JP2013237759A - Organic base - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic base which comprises a base material sheet and a structure part that is formed as a part in the base material sheet and has a different composition from that for the base material, wherein the structure part is rarely detached from the base material sheet even when an external force is applied to the structure part.SOLUTION: An organic base 1 comprises a base material sheet that is formed from a base material (A) 2 and a structure part 3 (B) that is formed in the base material sheet as a part of the organic base and has a different composition from that for the base material (A) 2, the organic base being characterized in that a composition gradation is formed in a boundary region between the base material (A) 2 and the structure part (B) 3. The structure part (B) 3 may be formed in the organic base as a part of the organic base such a manner that the structure part (B) 3 is exposed or unexposed on at least one surface of the organic base. The distance between the starting point of the unidirectional gradation on the base material (A) 2 side and the end point of the unidirectional gradation on the structure part (B) 3 side on the surface shape of the gradation region or a projected shape of the gradation region which is taken employing the surface of the organic base as a projection plane is, for example, 0.01 to 10 mm.

Description

  The present invention relates to an organic base material, and more particularly, to an organic base material in which a structural portion having a composition different from that of the base material is partially formed in the base material sheet. Since such an organic base material has a portion having a composition different from that of the base material in the base material sheet, the portion can have various functions and characteristics. Therefore, for example, it can be used for a decorative body, an electronics member, an optical member, an optoelectronic member, a car electronics member, a household appliance member, a housing equipment member, a building material, and the like.

  Various organic base materials having portions having different compositions in the base material sheet are known. For example, in Patent Document 1, a metal or ceramic harder than the base material is formed into a pattern by a plating method or a sputtering method on a base material made of a metal or a resin, and then pressed to form a metal or ceramic pattern base. A method for obtaining a decorative body embedded in a material is disclosed. However, the decorative body produced by this method has a problem that the base material portion and the pattern portion are clearly separated, and the pattern is easily peeled off due to deformation by an external force.

JP-A-5-330298

  Accordingly, an object of the present invention is an organic base material in which a structural part having a composition different from that of the base material is partially formed in the base material sheet. An object of the present invention is to provide an organic substrate that is difficult to peel off.

  As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that in the base material sheet, in the organic base material in which a structural part having a composition different from that of the base material is partially formed, When the composition forms a gradation in the boundary region with the structure part, even if a force is applied from the outside, stress is easily dispersed in the boundary region between the base material and the structure part, and the boundary is difficult to break. Since the adhesion in the region is improved, it has been found that the structural part is less likely to fall off, and the present invention has been completed.

  That is, the present invention is an organic base material in which a structural part (B) having a composition different from that of the base material (A) is partially formed in the base material sheet made of the base material (A), Provided is an organic base material characterized in that the composition forms a gradation in the boundary region between the base material (A) and the structure part (B).

  In the organic base material, the structural part (B) may be partially formed in a state where it is exposed or not exposed on at least one surface of the organic base material.

  The distance from the starting point on the base material (A) side to the ending point on the structure part (B) side of the gradation in one direction in the projected shape when the surface shape of the gradation region or the organic base material surface of the gradation region is the projection surface Is, for example, 0.01 to 10 mm.

  The surface shape of the structure part (B) or the projection shape when the organic base material surface of the structure part (B) is used as the projection surface is, for example, a substantially circular shape, a substantially polygonal shape, an amorphous shape, or a character, symbol or number. It is a shape, ring-shaped, or linear.

  The length of the major axis in the projection shape when the surface shape of the structure part (B) or the organic base material surface of the structure part (B) is used as the projection surface is, for example, 0.05 mm to 10 cm.

  In the base material sheet made of the base material (A), a plurality of structural portions (B) may be formed in a regular pattern. In this case, the distance between adjacent structural parts (B) may be 0.05 mm to 50 cm.

  The thickness of the organic substrate is, for example, 0.01 mm to 1 cm.

  According to the organic base material of the present invention, a structure part having a composition different from that of the base material is partially formed in the base material sheet, and the composition has a gradation in a boundary region between the base material and the structure part. Therefore, even if a force is applied to the organic base material from the outside, stress is easily dispersed in the boundary region between the base material and the structure part, and it is difficult to break. Since the adhesion is very high, the structure part is unlikely to fall off the base material sheet.

It is a schematic perspective view which shows an example of the organic base material of this invention. It is a schematic perspective view which shows the II-II line cross section of the organic base material of FIG. It is the graph which showed typically the pattern of the gradation in the gradation site | part of the organic base material of this invention. It is the schematic (sectional drawing) which shows an example of the manufacturing method of the organic base material of this invention. It is the schematic (sectional drawing) which shows the other example of the manufacturing method of the organic base material of this invention. It is the schematic (sectional drawing) which shows the other example of the manufacturing method of the organic base material of this invention. 2 is a photomicrograph showing a cross section of a structure part (B) (pattern part) formation site in an organic base material obtained in Example 1. FIG. Photograph showing the result obtained by imaging IR measurement of the cross section of the structure (B) (pattern part) formation site in the organic base material obtained in Example 1 [urethane bond to ester bond (near 1730 cm ⁻¹ ) ( The mapping image of the absorption intensity ratio at around 1530 cm ⁻¹ ]. It is the photograph (enlarged mapping image) which expanded FIG. Structure of the organic base material obtained in Example 1 (B) the absorption intensity of the urethane bonds of the surface direction in the cross section of the (pattern portion) forming site (1530 cm ^-1 vicinity) and ester bond (1730 cm around ^-1) ratio It is a graph which shows the change of [absorption strength of a urethane bond / absorption strength of an ester bond].

[Organic substrate]
The organic base material of the present invention is an organic base material in which a structural part (B) having a composition different from that of the base material (A) is partially formed in a base material sheet made of the base material (A). In the boundary region between the base material (A) and the structure part (B), the composition has a gradation. The composition has gradation, the ratio of the content of one component (one or more components) to the content of other components (one or more components) is the structure from the base material (A) side. It means that it gradually changes as it moves to the part (B) side.

  FIG. 1 is a schematic perspective view showing an example of the organic base material of the present invention, and FIG. 2 is a schematic perspective view showing a cross section taken along line II-II of the organic base material of FIG. 1 and 2, a sheet-like organic base material 1 includes a base material (A) in a base material sheet 2 (sometimes referred to as “base material part (A)”) made of the base material (A). The structural part (B) 3 having a different composition is partially and integrally formed. In FIG. 1 and FIG. 2, gradation display is omitted.

  In the present invention, the composition forms a gradation in the boundary region between the base material part (A) 2 and the structure part (B) 3. The gradation about a composition can be calculated | required by measuring the composition distribution of the cross section (cross section perpendicular | vertical to a surface direction) of the site | part containing the said boundary region of an organic base material. The composition distribution can be measured by using a known method such as imaging IR. More specifically, in the case of using imaging IR, for example, the absorption intensity of one specific absorption and the absorption of another specific absorption at each part of the cross section (cross section perpendicular to the surface direction) of the part including the boundary region. The composition distribution in the boundary region can be shown by obtaining the ratio with the intensity and imaging it. In addition, the gradation region can be displayed three-dimensionally by performing the same measurement for many cross sections.

  In the gradation part, the boundary between the base material part (A) 2 and the structure part (B) 3 is a composition ratio along a straight line from the base material part (A) 2 side toward the center part of the structure part (B) 3. To determine the average value of the maximum value (or minimum value) on the base material part (A) 2 side and the minimum value (or maximum value) on the structure part (B) 3 side of the composition ratio. it can.

  There are various patterns of gradation. 3A to 3D are graphs schematically showing examples of some gradation patterns. These drawings are parallel to the surface direction of the organic base material 1 in the cross section (cross section perpendicular to the surface direction) in the boundary region between the base material part (A) 2 and the structure part (B) 3 in the organic base material 1. It shows that the composition ratio changes along the straight line. The horizontal axis indicates the phase in the plane direction in the cross section of the organic substrate 1, and the vertical axis indicates the composition ratio. FIG. 3A shows an example in which the composition ratio linearly changes in the gradation portion, and there is a portion where the composition is constant in the structure portion (B). FIG. 3B shows an example in which the composition ratio changes linearly in the gradation part and there is no part where the composition is constant in the structure part (B) (example where the part showing the minimum value of the composition ratio is a point). It is. FIG. 3C is an example in which one or two or more peaks are formed in the structure portion (B) (an example in which a reverse gradation portion exists in the structure portion (B)). Such an example is caused by the diffusion of the composition for forming the structure part (B) when the structure part (B) is formed. FIG. 3D shows an example in which the composition ratio changes in a curve at the gradation portion. In addition to these, when the gradation shows a logarithmic curve or a quadratic curve, when the gradation changes suddenly, when it changes slowly, there are cases where a plurality of parts that change in a curved or linear manner are combined. . Furthermore, there are cases where the method of changing the gradation is indefinite (when there is no law).

  In the present invention, the structure portion (B) side from the starting point of the unidirectional gradation base material (A) side in the projection shape when the surface shape of the gradation region or the organic base material surface of the gradation region is the projection surface The distance to the end point is, for example, 0.01 to 10 mm. The lower limit of the distance is preferably 0.1 mm, more preferably 0.5 mm, and the upper limit is preferably 7 mm, more preferably 5 mm. The “one-way gradation” is a gradation in which the composition ratio gradually decreases or gradually increases from the base material part (A) side to the structure part (B) side, and the composition ratio decreases and increases. This means that gradations that include both of these are excluded. The distance from the starting point on the base material (A) side of the gradation in one direction to the ending point on the structure part (B) side is, for example, a cross section including the center part of the structure part (B) of the organic substrate (in the plane direction) In the vertical cross-section), the composition distribution is measured by, for example, imaging IR along a straight line including the central portion of the structure portion (B) and parallel to the surface direction, and the unidirectional gradation base material (A) side is measured. It can be determined by measuring the length from the start point to the end point on the structure (B) side.

  As will be described later, gradation in the boundary region between the base material part (A) and the structure part (B) includes both the base material part (A) formation part and the structure part (B) formation part in the manufacturing process of the organic base material. It is formed by going through a process in a liquid state (solution state, emulsion state, molten state, etc.).

  The structure part (B) 3 may be formed only in one place of the base material part (A) 2, and may be scattered or scattered in a plurality of places.

  The shape of the structure part (B) 3 is not particularly limited and can be appropriately selected depending on the purpose. For example, any of a columnar shape such as a substantially columnar shape or a substantially rectangular parallelepiped shape (particularly a columnar shape extending in the sheet thickness direction), an indefinite shape, etc. It may be.

  The structural part (B) 3 includes (i) a surface shape of the structural part (B) 3 or a projected shape when the surface of the organic substrate of the structural part (B) 3 is a projection surface (that is, The shape viewed from the surface side of the organic base material; hereinafter referred to as “base surface projection shape” may be substantially circular, substantially polygonal (substantially triangular, substantially rectangular, substantially pentagonal, substantially hexagonal, etc.), A solid columnar structure that is amorphous or has a shape that represents characters, symbols, or numbers (the entire inner part is filled with the material of the structure (B) from the boundary with the base material (A)), (Ii) A tubular (hollow columnar) structure portion (a region corresponding to the tubular hollow portion) whose surface shape or substrate surface projection shape of the structure portion (B) 3 is an annular shape (annular) is a base material portion (A )), And (iii) any of the structure portion (B) 3 whose surface shape or substrate surface projection shape is linear, etc. It may be. Moreover, the structure part (B) of these shapes may be mixed.

  When the structure portion (B) 3 is a cylindrical structure portion whose surface shape or substrate surface projection shape is an annular shape (annular), the region corresponding to the cylindrical cavity portion of the tubular structure portion is a mother portion. Since it is comprised with the material of a material (A) part, the area | region which hits a cylindrical cavity part can have the characteristic similar to a base material (A) part. One or more structural parts (i), (ii) or (iii) are further formed in the region made of the material of the base material (A) corresponding to the cylindrical cavity of the cylindrical structural part. May be.

  Moreover, when the said structure part (B) 3 is a structure part from which the surface shape or base-material surface projection shape becomes linear, this structure part (B) 3 suppresses expansion | extension to a specific direction. (Stretching restriction) and strength can be given in a specific direction.

  When the structure part (B) 3 is a solid columnar structure part extending in the sheet thickness direction, the length of the long axis (longest part) in the surface shape of the structure part (B) or the substrate surface projection shape (for example, The diameter is, for example, 0.05 mm to 10 cm. If this length is too small, the utility value of the structure part (B) will be small, and conversely if too large, it will be difficult to manufacture. The length of the long axis (longest part) of the structure part (B) is preferably 0.1 mm or more, more preferably 0.5 mm or more, further preferably 1 mm or more, particularly preferably 2 mm or more, especially 5 mm or more. Is preferred. Moreover, 8 cm is preferable and, as for the upper limit of the length (longest part) of the said major axis of a structure part (B), 5 cm is especially preferable.

  In the present invention, when the structure portion (B) 3 is a cylindrical structure portion whose surface shape or substrate surface projection shape is an annular shape (annular), the shape of the annular region (ring) (outer peripheral shape and / or The inner peripheral shape, particularly the outer peripheral shape, is not particularly limited, and can be appropriately selected according to the purpose. Etc.), amorphous (indeterminate), or a shape representing a character, symbol or number; a known figure, a shape representing a mark, or the like. When the surface shape of the cylindrical structure (B) or the projected surface shape of the substrate surface is a substantially polygon, the inner angle may be 90 degrees or less, or may be an angle exceeding 90 degrees. From the viewpoint of ease of manufacture, the surface shape of the cylindrical structure or the projected shape of the substrate surface (the outer peripheral shape and / or the inner peripheral shape, particularly the outer peripheral shape) is preferably substantially circular or rectangular. Moreover, the length (for example, diameter) of the said long axis (longest part of the shape which makes | forms an outer periphery) of a cylindrical structure part is 0.05 mm-10 cm, for example. When this length is too small, the utility value of a cylindrical structure part will become small, and when too large, it will become difficult to manufacture. The length of the long axis (the longest part of the shape forming the outer periphery) of the cylindrical structure portion is preferably 0.1 mm or more, more preferably 0.5 mm or more, still more preferably 1 mm or more, and particularly preferably 2 mm or more. In particular, 5 mm or more is preferable. Further, the upper limit of the length of the long axis in the surface direction of the cylindrical structure part (B) (the longest part of the shape forming the outer periphery) is preferably 8 cm, and particularly preferably 5 cm.

  The width of the annular zone (that is, the distance between the outer peripheral surface and the inner peripheral surface of the cylindrical structure portion; the thickness) which is the surface shape of the cylindrical structure portion or the projected surface of the base material can be appropriately selected according to the purpose. However, it is usually 1 to 40% of the length of the long axis (the longest part of the shape forming the outer periphery) of the cylindrical structure part. The lower limit of the width of the annular zone (thickness of the cylindrical structure portion) is preferably 2%, more preferably, the length of the long axis (longest portion of the shape forming the outer periphery) of the cylindrical structure portion. 5%. The upper limit of the width of the annular zone (thickness of the cylindrical structure portion) is preferably 30% with respect to the length of the long axis (the longest portion of the shape forming the outer periphery) of the cylindrical structure portion, Preferably it is 20%. The width of the ring zone (thickness of the cylindrical structure portion) is more specifically 0.01 mm to 4 cm, for example, and the lower limit thereof is preferably 0.02 mm, more preferably 0.1 mm, Further preferably, it is 0.2 mm, particularly preferably 0.4 mm, especially 1 mm, and the upper limit is preferably 3 cm, more preferably 2 cm.

  In the case where the surface shape of the structure part (B) 3 or the projected surface shape of the base material is a linear shape, the type of the linear shape is not particularly limited. Either a curved line or an amorphous linear shape may be used. Moreover, when the sheet-like organic base material 1 has a plurality of structure portions in which the surface shape or the substrate surface projection shape is linear, the plurality of structure portions (B) may be parallel. , May be crossed or in a twisted position. The width (line width) of the line that is the surface shape of the structural part (B) 3 or the projected surface shape of the base material can be appropriately set according to the purpose and application, and is, for example, 0.01 mm to 5 cm. The lower limit of the line width (line width) which is the surface shape of the structure part (B) 3 or the projected surface of the base material is preferably 0.05 mm, more preferably 0.1 mm. The upper limit of the line width (line width) which is the surface shape of the structure part (B) 3 or the substrate surface projected shape is preferably 2 cm, more preferably 1 cm. The length of the line which is the surface shape of the structure part (B) 3 or the projected surface of the base material can be appropriately set depending on the purpose and application, and is, for example, 0.5 mm to 10 m. The lower limit of the length of the line that is the surface shape of the structural part (B) 3 or the projected surface of the substrate surface is preferably 5 mm, more preferably 1 cm. The upper limit of the length of the line that is the surface shape of the structure part (B) 3 or the projected surface of the substrate surface is preferably 5 m, and more preferably 1 m. The ratio of the line length to the line width (line length / line width) which is the surface shape of the structure part (B) 3 or the substrate surface projection shape (line length / line width) is, for example, 3 or more, preferably 5 or more, more preferably It is 10 or more, more preferably 50 or more, and particularly preferably 100 or more.

  In the present invention, the structural part (B) 3 may be formed in any part of the base material (A) part 2, but at least one surface is used in that the structural part (B) 3 can be used effectively. It is preferably formed in an exposed state. The structure part (B) 3 may be formed in a state where it is not exposed on the surface of the organic base material. The surface shape (at least one surface shape) of the structure part (B) 3 or the projection shape when the surface of the organic base material of the structure part (B) 3 is the projection surface is substantially circular, substantially rectangular, indefinite, or ring Any of a strip shape (annular), a linear shape, or the like may be used. When the structure (B) 3 has a shape extending in the sheet thickness direction, the cross-sectional shape of the structure (B) 3 is often almost the same as the surface shape. From the viewpoint of ease of manufacture, the surface shape of the structure part (B) 3 is preferably substantially circular. The structural part (B) 3 may be formed at the end in the surface direction of the base material (A) part 2 or may be formed at a place other than the end [that is, the structural part (B). 3 may be formed in the state of being included in the base material (A) part 2 (except for both surfaces)].

  In the case where a plurality of structural parts (B) 3 are formed in the base material (A) part 2, the plurality of structural parts (B) 3 may be randomly formed and formed in a regular pattern. Also good. When the plurality of structure parts (B) 3 are formed in a regular pattern, the distance (shortest distance) between the adjacent structure parts (B) 3 is, for example, 0.05 mm to 50 cm, and the upper limit of the distance Is preferably 30 cm, more preferably 20 cm, still more preferably 15 cm, particularly preferably 10 cm. 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 structure part (B) 3 is formed in a regular pattern in advance, a large number of organic substrates can be efficiently produced by cutting. When a plurality of the structure parts (B) 3 are formed, the shapes and sizes of the plurality of structure parts (B) 3 may be the same or different. When the plurality of structural parts (B) 3 have the same shape and size, an organic substrate having the same shape and size can be produced with high production efficiency.

  The thickness of the organic base material 1 is 0.01 mm or more, for example, Preferably it is 0.03 mm or more, More preferably, it is 0.05 mm or more. The upper limit of the thickness of the organic base material 1 is, for example, 1 cm, preferably 5 mm, and more preferably 2 mm.

  The structural part (B) 3 may be formed continuously from one surface of the sheet-like organic base material 1 and is continuous from one surface of the sheet-like organic base material 1 to the other surface. May be formed. Moreover, the said structure part (B) 3 may be embedded and formed inside the sheet-like organic base material 1. FIG. In any case, the length (thickness) in the thickness direction of the structural part (B) 3 is preferably at least 1/50 of the thickness of the sheet-like organic base material 1 in terms of usefulness. Is at least 1/20, more preferably at least 1/10, particularly preferably at least 1/4. For example, when the structure part (B) 3 is continuously formed from one surface of the sheet-like organic substrate 1, the length (thickness) of the structure part (B) 3 in the thickness direction is used. ) Is preferably at least 1/3 of the thickness of the sheet-like organic base material 1, and more preferably at least 1/2 (especially at least 2/3).

[Constituent Materials of Base Material Part (A) and Structure Part (B)]
The base material part (A) 2 and the structure part (B) 3 can each be composed of a polymer. The polymer composing the base material part (A) 2 and the polymer composing the structural part (B) 3 can be appropriately selected depending on the desired properties, physical properties, functions to be imparted, etc. It may be an elastomer) or a thermosetting resin.

  Examples of the polymer include polyurethane polymers, polyurea polymers, polyurethane urea polymers, polyolefin polymers (particularly polydiene polymers), silicone polymers, polyester polymers, polyether polymers, polyamide polymers, and polystyrene polymers. (For example, styrene-based thermoplastic elastomers such as styrene-isoprene-styrene block copolymer and styrene-butadiene-styrene block copolymer), acrylic polymers, and the like are exemplified, but not limited thereto. The polymer constituting the base material part (A) 2 and the polymer constituting the structural part (B) 3 may each be a single kind or a combination of two or more kinds.

  As described above, the polymer can be selected according to the desired characteristics. Hereinafter, the case where the base material part (A) 2 is formed as a soft part (or an easily stretched part) will be described as an example.

The soft part (or easily stretchable part) is, 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, a polystyrene polymer chain, and the like. A curable polymer P having at least one polymer chain selected from the group consisting of polyacrylic chains and having an energy ray-curable group A ₁ in the main chain or side chain, or the curable polymer P and energy rays It can be formed by irradiating an energy ray to a mixture with a curable monomer M having a curable group A ₂ and curing it. The curable polymer P and the mixture of the curable polymer P and the curable monomer M having the energy ray curable group A ₂ are precursors of the polymer.

  Examples of the energy rays include ionizing radiation such as α rays, β rays, γ rays, neutron rays, and electron rays, ultraviolet rays, and visible rays. Among these, ultraviolet rays and electron beams are preferable, and ultraviolet rays are particularly preferable.

Examples of the energy ray-curable groups A ₁ and A ₂ include a group containing a carbon-carbon unsaturated bond (a group containing a radical polymerizable group) such as a (meth) acryloyl group or a vinyl group, an epoxy group, And cationically polymerizable groups such as oxetanyl group. When the energy ray-curable groups A ₁ in the curable polymer P having an energy ray-curable groups A ₁ is a group containing a radically polymerizable group in the main chain or side chain, having an energy ray-curable groups A ₂ The energy ray curable group A _{2 in the} curable monomer M is also preferably a group containing a radical polymerizable group, and the energy ray curable property in the curable polymer P having the energy ray curable group A ₁ in the main chain or side chain. When the group A ₁ is a cationic polymerizable group, the energy beam curable group A ₂ in the curable monomer M having the energy beam curable group A ₂ is also preferably a cationic polymerizable group.

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

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

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

  Examples of the polyisocyanate compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; alicyclic diisocyanates such as isophorone diisocyanate, dicyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, norbornene diisocyanate, and norbornane diisocyanate; naphthalene diisocyanate, Aromatic diisocyanates such as phenylene diisocyanate, tolylene diisocyanate, diphenyl diisocyanate, diphenylmethane diisocyanate, diphenyl ether diisocyanate, diphenylpropane diisocyanate; and araliphatic diisocyanates such as xylylene diisocyanate and tetramethylene xylylene diisocyanate ; 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 easily extensible polymer base material 2 and the hardly extensible polymer portion 3, the same kind of monomer as the polymer constituting the hardly extensible polymer portion as the curable monomer M (particularly, It is also preferred to use the same monomer).

When (meth) acrylic acid C _1-20 alkyl ester is used as curable monomer M, the proportion of (meth) acrylic acid C _1-20 alkyl ester in the entire curable monomer is, for example, 10% by weight or more (10 to 10% by weight). 100% by weight), preferably 40% by weight or more (40-100% by weight), more preferably 50% by weight or more (50-100% by weight), and still more preferably 60% by weight or more (60-100% by weight). . Further, as the curable monomer M, a (meth) acrylic acid C _1-20 alkyl ester, a (meth) acrylic acid ester having an alicyclic group such as isobornyl (meth) acrylate, or a carboxyl group such as (meth) acrylic acid Alternatively, an acid anhydride group-containing monomer or a hydroxyl group-containing monomer such as 2-hydroxyethyl (meth) acrylate may be used. In this case, the amount of (meth) acrylic acid ester having a cycloaliphatic group such as isobornyl (meth) acrylate, a carboxyl group or acid anhydride group-containing monomer, and a hydroxyl group-containing monomer is used with respect to the entire curable monomer. , For example, can be selected from the range of 0 to 90% by weight (about 0.1 to 90% by weight), preferably 0 to 50% by weight (about 0.1 to 50% by weight), and 1 to 45% by weight. About% may be used.

  As described above, the soft portion (or the easily stretchable portion) 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 polymer constituting the soft part (or easily stretchable part), selected from the group consisting of polyurethane chain, polyurea chain, polyurethane urea chain, polyolefin chain (especially polydiene chain), silicone chain, polyester chain, polyether chain and polyamide chain In the case of having at least one kind of polymer chain, the ratio of the at least one polymer chain part to the whole polymer is preferably 20% by weight or more (for example, 20 to 100% by weight), more preferably 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, for example, the extensibility tends to decrease. The polymer constituting the soft part is 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). In some cases, the proportion of polyacrylic chains in the total polymer may be 100% by weight.

  For the soft part (or easily stretchable part), if necessary, for example, a crosslinking agent (for example, an isocyanate-based crosslinking agent, an epoxy-based crosslinking agent, a melamine-based crosslinking agent, a peroxide-based crosslinking agent, a urea-based crosslinking agent). Metal alkoxide crosslinking agent, metal chelate crosslinking agent, metal salt crosslinking agent, carbodiimide crosslinking agent, oxazoline crosslinking agent, aziridine crosslinking agent, amine crosslinking agent, etc.), crosslinking accelerator, silane coupling agent, Tackifying resins (rosin derivatives, polyterpene resins, petroleum resins, oil-soluble phenols, etc.), anti-aging agents, fillers, colorants (pigments and dyes, etc.), UV absorbers, antioxidants, plasticizers, softeners, interfaces Additives such as an activator and an antistatic agent may be included as long as the characteristics of the present invention are not impaired.

  In the case where the base material part (A) 2 is formed as a soft part (or an easy extension part), the base material part (A) 2 as the soft part (or an easy extension part) is formed on the support, for example. A liquid precursor of a polymer constituting the part is applied to form a base material part (A) forming material layer, and a structure part (B) is formed at a predetermined portion of the base material part (A) forming material layer After the material is arranged, it can be formed by converting the liquid precursor in the base material part (A) forming material layer 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.

  In addition, the base material part (A) 2 as the soft part (or easily stretchable part) is formed by, for example, applying a solution or dispersion containing a polymer constituting the soft part on the support to form the base material part (A). ) After forming the forming material layer and arranging the forming material of the structural part (B) at a predetermined portion of the base material part (A) forming material layer, in the base material part (A) forming material layer It can also be formed by removing the solvent by drying. 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 base material part (A) 2 as the soft part (or the easy extension part) is formed on the support, for example, by forming a base material part (A) forming material layer from a single polymer constituting the soft part, It is also possible to form the base material part (A) by forming the structure part (B) at a predetermined portion of the forming material layer and then performing a melting / cooling process (hot melt process). The base material part (A) 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 base material part (A) forming material layer and the base material part (A) are often composed of substantially the same material composition. The melting / cooling treatment means cooling after melting.

  Next, the case where the structure part (B) 3 is formed as a hard part (or a difficult extension part) will be described.

  The hard part (or the difficult extension part) is, for example, (i) a monomer having a Tg of homopolymer of 5 ° C. or higher (more preferably 15 ° C. or higher, more preferably 50 ° C. or higher) [particularly, (meth) acrylic monomer ] The polymer containing 50% by weight or more (more preferably 60% by weight or more, more preferably 80% by weight or more) with respect to all the structural units of the polymer [for example, Tg is 5 ° C. or more, preferably Is derived from a polymer material containing a polymer (especially acrylic polymer)] at 15 ° C. or higher, and (ii) a polyfunctional monomer having two or more curable groups (radical polymerizable groups, cationic polymerizable groups) in the molecule. A polymer comprising 50% by weight or more (more preferably 60% by weight or more, more preferably 80% by weight or more) of the structural unit with respect to the total structural unit of the polymer The structural unit derived from a polyfunctional monomer having 2 or more radical polymerizable groups in the molecule (particularly an acrylic polyfunctional monomer) is 50% by weight or more (more preferably 60% by weight) based on the total structural unit of the polymer. (Iii) Tensile elastic modulus is 0.1 MPa or more (more preferably 0.5 MPa or more, more preferably 1 MPa or more, particularly preferably 5 MPa). The above polymer material can be used.

  In the case of (i), a hard part (or a difficultly stretched part) of a polymer containing 50% by weight or more of a structural unit derived from a monomer having a Tg of a homopolymer of 5 ° C. or higher based on the total structural unit of the polymer The proportion of the polymer material in the entire polymer material is, for example, 5% by weight or more, preferably 10% by weight or more, more preferably 15% by weight or more, and may be 50% by weight or more (eg 90% by weight or more). In the case of (ii), a hard part (or a hardly stretchable 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 proportion of the polymer material constituting the total is, for example, 5% by weight or more, preferably 10% by weight or more, more preferably 15% by weight or more, and may be 50% by weight or more (for example, 90% by weight or more). .

In (i) above, examples of the monomer having a Tg of homopolymer of 5 ° C. or higher include alicyclic rings such as isobornyl acrylate (homopolymer Tg: 97 ° C.) and cyclohexyl acrylate (homopolymer Tg: 15 ° C.). (Meth) acrylic acid ester having a formula group; (meth) acrylic acid tertiary alkyl ester such as t-butyl acrylate (homopolymer Tg: 41 ° C.); methyl methacrylate (homopolymer Tg: 105 ° C.); Methacrylic acid C _1-4 alkyl esters such as ethyl methacrylate (Tg of homopolymer: 65 ° C.), butyl methacrylate (Tg of homopolymer: 20 ° C.), isobutyl methacrylate (Tg of homopolymer: 67 ° C.); styrene Styrenic monomers such as (Tg of homopolymer: 100 ° C.); acrylonitrile (Homopolymer Tg: 100 ° C.).

  In the above (ii), as the polyfunctional monomer, for example, 1,6-hexanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly ) Propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate , Trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, trimethylolpropane EO-added tri (meth) acrylate, glycerin PO-added tri (meth) acrylate Rate and the like. Among the polyfunctional monomers, those having 3 or more functional groups (for example, 3 to 6 functional groups) are most preferable.

  In the above (iii), 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 part (or difficultly stretched part) is a polymer part formed by converting a polymer material precursor constituting the hard part (or difficultly stretched part) into the polymer material, and a solution or dispersion containing the polymer material Any of a polymer part formed by drying and removing the solvent therein, a polymer part formed by melting and cooling the polymer material, and the like may be used.

  For the hard part (or difficult extension part), for example, a crosslinking agent (for example, an isocyanate-based crosslinking agent, an epoxy-based crosslinking agent, a melamine-based crosslinking agent, a peroxide-based crosslinking agent, a urea-based crosslinking agent, Metal alkoxide crosslinking agent, metal chelate crosslinking agent, metal salt crosslinking agent, carbodiimide crosslinking agent, oxazoline crosslinking agent, aziridine crosslinking agent, amine crosslinking agent, etc.), crosslinking accelerator, silane coupling agent, adhesive Giving resins (rosin derivatives, polyterpene resins, petroleum resins, oil-soluble phenols, etc.), anti-aging agents, fillers, colorants (pigments and dyes, etc.), UV absorbers, antioxidants, plasticizers, softeners, surface activity Additives such as an agent and an antistatic agent may be included as long as the characteristics of the present invention are not impaired.

Hereinafter, the case where the structure part (B) 3 is formed as a hard part (or a difficult extension part) will be described. The structural part (B) as a hard part (or a difficultly stretched part), the structural unit derived from the monomer (i) having a Tg of 5 ° C. or higher for the homopolymer is 50% by weight or more based on the total structural unit of the polymer In the case of constituting with a polymer material containing a polymer, for example, a preformed base material part (A) containing, for example, a monomer component containing 50% by weight or more of the monomer having a Tg of 5 ° C. or more of the homopolymer After being disposed at a predetermined portion of the forming material layer, it can be formed by irradiating with energy rays and curing (polymerization). In this case, as a monomer other than the monomer having a homopolymer Tg of 5 ° C. or more, for example, a monomer exemplified as the curable monomer M having the energy ray curable group A ₂ can be appropriately selected and used.

50 parts by weight of the structural unit (B) as a hard part (or difficultly stretched part) derived from a polyfunctional monomer having (ii) two or more curable groups in the molecule relative to all structural units of the polymer In the case of a polymer material containing a polymer containing at least 50%, for example, a monomer component containing 50% by weight or more of the above-mentioned polyfunctional monomer in the total amount of the monomer is predetermined in the preformed base material part (A) forming material layer. It can be formed by irradiating with energy rays and curing (polymerization) after being disposed on the site. In this case, as a monomer other than the polyfunctional monomer, a monofunctional monomer can be appropriately selected from the monomers exemplified as the curable monomer M having the energy ray curable group A ₂ .

  When forming a hard part (or hard extension part), a photoinitiator is normally used in order to harden a curable group. It does not specifically limit as a photoinitiator, The photoinitiator similar to the case where the said soft part is formed can be used. Although it does not specifically limit as the usage-amount of a photoinitiator, It is 0.01-3 weight part with respect to 100 weight part of sclerosing | hardenable compound whole quantity, The upper limit becomes like this. Preferably it is 1 weight part, More preferably The lower limit is preferably 0.02 parts by weight, more preferably 0.05 parts by weight.

  In the case where the structural part (B) as the hard part (or the difficultly stretched part) is composed of the polymer material (iii) having a tensile modulus of elasticity of 0.1 MPa or more, a monomer (energy ray curable) that can be derived from the polymer. Monomer) or a partially polymerized product thereof, or the structural part (B) can be formed by curing or crosslinking a polymer that can be induced by curing or crosslinking to the polymer, or a polymer before crosslinking.

  The case where the base material part (A) is formed as a soft part (or an extended part) and the structure part (B) is formed as a hard part (or a difficultly extended part) has been described above, but by appropriately selecting a polymer and an additive. The base material part (A) and the structure part (B) having various characteristics, physical properties and functions can be formed.

  The polymer constituting the structural part (B) 3 includes a polymer constituting the base material part (A) 2 from the viewpoint of the integrity and adhesion of the base material part (A) 2 and the structural part (B) 3. A polymer having the same kind of polymer or a polymer chain (main chain or side chain) of the polymer constituting the base material part (A) 2 in the main chain or side chain is preferable.

  More specifically, as a preferred combination of the polymer constituting the base material part (A) 2 and the polymer constituting the structural part (B) 3, a combination of polyurethane polymers, a combination of polyurea polymers, a polyurethane urea system Combinations of polymers, combinations of polyolefin polymers, combinations of silicone polymers, combinations of polyester polymers, combinations of polyether polymers, combinations of polyamide polymers, combinations of polystyrene polymers, acrylic The combination of polymers is mentioned. A combination of a polystyrene polymer and an acrylic polymer is also preferable. Furthermore, as the preferred combination, a combination of polymers having a polyurethane chain, a combination of polymers having a polyurea chain, a combination of polymers having a polyurethane urea chain, a combination of polymers having a polyolefin chain, and a polymer having a silicone chain Combination of polymers having a polyester chain, combination of polymers having a polyether chain, combination of polymers having a polyamide chain, combination of polymers having a polystyrene-based polymer chain, between polymers having a polyacryl chain Combinations are mentioned.

  Among these, preferred combinations of the polymer constituting the base material part (A) 2 and the polymer constituting the structural part (B) 3 include a combination of polyurethane polymers, a combination of polymers having a polyurethane chain, and a polystyrene polymer. A combination of each other, a combination of polymers having a polystyrene polymer chain, a combination of acrylic polymers, a combination of polymers having a polyacryl chain, and a combination of a polystyrene polymer and an acrylic polymer are particularly preferable.

[Manufacture of organic base materials]
The 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: On a support, a base material (by a liquid precursor of the polymer (a) constituting the base material part (A), a solution or dispersion containing the polymer (a), or the polymer (a) alone ( A) A step of forming a forming material layer Step B: A step of arranging a structural portion (B) forming material at a predetermined portion of the base material portion (A) forming material layer,
Step C: At least one selected from a reaction, a solvent drying removal process, and a melting / cooling process for the base material part (A) forming material layer in which the structural part (B) forming material is arranged at a predetermined site The process which obtains the organic base material in which the structure part (B) was partially and integrally formed in the base material part (A) by performing two processes

  The gradation in the boundary region between the base material part (A) and the structure part (B) indicates that the base material part (A) formation part and the structure part (B) formation part are in a liquid state ( (Solution state, emulsion state, molten state, etc.). In particular, in the step C, it is preferable that both the base material part (A) formation site and the structure part (B) formation site pass through a liquid state.

  First, in Step A, a polymer (a) liquid precursor constituting the base material part (A), a solution or dispersion containing the polymer (a), or the polymer (a) alone is formed on the support. A material part (A) formation 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 base material part (A) include a monomer (such as an energy ray-curable monomer) that can be derived into the polymer (a), a partial polymer of the monomer, and a polymer ( Examples thereof include a polymer that can be derived into a), a polymer before curing or crosslinking. A mixture thereof may be used. Examples of the solution or dispersion containing the polymer (a) include an aqueous solution or an organic solvent solution of the polymer (a), an aqueous dispersion of the polymer (a), and an organic solvent dispersion. As a solvent, it can select and use suitably according to a polymer.

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

  In addition, formation of the base material part (A) formation material layer can also be performed using a suitable type | mold. In this case, the viscosity of the forming material may be lower than the above range.

  The thickness of the base material part (A) forming material layer is, for example, 0.01 mm to 1 cm, the upper limit is preferably 5 mm, more preferably 2 mm, and the lower limit is preferably 0.03 mm. Preferably it is 0.05 mm.

  Next, in the process B, the structure part (B) forming material is disposed at a predetermined portion of the base material part (A) forming material layer. The material for forming the structure part (B) is preferably a meltable solid, liquid, solution or dispersion in order to form a gradation in the boundary region between the base material part (A) and the structure part (B). . As a material for forming the structure part (B), a precursor (for example, an energy beam curable composition) of the material (polymer material) (b) constituting the structure part (B) and a material constituting the structure part (B) (Polymer material) (b) itself may be a solution or dispersion containing the material (polymer material) (b) constituting the structure (B).

  In the step B, as the material for forming the structural part (B), the structural part (B) may be, for example, (i) a structural unit derived from a monomer having a Tg of the homopolymer of 5 ° C. or higher as a whole structural unit of the polymer. Monomer component containing 50% by weight or more of the monomer having a Tg of 5 ° C. or more, or a partially polymerized product thereof, when the polymer material comprises a polymer containing 50% by weight or more of the polymer. A curable composition containing energy (such as an energy ray curable composition) can be used. This curable composition usually contains a polymerization initiator.

  Further, a polymer containing a polymer containing 50% by weight or more of structural units derived from a polyfunctional monomer having (ii) two or more curable groups in the molecule with respect to the structural unit (B) based on the total structural units of the polymer. In the case of constituting with a material, as a material for forming the structural part (B), a curing 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. Composition (such as an energy beam curable composition) can be used. This curable composition usually contains a polymerization initiator.

  When the structural part (B) is composed of (iii) a polymer material having a tensile elastic modulus of 0.1 MPa or more, the polymer material having the tensile elastic modulus of 0.1 MPa or more is used as the structural part (B) forming material. A curable composition (such as an energy beam curable composition) containing a monomer (such as an energy beam curable monomer) or a partial polymer thereof can be used.

  A method (means) for disposing the material for forming the structure part (B) at a predetermined portion of the material layer for forming the base material part (A) is not particularly limited. For example, (1) formation of the structure part (B) A method of coating, dripping, placing, driving or printing a material for a predetermined part of a base material part (A) forming material layer from above, (2) a structure part (B) forming material in a liquid form And (3) a structure portion on a support different from the support on which the base material portion (A) forming material layer is formed. Examples thereof include a method of coating, dropping, placing or printing the forming material of (B), and transferring this onto the base material part (A) forming material layer.

  When the structural part (B) forming material is in a liquid state, the viscosity of the liquid is a temperature at the time of coating, dripping, etc. from the viewpoint of workability and the like (for example, a predetermined temperature within a range of 10 to 40 ° C. In particular, at 25 ° C.), for example, 10 to 50000 mPa · s, the upper limit is preferably 30000 mPa · s, more preferably 20000 mPa · s, and the lower limit is preferably 20 mPa · s, more preferably 30 mPa · s. s. If this viscosity is too low, it will be difficult to obtain the hardly extensible polymer part (B) of the desired shape, and conversely if too high, the coating workability will tend to be reduced.

  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, and the like of the structural part (B) forming material disposed in a predetermined part of the base material part (A) forming material layer, the size of the structural part (B) ( The size and height in the surface direction can be controlled. When a plurality of structure portions (B) are formed, a material for forming the structure portion (B) is applied at an appropriate interval. In addition, the shape of the structure part (B) can be controlled by using a means for regulating the dropping and injection of the structure part (B) forming material. When the size of the structure portion (B) is relatively large, the dropping method is often used, and when the size of the structure portion (B) 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 base material part (A) so that it is not soiled. In the case of the injection method, the structure part (B) forming material is less likely to diffuse into the base material part (A) forming material layer than the dropping method, and the width of the gradation part is narrowed.

  In addition, when using the energy ray curable composition which is a precursor of the material (b) which comprises a structure part (B) as a structure part (B) formation material, this energy ray curable composition (application | coating) When the liquid) is disposed at a predetermined portion of the base material part (A) forming material layer, the energy ray curable composition (coating liquid) is diffused to the peripheral part (base material part (A) forming material layer). In order to adjust (in order to adjust the width of the gradation part), the energy beam curable composition may contain a polymer.

  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 control 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 adjusting 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 structure part (B), and the base material part (A) and the structure part. Any of the polymers exemplified as the polymer constituting (B) may be used, but from the viewpoint of the integrity and adhesion between the base material part (A) and the structure part (B), the base material part (A) It is preferable that the polymer is the same type as the polymer constituting the polymer, or the polymer having the same polymer chain (main chain or side chain) as the main chain or side chain in the polymer constituting the structural part (A).

  As the energy ray curable composition (coating liquid), the base material part (dropping amount: about 0.03 μL) after 60 seconds from dropping the coating liquid on the base material part (A) forming material layer ( A) The diameter of the coating solution on the forming 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. Moreover, the diameter of the coating liquid on the base material part (A) forming material layer 120 seconds after dropping the coating liquid on the base material part (A) forming material layer (dropping amount: about 0.03 μL) However, what becomes 1.4 times or less with respect to the diameter of the coating liquid immediately after dripping is preferable, and what becomes 1.3 times or less is more preferable. From the coating solution in which the diameter of the coating solution after 60 seconds or 120 seconds after dropping is larger than the diameter of the coating solution immediately after dropping, a pattern sheet of a target shape [base material part (A) An 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, dropping, placing, driving in, printing, pouring or transferring the structure part (B) forming material, the structure part (B) forming material is changed into the base material part (A) forming material as necessary. Let stand until it penetrates, migrates and settles to the desired depth of the layer.

  In Step C, the base material part (A) forming material layer in which the structure part (B) forming material is arranged at a predetermined site is subjected to a reaction, a solvent drying removal process, and a melting / cooling process (hot melt). At least one treatment selected from (treatment) is performed to obtain an organic base material in which the structural portion (B) is partially and integrally formed in the base material portion (A). In step C, an organic base material in which the structural portion (B) is partially and integrally formed in the base material (A) can be efficiently obtained by performing a treatment suitable for the form of each material. it can.

  Examples of the reaction include a polymerization reaction by energy rays and heat, curing, or a crosslinking reaction. The solvent is removed by drying at an appropriate temperature according to the type of the solvent. The solvent may be removed by drying at normal pressure or under reduced pressure. The melting is preferably performed at a temperature at which both the base material part (A) forming material layer and the structure part (B) forming material are melted.

  In the present invention, the combination of the form of the base material part (A) forming material used in the process A and the form of the structure part (B) forming material used in the process B includes the process C from the viewpoint of gradation formation. It is preferable that the combination is in a liquid state.

  For example, when an energy ray curable material [liquid precursor of polymer (a) (syrup or the like)] is used as the base material (A) forming material, a solvent-based material [solution containing polymer (a)] is used. In this case, in each case of using a dispersion-based material [emulsion containing polymer (a), etc.], as the material for forming the structure (B), a solvent-based material (polymer solution), a dispersion-based material (polymer emulsion, etc.) ), A material in the form of an energy ray curable material [a liquid precursor of a polymer (such as syrup)] is preferably used. Further, when a hot melt material [polymer (a) alone] is used as the base material (A) forming material, a solid [hot melt material (polymer simple substance) is used as the structure (B) forming material. The material of the form of] is preferable.

  More specifically, the form of the base material part (A) forming material and the structure part (B) forming material is a combination of energy ray curable materials (energy ray curable syrup, etc.), solvent-based material Combinations of (solutions), dispersion materials (emulsions, etc.), hot melt materials, and combinations of solvent materials (solutions) and dispersion materials (emulsions, etc.) (in no particular order) ), A combination of a hot-melt material and a solvent-based material (solution) (in no particular order), a combination of a hot-melt material and a dispersion-based material (emulsion, etc.) (in no particular order), and the like.

  Among these, as a form of the base material part (A) forming material and the structure part (B) forming material, an energy ray curable material (energy ray) can be formed from the point that gradation can be easily and smoothly formed. A combination of curable syrups), a combination of solvent-based materials (solutions), a combination of dispersion-based materials (emulsions, etc.), and a combination of hot-melt materials.

  Further, in order to form a gradation in the boundary region between the base material part (A) and the structure part (B), for example, the material for forming the base material part (A) and the material for forming the structure part (B) are common to each other. Alternatively, it is preferable to use a similar material (solvent, monomer, etc.) or a material (solvent, monomer, etc.) having an affinity for each other. Specifically, for example, the base material part (A) forming material and the structure part (B) forming material are both made of a material containing an acrylic monomer (such as a liquid precursor of a polymer). A gradation can be obtained. Such gradation is formed by diffusion and migration of monomer components, solvents, and the like, and subsequent curing, solvent removal, and the like. Therefore, in the gradation part of the organic base material which has this gradation, the composition assumed from the material for forming each part [structure part (B), base material part (A)] will be different. The degree of gradation (width) can be adjusted by the kind and amount of the base material (A) forming material and the structure (B) forming material (solvent, monomer, etc.). Further, as described above, in the case of using an energy ray curable composition as the structure part (B) forming material, when a polymer is blended in the energy ray curable composition, the type and amount of the polymer The gradation level (width) can be adjusted by the weight average molecular weight or the like.

  As a manufacturing method of the organic base material of this invention, the following aspect (I)-(III) is preferable from a viewpoint which can manufacture an organic base material efficiently.

  (I) In step A, a base material part (A) forming material layer is formed on the support with an energy ray-curable composition that is a liquid precursor of the polymer (a). An energy ray-curable composition that is a precursor of the material (b) constituting the structural part (B) is disposed at a predetermined part of the material part (A) forming material layer, and in the step C, the material (b) The base material part (A) forming material layer in which the energy ray curable composition which is a precursor of the base material is disposed at a predetermined site is irradiated with energy rays, and the two energy ray curable compositions are cured, thereby producing the base material. A method of obtaining an organic base material in which the structural part (B) is partially formed in the part (A) and the boundary region of both parts forms a gradation.

  (II) In step A, a base material part (A) forming material layer is formed on the support with a solution or dispersion containing the polymer (a), and in step B, the base material part (A) is formed. A material (b) (for example, a polymer) constituting the structure part (B) or a solution or dispersion containing the material (b) is disposed at a predetermined portion of the material layer, and in step C, the structure part (B) The base material part (A) forming material layer in which the material (b) or a solution or dispersion containing the material (b) is disposed at a predetermined site is subjected to a drying removal treatment of the solvent. (A) A method for obtaining an organic base material in which the structural part (B) is partially formed and the boundary region of both parts forms a gradation.

  (III) In step A, a base material part (A) forming material layer is formed on the support by the polymer (a) alone, and in step B, the base material part (A) forming material layer is predetermined. A material (b) (for example, a polymer) constituting the structural part (B) is disposed in the part, and in step C, a base material part (the material (b) constituting the structural part (B) is disposed in a predetermined part ( A) The forming material layer is subjected to a melting / cooling process (hot melt process) so that the structure part (B) is partially formed in the base material part (A) and the boundary region between the two parts has gradation. A method for obtaining an organic substrate.

More specifically, the organic base material of the present invention can be produced, for example, through the following steps.
Step A1: Step of forming a base material part (A) forming energy beam curable composition layer on a support Step B1: In a predetermined part of the base material part (A) forming energy beam curable composition layer, Step of arranging (containing) the energy beam curable composition for forming the structural part (B) Step C1: Energy for forming the base material part (A) in which the energy beam curable composition for forming the structural part (B) is arranged The energy curable composition layer for forming the structure part (B) and the energy ray curable composition layer for forming the base material part (A) are cured by irradiating the line curable composition layer with energy rays, A step of obtaining a sheet-like organic base material in which the structural part (B) is partially formed in the material part (A) and the boundary region of both parts forms a gradation

  This method is a specific example of the above aspect (I), and FIG. 4 is a schematic explanatory view (sectional view) thereof. In FIG. 4, (a) is a process A1, (b) is a process B1, (c), (d), (e), (f) [or (d '), (e'), (f)] Corresponds to step C1.

  In step A1, the base material part (A) forming energy beam curable composition layer 20 is formed on the support 4. As the support 4, those described above can be used.

The base material part (A) forming energy beam curable composition layer 20 is formed of, for example, the polyurethane chain, polyurea chain, polyurethane urea chain, polyolefin chain (particularly, polydiene chain), silicone chain, polyester chain, or polyether. A curable polymer P having at least one polymer chain selected from the group consisting of a chain, a polyamide chain, a polystyrene polymer chain, and a polyacryl chain, and having an energy ray-curable group A ₁ in the main chain or side chain Or a mixture of the curable polymer P and a curable monomer M having an energy beam curable group A ₂ and an energy beam curable composition containing a photopolymerization initiator are coated on the support 4. it can.

  A solvent may be added to the curable composition as necessary, but it is preferable not to use a solvent because a process for removing the solvent later increases. Moreover, in order to prevent the superposition | polymerization by a heat | fever, you may add a polymerization inhibitor to the said curable composition as needed.

  The curable composition is preferably in the form of a syrup. The viscosity of the curable composition and the coating method are the same as described above. In addition, formation of the base material part (A) formation energy-beam curable composition layer 20 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 base material part (A) forming energy beam curable composition layer 20 is the same as described above.

  In Step B1, the energy ray-curable composition 30 for forming the structural part (B) is arranged (contained) in the energy ray-curable composition layer 20 for forming the base material part (A).

  The energy ray curable composition 30 for forming the structural part (B) is preferably syrup-like. From the viewpoint of workability and the like, the viscosity of the energy ray curable composition 30 for forming the structural part (B) is a temperature at the time of coating (for example, a predetermined temperature within a range of 10 to 40 ° C, particularly 25 ° C). For example, the upper limit is preferably 30000 mPa · s, more preferably 20000 mPa · s, and the lower limit is preferably 20 mPa · s, more preferably 30 mPa · s. If the viscosity is too low, it is difficult to obtain a desired shape. Conversely, if the viscosity is too high, the coating workability tends to be lowered.

  The addition and injection method of the energy ray-curable composition 30 for forming the structure (B) is not particularly limited, and for example, a syringe, an appropriate dropping device, or the like can be used. Moreover, the transfer method of the energy ray-curable composition 30 for forming the structural part (B) is not particularly limited. For example, the method using an intaglio coating machine such as a gravure coater, the energy ray-curable property for forming the structural part (B). The support etc. which apply | coated and dripped the composition 30 and the method of bonding the energy beam curable composition layer 20 for base material part (A) formation can be used.

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

  In step C1, the base material part (A) forming energy beam curable composition layer 20 containing the structural part (B) forming energy beam curable composition 30 is irradiated with energy rays to form the structural part. (B) The forming energy beam curable composition 30 and the base material part (A) forming the energy ray curable composition layer 20 are cured, and the structural part (B) 3 is part of the base material part (A) 2. An organic base material that is formed in a uniform manner and has a boundary region between both parts is obtained.

  Although ultraviolet rays (UV) are used as energy rays in FIG. 4, as described above, ionizing radiation such as α rays, β rays, γ rays, neutron rays, electron rays, and visible rays may be used.

  The irradiation energy, irradiation time, irradiation method, and the like of the energy beam are not particularly limited as long as the photopolymerization initiator can be activated to cause the monomer component to react.

  As the energy beam irradiation device, a conventional device can be used. For example, when irradiating ultraviolet rays, a mercury lamp, a fluorescent lamp, a sodium lamp, a metal halide lamp, a xenon lamp, a neon tube, a neon lamp, a high-intensity discharge lamp, or the like can be used.

  Base material part (A) containing energy beam curable composition 30 for forming structure part (B) for the purpose of preventing curing inhibition by oxygen and the purpose of smoothing the surface during irradiation with energy rays The cover film 5 may be laminated on the surface of the forming energy beam curable composition layer 20. As the cover film 5, the same separator as the support 4 can be used. Lamination | stacking of the cover film 5 can be performed using a hand roller etc., for example.

Energy beam irradiation may be performed in several stages. For example, when irradiating with ultraviolet rays, as shown in FIG. 4 (c), irradiation is performed for a short time (for example, an integrated irradiation amount of 10 to 1000 mJ / cm ² ) at a high illuminance (for example, 50 to 1000 mW / cm ² ). Then, as shown in FIG. 4 (d), the cover film 5 is laminated, and then, as shown in FIG. 4 (e), it is long with a low illuminance (for example, 1 to 40 mW / cm ² ). You may irradiate with time (for example, integrated irradiation amount 500-10000mJ / cm < ² >). Thus, the workability at the time of lamination | stacking of the cover film 5 by a hand roller can be improved by irradiating energy beam irradiation in several steps. In the figure, 200 is a partially cured energy beam curable composition layer for forming a base material part (A), and 300 is a partially cured energy beam curable composition for forming a structure part (B).

When the energy beam irradiation is performed in one stage, for example, after the step B1, as shown in FIG. 4 (d ′), the energy beam curable composition 30 for forming the structure (B) is included. The cover film 5 may be laminated on the surface of the base material part (A) 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 the energy beam curable composition 30 for forming the structural part (B) and the energy beam curable composition layer 20 for forming the base material part (A) are cured as described above, it is shown in FIG. As necessary, the cover film 5 and the support 4 are peeled off as necessary, and cut into an appropriate size as necessary, and used as the organic substrate 1. The cutting operation may be performed before the cover film 5 or the support 4 is peeled off.

Moreover, the organic base material of this invention can also be manufactured by passing through the following process more specifically.
Step A2: Step of forming a base material part (A) forming material layer by applying a solution or dispersion containing the polymer a constituting the base material part (A) on the support Step B2: The base material Distributing (containing) a solution or dispersion containing the polymer constituting the structural part (B) to a predetermined part of the part (A) forming material layer by coating, dripping, placing, driving in, printing, or the like. Step Step C2: Drying the base material part (A) forming material layer provided with the polymer-containing solution or dispersion liquid constituting the structure part (B), removing the solvent, and the base material part (A) A step of obtaining a sheet-like organic base material in which the structure part (B) is partially formed and the boundary area between both parts forms a gradation

  This method is a specific example of the embodiment (II), and FIG. In FIG. 5, (g) corresponds to step A2, (h) corresponds to step B2, and (i) and (j) correspond to step C2. Reference numeral 21 denotes a layer (base material part (A) forming material layer) made of a solution or dispersion containing a polymer constituting the base material part (A), and reference numeral 31 contains a polymer constituting the structural part (B). Indicates a solution or dispersion. Reference numerals 1, 2, 3, and 4 are the same as described above.

Furthermore, the extensible organic base material of the present invention can be more specifically manufactured through the following steps.
Step A3: A step of forming a base material part (A) forming material layer by forming a sheet of polymer a constituting the base material part (A) on a support by hot pressing, extrusion molding, or the like Step B3: The base material A step of placing (containing) the polymer constituting the structural portion (B) by placing or dropping (melting) the predetermined portion of the material portion (A) forming material layer Step C3: The structural portion (B The base material part (A) forming material layer in which the polymer constituting the base material is disposed is heated and melted, and then cooled, so that the structural part (B) is partially formed in the base material part (A) and both parts. For obtaining a sheet-like organic base material in which the boundary area of the film forms a gradation

  This method is a specific example of the above-mentioned aspect (III), and FIG. 6 is a schematic explanatory view (cross-sectional view) thereof. 6K corresponds to the step A3, (l) corresponds to the step B3, and (m) and (n) correspond to the step C3. The code | symbol 22 shows the sheet | seat (base material part (A) formation material layer) which consists of a polymer which comprises a base material part (A), and the code | symbol 32 shows the polymer which comprises a structure part (B). Reference numerals 1, 2, 3, and 4 are the same as described above.

  The organic base material 1 obtained in this way is a member having parts having different properties, physical properties, and functions, as a member for an electronic product (transistor, integrated circuit, capacitor, sensor, actuator, etc.), an optical product (display, illumination, light guide). Components for wave circuits, etc., components for optoelectronic products (light emitting diodes, photodiodes, solar cells, etc.), components for car electronics products, members for household appliances, members for housing equipment, building materials, band members, binding members, hygiene It can be used as a product, clothing part, poultice base.

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

Production Example 1 (Manufacture of base material syrup)
In a reaction vessel equipped with a condenser, a thermometer, and a stirrer, 71 parts by weight of isobornyl acrylate (trade name “IBXA”, manufactured by Osaka Organic Chemical Industry Co., Ltd.) as a (meth) acrylic monomer, n -19 parts by weight of butyl acrylate (BA, manufactured by Toa Gosei Co., Ltd.), 10 parts by weight of acrylic acid (AA), poly (oxytetramethylene) glycol (PTMG650, Mitsubishi Chemical Corporation) having a number average molecular weight of 650 as a polyol 68.4 parts by weight) and 0.01 part by weight of dibutyltin dilaurate (DBTL) as a catalyst, and 25 g of hydrogenated xylylene diisocyanate (HXDI, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.) with stirring. 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 to obtain a base material syrup. It was. 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 resulting syrup had a viscosity (25 ° C.) of 8 Pa · s.

Production Example 2 (Manufacture of pattern portion forming syrup)
Trimethylolpropane EO-added triacrylate (trade name “Biscoat # 360”, manufactured by Osaka Organic Chemical Industry Co., Ltd.) is added to 100 parts by weight of red ink (trade name “Sachihata Stamp Stamp SGN-40 Red”, Sachihata ( 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) were added and dispersed. An acrylic monomer mixture (syrup for forming a pattern portion) was obtained.

Example 1
The base material syrup obtained in Production Example 1 is coated on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 μm) with an applicator to form a base material syrup layer having a thickness of 200 μm. did. Using a dispenser (trade name “SM300DS-S, MPP-1”, manufactured by Musashi Engineering Co., Ltd.) at a predetermined portion of the base material syrup layer, a syrup for forming a pattern portion obtained in Production Example 2 (about 0.00 mm). 03 μL) was injected to form 16 (longitudinal) × 16 (widthwise) patterns of island-shaped pattern portion forming syrup portions at intervals of 2 mm (center-to-center distance) in the longitudinal and width directions. Then, ultraviolet rays are irradiated from above with an ultraviolet lamp (metal halide type) (ultraviolet illuminance: 3.4 mW / cm ² , integrated irradiation amount: 100 mJ / cm ² ), and the base material syrup and the pattern portion forming syrup are semi-cured. After that, a cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 μm) is pasted onto the semi-cured syrup with a hand roller, and further irradiated with ultraviolet rays (ultraviolet rays) (ultraviolet rays) Illuminance: 3.4 mW / cm ² , integrated irradiation amount: 2000 mJ / cm ² ), syrup hardened portion (= structure) for forming a substantially cylindrical pattern in a hardened base syrup (= base material (A)) Part (B)) (diameter of about 1 mm) is arranged at a predetermined interval [2 mm interval (distance between centers), 16 pieces (longitudinal direction) × 16 pieces (width direction)] (thickness) : 200 μm).

Comparative Example 1
The base material syrup obtained in Production Example 1 is coated on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, Inc., thickness 38 μm) with an applicator to form a base material syrup layer having a thickness of 200 μm. On top of this, PET (trade name “Lumirror S10”, manufactured by Toray Industries, Inc., thickness 38 μm) punched into a circle with a diameter of 8 mm was disposed at 30 mm intervals (center distance) in the longitudinal direction. Then, a cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 μm) is bonded to the syrup with a hand roller, and further irradiated with ultraviolet rays (ultraviolet illuminance: 3.4 mW / cm <2>, integrated irradiation amount: 2000 mJ / cm <2>), and an organic base material (thickness: 200 [mu] m) having PET as a pattern portion was obtained. However, no composition gradation was observed in the boundary region between the PET and the organic substrate.

<Section observation>
The cross section of the site where the pattern portion of the organic substrate obtained in Example 1 was formed was observed with a microscope (Digital Microscope VHX-100F, manufactured by Keyence Corporation).
A cross-sectional photomicrograph is shown in FIG. The layer that looks dark inside the layer that looks white in the center of the photo in the vertical direction (actually red) is the pattern portion (thickness: 50 μm), and the layer that looks white is the base material sheet (total thickness of the two layers: 200 μm).

<Imaging IR>
The pattern part of the organic base material obtained in Example 1 was freeze-cut and a slice having a thickness of 2.5 μm was produced. Then, what sampled the section | slice on the optical cell made from a barium fluoride measured IR (iN10MX, Thermo Fisher Scientific). The measurement site is in the vicinity of the dotted rectangle in FIG.
It created a mapping image of the absorption intensity ratio of the urethane bond (1530 cm around ^-1) for an ester bond (1730 cm around ^-1). This mapping image is shown in FIG. An enlarged mapping image of the pattern portion is shown in FIG.
Moreover, the absorption intensity ratio [urethane bond (1535 cm ⁻¹ ) / ester bond (1731 cm ⁻¹ )] was calculated along the dotted arrow in FIG. This graph is shown in FIG. In FIG. 10, the horizontal axis indicates the phase in the surface direction of the organic substrate, and the vertical axis indicates the absorption intensity ratio [urethane bond (1535 cm ⁻¹ ) / ester bond (1731 cm ⁻¹ )]. From this graph, it can be seen that the composition forms a gradation in the boundary region between the pattern portion [corresponding to the structure portion (B)] and the base material sheet [corresponding to the base material portion (A)].

1 organic base material 2 base material (A) [base material part (A)]
20 Base Material Part (A) Forming Material Layer (Base Material Part (A) Energy Beam Curable Composition Layer)
21 Base material part (A) forming material layer 22 Base material part (A) forming material layer 200 Partially cured base material part (A) forming energy beam curable composition layer 3 Structure part (B)
30 Structure (B) Formation Material (Structure (B) Formation Energy Ray Curable Composition)
31 Structure (B) Forming Material 32 Structure (B) Forming Material 300 Partially Cured Structure (B) Forming Energy Beam Curable Composition 4 Support 5 Cover Film

Claims (8)

  An organic base material in which a structural part (B) having a composition different from that of the base material (A) is partially formed in the base material sheet made of the base material (A), and the base material (A) and An organic base material characterized in that the composition forms a gradation in the boundary region of the structural part (B).   The organic base material according to claim 1 or 2, wherein the structural part (B) is partially formed in a state where it is exposed or not exposed on at least one surface of the organic base material.   The distance from the starting point on the base material (A) side to the ending point on the structure part (B) side of the unidirectional gradation in the projected shape when the surface shape of the gradation area or the organic substrate surface of the gradation area is the projection surface The organic base material according to claim 1, wherein is 0.01 to 10 mm.   The surface shape of the structure portion (B) or the projection shape when the surface of the organic base material of the structure portion (B) is the projection surface represents a substantially circular shape, a substantially polygonal shape, an amorphous shape, or a character, symbol or number. The organic base material according to claim 1, wherein the organic base material has a shape, an annular shape, or a linear shape.   The length of the major axis in the projection shape when the surface shape of the structure portion (B) or the organic base material surface of the structure portion (B) is the projection surface is 0.05 mm to 10 cm. The organic base material of any one.   The organic base material according to any one of claims 1 to 5, wherein a plurality of structural portions (B) are formed in a regular pattern in a base material sheet made of the base material (A).   The organic base material according to claim 6 whose distance between adjacent structure parts (B) is 0.05 mm-50 cm.   The organic substrate according to any one of claims 1 to 7, which has a thickness of 0.01 mm to 1 cm.