JP2012214697A - Sheet-shaped organic base material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sheet-shaped flexible base material which has flexibility and a portion having a shape to be hardly changed even when deformed.SOLUTION: The sheet-shaped organic base material is the sheet-shaped organic base material obtained by forming a hard polymer part partially and integrally in a soft polymer matrix. The ratio (E'/E') (wherein E'(Pa) is the tensile elasticity of the hard polymer part, and E'(Pa) is the tensile elasticity of the soft polymer matrix) is greater than 1 when measured by using an apparatus for measuring viscoelastic properties of a solid (the size of a sample: 25 mm length×3 mm width, an interchuck distance: 5 mm, a mode: time dispersion, temperature: 27°C, frequency: 1 Hz, initial strain: 0.2%, measuring time: 120 seconds, measuring frequency: 10 times).

Description

  The present invention relates to a sheet-like organic base material, and more particularly to a flexible sheet-like organic base material in which a hard polymer portion is partially and integrally formed in a soft polymer base material. The sheet-like 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., utilizing its flexibility. Further, this sheet-like organic base material is flexible and deformable as a whole base material, but the hard polymer part is hard to be deformed and its shape is maintained. Can be applied, and other members can be held and fixed. For this reason, for example, it can utilize also for an electronics member, an optical member, an optoelectronic member, a car electronics member, a member for household appliances, a member for housing equipment, a building material, etc.

  Organic members having flexibility are widely used for band members, bundling members, sanitary products, clothing, poultice base fabrics, and the like. The organic member having flexibility is generally composed of a composition having uniform flexibility (Patent Document 1). However, when such a flexible member is deformed, every part of the flexible member is deformed. Therefore, even if a design is applied to a certain portion, the design is distorted if the flexible member is deformed. Further, when it is desired to fix another member to the flexible member, since all parts of the flexible member are deformed, it is difficult to reliably hold and fix the other member.

JP 2003-342169 A

  Accordingly, an object of the present invention is to provide a sheet-like flexible substrate having a portion that is flexible and hardly changes its shape even when deformed.

  As a result of intensive studies to achieve the above object, the present inventors have found that the above object can be achieved by forming a hard polymer part partially and integrally in a soft polymer base material. The present invention has been completed.

That is, the present invention is a sheet-like organic base material in which a hard polymer part is partially and integrally formed in a soft polymer matrix, and is 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 strain: 0.2%, measurement time: 120 seconds, number of measurements: 10 times Provided is a sheet-like organic base material characterized in that the ratio (E ′ ₁ / E ′ ₂ ) between the elastic modulus E ′ ₁ (Pa) and the tensile elastic modulus E ′ ₂ (Pa) of the soft polymer base material is greater than 1. To do.

The present invention is also a sheet-like organic base material in which a hard polymer portion is partially and integrally formed in a soft polymer base material, and a hardness test using a rubber hardness meter (test piece 30 mm × the ratio of 30mm sheet organic base ten laminate of needle pushing 10 seconds after the hardness, a hardness H ₂ of the hardness H ₁ and the soft polymer matrix of hard polymer portion as determined by a temperature 25 ° C.) Provided is a sheet-like organic base material characterized in that (H ₁ / H ₂ ) is larger than 1.

The present invention further relates to a sheet-like organic base material in which a hard polymer portion is partially and integrally formed in a soft polymer base material, and the nanoindentation measurement (indentation depth 4 μm, indentation speed 1. 5 [mu] m / sec, the sheet-shaped organic substrate ratio of the load P ₁ and the load P ₂ of the soft polymer matrix of hard polymer portion at a temperature _{25 ℃) (P 1 / P} 2) is equal to or greater than 1 provide.

  In the said sheet-like organic base material, in the soft polymer base material, the hard polymer part may be partially formed in the state exposed in the at least one surface, or the state which is not exposed. The surface shape of the hard polymer portion or the projection shape when the surface of the sheet-like organic base material of the hard polymer portion is the projection surface may be any of a substantially circular shape, a substantially rectangular shape, and an indefinite shape.

  A plurality of hard polymer portions may be formed in a regular pattern in the soft polymer base material. In this case, the distance between adjacent hard polymer parts is, for example, 0.05 mm to 50 cm.

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

  The length in the thickness direction of the hard polymer portion is preferably at least 1/50 of the thickness of the sheet-like organic substrate. Moreover, the said hard polymer part may be continuously formed from one surface of a sheet-like organic base material to the other surface. Further, the hardness characteristics may be gradation in the vicinity of the interface between the hard polymer portion and the soft polymer base material.

  The said sheet-like organic base material may have a stretching property.

  According to the sheet-like organic base material of the present invention, since the shape of the hard polymer portion hardly changes even when the base material is deformed, the shape-invariable portion has a desired function while having a function as a flexible member. Design can be applied, and other members can be held and fixed.

It is a schematic perspective view which shows an example of the sheet-like organic base material of this invention. It is a schematic perspective view which shows the II-II line cross section of the sheet-like organic base material of FIG. It is the schematic (sectional drawing) which shows an example of the manufacturing method of the sheet-like 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 organic base material of this invention. It is the schematic (sectional drawing) which shows the further another example of the manufacturing method of the sheet-like organic base material of this invention. It is a figure which shows the sample of the sheet-like organic base material used by the tension test and the hysteresis test. 4 is a graph showing the results of elongation gradation measurement in a sheet-like organic base material obtained in Example 3. It is a graph which shows the result of the elongation gradation measurement in the sheet-like organic base material obtained in Example 9. FIG. 2 is a photomicrograph showing a cross section of a hard polymer portion forming site in a sheet-like organic substrate obtained in Example 11. FIG. 4 is a photomicrograph showing a cross section of a hard polymer portion forming site in a sheet-like organic substrate obtained in Example 34. FIG.

[Sheet organic substrate]
The sheet-like organic base material of the present invention is a sheet-like organic base material in which a hard polymer portion is partially and integrally formed in a soft polymer base material.

  FIG. 1 is a schematic perspective view showing an example of the sheet-like organic base material of the present invention. FIG. 2 is a schematic perspective view showing a II-II cross section of the sheet-like organic substrate of FIG. 1 and 2, a sheet-like organic base material 1 includes a soft polymer base material 2 (soft polymer base material portion) and a hard polymer portion that is partially and integrally formed in the soft polymer base material 2. 3.

In the present invention, the tensile modulus, the hardness in the hardness test, or the hardness in the nanoindentation measurement is employed as a measure of the hardness of the soft polymer base material 2 and the hard polymer portion 3. That is, in the present invention, a solid viscoelasticity measuring apparatus (sample size: length 25 mm × width 3 mm, distance between chucks: 5 mm, mode: time dispersion, temperature: 27 ° C., frequency: 1 Hz, initial strain: 0.2%, measurement time: 120 sec, number of measurements: 10 times) the tensile modulus of the hard polymer portion 3 as measured by E _'1 (Pa) and the tensile modulus E of the soft polymer matrix 2' ₂ (Pa) ratio (E ' ₁ / E ′ ₂ ) is greater than 1, or a hardness test using a rubber hardness tester (10-sheet laminate of a sheet-like organic substrate 1 having a test piece of 30 mm × 30 mm, hardness after 10 seconds of needle pushing , the ratio between the hardness H ₁ and hardness of H ₂ soft polymer base material 2 of the hard polymer unit 3 as determined by the temperature of _{25 ℃) (H 1 / H} 2) is greater than 1, or, nanoindentation measurements (Indentation depth 4μm, indentation speed 1.5μm / sec It is important the ratio of the load P ₂ of the load P ₁ and the soft polymer matrix 2 of rigid polymeric portion 3 (P ₁ / P ₂₎ is greater than 1 at a temperature 25 ° C.). When such an organic base material is deformed, the portion of the soft polymer base material is deformed, but the hard polymer portion formed partially and integrally is not deformed or hardly deformed. For this reason, the design in which a shape is desired not to change can be given to a hard polymer part, or another member can be fixed and hold | maintained.

The ratio of the tensile modulus (E ′ ₁ / E ′ ₂ ) is preferably 5 or more, more preferably 10 or more, and particularly preferably 100 or more. The hardness ratio (H ₁ / H ₂ ) is preferably 1.01 or more, more preferably 1.10 or more, and particularly preferably 1.20 or more. Further, the ratio (P ₁ / P ₂ ) between the load P ₁ and the load P ₂ is preferably 1.01 or more, more preferably 1.10 or more, and particularly preferably 1.50 or more.

Since the base material is formed of a soft polymer, the sheet-like organic base material of the present invention usually has extensibility. For example, the sheet-like organic base material of the present invention has a sheet-like shape when the sheet-like organic base material 1 is extended up to 1.5 times in an extension test (temperature: 25 ° C.). For organic base materials, when stretched up to 1.25 times), the elongation ratio S ₂ (%) of the soft polymer base material portion (the ratio of the stretched length to the original length) and the stretch rate of the hard polymer portion S ₁ (%) ratio of (original length ratio of extending to the _{length) [S 2 (%) /} S 1 (%)] is greater than 1.

In such a sheet-like organic base material, when the base material is stretched in one direction, even if the soft polymer base material part 2 is stretched, the hard polymer part 3 is difficult to stretch and the shape is difficult to change. The design applied to the hard polymer portion 3 is not distorted, and the retainability of the member fixed to the hard polymer portion 3 is less likely to deteriorate. The ratio [S ₂ (%) / S ₁ (%)] is more preferably 2 or more, and further preferably 5 or more (particularly 10 or more).

  The extension test can be performed, for example, by using a tensile tester.

In the sheet-like organic base material of the present invention, when the sheet-like organic base material 1 is extended to 1.5 times (150% of the original length) in the extension test (temperature 25 ° C.) (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 hard polymer portion 3 (ratio of the stretched length to the original 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 organic substrate of the present invention is obtained when the sheet-like organic substrate 1 is stretched to 1.5 times (150% of the original length) in the elongation test (temperature 25 ° C.) (however, In the case of 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 ₂ (%) of the soft polymer base material part 2 and the elongation rate S of the hard polymer part 3 The difference of ₁ (%) [S ₂ (%) − S ₁ (%)] is preferably 20% or more, and more preferably 40% or more.

In this invention, it is preferable that the extensibility of a sheet-like organic base material is isotropic. For example, the elongation rate S ₂ (1) (%) of the soft polymer base material portion 2 in one direction and the elongation rate S ₂ (2) (2) of the soft polymer base material portion 2 in a direction orthogonal to the direction. %) [S ₂ (1) / S ₂ (2)] [where S ₂ (1) ≧ S ₂ (2)] is preferably 1 to 1.3, preferably 1 to 1.2. Is more preferable, and 1 to 1.1 is particularly preferable.

  The elongation (breaking elongation) of the sheet-like organic base material of the present invention in a tensile test (test specimen width 20 mm, distance between chucks 50 mm, temperature 25 ° C., tensile speed 200 mm / min) is preferably 50% or more. It is preferably 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.

  In the present invention, the hard polymer portion 3 only needs to be formed partially and integrally in the soft polymer base material 2, for example, it may be formed only at one location, and is not continuous at a plurality of locations. May be scattered or scattered.

  The shape of the hard polymer portion 3 is not particularly limited and can be appropriately selected according to the purpose. For example, the shape may be any of a shape extending in the sheet thickness direction such as a substantially columnar shape and a substantially rectangular parallelepiped shape, and an indefinite shape.

  In the present invention, the length (for example, diameter) of the long axis (longest portion) in the sheet surface direction of the hard polymer portion 3 is not particularly limited, and can be appropriately set depending on the application, for example, about 0.05 mm to 10 cm. It can be. When this length is too small, the utility value of a hard polymer part will become small, and when too large, it will become difficult to manufacture. Further, for example, when a plurality of hard polymer parts 3 are formed and the distance (shortest distance) between adjacent hard polymer parts 3 is, for example, 0.05 mm to 50 cm, the long axis in the surface direction of the hard polymer part 3 If the length of the (longest part) is less than 0.05 mm, the technical significance of having a shape-invariant portion is reduced even when the entire sheet-like organic base material 1 is extended in one direction. Moreover, when this length exceeds 10 cm, not only manufacture becomes difficult, but the said technical significance tends to become small.

  The length of the long axis (longest part) in the surface direction of the hard polymer part 3 is preferably 0.1 mm or more, more preferably 0.5 mm or more, still more preferably 1 mm or more, particularly preferably 2 mm or more, especially 5 mm. The above is preferable. Moreover, 8 cm is preferable and, as for the upper limit of the length (longest part) of the long axis of the surface direction of the hard polymer part 3, 5 cm is especially preferable.

  In the vicinity of the interface (boundary part) between the hard polymer part 3 and the soft polymer base material part 2, a gradation (gradient) in which the composition and / or physical properties [hardness characteristics, elongation characteristics (elongation rate, etc.), etc.] gradually change. It may be done. For example, in the vicinity of the interface between the hard polymer portion 3 and the soft polymer base material 2, the hardness characteristics of the hard polymer portion (for example, the tensile elastic modulus, the hardness in the hardness test, the hardness in the nanoindentation measurement, etc.) gradually. It may have a gradation that changes. The sheet-like organic base material 1 having such a gradation near the interface between the hard polymer part 3 and the soft polymer base material part 2 is obtained when, for example, the sheet-like organic base material 1 is elongated, the hard polymer part 3 and the soft polymer base material 1 are stretched. It has a characteristic that it is difficult to cut at the boundary with the material part 2. Moreover, gradation is exhibited not only in the vicinity of the interface (boundary part) between the hard polymer part 3 and the soft polymer base material part 2 but also in many or all of the hard polymer part 3 and / or the soft polymer base material part 2. May be. In the sheet-like organic base material having a gradation part, the boundary between the hard polymer part 3 and the soft polymer base part 2 is the hardness of the non-gradient part of the soft polymer base part 2 [over the entire soft polymer base part] When the gradation is exhibited, the hardness of the lowest hardness portion and the hardness of the non-gradient portion of the hard polymer portion 3 [when the gradation is exhibited over the entire hard polymer portion 3, the hardness is the highest. It can be determined by a line connecting the average value of the hardness of the high part].

  In the present invention, the hard polymer portion 3 may be formed in any part of the soft polymer base material 2, but is formed in a state where it is exposed on at least one surface in that the hard polymer portion 3 can be effectively used. It is preferable. Project the surface shape (at least one surface shape) of the hard polymer part 3 or the surface (at least one surface) of the sheet-like organic substrate 1 of the hard polymer part 3 when the hard polymer part 3 is not exposed on the surface. The projected shape (the shape seen from the surface side of the sheet-like organic base material 1) when the surface is used may be any of a substantially circular shape, a substantially rectangular shape, an indefinite shape, and the like. From the viewpoint of ease of production, the surface shape of the hard polymer portion 3 is preferably substantially circular. Moreover, in order to ensure smooth extensibility of the sheet-like organic base material 1, the hard polymer portion 3 is preferably formed at a place other than the end portion in the surface direction of the soft polymer base material 2. That is, the hard polymer portion 3 is preferably formed in a state (except for both surfaces) included in the soft polymer base material 2.

  When a plurality of hard polymer portions 3 are formed in the soft polymer base material 2, the plurality of hard polymer portions 3 may be formed randomly or in a regular pattern. When the plurality of hard polymer portions 3 are formed in a regular pattern, the distance between the adjacent hard polymer portions 3 (shortest distance) is, for example, 0.05 mm to 50 cm, and the upper limit of the distance is preferably It is 30 cm, more preferably 20 cm, still more preferably 15 cm, particularly preferably 10 cm. The lower limit of the distance is preferably 0.1 mm, more preferably 1 mm, still more preferably 3 mm, and particularly preferably 5 mm. If the hard polymer portion 3 is formed in a regular pattern in advance, a large number of sheet-like organic base materials 1 can be efficiently manufactured by cutting. When a plurality of hard polymer portions 3 are formed, the shapes and sizes of the plurality of hard polymer portions 3 may be the same or different. When the plurality of hard polymer portions 3 have the same shape and size, a sheet-like organic base material having the same shape and size can be produced with high production efficiency.

  The thickness of the sheet-like 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 organic base material 1 is, for example, 1 cm, preferably 5 mm, and more preferably 2 mm.

  The hard polymer portion 3 may be formed continuously from one surface of the sheet-like organic base material 1 or continuously from one surface of the sheet-like organic base material 1 to the other surface. It may be. Further, the hard polymer portion 3 may be formed by being buried in the sheet-like organic base material 1. In any case, the length (thickness) in the thickness direction of the hard polymer portion 3 is preferably at least 1/50, more preferably at least 1 of the thickness of the sheet-like organic base material 1 in any of the above cases. / 20, more preferably at least 1/10, particularly preferably at least 1/4. Moreover, from the viewpoint of the retention of other members, for example, when the hard polymer portion 3 is continuously formed from one surface of the sheet-like organic base material 1, the thickness of the hard polymer portion 3 is The length (thickness) in the direction is further preferably at least 1/3, particularly at least 1/2 (especially at least 2/3) of the thickness of the sheet-like organic substrate 1.

  The sheet-like organic substrate of the present invention may further have stretchability. When the sheet-like organic base material has stretchability, it can be suitably used in a field where stretchability is required such as a band member. By selecting a polymer having stretchability as the polymer constituting the soft polymer base material 2, stretchability can be imparted to the sheet-like organic substrate 1. In such a sheet-like organic base material having elasticity, a hysteresis test at 50% elongation using a tensile tester (test piece width 20 mm, chuck distance 50 mm, temperature 25 ° C., tensile speed 200 mm / min) The elongation recovery rate obtained is preferably 10% or more, more preferably 30% or more, still more preferably 50% or more (particularly preferably 70% or more). According to such a stretchable sheet-like organic base material, even if the base material is stretched, the shape of the hard polymer portion hardly changes, so that the shape remains unchanged while having a function as a stretchable member. It becomes possible to give a desired design to the part and hold and fix other members.

  The surface roughness Ra of the surface (at least one surface) of the soft polymer base material part 2 and the surface (at least one surface) of the formation site of the hard polymer part 3 is preferably 100 nm or less, more preferably 50 nm or less. Preferably, it is 30 nm or less. 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).

[Soft polymer matrix]
In this invention, the soft polymer base material 2 can be comprised with the soft polymer which has a softness | flexibility. Examples of soft polymers include polyurethane polymers, polyurea polymers, polyurethane urea polymers, polyolefin polymers (especially polydiene polymers), silicone polymers, polyester polymers, polyether polymers, polyamide polymers, and polystyrene polymers. Examples thereof include an acrylic polymer having a low glass transition temperature (Tg) (an acrylic polymer having a Tg of less than 5 ° C., preferably 0 ° C. or less, more preferably −5 ° C. or less). These polymers can be used alone or in combination of two or more. The proportion of these polymers in the entire polymer constituting the soft 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. .

  Among these, polyurethane polymers, polyurea polymers, polyurethane urea polymers, polyolefin polymers (particularly polydiene polymers), silicone polymers, polystyrene polymers (for example, styrene-isoprene-styrene block copolymers, styrene- Styrenic thermoplastic elastomers such as butadiene-styrene block copolymers are particularly preferred. Commercially available products (polymer alone, polymer aqueous dispersion, polymer organic solvent solution, etc.) can also be used as the polymer having extensibility (or further stretchability).

  The soft polymer base material portion 2 is formed by, for example, coating a liquid precursor of a polymer constituting the soft polymer base material on a support to form a soft polymer base material forming material layer, and for forming the soft polymer base material. After forming the hard polymer portion forming material at a predetermined portion of the material layer, the liquid precursor in the soft polymer base material forming material layer can be converted into a target polymer. 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.

  The soft polymer base material portion 2 is formed, for example, by applying a solution or dispersion containing a polymer constituting the soft polymer base material on a support to form a soft polymer base material forming material layer. It is also possible to form the hard polymer portion forming material at a predetermined portion of the base material forming material layer, and then dry and remove the solvent in the soft polymer base material forming material layer. 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 soft polymer base material part 2 forms, for example, a soft polymer base material forming material layer on a support with a single polymer constituting the soft polymer base material, and a predetermined portion of the soft polymer base material forming material layer. It can also be formed by performing a melting / cooling process (hot melt process) after a material for forming the hard polymer portion is disposed on the substrate. The soft polymer base material forming material layer in this case can be formed by subjecting the polymer alone to a general film forming method (extrusion molding, injection molding, compression molding, hot melt treatment, etc.). In this case, the soft polymer base material forming material layer and the soft 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 soft 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 polyacryl chain. Curable polymer P having at least one polymer chain selected from the group consisting of energy chain curable group A ₁ in the main chain or side chain, or curable polymer P and energy beam curable group A It can be formed by irradiating an energy ray to a mixture with the curable monomer M having ₂ and curing.

  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 is prepared by combining a polyisocyanate compound, a long-chain polyol compound, and a chain extender and other isocyanate-reactive compounds used as necessary. It can obtain by making it react.

  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 co-condensate of polyhexamethylene carbonate diol with polyester diol or polyether diol. Etc.

  The polyolefin polyol is a polyol having an olefin as a component of the skeleton (or main chain) of the polymer or copolymer and having at least two hydroxyl groups in the molecule (particularly at the terminal). The olefin may be an olefin having a carbon-carbon double bond at the terminal (for example, an α-olefin such as ethylene or propylene), or an olefin having a carbon-carbon double bond at a position other than the terminal. (For example, isobutene and the like) and diene (for example, butadiene, isoprene and the like) may be used. Typical examples of polyolefin polyols include butadiene homopolymers, isoprene homopolymers, butadiene-styrene copolymers, butadiene-isoprene copolymers, butadiene-isoprene copolymers such as butadiene or isoprene-based 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 (particularly diamines) such as 2-chloroaniline.

  Examples of the polymer having a polyurethane chain include a polyisocyanate compound, a long-chain polyol compound, and, if necessary, a chain extender and another isocyanate-reactive compound, the number of moles of isocyanate groups of the polyisocyanate, and a long-chain polyol. And the ratio (NCO / isocyanate reactive group) to the number of moles of isocyanate reactive groups (hydroxyl group, amino group, etc.) of the chain extender and the like is 0.8 to 2.0, particularly 0.95 to 1.5. What was obtained by making it react in the range which becomes is preferable. In order to accelerate the reaction, a catalyst such as a tertiary amine, an organometallic compound, or a tin compound may be used in the above reaction as necessary.

If the end of a polymer having a polyurethane chain is an isocyanate group can utilize the isocyanate group as a reactive functional group R _2. In this case, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, etc. can be used as the compound having the energy ray-curable group A ₁ and the reactive functional group R ₁ .

Further, when the end of the polymer having a polyurethane chain is a hydroxyl group, it can be used the hydroxyl groups as reactive functional groups R _2. In this case, (meth) acryloyloxyethyl isocyanate or the like can be used as the compound having the energy ray curable group A ₁ and the reactive functional group R ₁ .

Polymer having reactive functional group R ₂ and having polyurea chain, polymer having reactive functional group R ₂ and having polyurethane urea chain, polyolefin having reactive functional group R ₂ and polyolefin chain (particularly polydiene chain) ), A reactive functional group R ₂ and a silicone chain, a reactive functional group R ₂ and a polyester chain, a reactive functional group R ₂ and a polyether chain , A polymer having a reactive functional group R ₂ and a polyamide chain, and a polymer having a reactive functional group R ₂ and a polyacryl chain can also be obtained by 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 soft polymer base material 2 and the hard polymer portion 3, the same kind of monomer as the polymer constituting the hard polymer portion (particularly, the same monomer) is used as the curable monomer M. Is also preferable.

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 soft 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 soft polymer constituting the soft polymer base material 2, the group consisting of polyurethane chain, polyurea chain, polyurethane urea chain, polyolefin chain (particularly polydiene chain), silicone chain, polyester chain, polyether chain and polyamide chain. In the case of having at least one polymer chain selected more, the proportion of the at least one polymer chain portion in the whole polymer is preferably 20% by weight or more (for example, 20 to 100% by weight), more preferably Is 25% by weight or more (for example, 25 to 90% by weight), more preferably about 30% by weight or more (for example, 30 to 75% by weight). If this ratio is too small, the flexibility tends to decrease. The soft polymer constituting the soft 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, more preferably −5 ° C. or less. In the case of a polymer), the proportion of the polyacryl chain in the whole polymer may be 100% by weight.

  The soft polymer base material 2 may include, 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, if 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.

[Hard polymer part]
In the present invention, the material constituting the hard 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.

  For example, the hard polymer portion 3 is derived from a monomer [particularly (meth) acrylic monomer] having a Tg of (i) homopolymer of 5 ° C. or higher (more preferably 15 ° C. or higher, more preferably 50 ° C. or higher). 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 structural unit to be formed with respect to all the structural units of the polymer [for example, Tg is 5 ° C. or higher, preferably 15 ° C. A polymer material containing the above polymer (especially acrylic polymer)], (ii) a structural unit derived from a polyfunctional monomer having two or more curable groups (radical polymerizable groups, cationic polymerizable groups) in the molecule. , A polymer containing 50% by weight or more (more preferably 60% by weight or more, and further preferably 80% by weight or more) based on the total structural unit of the polymer [especially The structural unit derived from a polyfunctional monomer having 2 or more radically polymerizable groups in the molecule (particularly an acrylic polyfunctional monomer) is 50% by weight or more (more preferably 60% by weight) based on the total structural unit of the polymer. Or more, more preferably 80 wt% or more) containing polymer material], (iii) filler-containing polymer material, (iv) tensile modulus of 0.1 MPa or more (more preferably 0.5 MPa or more, more preferably 1 MPa or more, particularly preferably 5 MPa or more).

  In the case of (i) above, the entire polymer material constituting the hard polymer part of the polymer containing 50% by weight or more of the structural unit derived from the monomer having a Tg of the homopolymer of 5 ° C. or higher based on the total structural unit of the polymer. The occupying ratio 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), a polymer material constituting a hard polymer part of a polymer containing 50% by weight or more of a structural unit derived from a polyfunctional monomer having two or more curable groups in the molecule based on the total structural unit of the polymer The 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 (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 monomer 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 can the hard polymer portion 3 be imparted with hardness and difficult stretchability, but various functions such as conductivity and thermal conductivity can be imparted depending on the type of filler.

  The shape of the filler is not particularly limited, and may be any of a bulk shape, a spherical shape, a needle shape, a plate shape, and the like. 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 soft polymer base material and the Tg of the homopolymer exemplified as the polymer constituting the hard polymer portion 3 are as follows. The above-described (ii) curable group in the molecule is exemplified as a polymer containing 50% by weight or more of a structural unit derived from a monomer having a temperature of 5 ° C. or higher based on the total structural unit of the polymer, and a polymer constituting the hard polymer portion 3. (Iv) The tensile elastic modulus is 0.1 MPa or more, which will be described later as a polymer comprising 50% by weight or more of the structural unit derived from the polyfunctional monomer having the above, and the polymer constituting the hard polymer part 3 Any of polymer etc. may be sufficient. 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 hard polymer part 3 is obtained by drying and removing a polymer part formed by converting a precursor of a polymer material constituting the hard polymer part 3 into the polymer material, and a solution or dispersion containing the polymer material. Any of a polymer part formed, a polymer part formed by melting and cooling the polymer material, and the like may be used.

When the hard polymer portion 3 is composed of a polymer material containing a polymer containing (i) a structural unit derived from a monomer having a Tg of 5 ° C. or higher as a homopolymer in an amount of 50% by weight or more based on the total structural units of the polymer. For example, after placing a monomer component containing 50% by weight or more of the monomer having a Tg of 5 ° C. or more of the homopolymer on a predetermined portion of the material layer for forming a soft polymer base material, irradiation with energy rays is performed. It 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.

The hard polymer part 3 is composed of a polymer material containing a polymer containing (ii) 50% by weight or more of a structural unit derived from a polyfunctional monomer having two or more curable groups in the molecule based on the total structural unit of the polymer In this case, for example, a monomer component containing 50% by weight or more of the polyfunctional monomer in the whole monomer is disposed on a predetermined portion of the soft polymer base material forming material layer, and then cured (polymerized) by irradiation with energy rays. Can be formed. 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 the hard polymer portion 3 is formed, 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 soft 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.

  When the hard polymer part 3 is composed of the above-mentioned (iii) filler-containing polymer material, a dispersion containing a filler (an aqueous dispersion, an organic solvent dispersion, etc.) at a predetermined portion of the soft polymer base material forming material layer ), The hard polymer portion 3 can be formed by drying and removing the solvent in the dispersion. In this case, the hard polymer portion 3 is composed of the filler and the same polymer as the polymer constituting the soft polymer base material 2. In the case where the soft polymer base material forming material layer is formed from an organic solvent solution of a polymer constituting the layer, it is preferable to use an organic solvent dispersion of the filler, and the soft polymer base material forming material layer Is preferably formed from an aqueous dispersion of the polymer constituting the layer, an aqueous dispersion of filler is preferably used. In addition, a filler, a monomer (such as an energy ray-curable monomer) that can be derived into the polymer that should constitute the hard polymer part, or a partial polymer thereof, and a solvent as necessary Then, the hard polymer portion 3 can be formed by polymerizing the monomer or a partial polymer thereof. Furthermore, after arranging a mixed liquid containing a filler, a pre-crosslinking polymer that can be induced by crosslinking in a polymer that should constitute the hard polymer portion, and a crosslinking agent at a predetermined portion of the soft polymer base material forming material layer, A hard polymer portion can be formed by crosslinking the polymer. Furthermore, after placing the filler alone (powder) in a predetermined part of the soft polymer base material forming material layer, the soft polymer base material forming material layer is converted into the soft polymer base material, thereby simultaneously forming the hard polymer portion. Can be formed. In this case, the hard polymer portion is composed of the filler and the same polymer as that constituting the soft polymer base material. The usage-amount of a filler can be suitably adjusted with the magnitude | size of the hard polymer part to form, the intensity | strength of the desired hard polymer part, etc. For example, the filler content in the hard 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 hard 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 polymerized. Alternatively, the hard polymer portion 3 can be formed by curing or cross-linking a polymer that can be induced by curing or cross-linking to the polymer.

  If necessary, the hard polymer part 3 may be, 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 crosslinking agent). Agents, metal chelate crosslinking agents, metal salt crosslinking agents, carbodiimide crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, amine crosslinking agents), crosslinking accelerators, silane coupling agents, tackifying resins (rosin) Derivatives, polyterpene resins, petroleum resins, oil-soluble phenols, etc.), anti-aging agents, fillers, colorants (pigments, dyes, etc.), UV absorbers, antioxidants, plasticizers, softeners, surfactants, antistatic agents Additives such as an agent may be included as long as the characteristics of the present invention are not impaired.

  Among the materials constituting the hard polymer part, the polymer is the same type of polymer as the polymer constituting the soft polymer base material, or the soft polymer base material from the viewpoint of the integrity and adhesion between the soft polymer base material and the hard polymer member. It is preferable that the polymer has the same type of polymer chain in the main chain or side chain as the polymer chain (main chain or side chain) of the polymer constituting the.

  More specifically, as a preferred combination of the polymer constituting the soft polymer matrix and the polymer constituting the hard polymer portion, a combination of polyurethane polymers, a combination of polyurea polymers, a combination of polyurethane urea polymers, a polyolefin Combinations of polymer polymers, combinations of silicone polymers, combinations of polyester polymers, combinations of polyether polymers, combinations of polyamide polymers, combinations of polystyrene polymers, combinations of acrylic polymers It is done. 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 preferred combination of the polymer constituting the soft polymer matrix and the polymer constituting the hard polymer portion, a combination of polyurethane polymers, a combination of polymers having a polyurethane chain, a combination of polystyrene polymers, a polystyrene type A combination of polymers having a 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 organic substrate]
The sheet-like 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: For forming a soft polymer base material by using a liquid precursor of the polymer (a) constituting the soft polymer base material, a solution or dispersion containing the polymer (a), or the polymer (a) alone on the support. A step of forming a material layer Step B: a step of disposing a hard polymer part forming material at a predetermined portion of the soft polymer base material forming material layer,
Process C: At least one process selected from a reaction, a solvent dry removal process, and a melting / cooling process is performed on the soft polymer base material forming material layer in which the hard polymer part forming material is arranged at a predetermined site. And obtaining a sheet-like organic base material in which the hard polymer portion is partially and integrally formed in the soft polymer base material

  First, in step A, a soft polymer matrix is formed on a support by a polymer (a) liquid precursor constituting the soft polymer matrix, a solution or dispersion containing the polymer (a), or the polymer (a) alone. A 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 soft polymer matrix include monomers that can be derived into the polymer (a) (energy ray curable monomers, etc.), partial polymers of the monomers, and polymers (a) by curing or crosslinking. And a polymer before curing or cross-linking that can be induced into the polymer. 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 section of [Soft polymer matrix] can be used.

  When the soft polymer base material forming material layer is formed from the liquid precursor of the polymer (a) constituting the soft polymer base material, or a solution or dispersion containing the polymer (a), for example, on the support. By applying these, a soft 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 material layer for forming a soft polymer base material is formed of the polymer (a) alone, for example, a predetermined amount of the polymer (a) is placed on a support, and a support (separator or the like) is further provided thereon. And a soft polymer base material forming material layer can be formed by pressing this under heating (at a temperature equal to or higher than the melting temperature of the polymer). Moreover, the soft polymer base material forming material layer can be formed on the support by extruding the polymer (a). Furthermore, using the polymer (a), a layer to be a soft polymer base material forming material layer is prepared separately by an appropriate molding method, and the soft polymer base material forming material is transferred onto a support. Layers can also be formed.

  The formation of the soft 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 soft polymer base material forming material layer is, for example, 0.01 mm to 1 cm, the upper limit is preferably 5 mm, more preferably 2 mm, and the lower limit is preferably 0.03 mm, more preferably. 0.05 mm.

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

  In Step B, as the hard polymer part forming material, the hard polymer part is composed of 50% by weight of the structural unit derived from the monomer (i) having a Tg of the homopolymer of 5 ° C. or higher. In the case of comprising a polymer material containing a polymer containing the above, a curable composition containing a monomer component containing 50% by weight or more of the monomer having a Tg of 5 ° C. or more of the homopolymer, or a partial polymer thereof. A product (such as an energy beam curable composition) can be used. This curable composition usually contains a polymerization initiator.

  The hard polymer part is composed of a polymer material containing (ii) a polymer containing 50% by weight or more of a structural unit derived from a polyfunctional monomer having two or more curable groups in the molecule based on the total structural unit of the polymer. In this case, as a material for forming a hard polymer part, a curable composition (energy beam) containing a monomer component containing 50% by weight or more of a polyfunctional monomer having two or more curable groups in the molecule, or a partial polymer thereof. Curable compositions etc.) can be used. This curable composition usually contains a polymerization initiator.

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

  When the hard polymer part is composed of the polymer material having the above-mentioned (iv) tensile elastic modulus of 0.1 MPa or more, a monomer that can be derived into a polymer having a tensile elastic modulus of 0.1 MPa or more as the hard polymer part forming material ( An energy ray-curable monomer or the like) or a curable composition containing the partial polymer thereof (an energy ray-curable composition or the like) can be used.

  The method (means) for arranging the hard polymer portion forming material at a predetermined portion of the soft polymer base material forming material layer is not particularly limited. For example, (1) the hard polymer portion forming material is soft polymer A method of coating, dripping, placing, driving or printing from above onto a predetermined portion of the base material forming material layer, (2) a soft polymer base material forming material layer in a liquid form of the hard polymer portion forming material (3) Coating, dripping, placing or printing the material for forming the hard polymer part on a support different from the support on which the soft polymer base material forming material layer is formed. And a method of transferring this onto the soft polymer base material forming material layer.

  When the hard polymer part forming material is in a liquid state, the viscosity of the liquid is a temperature at the time of coating, dropping, etc. (for example, a predetermined temperature within a range of 10 to 40 ° C., particularly from the viewpoint of workability, etc. 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. is there. If the viscosity is too low, it is difficult to obtain a hard polymer portion having a desired shape. Conversely, if the viscosity is too high, the coating workability tends to decrease.

  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 type, amount of use, viscosity, etc., of the hard polymer part forming material disposed at a predetermined site of the soft polymer base material forming material layer, the size of the hard polymer part (the size in the plane direction and the size) Height) can be controlled. When a plurality of hard polymer parts are formed, the hard polymer part forming material is applied at an appropriate interval. In addition, the shape of a hard polymer part is controllable by using the means which regulates dripping and injection | pouring location of the hard polymer part forming material. When the size of the hard polymer portion is relatively large, the dropping method is often used, and when the size of the hard polymer portion is relatively small, the injection method is often used. 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 the soft polymer base material, so that it does not get dirty. In the case of the injection method, there is an advantage that the hard polymer part forming material is less likely to diffuse into the soft polymer base material forming material layer than the dropping method.

  In addition, when using the energy ray curable composition which is a precursor of the material (b) which comprises a hard polymer part as a material for hard polymer part formation, this energy ray curable composition (coating liquid) is soft. In order to suppress diffusion of the energy ray-curable composition (coating liquid) to the peripheral part (soft polymer matrix-forming material layer) when it is disposed at a predetermined position of the polymer matrix-forming material layer, the energy ray curing is performed. The composition may contain a polymer. In particular, when a large number of hard polymer parts are formed in a soft polymer base material, after a predetermined number of coating liquids are arranged in a predetermined part of the soft polymer base material forming material layer, the process proceeds to the step of irradiating energy rays. In the place where the coating liquid is arranged in the initial stage, the coating liquid diffuses to the peripheral part (bleeds) with the passage of time and hardens in that state, and a hard polymer part having a desired shape and size cannot be obtained. The outline of the hard polymer part may become unclear. In such a case, if a polymer is contained in the energy ray curable composition (coating liquid), the monomers and the like contained in the coating liquid are transferred to the peripheral part (soft polymer matrix forming material layer). Even when a large number of hard polymer portions are formed, it is possible to form a hard 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 ray curable composition (coating liquid) is disposed by dropping at a large number of predetermined portions of the soft 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 to be 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 hard polymer part, and is exemplified as the polymer constituting the soft polymer base material. Either a polymer or a polymer exemplified as the polymer constituting the hard polymer portion may be used, but the soft polymer base material is configured from the viewpoint of the integrity and adhesion between the soft polymer base material and the hard polymer portion. A polymer having the same kind of polymer chain as the polymer or a polymer chain (main chain or side chain) of the polymer constituting the soft polymer base material in the main chain or side chain is preferable.

  As the energy ray curable composition (coating liquid), the coating liquid is dropped onto the soft polymer base material forming material layer (drop amount: about 0.03 μL), and after 60 seconds for forming the soft polymer base material. The diameter of the coating solution on the material layer is preferably 1.2 times or less, more preferably 1.15 times or less than the diameter of the coating solution immediately after dropping. In addition, the diameter of the coating liquid on the soft polymer base material forming material layer 120 seconds after dropping the coating liquid on the soft polymer base material forming material layer (drop amount: about 0.03 μL) What becomes 1.4 times or less with respect to the diameter of this coating liquid 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 60 seconds or 120 seconds after dropping is larger than the diameter of the coating solution immediately after dropping, a pattern sheet [polymer base material (A) having a targeted shape is used. A sheet-like organic base material in which a large number of structural parts (B) are formed (for example, formed in a regular pattern) may not be obtained.

  After applying, dripping, placing, driving, printing, pouring or transferring the hard polymer part forming material, the hard polymer part forming material is brought to a predetermined depth of the soft polymer base material forming material layer as necessary. Leave until infiltration, migration and settling.

  In Step C, the soft polymer base material forming material layer in which the hard polymer part forming material is arranged at a predetermined site is selected from a reaction, a solvent dry removal process, and a melting / cooling process (hot melt process). The sheet-like organic base material in which the hard polymer portion is partially and integrally formed in the soft polymer base material is obtained by performing at least one treatment.

  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 the soft polymer base material forming material layer and the hard polymer portion forming material are melted together.

  In the present invention, the combination of the form of the soft polymer base material forming material used in Step A and the form of the hard polymer part forming material used in Step B is not particularly limited, and can be arbitrarily combined. For example, when using an energy ray curable material [liquid precursor of polymer (a) (syrup or the like)] as a soft polymer base material forming material, when using a solvent-based material [solution containing polymer (a)], In the case of using a dispersion-based material [emulsion containing polymer (a), etc.] or in the case of using a hot-melt material [polymer (a) alone], the hard polymer part forming material may be a solvent-based material (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.] Any form of material can be used. More specifically, the form of the soft polymer base material and the hard polymer part forming material is a combination of energy ray curable materials (energy ray curable syrup, etc.), solvent-based materials (solutions). , Combinations of dispersion materials (emulsions, etc.), combinations of hot melt materials, combinations of solvent materials (solutions) and dispersion materials (emulsions, etc.) (in no particular order), hot melt Combination of soluble material and solvent-based material (solution) (in no particular order), combination of hot-melt material and dispersion-based material (emulsion, etc.) (in no particular order), solvent-based material (solution) and filler (powder) , A dispersion material (emulsion, etc.) and a filler (powder), a hot-melt material and a filler (powder), or the like. In Step C, by performing a treatment suitable for the form of each material, a sheet-like organic base material in which the hard polymer portion is partially and integrally formed in the soft polymer base material can be obtained.

  In addition, the sheet-like organic base material which has gradation regarding composition and / or physical properties (hardness characteristics, elongation characteristics, etc.) at least in the vicinity of the interface between the hard polymer portion and the soft polymer base material portion is, for example, a soft polymer base material. As the material for forming and the material for forming the hard polymer part, it can be produced by using materials that are common or similar to each other (solvent, monomer, etc.), or materials that have an affinity for each other (solvent, monomer, etc.). Specifically, for example, the above gradation can be obtained by configuring both the soft polymer matrix forming material and the hard polymer portion forming material with a material (such as a polymer liquid precursor) containing an acrylic monomer. Can do. 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 portion of the sheet-like organic base material having the gradation is different from the composition assumed from the material for forming each portion (hard polymer portion, soft polymer base material portion). The degree of gradation (width) can be adjusted by the type and amount of the soft polymer base material forming material and the hard polymer part forming material (solvent, monomer, etc.). Further, as described above, in the case where an energy ray curable composition is used as the material for forming the hard polymer part, when the polymer is blended in the energy ray curable composition, the type, amount, and weight of the polymer The degree of gradation (width) can be adjusted by the average molecular weight or the like.

  In the manufacturing method of the sheet-like organic base material of the present invention, the following embodiments (I) to (III) are preferable from the viewpoint of efficiently producing the sheet-like organic base material.

  (I) In step A, a material layer for forming a soft polymer matrix is formed on the support using an energy ray-curable composition that is a liquid precursor of the polymer (a). In step B, the soft polymer matrix is formed. An energy ray-curable composition that is a precursor of the material (b) constituting the hard polymer portion is arranged at a predetermined portion of the material forming material layer, and in step C, the energy that is the precursor of the material (b) The soft polymer base material forming material layer in which the linear curable composition is arranged at a predetermined site is irradiated with energy rays, and the two energy ray curable compositions are cured, so that the hard polymer portion is in the soft polymer base material. A method of obtaining a sheet-like organic substrate formed partially and integrally.

  (II) In step A, a soft polymer base material forming material layer is formed on the support with a solution or dispersion containing the polymer (a). In step B, the soft polymer base material forming material layer A material (b) [for example, polymer, filler (powder), etc.] constituting the hard polymer part or a solution or dispersion containing the material (b) is arranged at a predetermined site. The soft polymer base material forming material layer in which the constituent material (b) or a solution or dispersion containing the material (b) is disposed at a predetermined site is subjected to a solvent dry removal treatment in the soft polymer base material. A method for obtaining a sheet-like organic base material in which a hard polymer portion is partially and integrally formed.

  (III) In step A, a soft polymer base material forming material layer is formed on the support by the polymer (a) alone, and in step B, a hard portion is formed on a predetermined portion of the soft polymer base material forming material layer. Forming a soft polymer matrix in which a material (b) [for example, a polymer, a filler (powder), etc.] constituting the polymer portion is arranged, and in step C, the material (b) constituting the hard polymer portion is arranged at a predetermined site. Method for obtaining a sheet-like organic base material in which the hard polymer part is partially and integrally formed in the soft polymer base material (A) by subjecting the material layer to melting and cooling treatment (hot melt treatment) .

More specifically, the sheet-like organic substrate of the present invention can be produced, for example, through the following steps.
Step A1: Step of forming an energy ray-curable composition layer for forming a soft polymer base material on a support Step B1: Forming a hard polymer portion at a predetermined portion of the energy ray-curable composition layer for forming a soft polymer base material Step C1: Disposing (containing) energy beam curable composition for use Step C1: Energy beam curable composition layer for forming soft polymer base material provided with energy beam curable composition for forming hard polymer part Irradiation is performed to cure the energy ray curable composition for forming a hard polymer portion and the energy ray curable composition layer for forming a soft polymer base material, so that the hard polymer portion is partially and integrally formed in the soft polymer base material. For obtaining a sheet-like organic base material having an extensibility formed on the surface

  This method is a specific example of the embodiment (I), and FIG. 3 is a schematic explanatory view (cross-sectional view) thereof. In FIG. 3, (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, an energy ray-curable composition layer 20 for forming a soft polymer base material is formed on the support 4. As the support 4, those described above can be used.

The energy ray-curable composition layer 20 for forming a soft polymer matrix is, for example, the polyurethane chain, polyurea chain, polyurethane urea chain, polyolefin chain (particularly, polydiene chain), silicone chain, polyester chain, polyether chain, A curable polymer P having at least one polymer chain selected from the group consisting of 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 It can be formed by coating the support 4 with an energy ray curable composition containing the mixture of the curable polymer P and the curable monomer M having the energy ray curable group A ₂ and a photopolymerization initiator.

  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 ray curable composition layer 20 for soft polymer base material formation can also be performed using a suitable type | mold. In this case, the viscosity of the curable composition may be lower than the above range.

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

  In step B1, the energy ray-curable composition 30 for forming a hard polymer portion is disposed (included) in the energy ray-curable composition layer 20 for forming a soft 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 (dropped) from above to a predetermined portion of the energy ray-curable composition layer 20 for forming a soft polymer base material. Or by injecting into a predetermined location in the energy ray-curable composition layer 20 for forming the soft polymer base material. Also, by transferring the energy ray-curable composition containing the monomer component and the photopolymerization initiator onto the energy ray-curable composition layer 20 for forming a soft polymer base material from the support coated and dropped. Can also be done.

  The hard polymer part-forming energy beam curable composition 30 is preferably in the form of a syrup. From the viewpoint of workability and the like, the viscosity of the energy ray-curable composition 30 for forming a hard polymer part is, for example, at a temperature at the time of coating (for example, a predetermined temperature within a range of 10 to 40 ° C, particularly 25 ° C), 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 the hard polymer portion is not particularly limited, and for example, a syringe, an appropriate dropping device, or the like can be used. Moreover, the transfer method of the energy beam curable composition 30 for forming a hard polymer portion is not particularly limited. For example, a method using an intaglio coating machine such as a gravure coater, an energy beam curable composition 30 for forming a hard polymer portion is used. For example, a method in which the coated / dropped support and the energy polymer curable composition layer 20 for forming a soft polymer base material are bonded to each other can be used.

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

  In step C1, the energy ray-curable composition layer 20 for forming a soft polymer matrix containing the energy ray-curable composition 30 for forming a hard polymer portion is irradiated with energy rays to form the energy for forming the hard polymer portion. A sheet-like organic material in which the hard polymer part 3 is partially and integrally formed in the soft polymer base material 2 by curing the wire curable composition 30 and the energy ray curable composition layer 20 for forming the soft polymer base material. A substrate is obtained.

  Although ultraviolet rays (UV) are used as energy rays in FIG. 3, ionizing radiation such as α rays, β rays, γ rays, neutron rays, electron rays, and visible rays may be used as described above.

  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.

  Energy beam for forming a soft polymer base material containing the hard polymer part-forming energy beam curable composition 30 for the purpose of preventing the inhibition of curing by oxygen and the purpose of smoothing the surface at the time of energy beam irradiation The cover film 5 may be laminated on the surface of the 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, in the case of irradiating ultraviolet rays, as shown in FIG. 3 (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 ). After that, as shown in FIG. 3D, the cover film 5 is laminated, and thereafter, as shown in FIG. 3E, the cover film 5 is long at 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 a soft polymer base material, and 300 is a partially cured energy beam curable composition for forming a hard polymer portion.

When energy beam irradiation is performed in one stage, for example, as shown in FIG. 3 (d ′) after step B1, a soft polymer containing the energy beam curable composition 30 for forming a hard polymer portion is contained. The cover film 5 may be laminated on the surface of the base material forming energy beam curable composition layer 20 and irradiated with ultraviolet rays 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 energy ray curable composition 30 for forming the hard polymer part and the energy ray curable composition layer 20 for forming the soft polymer base material as described above, as shown in FIG. The cover film 5 and the support 4 are peeled off as necessary, cut into a suitable size as necessary, and used as the sheet-like organic substrate 1. The cutting operation may be performed before the cover film 5 or the support 4 is peeled off.

Moreover, the sheet-like organic base material of this invention can also be manufactured by passing through the following process more specifically.
Step A2: Step of forming a soft polymer base material forming material layer by applying a solution or dispersion containing polymer a constituting the soft polymer base material on the support Step B2: For forming the soft polymer base material A solution or dispersion containing a polymer constituting the hard polymer part or a filler (powder) constituting the hard polymer part is applied to a predetermined part of the material layer by coating, dropping, placing, driving in, printing, or the like. Step (Creating) Step C2: Drying the polymer layer forming material layer in which the solution or dispersion containing the polymer constituting the hard polymer portion or the filler (powder) constituting the hard polymer portion is disposed And removing the solvent to obtain a sheet-like organic base material in which the hard polymer part is partially and integrally formed in the soft polymer base material.

  This method is a specific example of the embodiment (II), and FIG. 4 is a schematic explanatory view (cross-sectional view) thereof. In FIG. 4, (g) corresponds to step A2, (h) corresponds to step B2, and (i) and (j) correspond to step C2. Reference numeral 21 is a layer made of a solution or dispersion containing a polymer constituting the soft polymer matrix (soft polymer matrix forming material layer), 31 is a solution or dispersion containing a polymer constituting the hard polymer part, or The filler (powder) which comprises a hard polymer part is shown. Reference numerals 1, 2, 3, and 4 are the same as described above.

Furthermore, the sheet-like organic base material of this invention can also be manufactured by passing through the following process more specifically.
Step A3: Step of forming a material layer for forming a soft polymer base material by forming a sheet of polymer a constituting the soft polymer base material on a support by hot pressing, extrusion molding or the like Step B3: Forming the soft polymer base material A step of placing (containing) a polymer or filler (powder) constituting the hard polymer portion by placing or dropping (melting) or the like in a predetermined part of the material layer for use Step C3: constituting the hard polymer portion Extensibility in which a hard polymer part is partially and integrally formed in a soft polymer base material by heating and melting the material layer for forming a soft polymer base material with a polymer or filler (powder). For obtaining a sheet-like organic substrate having

  This method is a specific example of the above-described embodiment (III), and FIG. 5 is a schematic explanatory view (cross-sectional view) thereof. In FIG. 5, (k) corresponds to the process A3, (l) corresponds to the process B3, (m), and (n) corresponds to the process C3. Reference numeral 22 denotes a sheet made of a polymer constituting the soft polymer base material (soft polymer base material forming material layer), and reference numeral 32 denotes a polymer or filler (powder) constituting the hard polymer portion. Reference numerals 1, 2, 3, and 4 are the same as described above.

  The sheet-like organic base material 1 thus obtained is a member for an electronic product (transistor, integrated circuit, capacitor, sensor, actuator, etc.), an optical product (display, illumination, optical waveguide circuit, etc.) as a flexible member having a shape-invariant portion. ) Materials, optoelectronic products (light emitting diodes, photodiodes, solar cells, etc.), car electronics products, home appliances, housing equipment, building materials, band members, binding members, sanitary goods, clothing It can be used as a product part, a base material for a poultice, and the like. Moreover, the hard polymer part 3 is continuously formed (penetrated) from one surface of the sheet-like organic base material 1 to the other surface, and the hard polymer part 3 contains a conductive filler. In some cases, for example, it can be used as an anisotropic conductive sheet, a dicing tape capable of conducting an on-chip conduction test, or a base material thereof. Further, the hard polymer portion 3 is continuously formed (penetrated) from one surface of the sheet-like organic base material 1 to the other surface, and the hard polymer portion 3 contains a heat conductive filler. If it is, it can be used as, for example, 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 A)
In a reaction vessel equipped with a condenser, a thermometer, and a stirrer, 80 parts by weight of isobornyl acrylate (trade name “IBXA”, manufactured by Osaka Organic Chemical Industry Co., Ltd.) as a (meth) acrylic monomer, n -20 parts by weight of butyl acrylate (BA, manufactured by Toa Gosei Co., Ltd.), 68.4 parts by weight of poly (oxytetramethylene) glycol (PTMG650, manufactured by Mitsubishi Chemical Corporation) having a number average molecular weight of 650 as a polyol, As a catalyst, 0.01 part by weight of dibutyltin dilaurate (DBTL) was added, and 25.5 parts by weight of hydrogenated xylylene diisocyanate (HXDI, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.) was added dropwise with stirring. It was made to react for a time and the urethane polymer-acrylic-type monomer mixture was obtained. Thereafter, 6.1 parts by weight of hydroxyethyl acrylate (trade name “Acrix HEA”, manufactured by Toa Gosei Co., Ltd.) was further added and reacted at 65 ° C. for 1 hour, whereby an acryloyl group-terminated urethane polymer-acrylic monomer mixture. Got. Thereafter, 0.15 parts by weight of 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name “Irgacure 651”, 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 A) was 10.5 Pa · s.

Production Example 2 (Manufacture of base material syrup B)
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 B) was 8 Pa · s.

Production Example 3 (Production of base material syrup C)
In a reaction vessel equipped with a condenser, a thermometer, and a stirrer, 50 parts by weight of t-butyl acrylate (trade name “TBA”, manufactured by Osaka Organic Chemical Industry Co., Ltd.) as a (meth) acrylic monomer, n -Poly (oxytetramethylene) glycol (PTMG650, Mitsubishi Chemical Corp.) having a number average molecular weight of 650, 20 parts by weight of butyl acrylate (BA, manufactured by Toagosei Co., Ltd.), 30 parts by weight of acrylic acid (AA), and polyol. 73.4 parts by weight) and 0.01 part by weight of dibutyltin dilaurate (DBTL) as a catalyst, and 26.6 parts by weight of xylene diisocyanate (XDI, manufactured by Mitsui Chemicals Polyurethanes) while stirring. The mixture was added dropwise and reacted at 65 ° C. for 5 hours to obtain a urethane polymer-acrylic monomer mixture. Thereafter, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (trade name “Irgacure 2959”, manufactured by BASF) as a photopolymerization initiator. Urethane polymer-acrylic monomer by adding 0.3 part by weight, 0.05 part by weight of p-methoxyphenol (MEHQ, manufactured by Wako Pure Chemical Industries, Ltd.) as a polymerization inhibitor and reacting at 65 ° C. for 1 hour. A mixture was obtained. Thereafter, 0.15 parts by weight of 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name “Irgacure 651”, 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 C) was 7 Pa · s.

Production Example 4 (Production of syrup A for forming a hard polymer part)
100 parts by weight of trimethylolpropane EO-added triacrylate (trade name “Biscoat # 360”, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and blue dye (trade name “SZ7620”, manufactured by Dainichi Seika Kogyo Co., Ltd.) 1 part by weight and 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name “Irgacure 651” 0.1 parts by weight as a photopolymerization initiator) were added and dispersed, and an acrylic monomer mixture (hard The polymer part (hard part) forming syrup A) was obtained, and the viscosity (25 ° C.) of the obtained hard polymer part forming syrup A was 66 mPa · s.

Production Example 5 (Production of hard polymer part forming syrup B)
To 100 parts by weight of pentaerythritol tetraacrylate (trade name “Biscoat # 400”, manufactured by Osaka Organic Chemical Industry Co., Ltd.), red ink (trade name “Stamp Hatter Stamp Stamp SGN-40 Red”, manufactured by Shachihata Co., Ltd.) ) 0.1 parts by weight and 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name “Irgacure 651”) as a photopolymerization initiator and dispersed therein, and an acrylic monomer A mixture (syrup B for forming a hard polymer part) was obtained, and the viscosity (25 ° C.) of the obtained syrup B for forming a hard polymer part was 526 mPa · s.

Production Example 6 (Production of syrup C for forming a hard polymer part)
100 parts by weight of isobornyl acrylate (trade name “IBXA”, manufactured by Osaka Organic Chemical Industry Co., Ltd.), 0.1 part by weight of blue dye (trade name “SZ7620”, manufactured by Dainichi Seika Kogyo Co., Ltd.) and light 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name “Irgacure 651” 0.1 parts by weight as a polymerization initiator was added and dispersed into a nitrogen introduction tube, a cooling tube, and a temperature. An acrylic monomer mixture (for forming a hard polymer part) is charged into a reaction vessel equipped with a meter and a stirrer, and UV is irradiated from above in a nitrogen stream while stirring to convert some of the monomer into a polymer. Syrup C) was obtained, and the viscosity (25 ° C.) of the obtained syrup C for forming a hard polymer part was 5000 mPa · s.

Production Example 7 (Production of syrup D for forming a hard polymer part)
100 parts by weight of isobornyl acrylate (trade name “IBXA”, manufactured by Osaka Organic Chemical Industry Co., Ltd.), 0.1 part by weight of blue dye (trade name “SZ7620”, manufactured by Dainichi Seika Kogyo Co., Ltd.) and light As a polymerization initiator, 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name “Irgacure 651” 0.1 parts by weight is added and dispersed, and an acrylic monomer mixture (hard polymer part forming syrup) The viscosity (25 ° C.) of the obtained syrup D for forming a hard polymer part was 10 mPa · s.

Production Example 8 (Production of syrup E for forming a hard polymer part)
100 parts by weight of trimethylolpropane triacrylate (trade name “TMP3A”, manufactured by Osaka Organic Chemical Industry Co., Ltd.), 0.1 part by weight of blue dye (trade name “SZ7620”, manufactured by Dainichi Seika Kogyo Co., Ltd.) As a photopolymerization initiator, 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name “Irgacure 651” 0.1 part by weight is added and dispersed to prepare an acrylic monomer mixture (for forming a hard polymer part). Syrup E) was obtained, and the viscosity (25 ° C.) of the obtained hard polymer part forming syrup E was 120 mPa · s.

Production Example 9 (Manufacture of base material syrup D)
In a reaction vessel equipped with a nitrogen introduction tube, a cooling tube, a thermometer, and a stirrer, 60 isobornyl acrylate (trade name “IBXA”, manufactured by Osaka Organic Chemical Industry Co., Ltd.) is used as a (meth) acrylic monomer. Parts by weight, 40 parts by weight of n-butyl acrylate (BA, manufactured by Toagosei Co., Ltd.), bis (2,4,6-trimethylbenzoyl) phenyl-phosphine oxide (trade name “Irgacure 819”) as a photopolymerization initiator , Manufactured by BASF Co., Ltd.), and UV irradiation from above in a nitrogen stream while stirring to convert a part of the monomer into a polymer, thereby converting an acrylic monomer mixture (matrix syrup D) Obtained. The viscosity (25 ° C.) of the base material syrup D was 5 Pa · s.

Production Example 10 (Production of syrup F for forming a hard polymer part)
Trimethylolpropane EO-added triacrylate (trade name “Biscoat # 360”, manufactured by Osaka Organic Chemical Industry Co., Ltd.), 100 parts by weight of red ink (trade name “Stamp Hat Stamp Stamp SGN-40 Red”, Co., Ltd.) and 3.3 parts by weight of 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name “Irgacure 651”) as a photopolymerization initiator was added and dispersed. An acrylic monomer mixture (hard polymer part forming syrup F) was obtained.

Example 1
The base material syrup A obtained in Production Example 1 was applied to the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, length 400 mm, width 240 mm, thickness 38 μm) with an applicator, and the thickness A 300 μm base syrup layer was formed. The hard polymer part forming syrup A (about 0.01 g) obtained in Production Example 4 is dropped onto a predetermined portion of the base material syrup layer (30 mm in the longitudinal direction) from above, and the island-like hard polymer part is dropped. Forming syrup portions were formed at 30 mm intervals (center-to-center distance) in the longitudinal direction. Then, from above, ultraviolet rays were pre-irradiated with a metal halide lamp (MHL) (illuminance: 200 mW / cm ² , integrated irradiation amount: 200 mJ / cm ² ), and the base material syrup and the hard polymer part forming syrup were semi-cured. Then, a cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, length 400 mm, width 240 mm, thickness 38 μm) is pasted onto the semi-cured syrup with a hand roller, and further with an ultraviolet lamp (BL type) Irradiated with ultraviolet rays (ultraviolet illuminance: 3.4 mW / cm ² , integrated irradiation amount: 2000 mJ / cm ² ), and a hard polymer part forming syrup having a substantially columnar shape in a cured product of a base material syrup (= soft polymer base material) Hardened part (= hard polymer part; hard part) (diameter approximately 8.6 mm, height 300 μm) is a predetermined interval [30 mm interval (distance between centers) )] Is obtained. (Thickness: 300 μm) As a result of the structural evaluation described later, in the obtained sheet-like organic base material, the hard polymer part-forming syrup cured part was continuously formed from one surface of the sheet-like organic base material to a depth of 2/3 or more. However, it was not formed until it reached the other surface (embedded type).

Example 2
Except that the base material syrup B obtained in Production Example 2 was used as the base material syrup, the same operation as in Example 1 was performed, and a substantially cylindrical hard material in the cured base material syrup (= soft polymer base material). A sheet-like organic base material (thickness: 300 μm) in which polymer part-forming syrup cured parts (= hard polymer part) (diameter of about 7.0 mm) are arranged at a predetermined interval [30 mm interval (distance between centers)] is obtained. It was. As a result of the structural evaluation described later, in the obtained sheet-like organic base material, the hard polymer part-forming syrup cured part was continuously formed from one surface of the sheet-like organic base material to a depth of 2/3 or more. However, it was not formed until it reached the other surface (embedded type).

Example 3
Except that the base material syrup C obtained in Production Example 3 was used as the base material syrup, the same operation as in Example 1 was performed, and a substantially cylindrical hard material in the cured base material syrup (= soft polymer base material). A sheet-like organic base material (thickness: 300 μm) in which syrup cured parts (= hard polymer part) (diameter of about 7.1 mm) for polymer part formation are arranged at a predetermined interval [30 mm interval (distance between centers)] It was. As a result of the structural evaluation described later, in the obtained sheet-like organic base material, the hard polymer part-forming syrup cured part was continuously formed from one surface of the sheet-like organic base material to a depth of 2/3 or more. However, it was not formed until it reached the other surface (embedded type).

Example 4
In the cured product of the base material syrup (= soft polymer base material), except that the hard polymer part forming syrup B obtained in Production Example 5 was used as the hard polymer part forming syrup, A sheet-like organic base material in which a syrup hardened portion (= hard polymer portion) (diameter of about 7.3 mm) having a substantially cylindrical shape is disposed at a predetermined interval [30 mm interval (distance between centers)]. Thickness: 300 μm) was obtained. As a result of the structural evaluation described later, in the obtained sheet-like organic base material, the hard polymer part-forming syrup cured part was continuously formed from one surface of the sheet-like organic base material to a depth of 2/3 or more. However, it was not formed until it reached the other surface (embedded type).

Example 5
Example 1 except that the base material syrup B obtained in Production Example 2 was used as the base material syrup, and the hard polymer part forming syrup B obtained in Production Example 5 was used as the hard polymer part forming syrup. Operation is performed, and a syrup hardened part (= hard polymer part) for forming a hard polymer part (= hard polymer part) (diameter of about 7.0 mm, height of 300 μm) having a substantially cylindrical shape is predetermined in a hardened material (= soft polymer base material) of the base material syrup. The sheet-like organic base material (thickness: 300 micrometers) arrange | positioned by the space | interval [30-mm space | interval (distance between centers)] was obtained. As a result of the structural evaluation described later, in the obtained sheet-like organic base material, the hard polymer part-forming syrup cured part is continuously from one surface of the sheet-like organic base material to a depth of 1/2 or more and less than 2/3. Although it was formed, it was not formed until it reached the other surface (embedded type).

Example 6
Example 1 except that the base material syrup C obtained in Production Example 3 was used as the base material syrup, and the hard polymer part forming syrup B obtained in Production Example 5 was used as the hard polymer part forming syrup. The syrup hardened part (= hard polymer part) (diameter of about 6.9 mm) for forming a hard polymer part in a substantially columnar shape is set at a predetermined interval [30 mm in the hardened material of the base material syrup (= soft polymer base material). The sheet-like organic base material (thickness: 300 micrometers) arrange | positioned by the space | interval (distance between centers)] was obtained. As a result of the structural evaluation described later, in the obtained sheet-like organic base material, the hard polymer part-forming syrup cured part was continuously formed from one surface of the sheet-like organic base material to a depth of 2/3 or more. However, it was not formed until it reached the other surface (embedded type).

Example 7
In the cured product of the base material syrup (= soft polymer base material), the same operation as in Example 1 was performed except that the hard polymer part forming syrup C obtained in Production Example 6 was used as the hard polymer part forming syrup. In a sheet form, a syrup cured portion (= hard polymer portion) (diameter of about 9.5 mm, height of 300 μm) having a substantially cylindrical shape is disposed at a predetermined interval [30 mm interval (distance between centers)]. An organic base material (thickness: 300 μm) was obtained. As a result of the structural evaluation described later, in the obtained sheet-like organic base material, the hard polymer part-forming syrup cured part was continuously formed from one surface of the sheet-like organic base material to the other surface ( Penetration type).

Example 8
Example 1 except that the base material syrup B obtained in Production Example 2 was used as the base material syrup, and the hard polymer part forming syrup C obtained in Production Example 6 was used as the hard polymer part forming syrup. Operation is performed, and a syrup hardened part (= hard polymer part) for forming a hard polymer part (= hard polymer part) (diameter of about 9.7 mm, height of 300 μm) having a substantially cylindrical shape is predetermined in a hardened base syrup (= soft polymer base material) A sheet-like organic base material (thickness: 300 μm) arranged at intervals of [30 mm (distance between centers)] was obtained. As a result of the structural evaluation described later, in the obtained sheet-like organic base material, the hard polymer part-forming syrup cured part was continuously formed from one surface of the sheet-like organic base material to the other surface ( Penetration type).

Example 9
Example 1 except that the base material syrup C obtained in Production Example 3 was used as the base material syrup, and the hard polymer part forming syrup C obtained in Production Example 6 was used as the hard polymer part forming syrup. Operation is performed, and a substantially cylindrical hard polymer part forming syrup hardened part (= hard polymer part) (diameter of about 9.0 mm, height of 300 μm) is predetermined in a hardened base syrup (= soft polymer base material) A sheet-like organic base material (thickness: 300 μm) arranged at intervals of [30 mm (distance between centers)] was obtained. As a result of the structural evaluation described later, in the obtained sheet-like organic base material, the hard polymer part-forming syrup cured part was continuously formed from one surface of the sheet-like organic base material to the other surface ( Penetration type).

Example 10
The base material syrup B obtained in Production Example 2 was coated on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, length 400 mm, width 240 mm, thickness 38 μm) with an applicator, and the thickness A 300 μm base syrup layer was formed. A syrup A for forming a hard polymer portion (about 0.01 g) obtained in Production Example 4 is injected into a predetermined portion of this base material syrup layer (at intervals of 30 mm in the longitudinal direction) to form an island-shaped syrup for forming a hard polymer portion. The parts were formed at 30 mm intervals (center-to-center distance) in the longitudinal direction. Then, from above, ultraviolet rays were pre-irradiated with a metal halide lamp (MHL) (illuminance: 200 mW / cm ² , integrated irradiation amount: 200 mJ / cm ² ), and the base material syrup and the hard polymer part forming syrup were semi-cured. Then, a cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, length 400 mm, width 240 mm, thickness 38 μm) is pasted onto the semi-cured syrup with a hand roller, and further with an ultraviolet lamp (BL type) Irradiated with ultraviolet rays (ultraviolet illuminance: 3.4 mW / cm ² , integrated irradiation amount: 2000 mJ / cm ² ), and a hard polymer part forming syrup having a substantially columnar shape in a cured product of a base material syrup (= soft polymer base material) Hardened parts (= hard polymer part) (diameter approximately 8.6 mm, height 300 μm) are arranged at a predetermined interval [30 mm interval (distance between centers)]. The placed sheet-like organic base material (thickness: 300 μm) was obtained. As a result of the structural evaluation described later, in the obtained sheet-like organic base material, the hard polymer part-forming syrup cured part was continuously formed from one surface of the sheet-like organic base material to the other surface ( Penetration type).

Example 11
The base material syrup B obtained in Production Example 2 was coated on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, length 400 mm, width 240 mm, thickness 38 μm) with an applicator, and the thickness A 300 μm base syrup layer was formed. The hard polymer part forming syrup A (about 0.01 g) obtained in Production Example 4 is dropped onto a predetermined portion of the base material syrup layer (30 mm in the longitudinal direction) from above, and the island-like hard polymer part is dropped. Forming syrup portions were formed at 30 mm intervals (center-to-center distance) in the longitudinal direction. After that, a cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, length 400 mm, width 240 mm, thickness 38 μm) is pasted on the syrup and irradiated with ultraviolet rays (BL type) (ultraviolet illuminance: 3.4 mW / cm ² , cumulative irradiation amount: 2000 mJ / cm ² ), a substantially cylindrical hard polymer part-forming syrup cured part (diameter: about 8.6 mm, height: 211 μm) is predetermined in the cured material of the base material syrup The sheet-like organic base material (thickness: 336 micrometers) arrange | positioned by the space | interval [30-mm space | interval (distance between centers)] was obtained. As a result of the structural evaluation described later, in the obtained sheet-like organic base material, the hard polymer part-forming syrup cured part is continuously from one surface of the sheet-like organic base material to a depth of 1/2 or more and less than 2/3. Although it was formed, it was not formed until it reached the other surface (embedded type).

Example 12
Example 1 except that the base material syrup B obtained in Production Example 2 was used as the base material syrup, and the hard polymer part forming syrup B obtained in Production Example 5 was used as the hard polymer part forming syrup. The syrup hardened part (= hard polymer part) (hard polymer part) (approximately 6.8 mm in diameter) having a substantially cylindrical shape is formed in a hardened material (= soft polymer base material) of the base material syrup with a predetermined interval [30 mm. The sheet-like organic base material (thickness: 300 micrometers) arrange | positioned by the space | interval (distance between centers)] was obtained. As a result of the structural evaluation described later, in the obtained sheet-like organic base material, the hard polymer part forming syrup cured part is continuously from one surface of the sheet-like organic base material to a depth of 1/4 or more and less than 1/3. Although it was formed, it was not formed until it reached the other surface (embedded type).

Example 13
The base material syrup B obtained in Production Example 2 was used as the base material syrup, and the titanium oxide (trade name “TTO” was used as the hard polymer part forming syrup with respect to 100 parts by weight of the base material syrup B obtained in Production Example 2. -51 (C) ", particle shape: bulk, particle size: 0.01 to 0.03 [mu] m, manufactured by Ishihara Sangyo Co., Ltd.) The same operation as in Example 1 except that syrup was used. The syrup hardened part (= hard polymer part) (approximately 7 mm in diameter) for forming a hard polymer part in a substantially columnar shape in a hardened material (= soft polymer base material) of the base material syrup is set at a predetermined interval [30 mm interval (center-to-center) The sheet-like organic base material (thickness: 300 μm) arranged in the above) was obtained.

Example 14
The base material syrup B obtained in Production Example 2 was used as the base material syrup, and ATO-coated titanium oxide (trade name) was used as the hard polymer part forming syrup with respect to 100 parts by weight of the base material syrup B obtained in Production Example 2. Example 1 except that a syrup containing 10 parts by weight of “FT-3000”, particle shape: needle shape, major axis diameter: 5.15 μm, minor axis diameter: 0.27 μm, manufactured by Ishihara Sangyo Co., Ltd. The syrup hardened part (= hard polymer part) (hard polymer part) (approximately 6 mm in diameter) having a substantially cylindrical shape in the hardened material of the base material syrup (= soft polymer base material) is formed at a predetermined interval [ The sheet-like organic base material (thickness: 300 micrometers) arrange | positioned by 30 mm space | interval (distance between centers)] was obtained.

Example 15
The base material syrup B obtained in Production Example 2 was used as the base material syrup, and boron nitride (trade name “PT” was used as the hard polymer part forming syrup with respect to 100 parts by weight of the base material syrup B obtained in Production Example 2. -120 ", particle shape: plate-like, particle diameter: 8-14 μm, manufactured by Momentive Performance Materials Japan GK)) The same operation as in Example 1 was carried out except that 10 parts by weight of syrup was used. In the cured product of the base material syrup (= soft polymer base material), the syrup cured part for forming a hard polymer part (= hard polymer part) (diameter of about 5 mm) having a substantially cylindrical shape has a predetermined interval [30 mm interval (between the centers) The sheet-like organic base material (thickness: 300 μm) arranged in the distance)] was obtained.

Example 16
The base material syrup B obtained in Production Example 2 was used as a base material syrup, and calcium carbonate (trade name “heavy weight” was used as a hard polymer part forming syrup with respect to 100 parts by weight of the base material syrup B obtained in Production Example 2. Calcium carbonate ”, particle shape: bulk, average particle size: 12 μm, manufactured by Maruo Calcium Co., Ltd.) In the product (= soft polymer base material), a substantially cylindrical hard polymer portion forming syrup cured portion (= hard polymer portion) (diameter of about 7 mm) is arranged at a predetermined interval [30 mm interval (distance between centers)]. A sheet-like organic base material (thickness: 300 μm) was obtained.

Example 17
As the base material syrup, the base material syrup B obtained in Production Example 2 was used, and as the hard polymer part forming syrup, 100 parts by weight of the base material syrup B obtained in Production Example 2 was used for lipophilic mica (trade name “ The same operation as in Example 1 was performed except that a syrup containing 10 parts by weight of “Somasif MPE”, particle shape: plate shape, particle size: 5 to 7 μm, manufactured by Coop Chemical Co., Ltd. was used. Hard column (hard polymer part) syrup cured part (= hard polymer part) (diameter of about 8 mm) in a substantially cylindrical shape is arranged at a predetermined interval [30 mm interval (distance between centers)] in the cured product (= soft polymer base material). The obtained sheet-like organic base material (thickness: 300 μm) was obtained.

Example 18
Using the base material syrup B obtained in Production Example 2 as the base material syrup, and using 100 parts by weight of the base material syrup B obtained in Production Example 2 as the hard polymer part forming syrup, the lipophilic smectite (trade name “ The same operation as in Example 1 was carried out except that a syrup containing 10 parts by weight of “Lucentite SPN”, particle shape: plate shape, average particle size: 0.05 μm, manufactured by Coop Chemical Co., Ltd. was used. Syrup cured part (= hard polymer part) for forming a hard polymer part (= hard polymer part) (approximately 13 mm in diameter) in a substantially cylindrical shape in a cured product of syrup (= soft polymer base material) [30 mm interval (distance between centers)] The sheet-like organic base material (thickness: 300 micrometers) arrange | positioned by was obtained.

Example 19
As the base material syrup, the base material syrup B obtained in Production Example 2 was used, and as the hard polymer part forming syrup, 100 parts by weight of the base material syrup B obtained in Production Example 2 was tin oxide (trade name “S”). -2000 ", particle shape: bulk, average particle size: 0.03 μm, manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd.) The syrup cured part (= hard polymer part) for forming a hard polymer part (= hard polymer part) (approximately 12 mm in diameter) having a substantially cylindrical shape in a cured product of syrup (= soft polymer base material) has a predetermined interval [30 mm interval (distance between centers)]. The sheet-like organic base material (thickness: 300 micrometers) arrange | positioned by was obtained.

Example 20
As the base material syrup, the base material syrup B obtained in Production Example 2 was used, and as the hard polymer part forming syrup, 100 parts by weight of the base material syrup B obtained in Production Example 2 was silver powder (trade name “Ag− HWQ-400 ”, particle shape: bulk, average particle size: 13.2 μm, manufactured by Fukuda Metal Foil Powder Co., Ltd.) 10 parts by weight were used, and the same operation as in Example 1 was performed. In a cured product of the base material syrup (= soft polymer base material), a syrup cured portion for forming a hard polymer portion (= hard polymer portion) (approximately 4 mm in diameter) having a substantially cylindrical shape has a predetermined interval [30 mm distance (distance between centers). )] Is obtained. (Thickness: 300 μm)

Example 21
The base material syrup B obtained in Production Example 2 was used as the base material syrup, and the silica (trade name “AEROSIL R7200” was used as the hard polymer part forming syrup with respect to 100 parts by weight of the base material syrup B obtained in Production Example 2. ”, Particle shape: bulk, average particle size: 0.012 μm, manufactured by Nippon Aerosil Co., Ltd.) Except for using a syrup containing 1 part by weight, the same operation as in Example 1 was carried out to obtain a cured product of the base material syrup. (= Soft polymer base material) The substantially cylindrical hard polymer part-forming syrup cured part (= hard polymer part) (diameter of about 5 mm) is arranged at a predetermined interval [30 mm interval (distance between centers)]. A sheet-like organic base material (thickness: 300 μm) was obtained.

Example 22
The base material syrup B obtained in Production Example 2 was used as the base material syrup, and the silica (trade name “AEROSIL R7200” was used as the hard polymer part forming syrup with respect to 100 parts by weight of the base material syrup B obtained in Production Example 2. ”, Particle shape: bulk, average particle size: 0.012 μm, manufactured by Nippon Aerosil Co., Ltd.) The same procedure as in Example 1 was performed except that 10 parts by weight of syrup was blended, and a cured base syrup was obtained. (= Soft polymer base material) The substantially cylindrical hard polymer part forming syrup cured part (= hard polymer part) (diameter of about 7 mm) is arranged at a predetermined interval [30 mm interval (distance between centers)]. A sheet-like organic base material (thickness: 300 μm) was obtained.

Example 23
The base material syrup B obtained in Production Example 2 was used as the base material syrup, and the silica (trade name “AEROSIL R7200” was used as the hard polymer part forming syrup with respect to 100 parts by weight of the base material syrup B obtained in Production Example 2. ”, Particle shape: bulk, average particle size: 0.012 μm, manufactured by Nippon Aerosil Co., Ltd.) Except for using a syrup containing 20 parts by weight, a cured product of the base material syrup was used in the same manner as in Example 1. (= Soft polymer base material) The substantially cylindrical hard polymer part forming syrup cured part (= hard polymer part) (diameter of about 7 mm) is arranged at a predetermined interval [30 mm interval (distance between centers)]. A sheet-like organic base material (thickness: 300 μm) was obtained.

Example 24
The base material syrup B obtained in Production Example 2 was used as the base material syrup, and the hard polymer part forming syrup E 100 parts by weight of the hard polymer part forming syrup E obtained in Production Example 8 was treated with silica (trade name). The base material syrup was operated in the same manner as in Example 1 except that a syrup containing 40 parts by weight of “AEROSIL R7200”, particle shape: bulk, average particle size: 0.012 μm, manufactured by Nippon Aerosil Co., Ltd. was used. In a cured product (= soft polymer base material), a syrup cured part (= hard polymer part) (diameter of about 9 mm) for forming a hard polymer part in a substantially columnar shape has a predetermined interval [30 mm interval (distance between centers)]. The arrange | positioned sheet-like organic base material (thickness: 300 micrometers) was obtained.

Example 25
The base material syrup B obtained in Production Example 2 was used as the base material syrup, and the hard polymer part forming syrup A obtained in Production Example 4 was used as the hard polymer part forming syrup A with respect to 100 parts by weight of silica (trade name). The base material syrup was operated in the same manner as in Example 1 except that a syrup containing 30 parts by weight of “AEROSIL R7200”, particle shape: bulk, average particle size: 0.012 μm, manufactured by Nippon Aerosil Co., Ltd. was used. In a cured product (= soft polymer base material), a syrup cured part (= hard polymer part) (diameter of about 5 mm) for forming a hard polymer part in a substantially columnar shape has a predetermined interval [30 mm interval (distance between centers)]. The arrange | positioned sheet-like organic base material (thickness: 300 micrometers) was obtained.

Example 26
The base material syrup B obtained in Production Example 2 was used as the base material syrup, and the hard polymer part-forming syrup D 100 parts by weight obtained in Production Example 7 was used as silica (trade name) The base material syrup was operated in the same manner as in Example 1 except that a syrup containing 40 parts by weight of “AEROSIL R7200”, particle shape: bulk, average particle size: 0.012 μm, manufactured by Nippon Aerosil Co., Ltd. was used. In the cured product (= soft polymer base material), a substantially cylindrical hard polymer portion forming syrup cured portion (= hard polymer portion) (diameter of about 10 mm) is at a predetermined interval [30 mm interval (distance between centers)]. The arrange | positioned sheet-like organic base material (thickness: 300 micrometers) was obtained.

Example 27
The base material syrup B obtained in Production Example 2 was coated on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, length 400 mm, width 240 mm, thickness 38 μm) with an applicator, and the thickness A cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, Inc., 400 mm long) with a 300 μm base material syrup layer and holes with a diameter of 7 mm spaced at 30 mm intervals (center-to-center distance) in the longitudinal direction. , 240 mm in width and 38 μm in thickness) were bonded with a hand roller. Silica (trade name: “AEROSIL R7200”, particle shape: bulk, average particle size: 0.012 μm, manufactured by Nippon Aerosil Co., Ltd.) powder from above, from the hole in the cover separator, into the hole in the cover separator It was placed evenly until the exposed syrup part was completely hidden. From above, a cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, length 400 mm, width 240 mm, thickness 38 μm) is bonded with a hand roller, and ultraviolet rays are irradiated with an ultraviolet lamp (BL type). (Ultraviolet illuminance: 3.4 mW / cm ² , integrated irradiation amount: 2000 mJ / cm ² ), a hard-cured portion for forming a hard polymer portion (= A sheet-like organic substrate (thickness: 300 μm) in which hard polymer portions (diameter of about 7 mm, height of 300 μm) were arranged at a predetermined interval [30 mm interval (distance between centers)] was obtained.

Example 28
Example 1 except that the base material syrup D obtained in Production Example 9 was used as the base material syrup, and the hard polymer part forming syrup A obtained in Production Example 4 was used as the hard polymer part forming syrup. The syrup cured part (= hard polymer part) (hard polymer part) (approximately 10 mm in diameter) having a substantially columnar shape is formed in a hardened base material syrup (= soft polymer base material) at a predetermined interval [30 mm spacing]. The sheet-like organic base material (thickness: 300 μm) arranged in (Distance between centers)] was obtained.

Example 29
On the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, length 400 mm, width 240 mm, thickness 38 μm), a polyurethane water dispersion (trade name “Superflex E-2000” is used as a base polymer aqueous dispersion. ”, Solid content: 50% by weight, Tg = −38 ° C., manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was applied with an applicator to form a 140 μm-thick polyurethane aqueous dispersion matrix layer. A polyurethane aqueous dispersion (trade name “Superflex E-2000”, solid content: 50 wt.%) As a polymer aqueous dispersion for forming a hard polymer portion is formed on a predetermined portion of the base material layer (at intervals of 30 mm in the longitudinal direction). %, Tg = −38 ° C., manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) with 100 parts by weight of the solid content of the polyurethane water dispersion, silica aqueous dispersion (trade name “Adelite AT-50”, solid content: An aqueous dispersion (about 0.02 g) containing 50 wt%, average particle size: 0.05 μm, manufactured by ADEKA Co., Ltd. with a solid content of 85 parts by weight was added dropwise to form an island-like hard polymer part forming aqueous dispersion. The parts were formed at 30 mm intervals (center-to-center distance) in the longitudinal direction. By drying this in a drying oven (100 ° C.) for 10 minutes, a substantially cylindrical silica-containing polyurethane part (= hard polymer part) (diameter of about 7 mm) in a base material made of polyurethane (= soft polymer base material) Was obtained at a predetermined interval [30 mm interval (distance between centers)] (thickness: 70 μm).

Example 30
A polyurethane water dispersion (trade name “Superflex E-210”, solid content: 35% by weight, Tg = 41 ° C., manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was used as the polymer aqueous dispersion for forming the hard polymer part. The same operation as in Example 29 was performed except that the silica aqueous dispersion was not blended, and a substantially cylindrical high Tg polyurethane part (= hard polymer part) in a base material made of polyurethane (= soft polymer base material). ) (A diameter of about 7 mm) was obtained at a predetermined interval [30 mm interval (center-to-center distance)] to obtain a sheet-like organic substrate (thickness: 70 μm).

Example 31
On the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, length 400 mm, width 240 mm, thickness 38 μm), a styrene-isoprene-styrene block copolymer polymer (SIS) (product) A solution (namely, Clayton D-1107, manufactured by Kraton Polymer Japan Co., Ltd.) dissolved in toluene (solid content: 40% by weight) was applied with an applicator to form a polymer solution matrix layer having a thickness of 150 μm. did. From above, a styrene-isoprene-styrene block copolymer polymer (trade names “Clayton D-1107”, Clayton) is used as a polymer mixture for forming a hard polymer portion at a predetermined portion of the base material layer (30 mm in the longitudinal direction). Polymer (manufactured by Japan Co., Ltd.) in a solution (solid content: 40% by weight) dissolved in toluene, silica (trade name “AEROSIL R7200”, particle shape: bulk, An average particle size: 0.012 μm, manufactured by Nippon Aerosil Co., Ltd.) was added dropwise to a polymer mixture (about 0.02 g) containing 50 parts by weight of solids, and the island-like hard polymer part forming liquid part was elongated. It formed in the direction at intervals of 30 mm (distance between centers). By drying this in a drying oven (100 ° C.) for 10 minutes, a silica-containing styrene-isoprene having a substantially cylindrical shape in a base material (= soft polymer base material) composed of a styrene-isoprene-styrene block copolymer polymer. A sheet-like organic base material (thickness: 60 μm) in which styrene block copolymer polymer portions (= hard polymer portions) (diameter of about 7 mm) were arranged at a predetermined interval [30 mm intervals (distance between centers)] was obtained.

Example 32
A polymer solution (solid content: 9% by weight) in which polymethyl methacrylate (PMMA) (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in ethyl acetate was used as the polymer mixture for forming the hard polymer part (silica is Except for (not blended), the same operation as in Example 31 was performed, and a substantially cylindrical polymethyl methacrylate part (= soft polymer matrix) composed of a styrene-isoprene-styrene block copolymer polymer (= soft polymer matrix) ( = Hard polymer part (diameter: about 15 mm) A sheet-like organic base material (thickness: 60 μm) was obtained with a predetermined interval [30 mm interval (distance between centers)].

Example 33
In the center of the surface of the separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, Inc., length 200 mm, width 200 mm, thickness 38 μm), a styrene-isoprene-styrene block copolymer polymer (trade name “Clayton D” -1107 ", manufactured by Kraton Polymer Japan Co., Ltd.) was placed in an amount of about 8 g, and a similar separator was placed on the polymer. A polymer base material layer was formed by setting the spacer so as to be 1 mm in thickness with a 30-ton press and pressing it under predetermined conditions (pressure: 15 MPa, temperature: 160 ° C.) for 1 minute. . Styrene-ethylene-butylene-styrene block copolymer polymer (SEBS) (trade name “Dynalon 8630P”, JSR Corporation) as a polymer for forming a hard polymer portion from above to a predetermined portion of this base material layer (30 mm interval). Columnar pellets (about 0.017 g). A 30-ton press presses a spacer so as to have a thickness of 1 mm, and presses it under predetermined conditions (pressure: 15 MPa, temperature: 160 ° C.) for 5 minutes, whereby styrene-isoprene-styrene block copolymer A substantially cylindrical styrene-ethylene-butylene-styrene block copolymer polymer portion (= hard polymer portion) (diameter of about 6 mm) is formed at a predetermined interval [30 mm interval] in a base material made of a polymer (= soft polymer base material). (Distance between centers)] was obtained.

Example 34
The base material syrup B obtained in Production Example 2 was coated on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, length 400 mm, width 240 mm, thickness 38 μm) with an applicator, and the thickness A 200 μm base syrup layer was formed. Using a dispenser (trade name “SM300DS-S, MPP-1”, manufactured by Musashi Engineering Co., Ltd.) at a predetermined portion of the base material syrup layer, the syrup F for forming a hard polymer portion obtained in Production Example 10 (about 0.03 μL) was injected, and island-shaped hard polymer portion forming syrup portions were formed so as to be lined up by 50 mm or more in the longitudinal direction at intervals of 2 mm (distance between centers) in the longitudinal direction. From above, ultraviolet rays are irradiated 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 hard polymer part forming syrup are semi-cured. After that, a cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, length 400 mm, width 240 mm, thickness 38 μm) is pasted on a semi-cured syrup with a hand roller, and further an ultraviolet lamp (BL type) ) (Ultraviolet light illuminance: 3.4 mW / cm ² , integrated irradiation amount: 2000 mJ / cm ² ), and forming a hard polymer portion having a substantially cylindrical shape in the cured material of the base material syrup (= soft polymer base material) Sheet-like organic base material in which syrup hardened parts (= hard polymer part) (diameter of about 1 mm) are arranged at a predetermined interval [2 mm interval (distance between centers)] Thickness: 200μm) was obtained.

Example 35
The base material syrup B obtained in Production Example 2 was coated on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, length 400 mm, width 240 mm, thickness 38 μm) with an applicator, and the thickness A 200 μm base syrup layer was formed. Using a dispenser (trade name “SM300DS-S, MPP-1”, manufactured by Musashi Engineering Co., Ltd.) at a predetermined portion of the base material syrup layer, the syrup F for forming a hard polymer portion obtained in Production Example 10 (about 0.01 μL) was injected, and island-shaped hard polymer portion forming syrup portions were formed so as to be aligned 50 mm or more in the longitudinal direction at 1 mm intervals (center distance) in the longitudinal direction. Thereafter, the same operation as in Example 34 was performed, and a substantially cylindrical hard polymer portion-forming syrup hardened portion (= hard polymer portion) (having a diameter of about 0.00 mm) in a hardened material of the base material syrup (= soft polymer base material). 5 mm) was obtained at a predetermined interval [1 mm interval (center-to-center distance)] to obtain a sheet-like organic base material (thickness: 200 μm).

Example 36
The base material syrup B obtained in Production Example 2 was coated on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, length 400 mm, width 240 mm, thickness 38 μm) with an applicator, and the thickness A 200 μm base syrup layer was formed. Using a dispenser (trade name “SM300DS-S, MPP-1”, manufactured by Musashi Engineering Co., Ltd.) at a predetermined portion of the base material syrup layer, the syrup F for forming a hard polymer portion obtained in Production Example 10 (about 0.005 μL) was injected, and island-shaped hard polymer portion forming syrup portions were formed so as to be aligned 50 mm or more in the longitudinal direction at intervals of 0.6 mm in the longitudinal direction (center-to-center distance). Thereafter, the same operation as in Example 34 was performed, and a substantially cylindrical hard polymer portion-forming syrup hardened portion (= hard polymer portion) (having a diameter of about 0.00 mm) in a hardened material of the base material syrup (= soft polymer base material). 3 mm) was obtained in a sheet-like organic base material (thickness: 200 μm) arranged at a predetermined interval [0.6 mm interval (distance between centers)].

Example 37
The base material syrup B obtained in Production Example 2 was coated on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, length 400 mm, width 240 mm, thickness 38 μm) with an applicator, and the thickness A 200 μm base syrup layer was formed. A hard polymer part forming syrup F (about approx. 0.002 μL) was injected, and island-shaped hard polymer portion forming syrup portions were formed so as to be aligned in the longitudinal direction at intervals of 0.3 mm (center-to-center distance) by 50 mm or more in the longitudinal direction. Thereafter, the same operation as in Example 34 was performed, and a substantially cylindrical hard polymer portion-forming syrup hardened portion (= hard polymer portion) (having a diameter of about 0.00 mm) in a hardened material of the base material syrup (= soft polymer base material). 15 mm) was obtained at a predetermined interval [0.3 mm interval (center-to-center distance)] to obtain a sheet-like organic base material (thickness: 200 μm).

Example 38
The base material syrup B obtained in Production Example 2 was coated on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, length 400 mm, width 240 mm, thickness 38 μm) with an applicator, and the thickness A 200 μm base syrup layer was formed. Using a dispenser (trade name “SM300DS-S, MPP-1”, manufactured by Musashi Engineering Co., Ltd.) at a predetermined portion of the base material syrup layer, the syrup F for forming a hard polymer portion obtained in Production Example 10 (about 0.03 μL) was injected, and island-shaped hard polymer portion forming syrup portions were formed so as to be aligned in the longitudinal direction at intervals of 5 mm (center-to-center distance) by 50 mm or more in the longitudinal direction. Thereafter, the same operation as in Example 34 was performed, and a syrup cured portion for forming a hard polymer portion (= hard polymer portion) having a substantially cylindrical shape (= hard polymer portion) (approximately 1 mm in diameter) in a cured product of the base material syrup (= soft polymer base material). Was obtained at a predetermined interval [5 mm interval (distance between centers)] (thickness: 200 μm).

Comparative Example 1
Without using the syrup A for forming the hard polymer part, the same operation as in Example 1 was performed except that only the base material syrup A was used, and a sheet-like organic base material (thickness: 300 μm) was obtained.

Comparative Example 2
Without using the syrup A for forming the hard polymer part, the same operation as in Example 2 was performed except that only the base material syrup B was used, and a sheet-like organic base material (thickness: 300 μm) was obtained.

Comparative Example 3
Without using the syrup A for forming the hard polymer part, the same operation as in Example 3 was performed except that only the base material syrup C was used, and a sheet-like organic base material (thickness: 300 μm) was obtained.

Comparative Example 4
Without using the syrup A for forming the hard polymer part, the same operation as in Example 28 was performed except that only the base material syrup D was used, and a sheet-shaped organic base material (thickness: 300 μm) was obtained.

Comparative Example 5
The same procedure as in Example 29 was carried out except that only the base polymer aqueous dispersion was used without using the hard polymer part forming polymer aqueous dispersion, and a sheet-like organic base material consisting only of the base polymer (polyurethane). (Thickness: 70 μm) was obtained.

Comparative Example 6
The same operation as in Example 31 was performed except that only the base material polymer solution (the toluene solution of the styrene-isoprene-styrene block copolymer polymer) was used without using the polymer mixture for forming the hard polymer portion. A sheet-like organic base material (thickness: 60 μm) consisting only of a polymer (styrene-isoprene-styrene block copolymer polymer) was obtained.

Comparative Example 7
Example 33 and Example 33 except that only the base polymer (styrene-isoprene-styrene block copolymer polymer) was used without using the polymer for forming a hard polymer portion (styrene-ethylene-butylene-styrene block copolymer polymer). The same operation was performed to obtain a sheet-like organic base material (thickness: 60 μm) consisting only of the base polymer (styrene-isoprene-styrene block copolymer polymer).

Evaluation Test (1) Hardness Measurement-1
Ten sheets of the sheet-like organic base material obtained in the examples (length 30 mm × width 30 mm; having a hard polymer portion at the center) were laminated so that the hard polymer portions were in contact with each other. A needle of a rubber hardness tester (trade name “Asker Rubber Hardness Tester JA type (former JIS K6301 compliant)” manufactured by Kobunshi Keiki Co., Ltd.) is applied to the hard polymer portion at the top of this laminate and pushed in from above. The scale after the elapse of seconds was read, and the hardness H ₁ of the hard polymer portion was determined. Further, the sheet-like organic substrates obtained in Comparative Examples were measured in the same manner as the hardness of H ₂ base material. Further, the ratio (H ₁ / H ₂ ) was determined by dividing the hardness H ₁ of the hard polymer portion by the hardness H ₂ of the corresponding base material. The results are shown in Table 1-1.

(2) Hardness measurement-2
A sample of a sheet-like organic base material obtained in Examples (length 25 mm × width 3 mm; having a hard polymer portion in the entire width direction at the center) was cut out. A tensile viscoelasticity measuring jig is attached to a solid viscoelasticity measuring device (trade name “RSA III”, manufactured by TA Instruments Japan Co., Ltd.), and predetermined conditions (sample size: length 25 mm × The tensile elastic modulus was measured at a width of 3 mm, distance between chucks: 5 mm, mode: time dispersion, temperature: 27 ° C., frequency: 1 Hz, initial strain: 0.2%, measurement time: 120 seconds, number of measurements: 10 times) The tensile elastic modulus E ′ ₁ of the hard polymer portion of this sheet-like organic base material was used. Further, the sheet-like organic substrates obtained in Comparative Examples were measured tensile modulus E _'2 of the base material in the same manner. Further, divided by ₂ 'tensile modulus E of the base material corresponding to ₁ respectively' tensile modulus E of the hard polymer portion was determined the ratio (E _'1 / E' _2). The results are shown in Table 1-1 to Table 1-3.

(3) Hardness measurement-3
About the hard polymer part (pattern center part) and the soft polymer part (center part between hard part patterns) of the sample of the sheet-like organic base material obtained in the examples, nanoindenters (trade names “Tribo Scope”, Hystron ( Manufactured by Co., Ltd.) under predetermined conditions (indenter used: Berkovich, measurement method: single indentation test, indentation depth: 4 μm, indentation speed: 1.5 μm / sec, temperature: 25 ° C.) at an indentation depth of 4 μm. The load was measured, and the load of the hard polymer portion (hard portion) of the sheet-like organic base material was P ₁ , and the load of the soft polymer portion (soft portion) was P ₂ . Further, a load P ₁ of the rigid polymeric portion is divided by the load P ₂ of the soft polymer portion was determined the ratio (P ₁ / P _2). The results are shown in Table 1-1 to Table 1-3.

(4) Structural evaluation of hard polymer part forming syrup cured part (surface infrared spectroscopic analysis)
Infrared spectrophotometer (trade name “SPECTRUM 2000”) equipped with a fixture for attenuated total reflection infrared spectroscopy (trade name “Silver Gate” (single reflection ATR device Ge crystal), manufactured by System Engineering Co., Ltd.) Sample of a sheet-like organic base material obtained in Examples using a Perkin Elmer Co., Ltd. [length 30 mm × width 30 mm; having a syrup cured portion (= hard polymer portion) for forming a hard polymer portion in the center portion] Infrared spectroscopic analysis of the surface was carried out on both the front and back surfaces (sites where the hard polymer part-forming syrup cured part was formed). Moreover, the same infrared spectroscopic analysis was performed also about the sheet-like organic base material obtained by the comparative example. The absorbance ratio α _U (= A _U2 / A _U1 ) was determined from the absorbance A _U1 of 1538 cm ⁻¹ derived from the urethane bond and the absorbance A _U2 of 1161 cm ⁻¹ derived from the acryloyl group obtained from the infrared spectroscopic analysis of the comparative example. . EXAMPLE sheet organic substrates for the hard polymer unit formed syrup dripping or injection surface of infrared spectroscopy of the urethane bond derived from 1538cm ^-1 obtained from the analysis absorbance A _A1a and the hard polymer portion forming syrup hardened part surface The absorbance ratio α _Aa (= A _A2a / A _A1a ) was determined from the absorbance A _A2a at 1161 cm ⁻¹ derived from the acryloyl group. Further, the absorbance ratio from the absorbance A _A1b of 1538 cm ⁻¹ derived from the urethane bond on the surface opposite to the syrup dropping or injection surface for forming the hard polymer part of the sheet-like organic base material and the absorbance A _A2b derived from acryloyl group of 1161 cm ⁻¹ α _Ab (= A _A2b / A _A1b ) was determined in the same manner. Also, the difference P (= α _Ab −α _U ) is calculated as an index of the penetration degree of the hard polymer part forming syrup component, and the hard polymer part forming syrup hardened part is a sheet when the difference P is 0.500 or less. "Embedded type" formed on one surface of a glassy organic base material and not formed up to the other surface, a hard polymer part forming syrup hardened part is a sheet-like organic The structure of the hard polymer part forming syrup hardened part was classified as “penetrating type” (penetration = 1.00) formed continuously from one surface of the substrate to the other surface. The results are shown in Table 1-1.

(5) Structural evaluation of hard polymer part forming syrup cured part (cross-sectional observation)
The cross section of the portion where the hard polymer member forming syrup cured portion (= hard polymer portion) is formed in the sheet-like organic base material obtained in the examples is a microscope (digital microscope VHX-100F, manufactured by Keyence Corporation) ) And the ratio of the hard polymer part forming syrup cured part to the thickness of the sheet organic base material [(thickness of hard polymer part forming syrup cured part) / (thickness of sheet organic base material)] Was calculated. The results are shown in the column of “penetration (depth from the surface)” in Table 1-1. The penetration type penetration is 1.
Moreover, the microscope picture of the cross section of the syrup hardening part for hard polymer member formation (= hard polymer part) formation part in the sheet-like organic base material obtained in Example 11 is shown in FIG. Of the two layers found in the center in the vertical direction of the photograph, the upper layer is a hard polymer member-forming syrup hardened portion (thickness: 211 μm), and the lower layer is a base material syrup hardened portion (two layers) Total thickness: 336 μm).
Furthermore, the microscope picture of the cross section of the syrup hardening part for hard polymer part formation (= hard polymer part) formation part in the sheet-like organic base material obtained in Example 34 is shown in FIG. The layer that looks dark inside the layer that looks white in the vertical center of the photo (actually red) is the hard polymer part forming syrup cured part (thickness: 50 μm), and the layer that appears white is the base material syrup cured part Yes (total thickness of two layers: 200 μm).

(6) Tensile test (measurement of SS properties)
The sample (20 mm width) of the sheet-like organic base material obtained in the examples was installed so that two or more hard polymer portions (hard portions) were placed between the chucks (50 mm). Autograph AG-X 200N "(manufactured by Shimadzu Corporation) was subjected to a tensile test (temperature: 25 ° C., tensile speed: 200 mm / min) to determine the breaking stress (strength) (MPa) and breaking elongation (elongation) ( %) Was measured (see FIG. 6). In Examples 34 to 38, the hard polymer portions (hard portions) were installed so that the maximum number of hard polymer portions (hard portions) could be inserted in the direction in which the tensile direction was the same as the direction in which the hard polymer portions (hard portions) were arranged between the chucks. A similar tensile test was performed on a sample (20 mm width) of the sheet-like organic base material obtained in the comparative example. The results are shown in Table 2-1.

(7) Measurement of elongation amount In the above tensile test, at 0% elongation, at 25% elongation (125% of the original length), at 50% elongation (150% of the original length), at 100% elongation ( 200% of the original length), 150% elongation (250% of the original length), the elongation rate S ₁ (%) (average value) of the hard polymer part (two or more) in the extension direction, and the hard polymer The elongation ratio S ₂ (%) (average value) in the elongation direction of the site [soft polymer part (= soft part)] other than the part is measured, and the ratio (S ₂ / S ₁ ) and the difference (S ₂ -S ₁ ) (%) was calculated. The results are shown in Tables 2-1 to 2-3. When S ₁ = 0, S ₂ / S ₁ = ∞.
The elongation ratio S ₁ (%) is determined by measuring the diameter in the direction of elongation of the hard polymer portion (substantially the diameter of the substrate surface) before and after elongation, and the formula: {(length after elongation−length before elongation) ) / (Length before stretching)} × 100).
Elongation rate S ₂ (%) is marked with 6 marks in the extension direction of the part (soft polymer part) other than the hard polymer part forming syrup hardened part, and the length between adjacent marks before and after the extension. Measured and calculated by the formula: {(length after stretching−length before stretching) / (length before stretching)} × 100).

(8) Evaluation of stretchability (measurement of elongation recovery rate)
The sample of the sheet-like organic base material (width 20 mm) obtained in the example was placed so that the two hard polymer portions were placed between the chucks (50 mm) (the distance between the centers of the two hard polymer portions: 30 mm). , Hysteresis test at 50% elongation (temperature: 25 ° C., tensile speed: 200 mm / min, unloading speed: 200 mm / min) using a tensile tester (trade name “Autograph AG-X 200N”, manufactured by Shimadzu Corporation) ) And the residual strain (the amount of elongation when the load became zero after elongation) was measured (see FIG. 6). Based on this measured value, the elongation recovery rate was calculated by {25 mm (elongation at 50% elongation) − (residual strain)} / 25 mm (elongation at 50% elongation) × 100. The results are shown in Table 2-1.

  In addition, the breaking stress (strength) of the sheet-like organic base material obtained in Example 28 was 16 MPa, the breaking elongation was 193%, the residual strain was 25 mm, and the elongation recovery rate was 0%. Moreover, the breaking stress (strength) of the sheet-like organic base material obtained in Comparative Example 4 was 4 MPa, the breaking elongation was 400%, the residual strain was 25 mm, and the elongation recovery rate was 0%. The sheet-like organic base materials obtained in Example 28 and Comparative Example 4 had extensibility but did not have elasticity.

(9) Measurement of elongation gradation A dot pattern (diameter 50 μm, center distance 88 μm) is printed on the entire surface of the sample (width 20 mm) of the sheet-like organic substrate obtained in the example, and the hard polymer portion (hard portion) is formed. After installing 50% between the stretcher gaps (50 mm) and stretching 50%, the distance between the centers of the dot patterns was measured with a microscope. Twelve points near the interface between the soft part and the hard part were plotted on the graph from the soft part side. The measurement results of the sheet-like organic base materials obtained in Examples 3 and 9 are shown in FIGS. In the vicinity of the interface between the hard part and the soft part, there is a gradient in the distance between the centers of the dot patterns, and it can be seen that this part has a gradation regarding the elongation.

(10) Measurement of surface roughness The surface of the soft part on the surface opposite to the surface on which the hard polymer part forming material (hard polymer part forming syrup) of the sheet-like organic base material obtained in the example was dropped, and Surface roughness Ra (nm) of the surface of the hard part formation site is measured with an AFM measuring device (trade name “Dimension 3100 + Nanoscope V”, manufactured by Veeco, cantilever: Si single crystal, measurement mode: tapping mode, measurement range: 90 μm square). did. The results are shown in Table 1-1.

1 Sheet-like organic base material 2 Soft polymer base material (soft polymer base material part)
20 Polymer matrix forming material layer (soft polymer matrix forming energy beam curable composition layer)
21 Polymer Matrix Forming Material Layer 22 Polymer Matrix Forming Material Layer 200 Partially Cured Soft Polymer Matrix Forming Energy Beam Curable Composition Layer 3 Hard Polymer Part 30 Hard Polymer Part Forming Material (For Hard Polymer Part Forming) Energy ray curable composition)
31 Hard Polymer Portion Forming Material 32 Hard Polymer Portion Forming Material 300 Partially Cured Energy Polymer Curing Composition for Hard Polymer Portion Formation 4 Support 5 Cover Film

Claims (12)

A sheet-like organic base material in which a hard polymer part is partially and integrally formed in a soft polymer base material, and is 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 strain: 0.2%, measurement time: 120 seconds, number of measurements: 10 times, tensile modulus of elasticity E ′ ₁ ( A sheet-like organic base material, wherein a ratio (E ′ ₁ / E ′ ₂ ) between Pa) and a tensile modulus E ′ ₂ (Pa) of a soft polymer base material is greater than 1. A sheet-like organic base material in which a hard polymer portion is partially and integrally formed in a soft polymer base material, and a hardness test using a rubber hardness tester (test piece 30 mm × 30 mm sheet-like organic substrate) ten laminate of wood, staple pressing 10 seconds after the hardness, the ratio of the hardness H ₁ and hardness of H ₂ soft polymer matrix of hard polymer unit obtained by the temperature _{25 ℃) (H 1 / H} 2 ) Is larger than 1, a sheet-like organic base material characterized by that. Nano-indentation measurement (indentation depth 4 μm, indentation speed 1.5 μm / sec, temperature 25), which is a sheet-like organic base material in which a hard polymer portion is partially and integrally formed in a soft polymer matrix A sheet-like organic base material having a ratio (P ₁ / P ₂ ) between a hard polymer portion load P ₁ and a soft polymer base material load P _{2 at 1} ° C.) of greater than 1.   The sheet-like organic group according to any one of claims 1 to 3, wherein the hard polymer portion is partially formed in the soft polymer base material in a state of being exposed on at least one surface or not being exposed. Wood.   The sheet-shaped organic substrate according to claim 4, wherein the surface shape of the hard polymer portion or the projected shape when the surface of the sheet-shaped organic substrate of the hard polymer portion is a projection surface is substantially circular, substantially rectangular or indefinite.   The sheet-like organic base material according to any one of claims 1 to 5, wherein a plurality of hard polymer portions are formed in a regular pattern in the soft polymer base material.   The sheet-like organic base material according to claim 6, wherein a distance between adjacent hard polymer parts is 0.05 mm to 50 cm.   Thickness is 0.01 mm-1 cm, The sheet-like organic base material as described in any one of Claims 1-7.   The length of the thickness direction of a hard polymer part is at least 1/50 of the thickness of a sheet-like organic base material, The sheet-like organic base material as described in any one of Claims 1-8.   The sheet-like organic base material according to any one of claims 1 to 9, wherein the hard polymer portion is continuously formed from one surface of the sheet-like organic base material to the other surface.   The extensible organic base material as described in any one of Claims 1-10 in which the hardness characteristic has comprised gradation in the interface vicinity of a hard polymer part and a soft polymer base material.   The sheet-like organic base material according to any one of claims 1 to 11, which has stretchability.