JP2013155242A - Sheet-shaped stretchable organic base material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sheet-shaped stretchable base material which has stretchability in a planar direction, has a poorly stretchable section whose shape is hardly changed even when stretched, and further can suppress elongation in a specific direction or can impart strength in a specific direction.SOLUTION: There is provided a sheet-shaped organic base material in which a poorly stretchable polymer section is formed partially and integrally in an easily stretchable polymer matrix, where 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-shaped 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.

Description

  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.

  Organic members having extensibility and stretchability are widely used for band members, binding members, sanitary products, clothing items, poultice base fabrics, 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 part in the surface direction and a difficult-to-change part that does not easily change its shape even if it is stretched. Furthermore, it is possible to suppress stretching in a specific direction and to impart strength in a specific direction. The object is to provide a sheet-like extensible substrate.
Another object of the present invention is to have a stretchable portion in the surface direction and a difficultly stretchable portion that does not change its shape even when stretched, and further suppresses elongation in a specific direction and imparts strength in a specific direction. 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 line in the surface shape or projected shape of the hardly extensible polymer part 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 broken 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 projected shape of 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 substrate. 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 characteristics may have gradation.

  The sheet-like extensible organic substrate may further have stretchability.

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.
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. 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 Examples 1-5. 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 Examples 6-12. 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 Examples 13-14. 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. It is the schematic which shows the shape of the hardly extensible polymer part in the surface of the sheet-like extensible organic base material obtained in Examples 17-19. 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.

[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 difficulty 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 or the substrate surface projection shape of the hardly extensible polymer portion 3 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 line width (line width) which is the surface shape of the hardly extensible polymer part 3 or the projected surface shape 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 part) between the hardly extensible polymer part 3 and the easily extensible polymer base part 2, a gradation (gradient) in which the composition and / or physical properties (elongation characteristics, hardness, etc.) gradually change is formed. 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 (distance between center lines on the surface of the sheet-like extensible organic substrate 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 substrate 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 cross-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). 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 organic base material that does not stretch up to 1.5 times, when stretched up to 1.25 times), the elongation rate S ₁ (%) of the hardly extensible polymer portion 3 (original) The ratio of the extended length to the length) is preferably 49% or less, more preferably 40% or less, still 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. ) (When a sheet-like organic base material that does not extend up to 1.5 times is extended up to 1.25 times), the elongation rate S ₂ (% ) (Ratio of the stretched length to the original length) and the stretch ratio S ₁ (%) of the hardly extensible polymer portion [S ₂ (%) / S ₁ (%)] is preferably greater 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. ) (When a sheet-like organic base material that does not extend up to 1.5 times is extended up to 1.25 times), the elongation rate S ₂ (% ) And the elongation rate S ₁ (%) of the hardly extensible polymer part 3 [S ₂ (%) − S ₁ (%)] is preferably 20% or more, more preferably 40% or more. preferable.

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) Ratio (%) [S ₂ (1) / S ₂ (2)] [where S ₂ (1) ≧ S ₂ (2)] is preferably 1 to 1.3. -1.2 are more preferable, and 1-1.1 are 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).

In the sheet-like extensible organic base material of the present invention, the easily extensible polymer base material 2 is usually soft and the hardly extensible polymer portion 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 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 of the present invention, a solid viscoelasticity measuring device (sample size: length 25 mm × width 3 mm, distance between chucks: 5 mm, mode: time dispersion, temperature: 27 ° C., frequency: 1 Hz, initial stage The tensile elastic modulus E ′ ₁ (Pa) of the hardly extensible polymer portion 3 and the tensile elastic modulus of the easily extensible polymer base material 2 measured by strain: 0.2%, measurement time: 120 seconds, measurement number: 10 times) 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 ) with the load P _{2 of the} material 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 polymer, polyurea polymer, polyurethane urea polymer, polyolefin polymer (particularly polydiene polymer), silicone polymer, polystyrene polymer (for example, styrene-isoprene-styrene block copolymer, 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 stretchable 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 polyacryl chain, and having an energy ray-curable group A ₁ in the main chain or side chain, or the curable polymer P And curable monomer M having energy ray-curable group A ₂ can be formed by irradiating with energy rays and curing. 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 the 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 beam curable group A ₂ in the curable monomer M having the energy beam curable group A ₂ is also preferably a cationic polymerizable group.

The curable polymer P includes a compound having an energy ray curable group A ₁ and a reactive functional group R ₁ , and a reactive functional group R ₂ having reactivity to the reactive functional group R ₁ in the molecule. And at least one selected from the group consisting of a polyurethane chain, a polyurea chain, a polyurethane urea chain, a polyolefin chain (particularly a polydiene chain), a silicone chain, a polyester chain, a polyether chain, a polyamide chain, and a polyacryl chain. It can be obtained by reacting with a polymer having a polymer chain.

Examples of the combination (regardless of order) of the reactive functional group R ₁ and the reactive functional group R ₂ include a combination of a hydroxyl group and an isocyanate group, a combination of a hydroxyl group and an epoxy group, a carboxyl group, or an acid anhydride. A combination of a compound group and an isocyanate group, a combination of a carboxyl group or an acid anhydride group and an epoxy group, a combination of an amino group and an isocyanate group, a combination of an amino group and an epoxy group, a Si-H group and a carbon-carbon group. A combination with a group having a heavy bond is exemplified.

A polymer having a reactive functional group R ₂ and a polyurethane chain can be prepared by combining a polyisocyanate compound, a long-chain polyol compound, and a chain extender or other isocyanate-reactive compound used as necessary. It can obtain by making it react.

  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; xylylene diisocyanate, tetramethylene xylylene diisocyanate, etc. ; 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 10000, 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 cocondensate 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 the (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 such as 2-chloroaniline (particularly diamines).

  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 a known or conventional method.

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 the compound having the functional group R ₁ , the curable polymer P having the energy ray curable group A ₁ in the main chain or the side chain can be produced.

In the present invention, as the curable monomer M having the energy ray curable group A ₂ , a compound having a group (radical polymerizable group) containing a carbon-carbon unsaturated bond such as a (meth) acryloyl group or a vinyl 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) acrylate Isodecyl sulfate, 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 acid ester having T) Alkoxyalkyl (meth) acrylates such as methoxyethyl acrylate and ethoxyethyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylic acid 3 -Hydroxypropyl, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, vinyl alcohol, allyl alcohol and other hydroxyl group (hydroxyl group) -containing monomers; (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 phthalic acid, etc. No carboxyl group or acid Monomer group-containing monomers; sulfonic acid group-containing monomers such as sodium vinyl sulfonate, allyl sulfonic acid, styrene sulfonic acid, (meth) acrylamide propane sulfonic acid, sulfopropyl (meth) acrylate; phosphorus such as 2-hydroxyethyl acryloyl phosphate Acid group-containing monomers; Epoxy group-containing monomers such as glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, N Amido group-containing monomers such as methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide; N-vinyl-2-pyrrolidone, N-vinyl-2-piperide N-vinyl-2-caprolactam, N-vinyl piperazine, N-vinyl pyrrole, N-vinyl imidazole, nitrogen-containing heterocycle-containing monomers such as (meth) acryloylmorpholine; and (meth) acrylic acid tetrahydrofurfuryl Oxygen heterocycle-containing monomers; amino group-containing monomers such as aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, and t-butylaminoethyl (meth) acrylate; cyano groups such as acrylonitrile and methacrylonitrile Monomer; Imido group-containing monomer such as cyclohexylmaleimide and isopropylmaleimide; Isocyanate group-containing monomer such as 2-methacryloyloxyethyl isocyanate; Styrenic monomer such as styrene, α-methylstyrene, vinyltoluene; Olefin monomers such as tylene, propylene, isoprene, butadiene, 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; (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, trimethyl Uses polyfunctional monomers such as roll propane EO-added tri (meth) acrylate, glycerin PO-added tri (meth) acrylate, allyl (meth) acrylate, vinyl (meth) acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, urethane acrylate You can also “EO” represents ethylene oxide, and “PO” represents propylene oxide.

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 the curable monomers M having the energy ray curable group A ₂ , curable monomers having a radical polymerizable group are preferable. 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 preferred 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, 40% by weight or more (40 to 40% or more). 100% by weight), preferably 50% by weight or more (50-100% by weight), more preferably 60% by weight or more (60-100% by weight). Further, as the curable monomer M, together with a (meth) acrylic acid C _1-20 alkyl ester, a carboxyl group such as (meth) acrylic acid or an anhydride group-containing monomer, or a hydroxyl group such as 2-hydroxyethyl (meth) acrylate Containing monomers may be used. In this case, the use amount of the carboxyl group- or acid anhydride group-containing monomer and the hydroxyl group-containing monomer is, for example, in the range of 0 to 50% by weight (about 0.1 to 50% by weight), respectively, with respect to the entire curable monomer. It may be selected from about 1 to 45% by weight.

  As described above, the easily extensible polymer base material 2 can be formed by irradiating the curable polymer P or a mixture of the curable polymer P and the curable monomer M by irradiating with energy rays. 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 benzoin ether photopolymerization initiators, acetophenone photopolymerization initiators, and α-ketol photopolymerization initiators. 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.

When the energy ray curable groups A ₁ and A ₂ are cationic polymerizable groups, a known or conventional cationic curing catalyst can be used as a photopolymerization initiator.

  Although it does not specifically limit as the usage-amount of a photoinitiator, It is 0.01-3 weight part with respect to 100 weight part of sclerosing | hardenable compound whole quantity, The upper limit becomes like this. Preferably it is 1 weight part, 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 further preferably 80% by weight or more) of the unit with respect to all structural units of the polymer Therefore, the structural unit derived from a polyfunctional monomer having 2 or more radical polymerizable groups in the molecule (particularly an acrylic polyfunctional monomer) is 50% by weight or more (more preferably 60% by weight) based on the total structural unit of the polymer. (Iii) a filler-containing polymer material, (iv) a tensile modulus of elasticity of 0.1 MPa or more (more preferably 0.5 MPa or more, It is preferably 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 part of a polymer containing 50% by weight or more of structural units derived from a polyfunctional monomer having two or more curable groups in the molecule based on the total structural units of the polymer. The proportion of the 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.); acrylonitrile (Homopolymer Tg: 100 ° C.).

  In the above (ii), as the polyfunctional monomer, for example, 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 Rate and the like. Among the polyfunctional monomers, those having 3 or more functional groups (for example, 3 to 6 functional groups) are most preferable.

  In (iii) above, 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; carbonic acid 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. Moreover, 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 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, based on the total structural unit 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 part 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, the hard-extensible polymer part 3 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, as a monomer other than the polyfunctional monomer, a monofunctional monomer can be appropriately selected from the monomers exemplified as the curable monomer M having the energy ray curable group A ₂ .

  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. Although it does not specifically limit as the usage-amount of a photoinitiator, It is 0.01-3 weight part with respect to 100 weight part of sclerosing | hardenable compound whole quantity, The upper limit becomes like this. Preferably it is 1 weight part, More preferably The lower limit is preferably 0.02 parts by weight, more preferably 0.05 parts by weight.

  In the case where the hardly extensible polymer portion 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 part 3 can be formed by polymerizing, or curing or crosslinking a polymer that can be induced by curing or crosslinking to the polymer.

  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.

[Manufacture 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. A step of forming a base material forming material layer Step B: a step of arranging a hardly extensible polymer portion forming material at a predetermined portion of the easily stretchable polymer base material forming material layer,
Step C: At least one selected from a reaction, a solvent drying removal process, and a melting / cooling process on the easily stretchable polymer base material forming material layer in which the hardly stretchable polymer part forming material is arranged at a predetermined site. Process 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 matrix

  First, in step A, the polymer (a) liquid precursor constituting the easily extensible 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 adhesion substrate made of the above-mentioned 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 (energy ray-curable monomers and the like) that can be derived into the polymer (a), 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, a die coater, an extruder, a printing machine, or the like 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 easily extensible polymer base material forming material layer can also be performed using an appropriate 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, and 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 the process B, the 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.

  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. 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 product (such as an energy beam curable composition) can be used. This curable composition usually contains a polymerization initiator.

  When the hardly extensible polymer part is composed of the above-mentioned (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.

  When 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. Apply coating and droplets so that the cross-sectional shape of the polymer part is the desired shape. The mounting 置又 prints, and a method of transferring it to the easily extensible polymer matrix forming material layer.

  When the hardly extensible polymer part forming material is in a liquid state, the viscosity of the liquid is a temperature at the time of coating, dripping, etc. from the viewpoint of workability and the like (for example, a predetermined temperature within a 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 the viscosity is too low, it becomes difficult to obtain a difficult-extensible polymer portion having a desired shape. Conversely, if the viscosity is too high, the coating workability tends to be lowered.

  Coating, dripping, mounting, driving, printing, pouring, and transfer are not particularly limited, and can be performed by known or conventional methods. 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 hardly extensible polymer portion forming material disposed at a predetermined site 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 difficult-to-extend 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.

  Although it does not specifically limit as a weight average molecular weight of the polymer mix | blended in the said energy-beam curable composition, For example, it is 1000 or more, Preferably it is 2000 or more, More preferably, it is 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 the material for forming an inextensible polymer part, the material for forming an inextensible polymer part is a material for forming an easily extensible polymer base material as required. Let stand until it penetrates, migrates and settles to the desired depth of the layer.

  Then, in step C, the reaction, solvent drying and removal treatment, and the 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. At least one treatment selected from (Treatment) is performed to obtain a 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.

  Examples of the reaction include a polymerization reaction by energy rays and heat, curing, or a crosslinking 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 extensible polymer base material forming material used in step A and the form of the hardly extensible 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. Can be obtained.

  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 embodiments (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 with 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 material, is irradiated to the easily stretchable polymer base material forming material layer disposed 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 matrix.

  (II) In step A, an easily stretchable polymer base material forming material layer is formed on the support with a solution or dispersion containing the polymer (a), and in step B, the easily stretchable polymer base material is formed. A material (b) [for example, polymer, filler (powder), etc.] constituting the hardly extensible polymer part or a solution or dispersion containing the material (b) is disposed at a predetermined portion of the material layer, 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 easily stretchable polymer base material forming material layer is predetermined. 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 (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-beam 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.

  A solvent may be added to the curable composition as necessary, but it is preferable not to use a solvent because a process for 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 in the form of a syrup. 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 easily extensible polymer base material forming energy beam curable composition layer 20 is the same as described above.

  In step B1, the energy ray-curable composition 30 for forming a hardly extensible polymer part is disposed (included) in the energy ray-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. That. 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. Can also be done.

  It is preferable that the energy ray-curable composition 30 for forming a hardly extensible polymer part is in a syrup shape. 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 a temperature at the time of coating (for example, a predetermined temperature within a range of 10 to 40 ° C, particularly 25 ° C). For example, 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. Conversely, if the viscosity is too high, the coating workability tends to be lowered.

  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, and 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 extensible polymer matrix containing the hardly extensible polymer portion forming energy beam curable composition 30 is irradiated with an energy beam, and the difficult elongation is achieved. 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 part of the easily extensible polymer base material 2. A sheet-like organic substrate having extensibility formed integrally and integrally is obtained.

  Although ultraviolet rays (UV) are used as energy rays in FIG. 4, as described above, ionizing radiation such as α rays, β rays, γ rays, neutron rays, electron rays, and 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 irradiating with ultraviolet rays, as shown in FIG. 4 (c), irradiation is performed for a short time (for example, an integrated irradiation amount of 10 to 1000 mJ / cm ² ) at a high illuminance (for example, 50 to 1000 mW / cm ² ). Then, as shown in FIG. 4 (d), the cover film 5 is laminated, and then, as shown in FIG. 4 (e), it is long with a low illuminance (for example, 1 to 40 mW / cm ² ). You may irradiate with time (for example, integrated irradiation amount 500-10000mJ / cm < ² >). Thus, the workability at the time of lamination | stacking of the cover film 5 by a hand roller can be improved by irradiating 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. 4 (d ′), the energy beam curable composition 30 for forming a hardly extensible polymer portion is contained. 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 ultraviolet rays may be irradiated as shown in FIG. Illuminance of ultraviolet in this case, for example 1~40mW / cm ^2, integrated dose is, for example, 500~10000mJ / 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 described above, the cover film 5 and the support 4 are peeled off as necessary, cut into an appropriate size as necessary, and used as the sheet-like extensible organic substrate 1. The cutting operation may be performed before the cover film 5 or the support 4 is peeled off.

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. A step of arranging (including) coating, dripping, placing, driving in, printing, etc. so that the cross-sectional shape of the portion A becomes a desired shape Step C2: containing a polymer constituting the hardly extensible polymer portion 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 part 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 embodiment (II), and FIG. 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 in which a polymer or filler (powder) constituting the hardly stretchable polymer portion is placed. A 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-mentioned aspect (III), and FIG. 6 is a schematic explanatory view (cross-sectional view) thereof. 6K corresponds to the step A3, (l) corresponds to the step B3, and (m) and (n) correspond to the step C3. Reference numeral 22 denotes a sheet (material layer for forming an easily extensible polymer base material) made of a polymer constituting the easily extensible polymer base material, and reference numeral 32 denotes 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 building materials, band members, binding members, sanitary products, clothing parts, base fabrics for poultices, and the like.

  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 material 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.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited at all by these.

Production Example 1 (Manufacture of base material syrup)
In a reaction vessel equipped with a condenser, a thermometer, and a stirrer, 71 parts by weight of isobornyl acrylate (trade name “IBXA”, manufactured by Osaka Organic Chemical Industry Co., Ltd.) as a (meth) acrylic monomer, n -19 parts by weight of butyl acrylate (BA, manufactured by Toa Gosei Co., Ltd.), 10 parts by weight of acrylic acid (AA), 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. 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 a hardly extensible 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 Polyurethane Co., Ltd.) while stirring, and react at 65 ° C. for 5 hours. To obtain a urethane polymer. Thereafter, 18.3 parts by weight of hydroxyethyl acrylate (trade name “Acrix HEA”, manufactured by Toa Gosei Co., Ltd.) was added and reacted at 65 ° C. for 1 hour to obtain an acryloyl group-terminated urethane polymer. The weight average molecular weight of this acryloyl group-terminated urethane polymer was 5400.
Thereafter, 42.9 parts by weight of trimethylolpropane EO-added triacrylate (trade name “Biscoat # 360”, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and red ink (trade name) are added to 100 parts by weight of the acryloyl group-terminated urethane polymer. "Shachihata Stamp Stand Dedicated Stamp Ink SGN-40 Red" (manufactured by Shachihata Co., Ltd.) 4.7 parts by weight and bis (2,4,6-trimethylbenzoyl) phenyl-phosphine oxide (trade name " By adding 0.04 part by weight of “Irgacure 819” (manufactured by BASF), an acrylic monomer mixture (syrup for forming a 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 base material syrup (= extensible polymer base material) The sheet-like extensible organic base material (thickness: 300 micrometers) in which the syrup hardening part (= difficulty extensible polymer part; columnar difficult extension part) was arrange | positioned 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 represents 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) 9 is formed in the same manner as in Examples 1 to 5, except that a rectangular outer frame in FIG. 9 does not indicate the contour shape of the sheet-like stretchable organic base material. 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 syrup for forming an inextensible polymer part obtained in Production Example 2, 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 The sheet-like extensibility organic base material (thickness: 300 micrometers) was obtained by operation similar to Examples 1-5 except having 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 indicate the length (mm) of each straight line part constituting the polygonal line, and c is the distance between adjacent syrup parts for forming the hardly extensible polymer part (adjacent polygonal line) 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 center A pattern formed such 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 in the same manner as in Examples 1 to 5 except that it 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 value (mm) of the distance 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 line intervals extend in parallel with equal intervals, and the distance between adjacent wavy lines is constant; The sheet-like extensibility organic base material (thickness: 300 micrometers) was obtained by operation similar to Examples 1-5 except having 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 in the same manner 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 Corporation) 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 the difference (S ₂ −S ₁ ) (%) were calculated (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 (the width of the linear portion on the surface of the base material) before and after stretching, and the formula: {(length after stretching-stretching) 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.

1 Sheet-like extensible organic base material 2 Easy-extensible polymer matrix (Easily-extensible polymer matrix)
20 Material layer for polymer matrix formation (energy ray curable composition layer for easily extensible 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 difficult-to-extend polymer parts)
31 material for forming a hardly extensible polymer portion 32 material for forming a hardly extensible polymer portion 300 energy ray curable composition for forming a partially extensible polymer portion that has been partially cured 4 support 5 cover film

Claims (12)

  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.   The sheet-like extensible organic base material according to claim 1, wherein a line width of the line shape in 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 a linear shape, a broken line shape, a wavy line shape, an arc line shape, or an amorphous linear shape.   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 base material as described in any one of 1-3.   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.   Thickness is 0.01 mm-1 cm, The sheet-like extensible organic base material as described in any one of Claims 1-7.   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 property is gradation in the vicinity of the interface between the hardly extensible polymer portion and the easily extensible polymer base material.   Furthermore, the sheet-like extensible organic base material as described in any one of Claims 1-11 which has a stretching property.

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