energy ray-curable composition 30 for forming a hardly extensible polymer part, the size (size and height in the plane direction) of the hardly extensible polymer part 3 after curing can be controlled. . When a plurality of the hardly extensible polymer portions 3 are formed, the energy ray curable composition 30 for forming the hardly extensible polymer portions is applied at an appropriate interval. In addition, the shape of the hard-extensible polymer part 3 after hardening is controllable by using the means which regulates the addition or injection | pouring location of the energy-beam curable composition 30 for hard-extensible polymer part formation.

In step C1, the energy beam curable composition layer 20 for forming an easily stretchable polymer base material containing the energy beam curable composition 30 for forming a hardly stretchable polymer part is irradiated with an energy beam, and the difficult stretch is performed. The energy ray-curable composition 30 for forming the extensible polymer part and the energy ray-curable composition layer 20 for forming the easily extensible polymer base material are cured, and the hardly extensible polymer part 3 is partially in the easily extensible polymer base material 2. A sheet-like organic substrate having extensibility formed integrally and integrally is obtained.

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.

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.

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.

An easily extensible polymer base material containing the hardly extensible polymer portion forming energy ray curable composition 30 for the purpose of preventing curing inhibition by oxygen during the irradiation of energy rays or for the purpose of smoothing the surface. The cover film 5 may be laminated on the surface of the 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.

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) Then, as shown in FIG. 4D, the cover film 5 is laminated, and then, as shown in FIG. 4E, the film 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 beam curable composition layer for forming an easily extensible polymer base material, and 300 is a partially cured energy beam curable composition for forming an inextensible polymer portion.

In the case where the energy beam irradiation is performed in one 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 .

After curing the hardly extensible polymer part forming energy beam curable composition 30 and the easily extensible polymer matrix forming energy beam curable composition layer 20 as described above, it is shown in FIG. As necessary, the cover film 5 and the support 4 are peeled off as necessary, and 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.

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 hardly extensible polymer part or a filler (powder) constituting the hardly extensible polymer part is added to a predetermined part of the material layer for forming the extensible polymer base material. The step of arranging (including) by coating, dripping, placing, driving in, printing, etc. so that the cross-sectional shape of the part A becomes a desired shape Step C2: containing a polymer constituting the hardly extensible polymer part In the easily stretchable polymer base material by drying the easily stretchable polymer base material forming material layer in which the solution or dispersion liquid or the filler (powder) constituting the hardly stretchable polymer portion is disposed to remove the solvent Difficult to stretch Step Rimmer unit to obtain a partially and sheet-like organic substrate having an integrally formed extensibility

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 is 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 contains a polymer constituting the hardly extensible polymer part. The filler (powder) which comprises a solution or a dispersion liquid, or a hardly extensible polymer part is shown.

Reference numerals

1, 2, 3, and 4 are the same as described above.

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 hardly extensible polymer part is placed in a predetermined part of the extensible polymer base material forming material layer so that the cross sectional shape of the hardly extensible polymer part A becomes a desired shape. Step of placing (containing) by placing or dropping (melting) or the like Step C3: A material layer for forming an easily stretchable polymer base material provided with a polymer or filler (powder) constituting the hardly stretchable polymer portion. Step of obtaining a sheet-like organic base material having extensibility in which a hardly extensible polymer portion is partially and integrally formed in an easily extensible polymer base material after being heated and melted and then cooled.

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 indicates a sheet (material layer for forming an easily extensible polymer base material) made of a polymer constituting the easily extensible polymer base material, and reference numeral 32 indicates a polymer or filler (powder) constituting the hardly extensible polymer portion.

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). 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.

Moreover, in the said sheet-like extensible organic base material, since it is possible to suppress the elongation in a specific direction by the hardly extensible polymer portion, the medical taping base material, the medical wound covering base material, the follow-up to the specific shape It can be used for members that require high performance (workability). Furthermore, since strength in a specific direction can be imparted, it can be used as a base material for seam joining (for example, a car, an airplane, etc.). Furthermore, since the elongation can be concentrated in a specific portion, it can be used as a dicing tape that can be efficiently extracted or a base material thereof. Moreover, since the handleability of a thin film base material can be improved, it can utilize for a medical thin film base material (film dressing) etc. Furthermore, since an adherend can be strengthened, it can be utilized as a reinforcing member (glass cloth substitute) for a resin plate or a steel plate. Moreover, it can utilize as a shrink film which tracks a shape with a heat | fever by mix | blending a shape memory polymer with the said hardly extensible polymer part.

Further, the hardly extensible polymer portion is continuously formed (penetrated) from one surface of the sheet-like extensible organic base to the other surface, and the hardly extensible polymer portion is a conductive filler. Can be used, for example, as an anisotropic conductive sheet, a dicing tape capable of on-chip continuity test, or a base material thereof. Further, the hardly extensible polymer portion is continuously formed (penetrated) from one surface of the sheet-like extensible organic base material to the other surface, and the hardly extensible polymer portion is thermally conductive. When it contains a filler, for example, it can be used as a heat transfer sheet that can be extended or contracted.

[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.

15 (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 substrate A shown in (1) of FIG. 15 is an extension in which the hardly extensible polymer portion 3 is partially and integrally formed in the easily extensible polymer base material 2. It is an example which has the functional layer 6 in one surface of the sheet-like organic base material (sheet-like extensible organic base material) 1 which has property. The multifunctional sheet-like extensible organic base A shown in (2) of FIG. 15 is an extension in which the hardly extensible polymer portion 3 is 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 property. The multifunctional sheet-like extensible organic base material A shown in (3) of FIG. 15 is an extension in which the hardly extensible polymer portion 3 is partially and integrally formed in the easily extensible polymer base material 2. This is an example in which the sheet-like organic base material (sheet-like extensible organic base material) 1 itself having a property has other functions and characteristics other than extensibility or stretchability.

[Adhesive sheet-like extensible organic substrate]
As a sheet-like extensible organic substrate having adhesiveness, (i) a sheet-like organic substrate having extensibility, in which a hardly extensible polymer portion is partially and integrally formed in an easily extensible polymer matrix The pressure-sensitive adhesive layer has a pressure-sensitive adhesive layer (temperature 23 ° C., humidity 65% RH, tensile speed 300 mm / min, peel angle 180 °, vs. SUS304) of 0.1 N. / Sheet-like extensible organic base material of 20 mm or more, (ii) sheet-like organic base material having extensibility, in which a hardly extensible polymer portion is partially and integrally formed in an easily extensible polymer base material 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 substrate is 0.1 N / 20 mm or more. Some sheet-like extensibility Machine base materials. The sheet-like extensible organic base material of (ii) is a sheet-like organic base material having extensibility in which a hardly extensible polymer portion is partially and integrally formed in an easily extensible polymer base material (particularly, , An easily extensible polymer base material) itself has adhesiveness.

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 hardly extensible polymer portion formed in the film does not stretch or hardly stretches. For this reason, the design in which a shape is desired not to change can be given to a difficulty extensible polymer part, or another member can be fixed and hold | maintained. Moreover, since this sheet-like extensible organic base material has adhesiveness, it can be attached to any adherend.

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. 15, the functional layer 6 is an adhesive layer. In the multifunctional sheet-like stretchable organic substrate A shown in (2) of FIG. 15, 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.

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.

On the other hand, the sheet-like extensible organic base material having adhesiveness according to the present invention is an extensible sheet-like organic material in which a hardly extensible polymer portion is partially and integrally formed in an easily extensible polymer matrix. In the case of forming a laminate having an adhesive layer on at least one surface of the substrate, the adhesive strength of the adhesive layer (temperature 23 ° C., humidity 65% RH, tensile speed 300 mm / min, peel angle 180 ° 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.

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.

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.

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.

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 acid 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.

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.

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.

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.

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.

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, for example, 5 to 3000 μm, the lower limit is preferably 10 μm, and the upper limit is preferably 500 μm.

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.

An adhesive sheet-like extensible organic substrate is an electronic product (or an extensible member having adhesiveness and a shape-invariable portion) (or an elastic member having adhesiveness 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 household 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 extensible organic group in which a hardly extensible polymer portion is partially and integrally formed in an easily extensible polymer matrix containing a weathering agent Materials. In the multifunctional sheet-like extensible organic base material A shown in (3) of FIG. 15, the sheet-like organic base material 1 itself having extensibility corresponds to that having weather resistance.

When such a sheet-like stretchable organic base material is stretched in one direction (plane direction), the part of the easily stretchable polymer base material is stretched, but is the partially formed hardly stretchable polymer part not stretched? Or little elongation. For this reason, the design in which a shape is desired not to change can be given to a difficulty extensible polymer part, or another member can be fixed and hold | maintained. Moreover, since this sheet-like extensible organic base material contains a weathering agent, it can be used for a long time outdoors.

In the sheet-like extensible organic base material having the weather resistance, an easily extensible polymer base material (2 contains a weathering agent. The weathering agent is not particularly limited, and a known weathering agent can be used. The weathering agent is preferably at least one selected from ultraviolet absorbers and antioxidants, which can be used alone or in combination of two or more.

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 weatherproofing agent, and 2 or more types may be used together.

Examples of 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.

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.

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.

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.

Examples of the cyanoacrylate compound include alkyl-2-cyanoacrylate, cycloalkyl-2-cyanoacrylate, alkoxyalkyl-2-cyanoacrylate, alkenyl-2-cyanoacrylate, alkynyl-2-cyanoacrylate, and the like.

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.

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.

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.

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.

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-piperidi 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.

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 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 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 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 4% by weight, still more preferably 3% by weight.

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.

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 hardly extensible polymer portion at a predetermined portion of the easily extensible polymer base material forming material layer, the liquid in the easily extensible polymer base material forming material layer It can be formed by converting the precursor to the desired polymer.

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 hardly extensible polymer portion 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. It can also be formed by removing.

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 disposing a forming material for the hardly extensible polymer part at a predetermined portion of the easily extensible polymer base material forming material layer.

In the sheet-like extensible organic base material having weather resistance, the material constituting the hardly extensible polymer portion 3 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.

The hard-extensible polymer part 3 may contain a weathering agent, like the easy-extensible polymer base part 2. By adding a weathering agent to the hardly extensible polymer portion (hardly extensible portion), deterioration of the sheet-like extensible organic base material outdoors can be more significantly suppressed. The same weathering agent as described above can be used.

The content (total amount) of the weathering agent in the hardly extensible polymer part 3 is, for example, 0.001 to 10% by weight with respect to the whole hardly extensible polymer part (difficult part). 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 whole hardly stretchable polymer part (hardly stretchable part) 3, and the lower limit is preferably 0. 0.01% by weight, more preferably 0.1% by weight, still more preferably 0.3% by weight, and 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 whole of the hardly extensible polymer part (hardly stretchable part) 3, and the lower limit is preferably 0.01. 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 hardly extensible polymer portion 3, 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, wherein a weathering agent is blended in the material for forming an easily extensible polymer base 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, poultice base fabrics, and the like.

[Sheet-like extensible organic base material with unpleasant odor prevention]
As a sheet-like extensible organic base material having an unpleasant odor prevention property (or having a pleasant odor), (i) a hardly extensible polymer portion is partially and integrally formed in an easily extensible polymer matrix. A sheet-like organic base material having a stretchability, wherein the stretchable polymer base material and / or the hard-stretchable polymer portion contains a fragrance ("sheet of the first aspect" (Ii) a sheet-like organic group having extensibility in which a hardly extensible polymer portion is partially and integrally formed in an easily extensible polymer base material. A sheet-like extensible organic base material having a deodorizing layer on at least one surface of the material (sometimes referred to as “sheet-like extensible organic base material of the second embodiment”), (iii) an easily extensible polymer base material Partially and integrally shaped non-extensible polymer part inside A sheet-like extensible organic substrate comprising a sheet-like organic substrate having extensibility, 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 And a sheet-like extensible organic substrate (sometimes referred to as “sheet-like extensible organic substrate of the third embodiment”).

When such a sheet-like stretchable organic base material is stretched in one direction (plane direction), the part of the easily stretchable polymer base material is stretched, but is the partially formed hardly stretchable polymer part not stretched? Or little elongation. For this reason, the design in which a shape is desired not to change can be given to a difficulty extensible polymer part, or another member can be fixed and hold | maintained. Moreover, since this sheet-like extensible organic base material suppresses the generation of unpleasant odors, for example, adverse effects caused by substances that cause the unpleasant odors (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.

As a representative example of a sheet-like extensible organic base material having an unpleasant odor preventing 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. 15, the functional layer 6 is a deodorizing layer, 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 has an easily extensible polymer base material and / or a hardly extensible polymer portion (one or both of the easily extensible polymer base material and the hardly extensible polymer portion). Contains 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.

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

Examples of the fragrance classified as (1) include alcohols having 6 to 12 carbon atoms [for example, cis-3-hexenol, 3,3,5-trimethylhexanol and the like], 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] and the like. In addition, the organic chain | strand-shaped 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.

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.

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-shi , 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.

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.

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.

When a fragrance is contained in the difficultly stretched part (hardly stretchable polymer part), the content (total amount) of the fragrance in the difficultly stretched part is not particularly limited, but constitutes a difficultly stretched part (hardly stretchable polymer part). For example, 1.0 × 10 −5 to 1.0 × 10 −1 parts by weight with respect to 100 parts by weight of the 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. 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.

In the sheet-like extensible organic base material of the first aspect, the easily extensible polymer base material and / or the hardly extensible polymer portion contains a fragrance, so that the generation of unpleasant odor due to the fragrance of the fragrance is reduced. . 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 according to the second aspect is a sheet-like organic base material having extensibility in which a hardly extensible polymer portion 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).

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.

As the deodorant, a known or conventional deodorant can be used, and 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 expresses a very excellent deodorizing property, and as a result, generation of unpleasant odor from the sheet-like extensible organic base material is effective. There is a tendency to be suppressed or suppressed.

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.

As the metal component in the deodorant (inorganic powder carrying a 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.

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. .

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.

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.

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.

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.

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.

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.

The occurrence of unpleasant odor is reduced by having the deodorizing layer in the sheet-like extensible organic base material of the second aspect. The sheet-like extensible organic substrate of the second aspect is the same as the sheet-like extensible organic substrate of the first aspect. Any one or both of the polymer base material and the hardly extensible polymer part) 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.

The sheet-like extensible organic base material according to the third aspect is a sheet-like organic base material having extensibility in which a hardly extensible polymer portion is partially and integrally formed in an easily extensible polymer base material. The sheet-like extensible organic base material contains, and the amount of monomer generated when the sheet-like extensible organic base material 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.

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). This is derived from the residual monomer (residual monomer) contained in the polymer having, and the residual monomer (residual monomer) contained in the polymer (polymer material) constituting the hardly extensible polymer portion. 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 may be used. 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 according to the third aspect includes an amount of monomer 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.

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.

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.) are optimized to increase the monomer reaction rate (polymerization rate). It is done.

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. The sheet-like extensible organic substrate of the third aspect is similar to the sheet-like extensible organic substrate of the first aspect in that the easily extensible polymer base material and / or the hardly extensible polymer portion contains a fragrance. You may contain. 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.

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.

[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 color printing properties, (i) an extensible sheet-like organic group in which a hardly extensible polymer portion is partially and integrally formed in an easily extensible polymer matrix A sheet-like material in which an easily extensible polymer matrix and / or a hardly extensible polymer portion (one or both of the easily extensible polymer matrix and the hardly extensible polymer portion) contains a dye or a pigment An extensible organic base material, (ii) at least one surface of an extensible sheet-like organic base material in which a hardly extensible polymer portion is partially and integrally formed in an easily extensible polymer base material A sheet-like extensible organic substrate having a layer, (iii) at least an extensible sheet-like organic substrate in which a hardly extensible polymer portion is partially and integrally formed in an easily extensible polymer matrix Print layer on one side Sheet elongation organic substrate having the like.

When such a sheet-like stretchable organic base material is stretched in one direction (plane direction), the part of the easily stretchable polymer base material is stretched, but is the partially formed hardly stretchable polymer part not stretched? Or little elongation. For this reason, the design in which a shape is desired not to change can be given to a difficulty extensible polymer part, or another member can be fixed and hold | maintained. In addition, this sheet-like extensible organic base material is preferably used for applications that require designability (designability, etc.), for example, because designability is imparted or designability is easy to impart. it can.

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. 15, the functional layer 6 is a colored layer or a print layer. In the multifunctional sheet-like extensible organic base material A shown in (2) of FIG. 15, 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. 15, the sheet-like organic substrate 1 having extensibility itself (easily extensible) Examples thereof include those in which the polymer base material 2 and / or the hardly extensible polymer part 3) are colored.

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.

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.

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.

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.

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.

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.

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 hardly extensible polymer part 3 may contain a dye or a pigment, like the easily extensible polymer base part 2. The hardly extensible polymer part may contain both a dye and a pigment. Thereby, the hardly extensible polymer part is colored, and excellent designability is imparted to the sheet-like extensible organic base material of the present invention. The easily extensible polymer matrix part and the hardly extensible polymer part may be the same color, for example, the easily extensible polymer matrix part and the hardly extensible polymer part may be colored in different colors, It is also possible to impart even more excellent design properties by coloring the hardly extensible polymer portions in 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.

The content (total amount) of the dye in the hardly extensible polymer part 3 is, for example, 0.001 to 50% by weight with respect to the whole hardly extensible polymer part 3. 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 hardly extensible polymer part 3 is, for example, 0.001 to 50% by weight with respect to the whole hardly extensible polymer part 3. 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). In the sheet-like extensible organic substrate of the aspect (i), the easily extensible polymer base material and / or the hardly extensible polymer portion 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.

The sheet-like extensible organic base material of the aspect (ii) is a sheet-like organic base material having extensibility in which a hardly extensible polymer portion is partially and integrally formed in an easily extensible polymer base material. It is a sheet-like extensible organic base material which has a colored layer in at least one side (one side or both sides).

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.

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.

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.

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.

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.

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).

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.

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.

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. In addition, the sheet-like extensible organic base material of the aspect of (ii) is an easily extensible polymer base material and / or a hardly extensible polymer part similarly to the sheet-like extensible organic base material of the aspect of (i). May contain dyes or pigments. 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.

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-like organic group having extensibility in which a hardly extensible polymer portion is partially and integrally formed in an easily extensible polymer matrix. It is a sheet-like extensible organic base material having a printing layer (printing layer) on at least one side (one side or both sides) of the material.

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 (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.

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.

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 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.

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.

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. 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 hardly extensible polymer part 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.

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, a base material for a poultice, and the like.

[Sheet-like extensible organic base material with flame retardancy]
As a sheet-like extensible organic base material having flame retardancy, an extensible sheet-like organic base material in which an inextensible polymer base 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 / or A sheet-like extensible organic base material having a flame retardant layer on at least one surface of the sheet-like organic base material is exemplified.

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.

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 hardly extensible polymer portion does not stretch or hardly stretches. For this reason, the design in which a shape is desired not to change can be given to a difficulty extensible polymer part, or another member can be fixed and hold | maintained.

The sheet-like extensible organic base material having flame retardancy is an extensible sheet-like organic base material in which a hardly extensible polymer portion 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 flame retardant, and the sheet-like organic base material has a flame retardant layer on at least one side. A sheet-like organic base material, the sheet-like organic base material contains a flame retardant, and the sheet-like organic base material has a flame retardant layer on at least one side thereof It may be.

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. 15, the functional layer 6 is a flame-retardant layer. In the multifunctional sheet-like extensible organic base material A shown in (2) of FIG. 15, 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.

(When the extensible sheet-like organic base material contains a flame retardant)
The flame retardant may be contained in an easily extensible polymer base material that constitutes an extensible sheet-like organic base material, may be contained in the hardly extensible polymer portion, It may be contained in the hardly extensible polymer part.

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 It is difficult to use a material for forming a non-extensible polymer part containing a flame retardant as the material for forming a non-extensible polymer part, or an easy-to-extend polymer base material containing a flame retardant as the easy-to-extend polymer base material. It can manufacture by using the hardly extensible polymer part forming material containing a flame retardant as the extensible polymer part forming material.

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. 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.

Examples of the chlorinated compound 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 (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.

Examples of the antimony compound include antimony trioxide, antimony pentoxide, sodium antimonate, zirconium-antimony composite oxide, and the like.

Examples of the metal hydroxide include alkali metal hydroxides such as magnesium hydroxide, aluminum hydroxide, and calcium hydroxide.

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.

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%.

When the flame retardant polymer part contains a flame retardant, the content (total amount) of the flame retardant is, for example, 1 to 400% by weight with respect to the whole flame retardant polymer part. 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%.

(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.

As the flame retardant contained in the flame retardant layer, the above flame retardant can be used without any particular limitation.

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.

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.

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.

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%.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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 μm, the lower limit is preferably 10 μm, and the upper limit is preferably 500 μm.

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.

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.

[Sheet-like extensible organic base material having thermal conductivity]
As a sheet-like extensible organic base material having thermal conductivity, an extensible sheet-like organic base material in which a hardly extensible polymer portion is partially and integrally formed in an easily extensible polymer matrix. The sheet-like organic base material contains a thermally conductive substance (that is, the sheet-like organic base material (particularly, the easily stretchable polymer base material itself) has thermal conductivity), and / or Or what has a heat conductive layer in the at least single side | surface of this sheet-like organic base material is mentioned.

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.

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 hardly-extensible polymer portion does not stretch or hardly stretches. For this reason, the design in which a shape is desired not to change can be given to a difficulty extensible polymer part, or another member can be fixed and hold | maintained.

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. 15, the functional layer 6 is a heat conductive layer. In the multifunctional sheet-like extensible organic base material A shown in (2) of FIG. 15, 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.

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.

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 hardly extensible polymer portion does not stretch or hardly stretches. For this reason, the design in which a shape is desired not to change can be given to a difficulty extensible polymer part, or another member can be fixed and hold | maintained.

The sheet-like extensible organic base material having thermal conductivity is a sheet-like organic base material having extensibility in which a hardly extensible polymer portion 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. A sheet-like extensible organic base material, the sheet-like organic base material containing a heat conductive material, and a sheet having a heat conductive layer on at least one side of the sheet-like organic base material It may be a stretchable 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.

(When the stretchable sheet-like organic base material contains a heat conductive substance)
The thermally conductive material may be contained in the easily extensible polymer matrix constituting the sheet-like organic base material having extensibility, may be contained in the hardly extensible polymer portion, and the easily extensible polymer matrix. It may be contained in the material and the hardly extensible polymer part.

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 stretchable polymer part containing a thermally conductive material as a material for forming a stretchable polymer part, or a stretchable polymer containing a thermally conductive substance as a base material for a stretchable polymer It can be manufactured by using a base material and using a hardly extensible polymer part forming material containing a heat conductive substance as the hardly extensible polymer part forming material.

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.

Examples of the metal include a metal (eg, gold, silver, iron, aluminum, copper, nickel, titanium) alone, or an alloy thereof.

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.

Examples of the boron compound include BN and B4C.

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.

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.

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.

When the thermally conductive substance is contained in the hardly extensible polymer part, the content (total amount) of the thermally conductive substance is, for example, 1 to 1000% by weight with respect to the whole hardly extensible polymer part. 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.

(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.

As the heat conductive material contained in the heat conductive layer, the above heat conductive material can be used without any particular limitation.

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.

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.

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.

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.

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.

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.

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.

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.

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).

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.

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.

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.

[Sheet-like extensible organic base material with heat insulation]
A sheet-like organic base material having extensibility in which a hard-extensible polymer portion is partially and integrally formed in an easily extensible polymer base material as a sheet-like extensible organic base material having heat insulation properties. The sheet-like organic base material contains a heat-insulating agent (that is, the sheet-like organic base material (in particular, 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 a sheet-like organic base material is mentioned.

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.

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 hardly extensible polymer portion does not stretch or hardly stretches. For this reason, the design in which a shape is desired not to change can be given to a difficulty extensible polymer part, or another member can be fixed and hold | maintained.

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. 15, the functional layer 6 is a heat-insulating layer. In the multifunctional sheet-like stretchable organic substrate A shown in (2) of FIG. 15, 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.

The sheet-like extensible organic base material having heat insulation is a sheet-like organic base material having extensibility in which a hardly extensible polymer portion 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-insulating agent, and the sheet-like organic base material has a heat-insulating layer on at least one side. It may be an extensible organic substrate, the sheet-like organic substrate contains a heat-insulating agent, and the sheet-like organic substrate has a heat-insulating layer on at least one side. An organic base material may be sufficient. 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.

(When the sheet-like organic base material having extensibility contains a heat-insulating agent)
The heat insulating property-imparting agent may be contained in the easily extensible polymer matrix constituting the extensible sheet-like organic base material, may be contained in the hardly extensible polymer portion, or the easily extensible polymer matrix. It may be contained in the material and the hardly extensible polymer part.

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 stretchable polymer part forming material containing a heat insulating property imparting agent as a material for forming a hardly stretchable polymer part, or a heat stretchable polymer containing a heat insulating property imparting agent as an easily stretchable polymer base material. It can be manufactured by using a base material and a hardly extensible polymer part forming material containing a heat insulating property imparting agent as the hardly extensible polymer part forming material.

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.

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.

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.

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.

When the hardly stretchable polymer part 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 whole hardly stretchable polymer part. 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.

(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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

[Stretchable organic base material with impact resistance]
As a sheet-like extensible organic base material having impact resistance, an extensible sheet-like organic base material in which a hardly extensible polymer portion is partially and integrally formed in an easily extensible polymer matrix. The easily extensible polymer base material contains an impact resistance imparting agent, and the easily extensible polymer base material has a stretchable sheet shape in which a hardly extensible polymer portion is partially and integrally formed. Those having a shock absorbing layer on at least one surface of the organic substrate can be mentioned.

When such a sheet-like stretchable organic base material is stretched in one direction (plane direction), the part of the easily stretchable polymer base material is stretched, but is the partially formed hardly stretchable polymer part not stretched? Or little elongation. For this reason, the design in which a shape is desired not to change can be given to a difficulty extensible polymer part, or another member can be fixed and hold | maintained. 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.

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. 15, 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).

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.

(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.

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 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.

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.

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.

When the hardly extensible polymer part contains an impact resistance imparting agent, the content (total amount) is not particularly limited, but is, for example, 1 to 50% by weight with respect to the whole hardly extensible polymer part. 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 hardly extensible polymer part may be easily changed.

On the other hand, the sheet-like extensible organic base material having the above-mentioned excellent impact absorbability is a sheet-like extensibility in which a hardly extensible polymer portion 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 organic substrate, the impact absorbing layer is preferably the following impact absorbing layer.

(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.

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). 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.

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.

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).

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.

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.

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. 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.

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.

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.

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.

[Sheet-like extensible organic base material having gas barrier properties]
As the sheet-like extensible organic base material having gas barrier properties, at least the extensible sheet-like organic base material in which the hardly extensible polymer portion is partially and integrally formed in the easily extensible polymer base material. Examples thereof include a sheet-like extensible organic base material having a gas barrier layer on one surface 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

As a sheet-like extensible organic base material having other gas barrier properties, an extensible sheet-like organic base material in which a hardly extensible polymer portion is partially and integrally formed in an easily extensible polymer base material. And the sheet-like extensible organic base material in which this sheet-like extensible organic base material satisfy | fills any one or both of following [i] and [ii] is mentioned.
[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

When such a sheet-like stretchable organic base material is stretched in one direction (plane direction), the part of the easily stretchable polymer base material is stretched, but is the partially formed hardly stretchable polymer part not stretched? Or little elongation. For this reason, the design in which a shape is desired not to change can be given to a difficulty extensible polymer part, or another member can be fixed and hold | maintained. 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.

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.

As a representative example of a sheet-like extensible organic base material having gas barrier properties, the functional layer 6 is a gas barrier layer in the multifunctional sheet-like extensible organic base material A shown in (1) of FIG. 15 is a multifunctional sheet-like extensible organic base material A shown in (2), wherein 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.

When the sheet-like organic substrate having extensibility has a gas barrier property (particularly oxygen barrier property and / or water vapor barrier property), it should be 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

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.

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.

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.

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.

On the other hand, the sheet-like stretchable organic base material having gas barrier properties is a stretchable sheet-like organic base material having a stretchable polymer portion partially and integrally formed in a stretchable polymer base material. When configured as a laminate in which a gas barrier layer is provided on at least one surface, the sheet-like extensible organic substrate (laminate) satisfies 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

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.

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.

[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. For example, a thickness measured under the conditions of 20 ° C. and 70% RH in accordance with the JIS K7126-2 method. 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. For example, a thickness (under 40 ° C. and 90% RH conditions according to JIS K7129B method) (Thickness of sheet-like extensible organic base material) 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.

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. 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.

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.

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.

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.

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. 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.

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.

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.

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.

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.

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.

[Sheet-like extensible organic base material having moisture permeability]
As a sheet-like extensible organic substrate having moisture permeability, a sheet-like extensible organic substrate in which a hardly extensible polymer portion is partially and integrally formed in an easily extensible polymer base material, A sheet-like extensible organic base material 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 the K7129A method is 100 g / m 2 /0.1 MPa / day or more 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.

When such a sheet-like stretchable organic base material is stretched in one direction (plane direction), the part of the easily stretchable polymer base material is stretched, but is the partially formed hardly stretchable polymer part not stretched? Or little elongation. For this reason, the design in which a shape is desired not to change can be given to a difficulty extensible polymer part, or another member can be fixed and hold | maintained. 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.

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).

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.

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].

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.].

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.

Examples of the amphoteric surfactants 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.

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.

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.

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.

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.

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). 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 hardly stretchable polymer portion at a predetermined portion of the easily stretchable polymer base material forming material layer, and then forming the easily stretchable polymer base material. It can be formed by converting the liquid precursor in the forming material layer into a target polymer.

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. Then, an easily stretchable polymer base material forming material layer is formed, and after forming the hardly stretchable polymer portion forming material at a predetermined portion of the easily stretchable polymer base material forming material layer, the easily stretchable polymer base material is formed. It can also be formed by drying and removing the solvent in the material forming material layer.

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. Formed by forming the forming material layer, placing the forming material of the hardly-extensible polymer part at a predetermined part of the easily-extensible polymer base material forming material layer, and then performing a melting / cooling process (hot melt process) You can also

The hard-extensible polymer part 3 may contain a moisture permeability imparting agent, like the easy-extensible polymer base part 2. By adding a moisture permeability imparting agent to the hardly extensible polymer portion, the moisture permeability of the sheet-like extensible organic substrate can be remarkably improved. As 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 hardly extensible polymer part 3 is, for example, 0.01 to 80% by weight with respect to the whole hardly extensible polymer part 3. 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, when the content exceeds 80% by weight, the mechanical strength of the hardly extensible polymer part may be lowered 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). 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.

[Conductive sheet-like extensible organic base material]
A sheet-like organic base material having extensibility, in which a non-extensible polymer portion is partially and integrally formed in an easily extensible polymer base material as a conductive sheet-like extensible organic base material, The sheet-like organic base material contains a conductive substance (that is, the sheet-like organic base material (in particular, the easily extensible polymer base material itself) has conductivity), and / or the sheet And a sheet-like extensible organic base material having a conductive layer on at least one side of the organic base material.

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.

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 hardly extensible polymer portion does not stretch or hardly stretches. For this reason, the design in which a shape is desired not to change can be given to a difficulty extensible polymer part, or another member can be fixed and hold | maintained.

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. 15, the functional layer 6 is a conductive layer. In the multifunctional sheet-like stretchable organic substrate A shown in (2) of FIG. 15, 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.

The sheet-like extensible organic base material having conductivity is a sheet-like organic base material having extensibility, in which a hardly extensible polymer portion 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 the sheet-like organic base material has a conductive layer on at least one side. The sheet-like organic base material may contain a conductive substance, and the sheet-like organic base material has a conductive layer on at least one side of the sheet-like organic base material. It may be a material. 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.

(When the sheet-like organic substrate having extensibility contains a conductive substance)
The conductive material may be contained in the easily extensible polymer base material constituting the stretchable sheet-like organic base material, or may be contained in the hardly extensible polymer portion. And the hardly extensible polymer part.

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, the material for forming a hardly-extensible polymer part containing a conductive substance is used as the material for forming a hardly-extensible polymer part, or the polymer base material containing a conductive substance is used as the easily-extensible polymer base material. And it can manufacture by using the hardly extensible polymer part forming material containing a conductive substance as the hardly extensible polymer part 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.

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.

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.

Examples of the conductive polymer include polyaniline, polypyrrole, polythiophene, and derivatives thereof. These can be used alone or in combination of two or more.

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.

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.

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].

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.

Examples of the amphoteric surfactant include betaine-based amphoteric surfactants [for example, alkyl betaines, amide betaines, etc.], glycine-based amphoteric surfactants, and the like.

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.

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.

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.

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.

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.

When the hardly extensible polymer part contains a conductive substance, the content (total amount) of the conductive substance is, for example, 0.1 to 100% by weight with respect to the whole hardly extensible polymer part. 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. Further, the hardly extensible polymer portion 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.

(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.

As the conductive substance contained in the conductive layer, the conductive substance can be used without any particular limitation.

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.

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.

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.

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.

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.

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.

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.

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.

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.

[Sheet-like extensible organic base material having a surface layer]
As a sheet-like extensible organic substrate having a surface layer, at least one of the extensible sheet-like organic substrate in which a hardly extensible polymer portion 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 this surface. 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”.

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 hardly extensible polymer portion does not stretch or hardly stretches. For this reason, the design in which a shape is desired not to change can be given to a difficulty extensible polymer part, or another member can be fixed and hold | maintained. 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.

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. 15, the functional layer 6 is a surface layer. In the multifunctional sheet-like extensible organic base material A shown in 15 (2), the functional layer 6 is a surface layer.

[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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

In addition, the surface layer 6 may contain an additive as long as it does not impair the effects of the present invention. Examples of such additives include epoxy-based crosslinking agents, melamine-based crosslinking agents, peroxide-based crosslinking agents, urea-based crosslinking agents, metal alkoxide-based crosslinking agents, metal chelate-based crosslinking agents, metal salt-based 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.), antioxidants, 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. 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.

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 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.

[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.

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.

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.

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.

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.

[Sheet-like extensible organic base material having antireflection properties]
As a sheet-like extensible organic base material having antireflection properties, at least a sheet-like organic base material having extensibility in which a hardly extensible polymer portion is partially and integrally formed in an easily extensible polymer matrix. A sheet-like extensible organic base material having an antireflection layer on one surface is exemplified.

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 hardly extensible polymer portion does not stretch or hardly stretches. For this reason, the design in which a shape is desired not to change can be given to a difficulty extensible polymer part, or another member can be fixed and hold | maintained. 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.

As a representative example of a sheet-like extensible organic base material having antireflection properties, the functional layer 6 is an antireflection 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. 15, the functional layer 6 is an antireflection layer.

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.

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.

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.

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.

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.

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.

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.

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. Any appropriate temperature can be adopted as the drying and curing temperature when forming the antireflection layer 6. 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 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.

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. 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.

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.

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.

Production example (production 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), 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 were 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 further 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.

Production Example 2 (Manufacture of syrup for forming hardly stretchable polymer part)
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) with respect to 100 parts by weight of 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 hardly extensible polymer part) containing 70% by weight of an acryloyl group-terminated urethane polymer was obtained.

Examples 1-5
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 this base material syrup layer, formation of a hardly extensible polymer part obtained in Production Example 2 from above As shown in FIG. 8, a pattern as shown in FIG. 8 (a pattern in which a plurality of straight lines extend perpendicularly to the sheet length direction and in parallel at equal intervals; The outer frame does not show the contour shape of the sheet-like extensible organic base material). 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 the hardly extensible polymer After the part forming syrup is semi-cured, 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 ), forming a hardly extensible polymer part in a cured material of the base material syrup (= easily extensible polymer base material) A sheet-like extensible organic base material (thickness: 300 μm) on which the syrup cured part (= hardly-extensible polymer part; columnar difficult-extendable part) was arranged was obtained. As a result of microscopic observation of the cross section, in the obtained sheet-like extensible organic substrate, the hardly extensible polymer portion is continuously formed from one surface of the sheet-like extensible organic substrate 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, a indicates the distance (mm) between adjacent syrup portions for forming a hardly extensible polymer portion.

Examples 6-12
Using the hardly stretchable polymer part forming syrup obtained in Production Example 2 and following the dimensions in Table 2, a pattern as shown in FIG. 9 (a plurality of straight lines are perpendicular to the sheet length direction and parallel to non-uniform intervals) An elongated pattern; the rectangular outer frame in FIG. 9 does not indicate the contour shape of the sheet-like extensible organic base material), and the sheet-like extensibility is the same as in Examples 1-5. An organic base material (thickness: 300 μm) was obtained. As a result of microscopic observation of the cross section, in the obtained sheet-like extensible organic substrate, the hardly extensible polymer portion is continuously formed from one surface of the sheet-like extensible organic substrate 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, a1 to a5 each indicate a distance (mm) between adjacent syrup portions for forming a hardly extensible polymer portion.

Examples 13-14
Using the hardly extensible polymer part forming syrup obtained in Production Example 2, and according to the dimensions in Table 3, a pattern as shown in FIG. 10 (a plurality of broken lines have a center line perpendicular to the sheet length direction and a center A pattern formed so that the line intervals extend in parallel with equal intervals.The distance between adjacent polygonal lines is constant; the square outer frame in FIG.10 shows the contour shape of the sheet-like extensible organic base material A sheet-like extensible organic base material (thickness: 300 μm) was obtained in the same manner as in Examples 1 to 5 except that the above was formed. As a result of microscopic observation of the cross section, in the obtained sheet-like extensible organic substrate, the hardly extensible polymer portion is continuously formed from one surface of the sheet-like extensible organic substrate 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, a and b each show the length (mm) of each linear part which comprises a broken line, and c is the distance (adjacent broken line) between the adjacent syrup parts for forming a hardly extensible polymer part Distance) (mm).

Example 15
Using the refractory polymer part forming syrup obtained in Production Example 2, and according to the dimensions in Table 4, a pattern as shown in FIG. 11 (a plurality of broken lines have a center line perpendicular to the sheet length direction and A pattern formed so that line intervals extend in parallel with equal intervals, provided that the distance between adjacent polygonal lines has a maximum value and a minimum value; The sheet-like extensible organic base material (thickness: 300 μm) was obtained by the same operation as in Examples 1 to 5 except that the above-mentioned outline shape was not formed. As a result of microscopic observation of the cross section, in the obtained sheet-like extensible organic substrate, the hardly extensible polymer portion is continuously formed from one surface of the sheet-like extensible organic substrate 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, a and b each indicate the length (mm) of each straight line part constituting the polygonal line, c indicates the maximum distance (mm) between adjacent polygonal lines, and d is adjacent. The minimum value (mm) between broken lines is shown.

Example 16
Using the hardly stretchable polymer part forming syrup obtained in Production Example 2 and according to the dimensions in Table 5, a pattern as shown in FIG. 12 (a plurality of wavy lines with the center line perpendicular to the sheet length direction and the center A pattern formed so that the line intervals extend in parallel with equal intervals.The distance between adjacent wavy lines is constant; the square outer frame of FIG. 12 shows the contour shape of the sheet-like extensible organic base material A sheet-like extensible organic base material (thickness: 300 μm) was obtained in the same manner as in Examples 1 to 5 except that the above was formed. As a result of microscopic observation of the cross section, in the obtained sheet-like extensible organic substrate, the hardly extensible polymer portion is continuously formed from one surface of the sheet-like extensible organic substrate 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, a represents the wave pitch (mm) of the wavy line, b represents the wave height (difference between the last part and the lowest part) (mm), and c represents the adjacent hard stretch. The distance (distance between adjacent wavy lines) (mm) between the syrup parts for forming the conductive polymer part is shown.

Examples 17-19
Using the hardly extensible polymer part forming syrup obtained in Production Example 2, according to the dimensions in Table 6, a pattern as shown in FIG. 13 (a plurality of equally spaced linear groups extending obliquely with respect to the sheet length direction and A pattern in which a plurality of other equally-spaced straight line groups extending obliquely with respect to the sheet length direction intersect with each other to form a mesh; the rectangular outer frame in FIG. 13 is a sheet-like extensible organic group A sheet-like extensible organic base material (thickness: 300 μm) was obtained by the same operation as in Examples 1 to 5 except that the outline shape of the material was not formed. As a result of microscopic observation of the cross section, in the obtained sheet-like extensible organic substrate, the hardly extensible polymer portion is continuously formed from one surface of the sheet-like extensible organic substrate 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, a and b respectively indicate the length (mm) of each side of the formed mesh, and θ indicates the crossing angle (°) of the two straight line groups.

Example 20
Using the hardly extensible polymer part forming syrup obtained in Production Example 2, according to the dimensions in Table 7, a pattern as shown in FIG. 14 (a plurality of equidistant line groups extending obliquely with respect to the sheet length direction and A pattern in which a plurality of other equidistant polygonal line groups extending obliquely with respect to the sheet length direction intersect with each other to form a complex mesh shape; the rectangular outer frame in FIG. A sheet-like extensible organic base material (thickness: 300 μm) was obtained by the same operation as in Examples 1 to 5 except that the contour shape of the organic base material was not formed. As a result of microscopic observation of the cross section, in the obtained sheet-like extensible organic substrate, the hardly extensible polymer portion is continuously formed from one surface of the sheet-like extensible organic substrate 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, a and b respectively indicate the length (mm) of the straight line portion of one broken line group, and c and d indicate the length (mm) of the straight line portion of the other broken line group, respectively. Indicates.

Evaluation test (measurement of elongation)
The sample of the sheet-like extensible organic base material obtained in Example 4 [width 20 mm with respect to the length direction (perpendicular to the linear pattern); length 10 mm of the linear pattern] The tensile polymer (trade name “Autograph AG-X 200N”, manufactured by Shimadzu Corp.) is used for tensile testing (temperature). : 25 ° C., tensile speed: 200 mm / min), elongation rate S ₁ (%) (average value) in the direction of elongation of the linear hardly extensible polymer part at 50% elongation (150% of the original length) And the elongation rate S ₂ (%) (average value) in the elongation direction of the site other than the hardly extensible polymer portion [easily extensible polymer base material portion (= easy extensible portion)], and the ratio (S ₂ / _{S 1)} and difference _{_{(S 2 -S 1) (%}} ) Calculated by determined (see FIG. 7).
The elongation rate S ₁ (%) is determined by measuring the length in the direction of elongation of the hardly extensible polymer portion (width of the linear portion on the surface of the base material) before and after the elongation, and the formula: {(length after elongation-elongation) Previous length) / (Length before stretching)} × 100).
Elongation rate S ₂ (%) is marked with 6 marks in the extension direction of the part other than the hardly-extensible polymer part (easily-extensible polymer base material part), and the length between adjacent marks before and after extension. And calculated by the formula: {(length after stretching−length before stretching) / (length before stretching)} × 100).
As a result, S ₁ (%) = 5, S ₂ (%) = 53, (S ₂ / S ₁ ) = 10.6, and (S ₂ -S ₁ ) (%) = 48.
In addition, the sheet-like extensible organic base material obtained in Example 4 also had stretchability.

Hereinafter, examples relating to the multifunctional sheet-like extensible organic substrate of the sheet-like extensible organic substrate of the present invention will be described. In addition, the code | symbol of a member, a composition, etc. in a manufacture example and an Example is determined for every Example of each multifunctional sheet-like organic base material, and is a manufacture example of other multifunctional sheet-like organic base materials However, this is not the case with the examples.

[Example of sheet-like extensible organic base material having thermal conductivity]
Production Example A1 (Manufacture of base material syrup A)
In a reaction vessel equipped with a condenser, a thermometer, and a stirrer, 80 parts by weight of isobornyl acrylate (trade name “IBXA”, manufactured by Osaka Organic Chemical Industry Co., Ltd.) as a (meth) acrylic monomer, n -20 parts by weight of butyl acrylate (BA, manufactured by Toa Gosei Co., Ltd.), 68.4 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 catalyst, 0.01 part by weight of dibutyltin dilaurate (DBTL) was added, and 25.5 parts by weight of hydrogenated xylylene diisocyanate (HXDI, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.) was added dropwise with stirring. It was made to react for a time and the urethane polymer-acrylic-type monomer mixture was obtained. Thereafter, 6.1 parts by weight of hydroxyethyl acrylate (trade name “Acrix HEA”, manufactured by Toa Gosei Co., Ltd.) was further added and reacted at 65 ° C. for 1 hour, whereby an acryloyl group-terminated urethane polymer-acrylic monomer mixture. Got. Thereafter, by adding 0.15 parts by weight of bis (2,4,6-trimethylbenzoyl) phenyl-phosphine oxide (trade name “Irgacure 819”, manufactured by BASF) as a photopolymerization initiator, base material syrup A Got.

Production Example A2 (Manufacture of syrup A for forming a hardly extensible polymer part)
100 parts by weight of trimethylolpropane EO-added triacrylate (trade name “Biscoat # 360”, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and blue dye (trade name “SZ7620”, manufactured by Dainichi Seika Kogyo Co., Ltd.) 1 part by weight and 0.1 part by weight of 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name “Irgacure 651”, manufactured by BASF) as a photopolymerization initiator are added and dispersed, and acrylic A monomer mixture (Syrup A for forming a hardly extensible polymer portion (hardly stretchable portion)) was obtained. The viscosity (25 ° C.) of the obtained syrup A for forming a hardly extensible polymer part was 66 mPa · s.

Production Example A3 (Manufacture of syrup B for forming a hardly extensible polymer part)
50 parts by weight of boron nitride particles (trade name “HP-40”, manufactured by Mizushima Alloy Iron Co., Ltd.) are added uniformly to 100 parts by weight of the syrup A for forming a hardly extensible polymer part obtained in Production Example A2. To obtain a syrup B for forming a hardly extensible polymer part.

Example 21
The base material syrup A obtained in Production Example A1 is applied to the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 μm) with an applicator to form a base material syrup layer having a thickness of 120 μm. did. Using a dispenser (trade name “SM300DS-S, MPP-1”, manufactured by Musashi Engineering Co., Ltd.) at a predetermined portion of this base material syrup layer, formation of the hardly extensible polymer part obtained in Production Example A3 from above A grid-like pattern having a line width of 1 mm and a line width interval of 1 mm was formed using the syrup B (see FIG. 16). Immediately after pattern formation, ultraviolet rays are irradiated from above with a metal halide lamp (MHL) (ultraviolet illuminance: 200 mW / cm2, integrated irradiation amount: 200 mJ / cm2), and a base material syrup and a refractory polymer part forming syrup are prepared. After being semi-cured, 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 further irradiated with ultraviolet rays using an ultraviolet lamp (BL type). (Ultraviolet light illuminance: 3.4 mW / cm 2, integrated irradiation amount: 2000 mJ / cm 2), syrup hardened portion for forming a hardly extensible polymer portion (= difficult) in a cured product of the base material syrup (= easy extensible polymer base material) A sheet-like extensible organic base material (thickness: 120 μm) in which the extensible polymer part) was arranged in a lattice shape was obtained.

<Evaluation of thermal conductivity>
Using the xenon flash analyzer (trade name “LFA447 Nano Flash”, manufactured by NETZSCH) for the extensible organic substrate obtained in Example 21, the thermal conductivity in the plane direction and the thickness direction was measured by the laser flash method. The thermal conductivity was measured according to the following criteria. The results are shown in the table below.
Evaluation criteria ○: When the thermal conductivity is 0.5 W / m / K or more ×: When the thermal conductivity is less than 0.5 W / m / K

[Example of sheet-like extensible organic base material having conductivity]
Production Example B1 (Production of conductive water dispersion)
50 parts by weight of a polypyrrole aqueous dispersion (trade name “PPY-12”, manufactured by Maruhishi Oil Chemical Co., Ltd.), 40 parts by weight of polyglycerin having an average degree of polymerization of 10, an acetylene glycol surfactant (trade name “Surphy A conductive aqueous dispersion was obtained by uniformly mixing 10 parts by weight of “NOL”, manufactured by Air Products Co., Ltd.

Example 22
Polyurethane aqueous solution (trade name “Superflex E-2000”, Daiichi Kogyo Seiyaku Co., Ltd.) is coated on the surface of the separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, Inc., thickness 38 μm) with an applicator. Then, a polyurethane aqueous solution base material layer having a thickness of 140 μm was formed. Using a dispenser (trade name “SM300DS-S, MPP-1”, manufactured by Musashi Engineering Co., Ltd.) at a predetermined part of the base material layer, the conductive water dispersion obtained in Production Example B1 from above is used. A grid pattern having a line width of 1 mm and a line width interval of 1 mm was formed (see FIG. 17).
After pattern formation, by drying for 10 minutes in a drying oven (100 ° C.), the cured portion of the conductive aqueous dispersion (= hardly stretchable) in the cured polyurethane water dispersion (= highly stretchable polymer matrix). A sheet-like extensible organic base material (thickness: 70 μm) in which the polymer part) was arranged in a lattice shape was obtained.

<Electrical conductivity evaluation>
About the extensible organic base material obtained in Example 22, the surface resistivity of the sheet surface was measured using a surface resistance meter (trade name “Model MCP-UP450”, manufactured by Mitsubishi Chemical Corporation). The conductivity was evaluated according to the standard. The results are shown in the table below.
Evaluation criteria ◎: When the surface resistivity is less than 106Ω / □ ○: When the surface resistivity is 106Ω / □ or more and 1012Ω / □ or less ×: When the surface resistivity exceeds 1012Ω / □

According to the sheet-like extensible organic base material of the present invention, the shape of the hardly extensible polymer portion hardly changes even when the base material is extended in a certain direction, so that it has a function as an extensible member. A desired design can be applied to the shape-invariant portion, and other members can be held and fixed. In addition, the projection shape when the surface shape of the hardly extensible polymer part or the sheet-like extensible organic substrate surface of the hardly extensible polymer part is the projection surface is linear, and the hardly extensible polymer part is the sheet-like extensibility. Since it has a shape extending linearly when viewed from the surface of the organic substrate, it is possible to suppress elongation in a specific direction or to impart strength in a specific direction. 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 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)
DESCRIPTION OF SYMBOLS 21 Polymer base material forming material layer 22 Polymer base material forming material layer 200 Partially cured easily extensible polymer base material forming energy beam curable composition layer 3 Hardly stretchable polymer part 30 Hardly stretchable polymer part forming material (Energy beam curable composition for forming a hardly extensible polymer part)
31 material for forming a hardly extensible polymer part 32 material for forming a hardly extensible polymer part 300 energy ray curable composition for forming a partially extensible polymer part that has been partially cured 4 support 5 cover film A multifunctional sheet-like extensible organic material Substrate (adhesive sheet-like extensible organic substrate, etc.)
6 Functional layers (such as adhesive layers)

Claims

A sheet-like extensible organic base material in which a hardly extensible polymer portion is partially and integrally formed in an easily extensible polymer base material, the surface shape of the hardly extensible polymer portion, or the difficult stretch Sheet-like extensible organic substrate having a linear projection shape when the surface of the sheet-like extensible organic substrate of the conductive polymer portion is the projection plane.
2. The sheet-like extensible organic base material according to claim 1, wherein a line width of the surface shape or projected shape of the hardly extensible polymer portion is 0.01 mm to 5 cm.
The sheet-like extensible organic base material according to claim 1 or 2, wherein the surface shape or projected shape of the hardly extensible polymer portion is linear, broken line, wavy, arcuate or amorphous linear.
The surface shape or the projected shape has a plurality of hardly extensible polymer portions having a linear shape, and the plurality of hardly extensible polymer portions are parallel, intersecting, or in a twisted position. The sheet-like extensible organic substrate according to any one of 1 to 3.
5. The sheet-like extensible organic base material according to any one of claims 1 to 4, wherein the plurality of hardly extensible polymer portions are formed in a regular pattern.
6. The sheet-like extensible organic base material according to claim 5, wherein center lines of the surface shape or projected shape of a plurality of hardly extensible polymer portions are parallel.
The sheet-like extensible organic base material according to claim 6, wherein a distance between the center lines of the surface shape or projected shape of adjacent hardly extensible polymer portions is 0.01 mm to 50 cm.
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.
The sheet-like extensible organic substrate according to any one of claims 1 to 8, wherein the length of the hardly extensible polymer portion in the thickness direction is at least 1/50 of the thickness of the sheet-like extensible organic substrate.
The sheet-like extensible organic material according to any one of claims 1 to 9, wherein the hardly extensible polymer portion is continuously formed from one surface of the sheet-like extensible organic base material to the other surface. Base material.
The sheet-like extensible organic base material according to any one of claims 1 to 10, wherein the elongation characteristics are gradational in the vicinity of the interface between the hardly extensible polymer portion and the easily extensible polymer matrix.
The sheet-like extensible organic substrate according to any one of claims 1 to 11, which further has stretchability.