Manufacturing method of laminate

Abstract

To provide a method for continuously manufacturing a laminate which can control a surface uneven shape and has surface unevenness that is free from the risk of falling of particles.SOLUTION: A method for manufacturing a laminate includes at least: a resin layer precursor formation step (A) of coating a curable resin composition on one surface of a base material to obtain a base material with a resin layer precursor; a surface treatment step (B) of subjecting a semi-cured or uncured base material with the resin layer precursor to a surface treatment by a dry process to obtain a laminate having unevenness including a wrinkle structure on the outermost surface; and a winding step (C) of winding the laminate in a roll shape.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing a laminate having an uneven surface. [Background technology]

[0002] 2. Description of the Related Art Conventionally, techniques have been developed for forming minute irregularities on the surfaces of various materials. For example, it is known that in packaging materials, unevenness is formed on the lid material or the inner surface of the container to prevent the contents from adhering to the material. Also, there is known a technique of forming minute unevenness on an optical material to increase the haze and suppress transmission or surface reflection. For each of these applications, there is an optimum surface unevenness structure, and the unevenness structure is formed by controlling it.

[0003] Patent Document 1 discloses a water-repellent laminate comprising, in this order, a substrate, an organic solvent-resistant sealant film layer, and an anti-adhesion layer, wherein the anti-adhesion layer contains a thermoplastic resin, water-repellent fine particles, and bead particles having an average particle size larger than that of the water-repellent fine particles. It has been shown that such a laminate has an anti-adhesion layer that contains two types of particles of different sizes, which forms a unique uneven structure on the surface, significantly improving the anti-adhesion and water repellency of viscous contents. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2017-226199 Summary of the Invention [Problem to be solved by the invention]

[0005] However, as disclosed in Patent Document 1, when unevenness is formed using particles, it is not possible to prevent particles present near the surface from falling off. For example, when used as a packaging material, it is easy for foreign matter to be mixed into the contents, making it difficult to apply to anything other than a lid material. Furthermore, Patent Document 1 does not specifically disclose a method for controlling the concave-convex structure, and further improvements are needed to control the concave-convex structure. Furthermore, in the unevenness forming technology of Patent Document 1, a laminate is produced by a batch process, but for mass production, it is required to produce a large area continuously.

[0006] Therefore, an object of the present invention is to provide a manufacturing method for continuously manufacturing a laminate having a surface irregularity in which the surface irregularity shape can be controlled and there is no risk of particles falling off. [Means for solving the problem]

[0007] The gist of the present invention is as set forth in the following [1] to

[20] . [1] A resin layer precursor forming step (A) of applying a curable resin composition to at least one surface of a substrate to obtain a substrate with a resin layer precursor; a surface treatment step (B) of performing a surface treatment by a dry process on the semi-cured or uncured substrate with the resin layer precursor to obtain a laminate having irregularities on the outermost surface; and (C) a winding step of winding the laminate into a roll. [2] After the resin layer precursor forming step (A), a winding step (X) of winding the substrate with the resin layer precursor into a roll; an unwinding step (Y) of unwinding the substrate with the resin layer precursor from the roll; The method for producing a laminate according to the above [1], further comprising the step of (B) performing a surface treatment thereafter. [3] The method for producing a laminate according to the above [2], wherein the surface treatment step (B) and the winding step (C) are carried out while transporting the substrate with the resin layer precursor. [4] The method for producing a laminate according to the above [1], wherein the resin layer precursor forming step (A), the surface treatment step (B), and the winding step (C) are carried out continuously while the substrate is being transported. [5] After the resin layer precursor forming step (A), A semi-curing step (P) is performed to semi-cure the resin layer precursor. The method for producing a laminate according to any one of the above [1] to [4], wherein a surface treatment step (B) is then carried out. [6] The method for producing a laminate according to any one of the above [1] to [5], wherein the surface treatment is any one of chemical vapor deposition, physical vapor deposition, and plasma treatment. [7] The method for producing a laminate according to any one of the above [1] to [6], wherein the temperature of the film in the surface treatment step (B) is 30°C or higher and 120°C or lower. [8] The curable resin composition is a thermosetting resin composition, The method for producing a laminate according to any one of the above [1] to [7], wherein the ratio (number of isocyanate groups) / (number of hydroxyl groups) in the thermosetting resin composition is 10 or less. [9] The method for producing a laminate according to any one of the above [1] to [8], wherein the unevenness on the outermost surface of the laminate includes a wrinkle structure.

[10] The method for producing a laminate according to any one of [1] to [9] above, wherein the wrinkle structure includes a primary wrinkle structure and a secondary wrinkle structure having a smaller undulation period than the primary wrinkle structure.

[11] The method for producing a laminate according to any one of the above [1] to

[10] , wherein the specific surface area (S / A) of the outermost surface of the laminate is 1.001 or more.

[12] The method for producing a laminate according to any one of the above [1] to

[11] , wherein the outermost surface of the laminate has an arithmetic mean roughness (Sa) of 20 nm or more.

[13] The method for producing a laminate according to any one of the above [1] to

[12] , wherein the outermost surface of the laminate has a Sz (maximum height) of 1000 nm or more.

[14] The method for producing a laminate according to any one of the above [1] to

[13] , wherein the absolute value of Ssk (degree of deviation) of the outermost surface of the laminate is 20 or less.

[15] The method for producing a laminate according to any one of the above [1] to

[14] , wherein the thickness (tb) of the resin layer is 0.1 μm or more and 15 μm or less.

[16] The method for producing a laminate according to any one of the above [1] to

[15] , wherein a cover layer is formed by the dry process.

[17] The method for producing a laminate according to the above

[16] , wherein the cover layer is either an inorganic substance-containing layer or a cover resin layer.

[18] The method for producing a laminate according to the above

[17] , wherein the inorganic substance-containing layer is formed from at least one material selected from the group consisting of diamond-like carbon, metal, metal oxide, metal nitride, metal carbide, and composites thereof.

[19] The method for producing a laminate according to any one of the above

[16] to

[18] , wherein the thickness (ta) of the cover layer is 5 nm or more and 300 nm or less.

[20] The method for producing a laminate according to any one of the above

[16] to

[19] , wherein the ratio (ta / tb) of the thickness of the cover layer (ta, unit: nm) to the thickness of the resin layer (tb, unit: μm) is 0.1 or more and 3500 or less. [Effects of the Invention]

[0008] According to the present invention, it is possible to continuously produce a laminate having a surface irregularity in which the surface irregularity shape can be controlled and there is no risk of particles falling off. [Brief explanation of the drawings]

[0009] [Figure 1] 1 is a schematic diagram illustrating an example of a laminate manufacturing apparatus according to a first embodiment of the present invention. [Figure 2] 1 is a schematic diagram illustrating an example of a laminate manufacturing apparatus according to a first embodiment of the present invention. [Figure 3] 1 is a schematic cross-sectional view showing an example of a laminate of the present invention. [Figure 4] 1 is a schematic cross-sectional view showing an example of a laminate of the present invention. [Figure 5] 1 is a schematic diagram illustrating an example of a laminate of the present invention. [Figure 6]1 is a schematic diagram illustrating an example of a laminate of the present invention. [Figure 7] 1 is an image of the outermost surface of the laminate having irregularities in Example 1, observed at a magnification of 10,000 times using a scanning electron microscope (SEM). [Figure 8] 1 is an image of the outermost surface of the laminate having irregularities in Example 2, observed at a magnification of 10,000 times using a scanning electron microscope (SEM). [Figure 9] 1 is an image of the outermost surface of the laminate having irregularities in Example 3, observed at a magnification of 10,000 times using a scanning electron microscope (SEM). [Figure 10] 1 is an image of the outermost surface of the laminate having irregularities in Example 4, observed at a magnification of 10,000 times using a scanning electron microscope (SEM). [Figure 11] 1 is an image of the outermost surface of the laminate having irregularities in Example 4, observed at a magnification of 50,000 times using a scanning electron microscope (SEM). [Figure 12] 1 is an image of the outermost surface of the laminate having irregularities in Example 5, observed at a magnification of 10,000 times using a scanning electron microscope (SEM). [Figure 13] 1 is an image of the outermost surface of the laminate having irregularities in Example 5, observed at 50,000 times magnification using a scanning electron microscope (SEM). [Figure 14] 1 is an image of the outermost surface of the laminate having irregularities in Example 6, observed at a magnification of 10,000 times using a scanning electron microscope (SEM). [Figure 15] 10 is an image of the outermost surface of the laminate having irregularities in Example 7, observed at 10,000 times magnification using a scanning electron microscope (SEM). [Figure 16] 1 is an image of the outermost surface of the laminate having irregularities in Example 8, observed at 10,000 times magnification using a scanning electron microscope (SEM). [Figure 17] 10 is an image of the outermost surface of the laminate having irregularities in Example 9, observed at 10,000 times magnification using a scanning electron microscope (SEM). DETAILED DESCRIPTION OF THE INVENTION

[0010] Next, the present invention will be described in detail based on the embodiments of the present invention, but the present invention is not limited to the embodiments described below.

[0011] <<Laminate manufacturing method>> The method for producing a laminate of the present invention (hereinafter also referred to as "the present production method") includes at least a resin layer precursor forming step (A) of applying a curable resin composition to at least one surface of a substrate to obtain a substrate with a resin layer precursor; a surface treatment step (B) of performing a surface treatment by a dry process on the semi-cured or uncured substrate with the resin layer precursor to obtain a laminate having irregularities on the outermost surface; and a winding step (C) of winding up the laminate into a roll. This manufacturing method can form a textured structure without using particles, eliminating the risk of particle shedding and enabling the laminate to be used in a wider range of applications. Furthermore, because the manufacturing method performs surface treatment continuously while the film is being transported, it offers higher productivity than conventional batch processing.

[0012] In the present manufacturing method, after the resin layer precursor forming step (A), a semi-curing step (P) of semi-curing the resin layer precursor may be carried out, and then a surface treatment step (B) may be carried out. In the present manufacturing method, the cover layer is preferably formed by a dry process.

[0013] The materials for the substrate, resin layer, and cover layer, and each step in the present invention will be described in detail below. In the present invention, the resin layer before surface treatment by a dry process may be referred to as a "resin layer precursor."

[0014] <Base material> The substrate in the present invention is not particularly limited as long as it is flexible and can be wound up, and examples of the material include organic substances such as resins, inorganic substances such as metals and metal oxides, and organic-inorganic composites. Examples of the substrate shape include sheets, films, and substrates. Among these, from the viewpoint of continuous productivity, the substrate shape is preferably a film, and a resin film is preferred because it is lightweight and easy to handle.

[0015] [Resin film] The resin film used as the substrate is not limited in material or structure as long as it has sufficient rigidity. The resin film may have a single layer structure or a multilayer structure. When the resin film has a multilayer structure, it may have a two-layer or three-layer structure, or may have four or more layers as long as the effects of the present invention are not impaired.

[0016] Examples of resins used in the resin film include polyester, polyarylates, polyethersulfone, polycarbonate, polyetherketone, polysulfone, polyphenylene sulfide, polyester-based liquid crystal polymer, triacetyl cellulose, cellulose derivatives, polypropylene, polyamides, polyimide, polycycloolefins, etc. These resins may be used alone or in combination of two or more in the resin film. When the resin film is multi-layered, the resins constituting each layer may be different from each other or may be the same as each other. The resin film may be a single layer or a multi-layered film, with each layer being constituted by a combination of two or more of the above resins.

[0017] Whether the resin film has a single layer structure or a multi-layer structure, it is preferably a polyester film in which the main component resin of each layer is polyester. In this case, "main component resin" means the resin that is contained in the largest proportion among the resins that make up the polyester film, for example, a resin that accounts for 50% by mass or more, preferably 70% by mass or more, and more preferably 80% by mass or more (including 100% by mass) of the resins that make up the polyester film. As long as each layer of the resin film contains polyester as the main resin component, it may contain a resin other than polyester or a component other than resin.

[0018] The polyester may be a homopolyester or a copolymer polyester. In the case of a homopolyester, it is preferably one obtained by polycondensation of an aromatic dicarboxylic acid and an aliphatic glycol. Examples of the aromatic dicarboxylic acid include terephthalic acid and 2,6-naphthalenedicarboxylic acid. Examples of the aliphatic glycol include ethylene glycol, diethylene glycol, and 1,4-cyclohexanedimethanol.

[0019] On the other hand, examples of the dicarboxylic acid component of the copolymer polyester include one or more of isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, sebacic acid, etc., and examples of the glycol component include one or more of ethylene glycol, diethylene glycol, propylene glycol, butanediol, 4-cyclohexanedimethanol, neopentyl glycol, etc.

[0020] Specific examples of polyester include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), and polybutylene naphthalate (PBN). Of these, PET and PEN are preferred, and PET is more preferred.

[0021] The resin film may contain particles for the purpose of forming a fine uneven structure on the film surface to impart various functions and for the main purpose of preventing scratches from occurring in each process. The type of particles is not particularly limited as long as they are particles that can impart lubricity. Examples include inorganic particles such as silica, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, magnesium phosphate, kaolin, aluminum oxide, and titanium oxide, and organic particles such as acrylic resin, styrene resin, urea resin, phenolic resin, epoxy resin, and benzoguanamine resin. These may be used alone or in combination of two or more. Furthermore, precipitated particles obtained by precipitating and finely dispersing a portion of a metal compound such as a catalyst during the process of producing a resin component such as polyester may also be used. The shape of the particles is not particularly limited. For example, they may be spherical, lumpy, rod-like, flat, or the like. Furthermore, the hardness, specific gravity, color, and the like of the particles are also not particularly limited. Two or more types of these particles may be used in combination as needed.

[0022] The average particle size of the particles is preferably 5 μm or less, more preferably 0.01 μm to 3 μm, and even more preferably 0.5 μm to 2.5 μm. By setting the particle size to 5 μm or less, the surface roughness of the resin film is prevented from increasing, and problems are less likely to occur when forming the resin layer and cover layer.

[0023] The particle content is preferably 5% by mass or less, more preferably 0.0003% by mass or more and 3% by mass or less, and even more preferably 0.01% by mass or more and 2% by mass or less, relative to 100% by mass of the resin film. By setting the particle content within this range, it is possible to achieve both smoothness and transparency of the film.

[0024] The method of adding particles to a resin film is not particularly limited, and a conventionally known method can be used. For example, particles can be added during the process of producing a resin component. For example, in the case of a polyester film, particles can be added at any stage of polyester production. Preferably, particles are added after the completion of an esterification or transesterification reaction.

[0025] If necessary, conventionally known additives such as antioxidants, antistatic agents, heat stabilizers, lubricants, dyes, pigments, and ultraviolet absorbers may be added to the resin film.

[0026] The thickness of the resin film is not particularly limited as long as it is within the range that allows it to be formed into a film, but is preferably 12 μm or more and 250 μm or less, more preferably 25 μm or more and 250 μm or less, and even more preferably 50 μm or more and 200 μm or less.

[0027] The resin film can be formed by, for example, forming a resin composition into a film shape by a melt casting method or a solution casting method. In the case of a multilayer structure, coextrusion may be used. Furthermore, the resin film may be uniaxially or biaxially stretched, with biaxially stretched films being preferred from the viewpoint of rigidity.

[0028] [Base material other than resin] The substrate other than resin is not particularly limited as long as the resin layer described below can be fixed onto the substrate, but examples thereof include metals, semi-metals, ceramics, and composite materials. Examples of metals include aluminum, copper, silver, gold, iron, and nickel. These metals may be used alone or in the form of an alloy, and preferred examples include aluminum, copper, and SUS, a steel-based material. Examples of semimetals include silicon and germanium, and these semimetals may be used alone or in the form of an alloy. Examples of ceramics include inorganic solid materials such as oxides, carbides, nitrides, and borides, and preferably glass. Composite materials are materials that combine two or more different materials, such as resins, metals, semi-metals, and ceramics, and examples of such materials include glass fiber reinforced plastics, carbon fiber reinforced plastics, and nanocomposite materials.

[0029] <Resin layer> The resin layer in the present invention is a cured product formed by curing a curable resin composition. When the curable resin composition is cured, it can easily adhere to a substrate, a cover layer, etc. Furthermore, in this manufacturing method, if the resin layer is left in an uncured or semi-cured state and subjected to a surface treatment by a dry process, it can buckle in response to a compressive stress acting along the surface direction, forming a wrinkled structure. The curable resin composition in the present invention is preferably a heat- or active energy ray-curable resin composition. A heat-curable resin composition is more preferable in that it is easy to control the uneven structure of the laminate. Furthermore, an active energy ray-curable resin composition is more preferable in that the semi-curing step (P) can be easily performed in a short time.

[0030] [Thermosetting resin composition] When the curable resin composition is a thermosetting resin composition, the thermosetting resin composition preferably contains a binder resin, more preferably contains a binder resin and a curing agent. By containing the binder resin and the curing agent, the thermosetting resin composition ensures adhesion to a substrate, a cover layer, etc., and is prone to buckling when a compressive stress is applied, making it prone to forming a wrinkled structure.

[0031] (binder resin) The binder resin is a thermosetting resin that can be cured by heating, and when the thermosetting resin composition contains a curing agent, it is a resin that cures in the presence of the curing agent. Examples of binder resins include polyester resins, urethane resins, acrylic resins, vinyl alcohol resins, ethylene vinyl alcohol resins, vinyl-modified resins, oxazoline group-containing resins, carbodiimide group-containing resins, epoxy group-containing resins, isocyanate group-containing resins, alkoxyl group-containing resins, modified styrene resins, and modified silicone resins, and these can be used alone or in combination of two or more. Binder resins may be reacted with each other to form a resin layer. Among these, from the viewpoints of adhesion to the substrate or to the substrate and the cover layer, and hot water resistance, it is preferable to use at least one resin selected from polyester resins, urethane resins, acrylic resins, epoxy group-containing resins, and alkoxyl group-containing resins, either alone or in combination, and acrylic resins are more preferable. The binder resin may be any resin capable of thermal crosslinking, such as urethane curing or epoxy curing, and from the viewpoint of reactivity with an isocyanate compound that is preferably used as a curing agent, as described below, a resin having a hydroxyl group, a carboxyl group, or an amino group is preferred, and a resin having a hydroxyl group is more preferred. Among these, polyols having two or more hydroxyl groups in one molecule are preferred, and acrylic polyols are particularly preferred.

[0032] Examples of acrylic resins include (meth)acrylic polymers obtained by polymerizing polymerizable monomers including (meth)acrylic monomers. The (meth)acrylic polymers may be homopolymers or copolymers, or may be copolymers with polymerizable monomers other than (meth)acrylic monomers. The (meth)acrylic monomer is a monomer having a (meth)acryloyl group. The polymerizable monomer other than the (meth)acrylic monomer is a monomer having a polymerizable functional group, and the polymerizable functional group may be a functional group containing a carbon-carbon unsaturated bond other than the (meth)acryloyl group, such as a vinyl group. In this specification, when the expression "(meth)acryloyl group" is used, it means one or both of "acryloyl group" and "methacryloyl group", and the same applies to other similar terms.

[0033] Examples of polymerizable monomers include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, isoamyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, pentadecyl (meth)acrylate, and dodecyl (meth)acrylate; cyclic alkyl (meth)acrylates such as cyclohexyl (meth)acrylate and isobornyl (meth)acrylate; and hydrocarbon (meth)acrylates in which the portion other than the polymerizable functional group is a hydrocarbon, such as (meth)acrylates having an aromatic ring, such as phenyl (meth)acrylate. Among these, alkyl (meth)acrylates or cyclic alkyl (meth)acrylates are preferred, with methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and cyclohexyl (meth)acrylate being more preferred, and methyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and cyclohexyl (meth)acrylate being even more preferred. In the (meth)acrylic polymer, the content of structural units derived from hydrocarbon-based (meth)acrylate is preferably, for example, 20% by mass or more and 90% by mass or less, or 30% by mass or more and 80% by mass or less.

[0034] As the polymerizable monomer, a monomer component other than hydrocarbon-based (meth)acrylate may be used, and specifically, a hydroxyl group-containing monomer is preferably used. Examples of the hydroxyl group-containing monomer include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 6-hydroxyhexyl (meth)acrylate. The hydroxyl group in the hydroxyl group-containing monomer is a hydroxyl group that is not directly bonded to an aromatic ring. Among these, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate are preferred. The hydroxyl group-containing monomer is preferably used in combination with the hydrocarbon (meth)acrylate, and therefore the acrylic resin is preferably a (meth)acrylic copolymer obtained by copolymerizing a hydrocarbon (meth)acrylate with a hydroxyl group-containing monomer, or a (meth)acrylic copolymer obtained by copolymerizing a hydrocarbon (meth)acrylate with a hydroxyl group-containing monomer and a monomer component other than these (other monomer component). This allows the (meth)acrylic copolymer to be an acrylic polyol containing multiple hydroxyl groups. In the (meth)acrylic polymer, the content of structural units derived from hydroxyl group-containing monomers is, for example, preferably from 0.5% to 80% by mass, and more preferably from 1% to 70% by mass.

[0035] As the polymerizable monomer, a monomer component (other monomer component) other than hydrocarbon-based (meth)acrylates and hydroxyl group-containing monomers may be used. Specifically, carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, and citraconic acid; amino group-containing monomers such as dimethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)methacrylate, and diethylaminoethyl (meth)acrylate; glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and α-methyl-o-vinylbenzyl glycidyl Examples of suitable epoxy group-containing monomers include ethylene glycol monomethyl ether acrylate, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, and 3,4-epoxycyclohexylmethyl (meth)acrylate; alkylene glycol monoalkyl ether (meth)acrylates such as ethylene glycol monomethyl ether acrylate and ethylene glycol monomethyl ether methacrylate; acrylamide compounds such as (meth)acrylamide, diacetone acrylamide, and N-methylolacrylamide; (meth)acrylonitrile; styrene derivatives such as styrene, α-methylstyrene, divinylbenzene, and vinyltoluene; and various vinyl halides such as vinyl chloride and vinylidene chloride. Furthermore, from the viewpoint of improving the light resistance of the resin layer, a monomer having a functional group with an ultraviolet absorbing function may be used as the polymerizable monomer. Specific examples include monomers having an ultraviolet absorbing functional group such as a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, or a hindered amine skeleton, and a polymerizable functional group such as a (meth)acryloyl group.

[0036] The content of structural units derived from other monomer components (monomer components other than hydrocarbon (meth)acrylates and hydroxyl group-containing monomers) in the (meth)acrylic polymer is, for example, 50% by mass or less, preferably 40% by mass or less. There is no particular lower limit, and it may be 0% by mass or more. It should be noted that each of the above-mentioned monomer components (hydrocarbon (meth)acrylate, hydroxyl group-containing monomer, and other monomer components) is preferably a monofunctional monomer having one polymerizable functional group in the molecule, as exemplified above, but may also contain a polyfunctional monomer having two or more polymerizable functional groups as appropriate, as long as the effects of the present invention are not impaired.

[0037] (hardening agent) As the curing agent, any compound capable of reacting with the binder resin and curing may be used, but from the viewpoint of curability with the binder resin, an isocyanate compound is preferred.

[0038] The isocyanate compound is preferably an aromatic or aliphatic diisocyanate or a trivalent or higher polyisocyanate. Examples of the isocyanate compound that can be used include tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, cyclohexane diisocyanate, dicyclohexyl diisocyanate, and trimers thereof. Alternatively, a terminal isocyanate group-containing compound obtained by reacting an excess amount of any of these isocyanate compounds with a low-molecular-weight active hydrogen compound such as ethylene glycol, propylene glycol, trimethylolpropane, glycerin, sorbitol, biuret, cyanuric acid, ethylenediamine, monoethanolamine, diethanolamine, or triethanolamine, or an active hydrogen polymer compound such as polyester polyol, polyether polyol, or polyamide, may be used.

[0039] (Preferred form of thermosetting resin composition) When the resin layer is formed from a thermosetting resin composition, the resin layer preferably contains a resin having a urethane bond and / or a urea bond. The use of a resin having a urethane bond and / or a urea bond ensures flexibility and makes the layer more susceptible to buckling due to compressive stress generated when the surface is treated by a dry process. The urethane bond and urea bond are preferably formed by at least one of the reactions between the binder resins, the curing agent, and the binder resin and the curing agent, and more preferably by the reaction between the binder resin and the curing agent. Forming a urethane bond and / or urea bond by such a reaction facilitates improving the adhesion of the resin layer to the cover layer, substrate, etc.

[0040] From the viewpoints of accelerating the curing with the binder resin, the adhesion of the resin layer to the cover layer and substrate, and ease of forming a secondary wrinkle structure, it is preferable to use an isocyanate compound as the curing agent. When both a binder resin and a curing agent are used as the thermosetting resin composition, it is preferable to use an isocyanate compound as the curing agent and a polyol as the binder resin, and when an acrylic resin is used as the binder resin, it is preferable that the acrylic resin is an acrylic polyol containing multiple hydroxyl groups in one molecule.

[0041] By adjusting the compounding ratio of the binder resin and the curing agent, it is possible to control the shape of the wrinkle structure described below. When an isocyanate compound is used as the curing agent and a polyol is used as the binder resin, the smaller the amount of polyol relative to the isocyanate compound, the longer the fluidity of the thermosetting resin composition is maintained during curing, making it easier to form a high-order wrinkle structure. From the above viewpoints, R ((the number of isocyanate groups in the curing agent) / (the number of hydroxyl groups in the binder resin)) in the thermosetting resin composition is preferably 0.1 or more, more preferably 0.5 or more, even more preferably 1 or more, and even more preferably 1.3 or more. Furthermore, the thermosetting resin composition may not contain a binder resin, i.e., the number of hydroxyl groups may be 0 (R=∞). From the viewpoint of reducing tackiness in a semi-cured or uncured state, R is preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less.

[0042] The R in the resin layer can be determined by combining analytical methods such as NMR, pyrolysis GC / MS, and TOF-SIMS. More specifically, first, unreacted curing agent is extracted from the cured resin layer, and the parent structure of the curing agent and the number of isocyanate groups (valence) are identified using the analytical method. Then, the structure of the monomers constituting the binder resin and the number of hydroxyl groups (valence) are identified from the cured resin layer using the analytical method. R can then be determined from the ratio of the parent structure of the curing agent to the monomers constituting the binder resin and their respective valences.

[0043] When the thermosetting resin composition contains an excess of an isocyanate compound relative to the polyol (R exceeds 1), the cured resin layer has urethane bonds formed by the reaction of the polyol with the isocyanate compound and urea bonds formed from the excess isocyanate compound. Therefore, the above R can also be determined from the ratio of urethane bonds to urea bonds in the cured resin layer using solid-state NMR, FT-IR, etc.

[0044] [Active energy ray-curable resin composition] (Photopolymerizable compound) When the curable resin composition is an active energy ray-curable resin composition, the active energy ray-curable resin composition contains a photopolymerizable compound. The photopolymerizable compound is a compound that can be polymerized by irradiation with active energy rays. Details of the active energy rays are as described in the production method described below. The resin component of the resin layer formed from the active energy ray-curable resin composition may be a mixture of a prepolymer such as epoxy(meth)acrylate, urethane(meth)acrylate, polyester(meth)acrylate, or acrylic(meth)acrylate with a photopolymerizable monomer, or the photopolymerizable monomer may be used alone.

[0045] The photopolymerizable monomer is not particularly limited as long as it is a compound having a radical polymerizable group, and examples thereof include polyfunctional photopolymerizable monomers. The number of radical polymerizable groups contained in one molecule of the polyfunctional photopolymerizable monomer is not particularly limited, as long as it is two or more. The radical polymerizable group includes functional groups containing a carbon-carbon unsaturated bond, such as a (meth)acryloyl group and a vinyl group, and among these, a (meth)acryloyl group is preferred.

[0046] Examples of photopolymerizable monomers include polyfunctional (meth)acrylates having an aromatic ring. Specifically, polyfunctional (meth)acrylates having a benzene ring, a naphthalene ring, an anthracene ring, a fluorene ring, a phenanthrene ring, a phenalene ring, or the like are preferred. Among these, fluorene-based polyfunctional (meth)acrylates having a fluorene ring are preferred. Examples of fluorene-based polyfunctional (meth)acrylates include 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)-3-methylphenyl]fluorene, 9,9-bis[4-(2-(meth)acryloyloxypropoxy)-3-methylphenyl]fluorene, and 9,9-bis[4-(2-(meth)acryloyloxyethoxy)-3,5-dimethylphenyl]fluorene. , 9,9-bis[4-((meth)acryloyloxypoly(ethyleneoxy))phenyl]fluorene, 9,9-bis[4-((meth)acryloyloxypolyethyleneoxy)-3-methylphenyl]fluorene, 9,9-bis[4-((meth)acryloyloxypoly(propyleneoxy))-3-methylphenyl]fluorene, 9,9-bis[4-((meth)acryloyloxypoly(ethyleneoxy))-3,5-dimethylphenyl]fluorene, and the like.

[0047] Furthermore, as the photopolymerizable monomer, various polyfunctional (meth)acrylates other than polyfunctional (meth)acrylates having an aromatic ring can be used, and examples thereof include aliphatic polyfunctional (meth)acrylates such as ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, nonanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate. The above-mentioned photopolymerizable monomers may be used alone or in combination of two or more. Among the above, polyfunctional (meth)acrylates having an aromatic ring are preferred, and polyfunctional (meth)acrylates having an aromatic ring may be used in combination with other photopolymerizable compounds. The photopolymerizable monomer may be used alone or in combination with a monofunctional photopolymerizable compound described below.

[0048] The photopolymerizable monomer is not limited to a polyfunctional one, and may be a monofunctional photopolymerizable monomer. The monofunctional photopolymerizable monomer may be used alone, or may be used in combination with a polyfunctional photopolymerizable monomer as described above. Examples of the monofunctional photopolymerizable monomer include alkyl (meth)acrylates, cyclic alkyl (meth)acrylates, (meth)acrylates having an aromatic ring, hydroxyl group-containing monomers, carboxyl group-containing monomers, amino group-containing monomers, epoxy group-containing monomers, acrylamide compounds, (meth)acrylonitrile, styrene derivatives, vinyl halides, etc. Specific examples of these compounds include those exemplified for the (meth)acrylic polymers described above.

[0049] (Photopolymerization initiator) When the curable resin composition contains a photopolymerizable compound, it preferably further contains a photopolymerization initiator, which makes it possible to easily cure the resin layer precursor by irradiating the resin layer precursor with active energy rays, as described below. Examples of photopolymerization initiators include benzil, benzophenone and derivatives thereof, thioxanthones, benzil dimethyl ketals, α-hydroxyalkylphenones, α-hydroxyacetophenones, hydroxyketones, aminoalkylphenones, acylphosphine oxides, oxime ester compounds, etc. Among these, α-hydroxyalkylphenones are preferred because they are less likely to yellow during curing and can produce transparent cured products. The content of the photopolymerization initiator is preferably in the range of 0.05 to 5 parts by mass, more preferably 0.2 to 3 parts by mass, relative to 100 parts by mass of the curable resin composition. When the content of the photopolymerization initiator is 0.05 parts by mass or more, the desired initiation effect can be obtained, and when the content of the photoinitiator is 5 parts by mass or less, the curable resin composition is not over-cured by irradiation with active energy rays, and is more likely to remain in a semi-cured state.

[0050] In the above description, the curable resin composition is either heat-curable or active energy ray-curable, but the curable resin composition may be heat- and active energy ray-curable, which can be cured by both heat and active energy rays. In this case, the curable resin composition may contain both a binder resin and a photopolymerizable compound.

[0051] The curable resin composition may contain, as needed, within the scope of the present invention, an antifoaming agent, a coatability improver, a thickener, an organic lubricant, an ultraviolet absorber, an antioxidant, a foaming agent, a dye, a pigment, inorganic particles, organic particles, etc. These additives may be used alone, or two or more types may be used in combination as needed.

[0052] [Resin layer thickness] The thickness (tb) of the resin layer can be adjusted according to the level difference of the concave and convex portions to be formed and the intended use, but is preferably 0.1 μm or more and 15 μm or less. If it is 15 μm or less, peeling from the substrate due to the internal stress of the resin layer itself can be prevented. If the thickness is 0.1 μm or more, the thickness of the resin layer can be kept uniform, and a certain level of roughness can be ensured by the wrinkle structure. From this perspective, the thickness (tb) of the resin layer is more preferably 0.5 μm or more, even more preferably 1 μm or more, and even more preferably 1.2 μm or more, and is preferably 10 μm or less, more preferably 7 μm or less. The thickness of the resin layer and the cover layer described later can be determined by measuring the maximum thickness (peak of a convex portion) and the minimum thickness (valley of a concave portion) by measuring the step using a micro-profile measuring instrument or by observing the cross section using a scanning electron microscope (SEM) and / or a transmission electron microscope (TEM), and then calculating the average value of these.

[0053] <Cover layer> In the present invention, it is preferable to form a cover layer on the resin layer, which can impart properties such as water repellency, oil repellency, and hydrophilicity to the outermost surface of the laminate. The cover layer may be formed on the resin layer so as to be in direct contact with the resin layer. Specific examples of the cover layer include an inorganic substance-containing layer and a cover resin layer. Of these, an inorganic substance-containing layer is preferred.

[0054] [Inorganic content layer] The inorganic substance-containing layer is a layer formed from an inorganic substance and containing an inorganic substance as a main component. "Containing an inorganic substance as a main component" means that the inorganic substance accounts for 50% by mass or more of the inorganic substance-containing layer, preferably 70% by mass or more, preferably 80% by mass or more, preferably 90% by mass or more, and preferably 100% by mass. The inorganic substance-containing layer is preferably formed from an inorganic substance that has good adhesion to the resin layer. Furthermore, the inorganic substance-containing layer is preferably formed using a material that can be easily formed into a film on the resin layer by a dry process.

[0055] The inorganic material-containing layer is preferably formed from at least one inorganic material selected from diamond-like carbon (DLC), metals, metal oxides, metal nitrides, metal carbides, and composites thereof. Note that the term "metal" as used herein also includes so-called semimetals such as silicon, boron, and germanium. In the inorganic substance-containing layer, examples of the metal constituting the metal, metal oxide, metal nitride, metal carbide, or composite thereof include silicon, aluminum, zinc, titanium, niobium, gold, silver, copper, indium, tin, and nickel, and among these, silicon and niobium are preferred, and silicon is more preferred.

[0056] The inorganic substance used in the inorganic substance-containing layer is preferably at least one selected from silicon-based compounds such as silicon, silicon oxide, silicon nitride, silicon oxynitride, silicon oxide carbide, silicon oxycarbonitride, silicon carbide, fluorine-containing silicon oxide, and fluorine-containing silicon carbide; aluminum-based compounds such as aluminum oxide, aluminum nitride, aluminum oxynitride, and aluminum oxide carbide; niobium-based compounds such as niobium oxide; zinc-based compounds such as zinc oxide; titanium-based compounds such as titanium oxide; diamond-like carbon, fluorine-containing diamond-like carbon; and conductive oxides such as ITO and IZO.

[0057] From the viewpoint of increasing the hardness of the laminate and improving the durability of the laminate, the inorganic-substance-containing layer is preferably a layer containing at least one of diamond-like carbon (DLC), silicon, silicon oxide, niobium oxide, silicon carbide oxide, and silicon carbide as an inorganic substance, more preferably a layer containing at least one of DLC, silicon, and silicon oxide, and even more preferably a layer containing either silicon or silicon oxide.

[0058] [Cover resin layer] The cover resin layer is preferably formed on the resin layer by a dry process. The cover resin layer is formed from a resin component and is a layer containing the resin component as a main component. Here, "containing the resin component as a main component" means that the resin component accounts for 50% by weight or more of the cover resin layer, preferably 70% by weight or more, preferably 80% by weight or more, preferably 90% by weight or more, and preferably 100% by weight.

[0059] The resin component used for the cover resin layer is preferably a resin component that can be formed on the resin layer by a dry process. Specific resin components include fluorine-based resins, polyethylene, polystyrene, etc., and among these, a fluorine-based resin layer formed from a fluorine-based resin is preferred. By using a fluorine-based resin, the cover resin layer can be easily formed on the resin layer by a dry process. Furthermore, by using a fluorine-based resin, when the cover resin layer is the outermost surface, it becomes easier to impart chemical resistance, slip properties, or liquid repellency to the laminate. Examples of the fluorine-based resin include polytetrafluoroethylene and tetrafluoroethylene-ethylene copolymer.

[0060] [Cover layer formation] The cover layer does not necessarily have to be formed by a dry process. If the cover layer is not formed by a dry process, the concaves and convexes may be formed in the resin layer in advance by a separate dry process, and then the cover layer may be formed. When the cover layer is formed by a process other than the dry process, inorganic substances and resin components used in the inorganic substance-containing layer and the cover resin layer may be other than those described above. Specifically, in addition to the resin components described above, the resin components exemplified below as resin components usable in the overcover layer may also be used.

[0061] [Cover layer thickness] The thickness (ta) of the cover layer is preferably 5 nm or more and 300 nm or less. By keeping the thickness (ta) of the cover layer within this range, appropriate film stress is generated when the film is formed by a dry process, which applies appropriate compressive stress to the resin layer and makes it easier to form a wrinkle structure with the desired roughness. From the viewpoint of making it easier to form the desired unevenness on the outermost surface of the laminate, the thickness (ta) of the cover layer is more preferably 10 nm or more and 250 nm or less, and even more preferably 20 nm or more and 200 nm or less.

[0062] [Thickness ratio of cover layer to resin layer (ta / tb)] In the present invention, the ratio (ta / tb) of the thickness of the cover layer (ta, unit: nm) to the thickness of the resin layer (tb, unit: μm) is preferably 0.1 or more and 3500 or less. By setting the thickness ratio within the above range, when the cover layer is formed by a dry process, it becomes easier to form irregularities of the desired roughness by the dry process. Furthermore, if irregularities are formed on the surface of the resin layer before the cover layer is formed, smoothing of the irregularities by the cover layer can be prevented. From the viewpoint of making it easier to form the desired irregularities on the outermost surface of the laminate, the thickness ratio (ta / tb) is more preferably 1 or more and 500 or less, even more preferably 2 or more and 400 or less, and even more preferably 5 or more and 250 or less.

[0063] <Manufacturing method according to the first embodiment> In the manufacturing method according to the first embodiment of the present invention (hereinafter also referred to as the "first manufacturing method"), after the resin layer precursor forming step (A), the substrate with the resin layer precursor is wound into a roll and then unwound again to perform the surface treatment step (B). That is, the first manufacturing method includes a resin layer precursor forming step (A), followed by a winding step (X) of winding the substrate with the resin layer precursor into a roll, and an unwinding step (Y) of unwinding the substrate with the resin layer precursor from the roll, and then a surface treatment step (B). By winding the film once before the surface treatment step (B), for example, when a treatment under reduced pressure is performed in the surface treatment step (B), it becomes easier to set up a reduced pressure environment, for example, to remove moisture contained in the substrate and the resin layer precursor in advance. Furthermore, by storing the film in a constant temperature environment after winding, it is also possible to perform a semi-curing step (P) in which the resin layer precursor is semi-cured.

[0064] In the present production method, from the viewpoint of improving continuous productivity, it is preferable to carry out the surface treatment step (B) and the winding step (C) while transporting the substrate with the resin layer precursor. The conveying speed in the surface treatment step (B) and the winding step (C) is preferably 0.1 m / min to 30 m / min, more preferably 0.2 m / min to 20 m / min, and even more preferably 10 m / min or less. By setting the conveying speed within the above range, the surface treatment can be sufficiently carried out while improving productivity, and unevenness including a wrinkle structure can be easily formed.

[0065] The resin layer precursor forming step (A), the semi-curing step (P), the winding step (X), the unwinding step (Y), the surface treatment step (B), and the winding step (C) will be described below. Note that, hereinafter, the substrate with the resin layer precursor wound into a roll in the winding step (X) will also be referred to as a "first wound body," and the laminate wound into a roll in the winding step (C) will also be referred to as a "second wound body."

[0066] 1. Resin layer precursor formation step (A) In the resin layer precursor forming step (A), a curable resin composition is applied to at least one surface of a substrate to form a resin layer precursor. The details of the substrate and the curable resin composition used in the resin layer precursor forming step (A) are as described above. The curable resin composition may be diluted with a solvent such as water or an organic solvent as needed. When diluted with a solvent such as water or an organic solvent, the amount (parts by mass, etc.) of the curable resin composition described above and the amount of each component constituting the composition are based on the solid content. The organic solvent to be used is not particularly limited, and may be selected from the viewpoint of solubility, dispersibility, etc. depending on the composition of the curable resin composition. Examples of the organic solvent include alcohol-based solvents such as methyl alcohol, ethyl alcohol, and isopropyl alcohol; ether-based solvents such as dimethyl glycol and ethylene glycol monoethyl ether; ester-based solvents such as ethyl acetate; acetate-based solvents such as propylene glycol monomethyl ether acetate; ketone-based solvents such as methyl isobutyl ketone and methyl ethyl ketone; aliphatic hydrocarbon-based solvents such as various alkanes; and aromatic hydrocarbon-based solvents such as toluene, xylene, and benzene. The organic solvent may be one kind or two or more kinds, if necessary. The components constituting the curable resin composition may be dissolved in the solvent or may be dispersed in the solvent. When the curable resin composition is diluted with water, an organic solvent, or the like, it is preferable to adjust the solid content concentration to, for example, about 0.1% by mass or more and 50% by mass or less, and preferably about 3% by mass or more and 40% by mass or less.

[0067] The curable resin composition can be applied to a substrate by any conventional coating method such as reverse gravure coating, direct gravure coating, roll coating, die coating, bar coating, curtain coating, spray coating, dip coating, or spin coating. When the substrate is a resin film, the curable resin composition may be applied by in-line coating, which refers to applying the curable resin composition on the production line where the resin film is formed. The solvent after application can be dried by heating in an oven or by drying without heating in a reduced pressure dryer. The surface of the substrate to which the curable resin composition is to be applied may be previously subjected to a surface treatment such as corona treatment, plasma treatment, UV ozone treatment or the like.

[0068] 2. Semi-curing process (P) In the semi-curing step (P), the resin layer precursor formed in the resin layer precursor forming step (A) is semi-cured. Although the semi-curing step (P) is not essential in the first manufacturing method, it is preferable to perform the semi-curing step (P) from the viewpoint of improving the handleability of the substrate with the resin layer precursor and from the viewpoint of being able to control the wrinkle structure formed in the surface treatment step (B). For example, if the resin layer precursor obtained in the resin layer precursor forming process (A) is tacky and difficult to handle, it is preferable to perform a semi-curing process (P) between the resin layer precursor forming process (A) and the winding process (X). However, if there are no problems with handling, this process (P) is not essential, and the resin layer precursor may be transported to the winding process (X) in an uncured state without being heated or irradiated with energy rays. Furthermore, since the semi-cured state of the curable resin composition makes the resin layer precursor more susceptible to buckling due to surface treatment by a dry process, if it is desired to control the uneven structure, it is preferable to carry out a semi-curing step (P) between the winding step (X) and the unwinding step (Y), or between the unwinding step (Y) and the surface treatment step (B).

[0069] Here, semi-cured in the present invention refers to a state in which the curable resin composition is not completely cured, and refers to a state in which the curing of the curable resin composition further progresses when further irradiated with heat or energy rays. Whether or not the curable resin composition is semi-cured can be confirmed, for example, by gently rubbing the surface of the resin layer precursor 50 times with a cotton swab soaked in a solvent and checking whether or not the surface of the substrate is exposed. If the curable resin composition is completely cured, the surface of the substrate will not be exposed even when the surface of the resin layer precursor is rubbed. The degree of semi-curing can be determined from the number of rubs at which the surface of the resin layer precursor begins to thin or the number of rubs until the surface of the substrate is exposed. It is preferable to use the same solvent in which the cotton swab is immersed as the solvent in which the curable resin composition is diluted.

[0070] When the curable resin composition is thermosetting, the resin layer precursor formed in the resin layer precursor-forming step (A) is semi-cured by heating in the semi-curing step (P). The method of semi-curing the resin layer precursor may be performed at room temperature, such as by natural drying, but from a practical standpoint, it is preferable to perform it by heating, such as by heat drying. Note that when the solvent in the resin layer precursor-forming step (A) is dried by heat drying, the drying of the solvent may also serve as the semi-curing step (P). Furthermore, when the curable resin composition is active energy ray curable, the resin layer precursor formed in the resin layer precursor forming step (A) is semi-cured by irradiating the resin layer precursor with active energy rays in the semi-curing step (P). However, when a heat- and active energy ray-curable resin composition is used as the resin layer component, the resin layer precursor may be semi-cured by heating alone or by irradiating with active energy rays alone, or by using both heating and active energy irradiation.

[0071] When the resin layer precursor is semi-cured by heating, the heating temperature and heating time may be set according to the components contained in the curable resin composition, but the resin layer precursor is heated, for example, at a temperature of 50°C or higher and 200°C or lower, preferably 70°C or higher and 150°C or lower, for a time of, for example, 3 seconds or higher and 30 minutes or lower, preferably 30 seconds or higher and 10 minutes or lower, and more preferably 40 seconds or higher and 5 minutes or lower.

[0072] Furthermore, when the resin layer precursor is semi-cured by irradiating it with active energy rays, the active energy rays that can be used include light rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, and infrared rays, electromagnetic waves such as X-rays and gamma rays, as well as electron beams, proton beams, and neutron beams. However, curing by ultraviolet irradiation is advantageous in terms of curing speed, ease of obtaining irradiation equipment, cost, and the like. When semi-curing the resin layer precursor by ultraviolet irradiation, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an electrodeless discharge lamp, an LED lamp, or the like, which emits light in the wavelength range of 150 to 450 nm, may be used. The ultraviolet light may be irradiated to the extent that the resin layer precursor is semi-cured, and the irradiation amount is not particularly limited, but may be, for example, 0.5 to 5000 mJ / cm. 2 , preferably 1 to 2000 mJ / cm 2 It is sufficient to irradiate ultraviolet light with an integrated light intensity of about this level.

[0073] In this embodiment, a dry process is used to perform surface treatment on a resin layer precursor that has not yet been sufficiently cured. Therefore, in order to stably form a wrinkled structure, it is preferable to adjust the time and storage temperature between the resin layer precursor formation step (A) and the surface treatment step (B) (for example, between the winding step (X) and the unwinding step (Y)). The interval between the resin layer precursor forming step (A) and the surface treatment step (B) (i.e., the time from the end of heating and / or active energy ray irradiation to the start of surface treatment by the dry process) is not particularly limited as long as the resin layer precursor is in the desired semi-cured state when the surface treatment is started, but is, for example, 3 days or less, preferably 2 days or less, and more preferably 24 hours or less. The lower limit of the interval is not particularly limited, and may be 0 minutes or more. The interval between the resin layer precursor forming step (A) and the surface treatment step (B) is not particularly limited, but the substrate on which the resin layer precursor has been formed may be left at a temperature of, for example, 0°C or higher and 60°C or lower, preferably 5°C or higher and 40°C or lower, and more preferably 5°C or higher and 30°C or lower. Furthermore, when the interval time is long, the heating conditions and active energy ray irradiation conditions in the resin layer precursor forming process (A) can be appropriately selected, taking into consideration that curing progresses between the resin layer precursor forming process (A) and the surface treatment process (B).

[0074] 3. Winding process (X) In the winding step (X), the substrate with the resin layer precursor is wound around a core and wound into a roll to obtain a first wound body. The core refers to a cylindrical core used for winding up the film. The material of the core is not particularly limited, but examples thereof include paper, resin-impregnated paper, acrylonitrile-butadiene-styrene copolymer (ABS resin), FRP, phenolic resin, and inorganic-containing resin. Among these, from the viewpoints of a small thermal expansion coefficient, high rigidity, low swelling due to humidity, and excellent winding properties, it is preferable to use a resin such as acrylonitrile-butadiene-styrene copolymer (ABS resin), FRP, phenolic resin, or inorganic-containing resin. When the core material is paper, the desired properties can be easily obtained by coating the surface with a resin, etc. Furthermore, from the viewpoint of surface smoothness, it is also preferable that the core be a tube made of resin-impregnated paper.

[0075] The length of the substrate with the resin layer precursor wound into a roll is not particularly limited, but is preferably 5 m or more, more preferably 10 m or more, and even more preferably 50 m or more. The length of the film is preferably 10,000 m or less. A film length of 5 m or more improves productivity.

[0076] The winding tension in the winding step (X) may be selected depending on the rigidity, width, and thickness of the substrate, but is preferably 10 to 500 N from the viewpoint of preventing the wound body from slipping.

[0077] 4. Unwinding process (Y) In the unwinding step (Y), the substrate with the resin layer precursor is unwound from the roll (first wound body). The unwound substrate with the resin layer precursor may be transported as is to be subjected to the semi-curing step (P) or the surface treatment step (B), or may be slit to a width suitable for the subsequent step or shortened in length. When the length of the substrate with the resin layer precursor is shortened, it is preferably 5 m or more and 5000 m or less, more preferably 10 m or more and 1000 m or less, and even more preferably 50 m or more, from the viewpoint of facilitating continuous performance of the surface treatment step (B) described below.

[0078] 5. Surface treatment process (B) In the surface treatment step (B), the substrate with the semi-cured or uncured resin layer precursor is subjected to a surface treatment by a dry process. By performing the surface treatment by a dry process while the resin layer precursor is in a semi-cured or uncured state, unevenness including a wrinkle structure can be formed. The dry process is a method of performing a surface treatment on a semi-cured or uncured resin layer precursor under reduced pressure or in vacuum.

[0079] In the surface treatment step (B), a cover layer may be formed by a dry process, but a dry process treatment without forming a film may also be performed without forming a cover layer. The wrinkle structure may have a high-order wrinkle structure as described below, and the high-order wrinkle structure is preferably formed in the surface treatment step (B).

[0080] In this embodiment, the principles by which the unevenness including the wrinkle structure is formed by the surface treatment using the dry process, and the principles by which the high-order wrinkle structure is formed are not clear, but are presumed to be as follows. When a cover layer is formed on a semi-cured or uncured resin layer precursor by a dry process, it is believed that the resin layer precursor receives energy from the dry process (light from plasma, radiant heat, electrons and ions, or energy from incident particles) and hardens. During this process, the resin layer precursor, which has received energy from the dry process, heats up and shrinks, losing its fluidity, while simultaneously generating film stress as the cover layer grows. It is believed that the compressive stress along the surface direction of the resin layer precursor increases, and when the resin layer precursor can no longer resist this compressive stress, buckling occurs, forming a wrinkled structure. Furthermore, even in the case of a dry process that does not form a cover layer or involve film deposition, it is estimated that the energy from the dry process treatment similarly generates compressive stress along the surface direction in the resin layer precursor, and when the resin layer precursor can no longer resist the compressive stress, buckling occurs and a wrinkle structure is formed. Furthermore, when forming the cover layer, if the film stress generated during the deposition of the cover layer is large, the first buckling will occur at an early stage, generating large swells (primary wrinkle structure), and then, when the resin fluidity has slightly decreased, the second buckling will occur, generating small swells (secondary wrinkle structure).

[0081] The size of the waviness in the wrinkle structure (i.e., surface roughness (Sa, Sz), specific surface area S / A, etc.) is presumed to vary depending on the balance between the thickness of the resin layer and the cover layer, the hardness of the resin layer precursor in a semi-cured or uncured state, and the resin fluidity. Therefore, the size of the waviness can be adjusted by appropriately changing the thickness of the resin layer and the cover layer, the components contained in the resin layer and the cover layer, the curing conditions, etc. Furthermore, the surface treatment by the dry process promotes the curing of the resin layer precursor as described above, and the resin layer may be fully cured in the surface treatment step (B), for example. Full curing means a state in which the curing does not substantially proceed even when the resin layer is heated or irradiated with active energy rays.

[0082] In this manufacturing method, it is preferable to form the cover layer by surface treatment using a dry process. When the cover layer is formed by surface treatment using a dry process, membrane stress occurs as described above, making it easier to form a wrinkle structure, and even a high-order wrinkle structure can be formed. Furthermore, by forming the cover layer by surface treatment using a dry process, the cover layer can be formed while forming the unevenness including the wrinkle structure in the surface treatment step (B), thereby simplifying the process. Whether or not a dry process has been performed can be determined by observing the cross section with an SEM and / or TEM. For example, if the cover layer is made of a crystalline material, if the crystal grain size changes in the thickness direction of the cover layer, it can be determined that a dry process has been performed. As the film formation by the dry process progresses, the crystal nuclei generated on the surface of the resin layer grow and the grain size gradually increases, so the crystal grain size at the surface of the cover layer tends to be largest and to become smaller as it approaches the resin layer. On the other hand, such changes in crystal grain size are not observed when wet processing is used, in which a solvent is applied. In wet processing, the solvent evaporates during the drying process of the coating, which tends to create tiny voids throughout the thickness of the cover layer, resulting in a low-density film.

[0083] When the cover layer is formed by surface treatment using a dry process, examples of the surface treatment using the dry process include chemical vapor deposition (CVD) and physical vapor deposition (PVD). The dry process is preferably a treatment carried out in a vacuum or under reduced pressure. When the surface treatment is carried out in a vacuum or under reduced pressure, the semi-cured or uncured resin layer precursor is placed in an oxygen-poor atmosphere, which facilitates curing by the dry process. Therefore, when the dry process is carried out in a vacuum or under reduced pressure, a wrinkle structure is likely to form. In particular, in the case of an active energy ray-curable resin composition, oxygen inhibition, which hinders radical polymerization, is suppressed, which facilitates crosslinking. The pressure in a dry process carried out under vacuum or reduced pressure depends on the dry process technique, but is, for example, 15 Pa or less, preferably 10 Pa or less, and more preferably 1 Pa or less. The lower limit of the pressure in the dry process is not particularly limited, but considering the performance limit of each device, it is, for example, 1×10 -7 It is Pa. When the cover layer is formed by a dry process, the film may be heated, preferably at a temperature of 30° C. or higher and 120° C. or lower, more preferably at a temperature of 40° C. or higher and 100° C. or lower. Heating the film increases the fluidity of the resin layer precursor, making it easier to form a high-order wrinkle structure.

[0084] [CVD] The CVD is not particularly limited, and may be plasma CVD, thermal CVD, cat-CVD (catalytic chemical vapor deposition), or the like, but plasma CVD is preferred. The use of plasma CVD facilitates the formation of a wrinkled structure. CVD is preferably carried out under reduced pressure in order to facilitate the formation of a wrinkled structure, and the pressure when forming the cover layer is preferably 15 Pa or less, more preferably 1×10 in terms of the film formation rate and the ability to form a concave-convex structure. -2 Pa or more and 10 Pa or less, more preferably 1×10 -1 Pa or more and 1 Pa or less.

[0085] When performing surface treatment by CVD, the output conditions for forming the cover layer are preferably 100 W or more and 1500 W or less, more preferably 300 W or more and 1200 W or less, and even more preferably 400 W or more and 1000 W or less, from the viewpoint of generating a necessary and sufficient film stress in the cover layer. The thickness of the cover layer can be adjusted by known methods. For example, when plasma CVD is used, the thickness can be adjusted by adjusting the output, pressure of the raw material gas, concentration of the raw material gas, plasma generation time, etc. When the surface treatment is carried out by CVD, the cover layer may be subjected to a crosslinking treatment by electron beam irradiation, if necessary, in order to improve water resistance and durability.

[0086] CVD is preferably used, for example, when forming an inorganic-substance-containing layer or a cover resin layer, and is particularly suitable for use when forming an inorganic-substance-containing layer containing DLC ​​as the inorganic substance, an inorganic-substance-containing layer containing silicon carbide and / or silicon oxide as the inorganic substance, or a fluorine-based resin layer containing a fluorine-based resin or the like as a resin component.

[0087] For example, when an inorganic material-containing layer containing DLC ​​as an inorganic material is formed by CVD, a hydrocarbon or the like may be used as a raw material. 4n+6 H 4n+12(n is an integer of 1 or more), for example, alicyclic hydrocarbons such as adamantane, diamantane, triamantane, pentamantane, tetramantane, etc., aromatic hydrocarbons such as benzene, toluene, xylene, etc., and aliphatic hydrocarbons such as acetylene, ethylene, propylene, methane, ethane, propane, etc. These raw materials may be used alone or in combination of two or more. Furthermore, the raw material gas may be diluted with a rare gas such as argon (Ar) or helium (He) before use.

[0088] For example, when an inorganic-substance-containing layer containing silicon as an inorganic substance is formed by CVD, a silicon component such as silane or disilane may be used as a raw material. Furthermore, when forming an inorganic-containing layer containing silicon oxide as an inorganic material by CVD, it is preferable to use tetraethoxysilane as a raw material, or to use a silicon component such as silane or disilane as a mixed gas with dinitrogen oxide (nitrous oxide). The source gas may be diluted with hydrogen or a rare gas such as argon (Ar) or helium (He) before use.

[0089] Furthermore, when forming an inorganic-containing layer containing silicon carbide as the inorganic material by CVD, organosilanes such as tetramethylsilane and hexamethyldisilane may be used as raw materials. Alternatively, hydrogen gas may be mixed into a mixed gas of a silicon component such as silane or disilane and a carbon component such as an alkane having 1 to 6 carbon atoms. However, other raw materials may be used as long as they are capable of forming silicon carbide. Furthermore, for example, when a fluororesin layer is formed by CVD, fluorine-based gases such as CF4, C2F4, C2F6, C3F8, C4F8, and C5F8 may be used as raw materials.

[0090] Furthermore, for example, when an inorganic-containing layer containing silicon carbide oxide as the inorganic material is formed by CVD, a silicon compound (hereinafter also referred to as "silicon compound raw material") may be used as a raw material. The silicon compound raw material may be used in any state of gas, liquid, or solid at room temperature and normal pressure. If it is a gas, it may be introduced directly into the reactor (for example, the discharge space). If it is a liquid or solid, it may be vaporized by means of heating, bubbling, decompression, ultrasonic irradiation, or the like before use. It may also be used after dilution with a solvent, and the solvent may be an organic solvent such as methanol, ethanol, or n-hexane, or a mixture thereof.

[0091] Examples of the silicon compound raw material include silane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetra-t-butoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, phenyltriethoxysilane, (3,3,3-trifluoropropyl)trimethoxysilane, hexamethoxysilane, and the like. Tyldisiloxane, bis(dimethylamino)dimethylsilane, bis(dimethylamino)methylvinylsilane, bis(ethylamino)dimethylsilane, N,O-bis(trimethylsilyl)acetamide, bis(trimethylsilyl)carbodiimide, diethylaminotrimethylsilane, dimethylaminodimethylsilane, hexamethyldisilazane, hexamethylcyclotrisilazane, heptamethyldisilazane, nonamethyltrisilazane, octamethylcyclotetrasilazane, tetrakis(dimethyla (amino)silane, tetraisocyanatosilane, tetramethyldisilazane, tris(dimethylamino)silane, triethoxyfluorosilane, allyldimethylsilane, allyltrimethylsilane, benzyltrimethylsilane, bis(trimethylsilyl)acetylene, 1,4-bistrimethylsilyl-1,3-butadiyne, di-t-butylsilane, 1,3-disilabutane, bis(trimethylsilyl)methane, cyclopentadienyltrimethylsilane, phenyldimethylsilane, phenyltrimethylsilane Examples of suitable methylsilanes include methylsilane, propargyltrimethylsilane, tetramethylsilane, trimethylsilylacetylene, 1-(trimethylsilyl)-1-propyne, tris(trimethylsilyl)methane, tris(trimethylsilyl)silane, vinyltrimethylsilane, hexamethyldisilane, octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, hexamethylcyclotetrasiloxane, and methyl silicate (for example, "Methyl Silicate 51" manufactured by Colcoat Co., Ltd.).

[0092] [PVD] Examples of PVD include vacuum deposition, sputtering, and ion plating, among which vacuum deposition and sputtering are preferred. PVD is suitable, for example, when the inorganic substance contained in the inorganic substance-containing layer is a metal, a metal oxide such as niobium oxide or silicon oxide, or a metal nitride. Vacuum deposition is also suitable when the inorganic substance contained in the inorganic substance-containing layer is a metal such as gold, silver, copper, aluminum, or silicon; a metal oxide such as silicon oxide, titanium oxide, or aluminum oxide; or a fluoride such as calcium fluoride; and sputtering is also suitable when the inorganic substance contained in the inorganic substance-containing layer is a metal such as gold, silver, copper, aluminum, or silicon; a metal oxide such as titanium oxide, aluminum oxide, niobium oxide, silicon oxide, ITO, or IZO; or a covalently bonded material such as DLC.

[0093] The pressure when forming the cover layer by PVD is preferably 1×10 -7 Pa or more and 20 Pa or less, preferably 1×10 -6 Pa or more and 10 Pa or less, more preferably 1×10 -4 Pa or more and 5 Pa or less.

[0094] In the dry process of the surface treatment step (B), a cover layer may not be formed. When a cover layer is not formed, the surface treatment is not particularly limited as long as the resin layer precursor can be buckled by the surface treatment to form irregularities including a wrinkle structure, and examples thereof include ion beam irradiation treatment, plasma treatment, and UV irradiation treatment. The ion beam irradiation process is not particularly limited, but an anode layer source (ALS) that generates a linear ion beam can be used to irradiate ions of gases such as argon, nitrogen, and oxygen. Only one of these gases may be used, or two or more types of gases may be mixed. Among these, argon is preferred. The plasma treatment is not particularly limited, and may be performed by a method such as vacuum or reduced pressure plasma treatment, with vacuum plasma treatment being preferred. The plasma treatment may be performed by converting a gas into plasma. Examples of the gas used include oxygen gas, hydrogen gas, nitrogen gas, and rare gases such as argon and helium. Only one of these gases may be used, or two or more types of gases may be mixed. Among these, argon is preferred. The UV irradiation treatment is not particularly limited, but may be performed using a UV-LED irradiation device or the like, particularly when the curable resin composition is an active energy ray-curable resin composition. The wavelength of the UV light that can be used may be 365 nm, 385 nm, 395 nm, 405 nm, or the like, but 365 nm is preferably used.

[0095] 6. Winding process (C) In the winding step (C), the laminate obtained after the surface treatment is wound around a core and wound into a roll to obtain a second wound body. The core of the second wound body can be the same as the core described in the above 3. Winding step (X). The length of the film wound into a roll is not particularly limited, but is preferably 5 m or more, more preferably 10 m or more, and even more preferably 50 m or more. The length of the film is preferably 10,000 m or less. The winding tension in the winding step (C) may be selected depending on the stiffness, width and thickness of the laminate, but is preferably 10 to 500 N from the viewpoint of preventing the wound body from slipping.

[0096] <Manufacturing apparatus according to the first embodiment> An example of the laminate manufacturing apparatus according to the first embodiment will be described below with reference to FIGS. The laminate manufacturing apparatus according to the first embodiment comprises a first apparatus 100a and a second apparatus 100b.

[0097] In the first apparatus 100a shown in FIG. 1, the resin layer precursor forming step (A) and the winding step (X) of the first embodiment are performed to obtain a first wound body consisting of a substrate α with a resin layer precursor. The first apparatus 100a has at least an application means 101 that applies a curable resin composition to a substrate 11, and a first winding means 102 that winds the substrate with the resin layer precursor into a roll. The first apparatus 100a may also have a drying means 103 that dries the resin layer precursor. Furthermore, when the substrate 11 is in a roll form, it may also have a first unwinding means 104.

[0098] The coating means 101 is not particularly limited as long as it can adopt the above-mentioned coating method, and a known coating device may be used. The coating means 101 coats the curable resin composition on the substrate 11, thereby obtaining a substrate α with a resin layer precursor. A known device capable of winding a film into a wound body may be used as the first winding means 102. The first winding means 102 winds the substrate α with the resin layer precursor around the core. As the drying means 103, a known drying device such as an oven or a reduced pressure dryer can be used. As the first unwinding means 104, a known unwinding device capable of unwinding a roll of film may be used.

[0099] 2, the unwinding step (Y), the surface treatment step (B), and the winding step (C) in the first embodiment are performed. As the second device 100b, a roll coater such as the W35 series manufactured by Kobe Steel, Ltd. may be used.

[0100] The second device 100b is an example of a device that performs surface treatment by sputtering. The second device 100b has at least a second unwinding means 105 that unwinds the substrate α with resin layer precursor from the first wound body, surface treatment means 106a and / or 106b, and a second winding means 107 that winds the obtained laminate 10 into a roll. The second device 100b is a roll-to-roll type film transport device, and it is preferable that the second unwinding means 105, the surface treatment means 106a and / or 106b, and the second winding means 107 are arranged in this order along the transport direction. In the second device 100b, the substrate α with the resin layer precursor unwound by the second unwinding means 105 is guided and transported by the film-forming roller 108 and guide rollers 109a to 109e, and is surface-treated by the surface treatment means 106a and / or 106b, and is then wound up as a second wound body by the second winding means 108. 2 is an example and is not particularly limited to the number of film-forming rollers and guide rollers. Furthermore, the film may be transported by a transport means other than guide rollers.

[0101] As the second unwinding means 105, a known unwinding device capable of unwinding a roll of film may be used. Only one of the surface treatment means 106a and 106b may be used. When a plurality of surface treatment means are provided as shown in Fig. 2, the surface treatment means 106a at the front stage may be configured with an ion beam irradiation mechanism or the like that does not involve film formation, and the surface treatment means 106b at the rear stage may be configured with a sputtering device or the like that is capable of film formation. Furthermore, when performing surface treatment by heating the substrate α with the resin layer precursor, it is preferable to use a film formation roller 108 that can be controlled in temperature. A known device capable of winding a film into a wound body may be used as the second winding means 107. The second winding means 107 winds the laminate 10 around a core.

[0102] <Manufacturing method according to the second embodiment> A manufacturing method according to a second embodiment of the present invention (hereinafter also referred to as the "second manufacturing method") involves continuously carrying out a resin layer precursor forming step (A), a surface treatment step (B), and a winding step (C) while transporting a substrate. According to the second manufacturing method, the manufacturing steps can be further shortened, resulting in better productivity. In addition, "continuously" means that the manufacturing is carried out without unwinding or winding in between, and does not preclude the insertion of processes other than unwinding and winding between the resin layer precursor forming process (A), the surface treatment process (B), and the winding process (C). The second manufacturing method is suitable for use in the case where a CVD method or the like that does not require a high degree of vacuum is used in the surface treatment step (B). To continuously transport the substrate from atmospheric pressure to a reduced pressure environment, for example, an ATV (Air to Vacuum) device (manufactured by Hitachi Zosen Corporation) or the like can be used.

[0103] The resin layer precursor forming step (A), semi-curing step (P), surface treatment step (B) and winding step (C) in the second manufacturing method are the same as the resin layer precursor forming step (A), semi-curing step (P), surface treatment step (B) and winding step (C) described in the first manufacturing method. However, in the second manufacturing method, the substrate with the resin layer precursor obtained in the resin layer precursor forming step (A) is not wound up, but is transported as is to the surface treatment step (B).

[0104] The length of the substrate is preferably 5 m or more and 5000 m or less, more preferably 10 m or more and 1000 m or less, and even more preferably 50 m or more, from the viewpoint of facilitating continuous performance of the resin layer precursor forming step (A) and the surface treatment step (B).

[0105] In the second production method, the conveying speed in the resin layer precursor forming step (A), the surface treatment step (B), and the winding step (C) is preferably 0.1 m / min to 30 m / min, more preferably 0.2 m / min to 20 m / min, and even more preferably 10 m / min or less. By setting the conveying speed within the above range, the surface treatment can be sufficiently performed while improving productivity, and unevenness including a wrinkle structure can be easily formed.

[0106] The semi-curing step (P) is not essential in the second manufacturing method either, but if it is desired to control the uneven structure, it is preferable to perform the semi-curing step (P) between the resin layer precursor forming step (A) and the surface treatment step (B).

[0107] <<Laminate>> A laminate 10 obtained by the manufacturing method of the present invention has a substrate 11 and a resin layer 12 provided on at least one surface 11A of the substrate 11, as shown in FIGS.

[0108] In the laminate 10, no other layer may be provided on the resin layer 12, and the resin layer 12 may be the outermost surface 10A of the laminate 10 on one surface 11A of the substrate 11, as shown in Fig. 3. In addition, the laminate 10 preferably has a cover layer 13 provided on the resin layer 12, as shown in Fig. 4. In the laminate 10, the resin layer 12 may be formed on the substrate 11 so as to be in direct contact with it, or an adhesive layer or other layer may be appropriately provided between the resin layer 12 and the substrate 11. The laminate obtained by the production method of the present invention will be described in more detail below.

[0109] <Unevenness on the top surface> In the laminate 10, the outermost surface 10A of the laminate 10 on one surface 11A side of the substrate 11 has irregularities. The laminate 10 has irregularities on the outermost surface, and is therefore applicable to various uses that utilize the fine irregularities on the surface (such as adhesion prevention and light transparency). For example, if a liquid-repellent material is selected for the layer that forms the outermost surface 10A of the laminate 10, the contents will not easily adhere to the surface of the laminate, making it applicable to packaging materials. Furthermore, if the adhesion of cells, bacteria, etc. can be reduced by controlling the uneven structure, it could also be used in sanitary materials. Furthermore, by providing the outermost surface with irregularities, good fogging properties can be achieved, and for example, the haze and light transmittance of the laminate can be controlled.

[0110] The unevenness on the outermost surface preferably has a wrinkle structure. Here, the wrinkled structure refers to a wrinkled shape that occurs when the resin layer 12 buckles, and is different from the uneven shape formed by particles, which has many dot-like protrusions. In this embodiment, the unevenness is formed by the buckling of the resin layer itself, so that an uneven surface can be formed that is free from the risk of particles falling off. Furthermore, because this wrinkled structure is formed spontaneously, a mold such as a transfer sheet is not required.

[0111] FIG. 5 shows a schematic diagram of a wrinkle structure. The wrinkle structure is made up of a plurality of undulations c, each of which has a protrusion a and a groove b. The protrusion a and the groove b each have a straight line, a curve, or a combination of these. The protrusion a is formed irregularly. The protrusion a may be formed continuously or discontinuously.

[0112] The wrinkle structure is formed when compressive stress is applied along the surface direction to the resin layer 12. It is presumed that the compressive stress is applied in multiple directions along the surface direction, which causes the irregular formation of protrusions a and grooves b. The presence or absence of a wrinkle structure can be confirmed by observing the outermost surface of the laminate with a microscope such as a scanning electron microscope (SEM) at a magnification of, for example, about 1,000 to 100,000 times (see Figures 7 to 17). When a wrinkle structure is present, the protrusions a and grooves b appear to form undulations c. The undulations c can be observed in a square or rectangular observation image with a side of, for example, about 0.5 to 500 μm, preferably about 1 to 100 μm. The protrusions a that form the wrinkle structure are irregular, and the undulations c appear at a period on the order of micrometers. Therefore, as shown in Figures 7 to 17, the undulations c formed by the protrusions a and grooves b appear multiple times (e.g., five or more times) in the observation image, even when viewed in multiple directions (e.g., three directions) such as the vertical, horizontal, and diagonal directions. The period of the undulations c is typically not constant, and therefore the distance between the tops of the protrusions a and the distance between the bottoms of the grooves b are also not constant. The "period of the waviness c" refers to the distance d between the apex of a protrusion a and the apex of the protrusion a adjacent to a groove b adjacent to the protrusion a, as shown in FIG.

[0113] The wrinkle structure may also have two or more wrinkle structures with different undulation periods (hereinafter also referred to as a "high-order wrinkle structure"). For example, the wrinkle structure may include a primary wrinkle structure and a secondary wrinkle structure having a smaller undulation period than the primary wrinkle structure. A schematic diagram of a structure including a primary wrinkle structure and a secondary wrinkle structure is shown in Fig. 6. In Fig. 6, the primary wrinkle structure is made up of a plurality of undulations c, and the secondary wrinkle structure is made up of a plurality of undulations c' with a smaller period than the undulations c in each of the ridges a and grooves b that make up the plurality of undulations c. In other words, the wrinkle structure preferably has a primary wrinkle structure and a secondary wrinkle structure formed by finer ridges a' and grooves b' in the relatively large ridges a and grooves b that form the primary wrinkle structure. In this way, by having a secondary wrinkle structure in addition to the primary wrinkle structure, it is possible to form a pseudo-fractal surface. Whether or not a primary and secondary wrinkle structure is present can be determined by whether undulations appear in both of two observation images taken at different magnifications. For example, even if the ratio (Y / X) of the magnification (X) of one observation image to the magnification (Y) of the other observation image is 5 or more (Y>X), it can be determined that a primary and secondary wrinkle structure is present if the undulations are observed in both observation images.

[0114] The fact that the unevenness on the outermost surface 10A of the laminate 10 has a wrinkle structure formed spontaneously is reflected in the value of Ssk (skewness), for example. Ssk is a parameter that indicates the degree of unevenness of a surface. This unevenness Ssk represents the cube mean of Z(x,y) on a reference plane that has been made dimensionless by the cube of the root mean square height Sq. It means skewness and is a numerical value that indicates the symmetry of the peaks and valleys around the mean plane. Therefore, if the unevenness Ssk<0, it means that there is a downward bias from the mean line, meaning that there are more concave valleys than convex peaks. On the other hand, if Ssk>0, it means that there is an upward bias from the mean line, meaning that there are more convex peaks than concave valleys. And if the unevenness Ssk=0, it means that there is symmetry (normal distribution) with respect to the mean line.

[0115] The wrinkle structure of the outermost surface 10A of the laminate 10 of the present invention is a wrinkled shape caused by buckling of the resin layer 12. Therefore, compared to the uneven shape formed by particles, the symmetry of the convex peaks and concave valleys is higher. Therefore, it is considered that the Ssk of the wrinkle structure of the laminate 10 of the present invention is closer to 0 than the Ssk of the uneven shape formed by particles. From this viewpoint, the absolute value of Ssk of the outermost surface 10A of the laminate 10 is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. Of these, 8 or less is preferable, 6 or less is more preferable, and 4 or less is even more preferable. Furthermore, 2 or less is preferable, 1 or less is more preferable, and 0.8 or less is even more preferable. Furthermore, 0.5 or less is preferable, 0.3 or less is more preferable, and 0.1 or less is even more preferable.

[0116] Ssk is a parameter based on ISO25178 and can be calculated, for example, by the following method. Using a three-dimensional non-contact surface shape measuring device (VertScan2.0 R5200G manufactured by Ryoka Systems Co., Ltd.), measurements were taken using a SONY HR-50 1 / 3 inch CCD camera (10x objective lens, 530nm white wavelength filter) in measurement mode: Wave, with a measurement area of ​​469.17μm x 351.89μm. The attached analysis software (VS-Viewer Version 5.1.3) was used to remove the waviness components from the captured image using polynomial fourth-order approximation surface correction, and then interpolation processing (a process in which height data is calculated from surrounding pixels to fill in the gaps for pixels where height data could not be obtained) was performed to calculate the height.

[0117] The outermost surface 10A of the laminate preferably has a specific surface area (S / A) of 1.001 or more. A specific surface area of ​​1.001 or more means that the wrinkle structure provides a sufficiently large surface area. This makes the laminate more susceptible to haze in optical applications, and adjusting the specific surface area allows for adjustment of the haze value of the laminate. From the above viewpoint, the specific surface area (S / A) is more preferably 1.005 or more, even more preferably 1.01 or more, still more preferably 1.05 or more, and even more preferably 1.1 or more. Furthermore, the specific surface area (S / A) is not particularly limited, but in order to prevent the protrusions of the wrinkle structure from becoming too high and reducing the structural strength, it is preferably 2 or less, more preferably 1.7 or less, and even more preferably 1.5 or less. The specific surface area (S / A) can be calculated by S / A, where A is the area of ​​the measurement target area on the outermost surface 10A and S is the surface area of ​​the measurement target area. More specifically, it can be determined by the method shown in the examples described later.

[0118] The Sa (arithmetic mean roughness) of the outermost surface 10A of the laminate is not particularly limited, but is, for example, 20 nm or more. By setting Sa to 20 nm or more, it means that sufficient unevenness is formed by the wrinkle structure, and when applied to optical materials, for example, haze can be adjusted. From these perspectives, Sa (arithmetic mean roughness) is preferably 30 nm or more, more preferably 50 nm or more, and even more preferably 100 nm or more. Furthermore, the arithmetic mean roughness (Sa) is not particularly limited, but from the viewpoint of maintaining the physical strength of the wrinkle structure, it is preferably 3000 nm or less, more preferably 2000 nm or less, even more preferably 1500 nm or less, even more preferably 1000 nm or less, and of these, preferably 500 nm or less.

[0119] The Sz (maximum height) of the outermost surface 10A of the laminate is not particularly limited, but is preferably 1000 nm or more, more preferably 1500 nm or more, and even more preferably 2000 nm or more. If Sz is equal to or greater than these lower limits, sufficient buckling progresses, and a wrinkled structure with high protrusions is formed. Therefore, if applied to optical materials, for example, the haze can be adjusted. Although Sz (maximum height) is not particularly limited, from the viewpoint of maintaining the physical strength of the wrinkle structure, it is preferably 20,000 nm or less, more preferably 15,000 nm or less, and even more preferably 10,000 nm or less. Sa and Sz can be measured by the method shown in the examples below.

[0120] <Applications of laminates> The laminate of the present invention can be suitably used for packaging food, daily necessities, industrial products, pharmaceuticals, etc. Specifically, it can be used as a packaging material such as a film. In packaging materials, by imparting water repellency and oil repellency, it can be suitably used as a component for preventing adhesion of contents and dirt. The laminate can also be used as an optical material, where the haze and light transmittance of the optical material can be controlled by imparting cloudiness with the unevenness of the wrinkle structure, making the laminate suitable for use as a light-shielding film for windowpanes.

[0121] The laminate of the present invention may have a coating layer on the resin layer or cover layer that is the outermost surface of the laminate depending on the application, to the extent that the effect of the present invention is not impaired. For example, in an anti-adhesion application, the surface of the laminate can be imparted with anti-adhesion properties by providing a coating layer having a liquid-repellent effect.

[0122] <Explanation of terms> In the present invention, the term "film" includes the term "sheet", and the term "sheet" includes the term "film". [Example]

[0123] The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples. The measurement and evaluation methods used in the present invention are as follows.

[0124] (1) How to measure the thickness of the resin layer The surface of the resin layer was stained with RuO4 and embedded in epoxy resin. Then, sections prepared by ultrathin sectioning were stained with RuO4 again, and the cross section of the resin layer was measured using a TEM (Hitachi High-Technologies Corporation "H-7650", accelerating voltage 100 kV). The thickness was determined as the average value of the maximum and minimum thicknesses.

[0125] (2) How to measure the thickness of the cover layer Samples were prepared by epoxy resin embedding and ultrathin sectioning, and measured using a cross-sectional TEM (JEOL Ltd., "JEM-1200EXII") at an accelerating voltage of 120 kV.

[0126] (3) Sa (arithmetic mean roughness), Sz (maximum height) and specific surface area (S / A) The Sa, Sz, and specific surface area (S / A) of the outermost surface of the laminate were measured using a three-dimensional non-contact surface profiler (VertScan2.0 R5200G, manufactured by Ryoka Systems Co., Ltd.) with a 10x objective lens over an area of ​​496.17 μm × 351.89 μm. In the specific surface area (S / A), A represents the area of ​​the area to be measured, S represents the surface area of ​​the area to be measured, and S / A represents the specific surface area of ​​the area to be measured.

[0127] (4) Measurement of bias In accordance with ISO25178, the deviation Ssk of the outermost surface of the laminate obtained by the method described in the specification was measured.

[0128] (5) Surface observation The outermost surface of the laminate on one side of the substrate was photographed at 10,000 and 50,000 magnifications using a scanning microscope to obtain 12.7 μm×9.5 μm and 2.5 μm×1.9 μm observation images. If the wrinkle structure was visible in both the 12.7 μm x 9.5 μm observation image and the 2.5 μm x 1.9 μm observation image, the sample was rated as A (primary and secondary wrinkles present), if the wrinkle structure was visible in either observation image, the sample was rated as B (primary wrinkles present), and if the wrinkle structure was not visible in either observation image, the sample was rated as C (no wrinkles).

[0129] Example 1 (Preparation of Thermosetting Resin Composition (AC1)) A dilution of thermosetting resin composition (AC1) was prepared by mixing 42.4 parts by weight of acrylic polyol (product name "UV-G301" manufactured by Nippon Shokubai Co., Ltd., 42.4% solids in an ethyl acetate solution) as a binder resin and 18.46 parts by weight of an isocyanate compound (product name "Takenate D-165N" manufactured by Mitsui Chemicals, Inc., hexamethylene diisocyanate compound, 100% solids) as a curing agent with a solvent mixture of methyl ethyl ketone, propyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate in a ratio of 5:2:2:1 to obtain a solids concentration of 15% by weight. The R (number of isocyanate groups in the curing agent) / (number of hydroxyl groups in the binder resin) of the thermosetting resin composition (AC1) was 1.5.

[0130] A substrate wound around a core was transported at a speed of 5 m / min. A diluted solution of the thermosetting resin composition (AC1) was applied to one side of the PET film using a two-roll reverse coating method. The film was then heated for a total of 72 seconds in a drying oven set at 80 ° C and another oven set at 100 ° C to form a resin layer precursor. The resin layer precursor was then wound around the core with a winding tension of 70 N so that the resin layer precursor was on the outside, resulting in a first wound body consisting of a substrate with a resin layer precursor. The wound body was then left at room temperature (23 ° C) for 22 hours, and the sputtering process described below was initiated.

[0131] (Cover layer formation) Using a sputter roll coater (W35 series, manufactured by Kobe Steel, Ltd.), the first wound body was unwound and transported at a transport speed of 0.3 m / min, and sputtering was performed using a roll-to-roll method.The resulting laminate was then wound around a core with a winding tension of 60 N, with the cover layer facing outward, to obtain a second wound body having a laminate structure of substrate / resin layer / cover layer. During sputtering, the temperature of the deposition roller in contact with the substrate (MR temperature) was set to 40°C, silicon (polycrystalline silicon) was used as the target material, and reactive sputtering was performed using a dual magnetron sputtering method, introducing 350 sccm of argon and 40 sccm of oxygen, under reduced pressure of 0.48 Pa and with a power of 5 kW, to form a 100 nm thick inorganic-containing layer (silicon oxide layer) on the semi-cured resin layer precursor.

[0132] Example 2 The same procedure as in Example 1 was carried out, except that the conveying speed in the sputter roll coater was changed to 1 m / min.

[0133] Example 3 The same procedure as in Example 2 was carried out, except that the thickness of the resin layer was changed as shown in Table 1 by adjusting the gap between the two rolls and the rotational speed ratio in the reverse coating method.

[0134] Example 4 The same procedure as in Example 1 was carried out, except that the temperature of the film-forming roller (MR temperature) in the sputter roll coater was changed to 60°C.

[0135] Example 5 The same procedure as in Example 1 was carried out, except that the temperature of the film-forming roller (MR temperature) in the sputter roll coater was changed to 80°C.

[0136] Example 6 The same procedure as in Example 1 was carried out except that the flow rates of the gases introduced into the sputter roll coater were 150 sccm of argon and 38 sccm of oxygen, and the film formation pressure was changed to 0.24 Pa.

[0137] Example 7 The same procedure as in Example 1 was carried out except that the flow rates of the gases introduced during sputtering were changed to argon 350 sccm and oxygen 0 sccm to form a silicon layer.

[0138] Example 8 The first wound body was unwound using a sputter roll coater, transported at a transport speed of 0.3 m / min, and irradiated with argon ions using an ion beam irradiation mechanism (ALS: Anode Layer Source) under the following conditions: ALS voltage: 2000 V, argon flow rate: 27 sccm, and pressure during treatment: 0.05 Pa. The resulting laminate was then wound around a core to obtain a second wound body having a laminate structure of substrate / resin layer.

[0139] Example 9 In the sputter roll coater, after unwinding the first wound body, the same procedure as in Example 1 was carried out, except that argon ions were irradiated using an ion beam irradiation mechanism (ALS: Anode Layer Source) under the following conditions before sputtering: ALS voltage: 2000 V, argon flow rate: 27 sccm, and pressure during treatment: 0.05 Pa.

[0140] Comparative Example 1 The PET film (manufactured by Mitsubishi Chemical Corporation, product name "T100-75S") used alone as the substrate was used as Comparative Example 1.

[0141] [Table 1]

[0142] 7 to 17 show images of the laminates of Examples 1 to 9 observed with a scanning microscope. In Examples 1 to 9, by performing surface treatment on the semi-cured resin layer precursor by a dry process using a roll-to-roll method, it was possible to form irregularities including a wrinkle structure on the outermost surface of the laminate.

[0143] Comparing Example 1 and Example 2, it was confirmed that the faster the conveying speed in the dry process, the finer the unevenness formed, with a smaller arithmetic mean roughness Sa. This is thought to be because when energy is applied in a reduced-pressure, dry environment, fine wrinkles form in the surface layer of the resin layer precursor due to cure shrinkage in a short period of time, and if the treatment time is further extended, the temperature rises to the lower layer of the resin layer precursor, increasing its fluidity and causing the unevenness on the surface of the laminate to grow significantly.

[0144] Comparing Example 1 with Examples 4 and 5, it was confirmed that the higher the temperature of the film-forming roller (MR temperature), the more fine, high-order wrinkle structures were formed. This is thought to be because, as the temperature of the deposition roller (MR temperature) increases, the resin layer precursor becomes more fluid, and large undulations (primary wrinkle structure) are generated by buckling due to the cure shrinkage of the resin layer precursor.Furthermore, buckling due to the membrane stress associated with the deposition of the cover layer also becomes more likely to occur, generating small undulations (secondary wrinkle structure) on the surface layer.

[0145] Comparing Example 1 and Example 6, it was confirmed that the lower the film formation pressure in the dry process, the more clearly the unevenness formed. This is thought to be because the lower the film-forming pressure, the easier it is for energy to be transmitted to the resin layer precursor, resulting in a large curing shrinkage force.

[0146] Furthermore, it was confirmed from Example 7 that the uneven structure changes when the film-forming species in the dry process is changed.

[0147] In Example 8, it was confirmed that unevenness was formed even when the surface treatment was performed by a dry process that did not involve film formation. Furthermore, when Example 1 and Example 8 are compared, it was confirmed that the uneven surface was smoothed by carrying out the ion beam irradiation treatment. This is thought to be because ion beam irradiation is a process that does not involve film formation, so no film stress is generated and the remaining resin layer body flows and deforms while maintaining its smoothness.

[0148] Unlike the technology disclosed in Patent Document 1, the present invention does not use particles to form the irregularities, so there is no concern about particles falling off, and the present invention can be used in a wider range of applications. [Explanation of symbols]

[0149] 100a First device 100b Second device 101 Application means 102 First winding means 103 Drying means 104 First unwinding means 105 Second unwinding means 106a, 106b Surface treatment means 107 Second winding means 108 Coating roller 109a~109e Guide rollers α Substrate with resin layer precursor 10 Laminate 10A Top surface of laminate 11 Base material 11A One side of the substrate 12 Resin layer 13 Cover Layer

Claims

1. a resin layer precursor-forming step (A) of applying a curable resin composition to at least one surface of a substrate to obtain a substrate with a resin layer precursor; a surface treatment step (B) of performing a surface treatment by a dry process on the semi-cured or uncured substrate with the resin layer precursor to obtain a laminate having irregularities on the outermost surface; and a winding step (C) of winding the laminate into a roll, After the resin layer precursor forming step (A), a winding step (X) of winding the substrate with the resin layer precursor into a roll; an unwinding step (Y) of unwinding the substrate with the resin layer precursor from the roll; The method for producing a laminate further comprises carrying out a surface treatment step (B).

2. The method for producing a laminate according to claim 1 , wherein the surface treatment step (B) and the winding step (C) are performed while the substrate with the resin layer precursor is being transported.

3. a resin layer precursor-forming step (A) of applying a curable resin composition to at least one surface of a substrate to obtain a substrate with a resin layer precursor; a surface treatment step (B) of performing a surface treatment by a dry process on the semi-cured or uncured substrate with the resin layer precursor to obtain a laminate having irregularities on the outermost surface; and a winding step (C) of winding the laminate into a roll, the unevenness on the outermost surface of the laminate includes a wrinkle structure, A method for manufacturing a laminate, wherein the wrinkle structure includes a primary wrinkle structure and a secondary wrinkle structure having a smaller undulation period than the primary wrinkle structure.

4. The method for producing a laminate according to claim 3 , wherein the resin layer precursor forming step (A), the surface treatment step (B), and the winding step (C) are carried out continuously while the substrate is being transported.

5. After the resin layer precursor forming step (A), a semi-curing step (P) of semi-curing the resin layer precursor; The method for producing a laminate according to any one of claims 1 to 4, further comprising the step of (B) performing a surface treatment thereafter.

6. The method for producing a laminate according to any one of claims 1 to 5, wherein the surface treatment is any one of chemical vapor deposition, physical vapor deposition, and plasma treatment.

7. The method for producing a laminate according to any one of claims 1 to 6, wherein the temperature of the film in the surface treatment step (B) is 30°C or higher and 120°C or lower.

8. the curable resin composition is a thermosetting resin composition, The method for producing a laminate according to any one of claims 1 to 7, wherein the ratio (number of isocyanate groups) / (number of hydroxyl groups) in the thermosetting resin composition is 10 or less.

9. The method for producing a laminate according to any one of claims 1 to 8, wherein the specific surface area (S / A) of the outermost surface of the laminate is 1.001 or more.

10. The method for producing a laminate according to any one of claims 1 to 9, wherein the outermost surface of the laminate has an arithmetic mean roughness Sa (arithmetic mean roughness) of 20 nm or more.

11. The method for producing a laminate according to any one of claims 1 to 10, wherein the outermost surface of the laminate has a maximum height Sz of 1000 nm or more.

12. The method for producing a laminate according to any one of claims 1 to 11, wherein the absolute value of Ssk (degree of deviation) of the outermost surface of the laminate is 20 or less.

13. The method for producing a laminate according to any one of claims 1 to 12, wherein a thickness (tb) of a resin layer formed by curing the applied curable resin composition is 0.1 µm or more and 15 µm or less.

Images