JP7549448B2 - Copolymer, curable polymer composition, cured product, laminate - Google Patents

Description

The present invention relates to a polymer, a curable polymer composition containing the polymer, a cured product of the curable polymer composition, and a laminate having a layer made of the cured product.

In order to impart a matte finish to building materials such as wallpaper, display members, decorative films, and other members, fine irregularities are sometimes imparted to the surface of a substrate. In addition, these members are sometimes required to have antifouling properties.
Patent Document 1 discloses a method for providing a fine uneven shape by hairline processing, sandblasting, matte processing, etc., on a film for transfer foil used in the production of decorative sheets for building materials, various parts of home appliances such as refrigerators and washing machines, various parts of office automation products such as personal computers, packaging containers, etc., by molding.
Furthermore, Patent Document 2 discloses a method for forming surface irregularities on a light diffusing film used in a backlight unit of a liquid crystal display, in which acrylic particles are dispersed in a resin binder.

JP 2004-231727 A Japanese Patent Application Publication No. 7-218705

However, the method of forming the unevenness described in Patent Document 1 does not provide a sufficient matte effect. In addition, sand remaining in the film by sandblasting can cause quality problems. It is difficult to impart antifouling properties because the surface is polished.
Furthermore, in the method described in Patent Document 2, the acrylic particles may fall off during use, which may impair the visibility of the display.
An object of the present invention is to solve these problems and to provide a polymer capable of imparting matte properties and stain resistance to a cured product, a curable polymer composition containing the polymer, a cured product of the curable polymer composition, and a laminate having a layer composed of the cured product.

The present invention has the following aspects.
[1] A copolymer having a unit based on a monomer (x) having an active group that generates radicals upon irradiation with active energy rays, and a unit based on a monomer (f) having a fluorine atom or a silicon atom.
[2] The copolymer according to [1], wherein the active group is at least one selected from the group consisting of a benzophenone group, an acetophenone group, a benzoin group, an α-hydroxyketone group, an α-aminoketone group, an α-diketone group, an α-diketone dialkyl acetal group, an anthraquinone group, a thioxanthone group, and a phosphine oxide group.
[3] The copolymer according to [1] or [2], wherein the content of the active group per 1 g of the copolymer is 0.1 to 3.5 mmol/g.
[4] The copolymer according to any one of [1] to [3], wherein the monomer (f) contains at least one selected from the group consisting of a compound having a fluoroalkyl group and a radically polymerizable group, and a compound having a polydimethylsiloxane chain and a radically polymerizable group.
[5] The copolymer according to any one of [1] to [4], wherein the content of units based on the monomer (f) is 5 to 70 mass% based on the total mass of all units constituting the copolymer.
[6] The copolymer according to any one of [1] to [5], further comprising a unit based on a monomer (r) having an alkyl group having 4 or more carbon atoms.
[7] A curable polymer composition comprising the copolymer (A) according to any one of [1] to [6], and a polyfunctional compound (B) having two or more radically polymerizable groups in one molecule.
[8] The curable polymer composition according to [7], wherein the content of the copolymer (A) is 0.5 to 50 mass% based on the non-volatile content of the curable polymer composition.
[9] A cured product of the curable polymer composition according to [7] or [8].
[10] A laminate having a base layer and a layer made of the cured product of [9].

The copolymer of the present invention can impart matte finish and stain resistance to a cured product.
The curable composition of the present invention can form a cured product having a matte finish and antifouling properties.
The cured product of the present invention has a matte finish and antifouling properties.
The laminate of the present invention has a matte finish and antifouling properties.

FIG. 1 is a schematic cross-sectional view showing an example of a laminate of the present invention. FIG. 2 is a schematic cross-sectional view showing another example of the laminate of the present invention.

Hereinafter, an embodiment of the present invention will be described in detail.
In the present invention, "(meth)acrylate" is a general term for acrylate or methacrylate, and "(meth)acrylic" is a general term for acrylic and methacrylic.
The use of "to" indicating a range of numerical values means that the numerical values before and after it are included as the lower limit and upper limit.

<Curable polymer composition>
The curable polymer composition contains a unit based on a monomer (x) having an active group that generates a radical when irradiated with active energy rays (hereinafter, also simply referred to as an active group) and a monomer ( The copolymer (A) has units based on the above-mentioned copolymer (f), and a polyfunctional compound (B) has two or more radically polymerizable groups in one molecule.
When the curable polymer composition is irradiated with active energy rays, radicals are generated from the active groups of the copolymer (A), and the generated radicals serve as starting points for reactions between the radically polymerizable groups of the polyfunctional compound (B). For example, when a coating film of the curable polymer composition is formed and this coating film is irradiated with active energy rays, the surface side of the coating film is cured first. When the inside of the coating is subsequently cured, the cured coating on the surface side buckles, forming a cured product with wrinkled irregularities on the surface (hereinafter also referred to as an "irregular layer"). When the unevenness appears on the surface of the cured product, functions such as a matte finish are obtained. The method for forming the unevenness layer will be described in detail later.
The curable polymeric composition may optionally further comprise an organic solvent.
The curable polymeric composition may further contain other components in addition to those described above, if necessary.

<Copolymer (A)>
[Monomer (x)]
The monomer (x) may be a compound having an active group and a radically polymerizable group.
The active group may have a structure that generates radicals by irradiation with active energy rays (a structure having photopolymerization initiation). As the structure having photopolymerization initiation, various known structures can be used, such as a hydrogen abstraction type, an electron transfer type, and an intramolecular cleavage type.
Specific examples of the active group include a benzophenone group, an acetophenone group, a benzoin group, an α-hydroxyketone group (for example, a group in which one hydrogen atom has been removed from the "hydroxyl group in 2-hydroxyethoxy" of 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-methylpropanone), an α-aminoketone group, an α-diketone group, an α-diketone dialkyl acetal group, an anthraquinone group, a thioxanthone group, a phosphine oxide group, and the like. Among these, the benzophenone group, the acetophenone group, and the α-hydroxyketone group are preferred in that they are less susceptible to oxygen inhibition during curing and provide good surface curing properties when forming a concave-convex layer.

The radically polymerizable group of the monomer (x) may be a functional group containing a radically polymerizable unsaturated bond (such as a carbon-carbon double bond), and specific examples thereof include a (meth)acryloyl group and a vinyl group.
As the monomer having an active group, from the viewpoints of ease of synthesis of the polymer (A) and ease of adjustment of the amount of the active group introduced, a (meth)acrylic acid ester having an active group is preferred.
Examples of monomers having an active group include 4-methacryloyloxybenzophenone and 2-[4-(2-hydroxy-2-methyl-1-oxopropyl)phenoxy]ethyl methacrylate.

[Monomer (f)]
The monomer (f) may be a compound having a fluorine atom or a silicon atom and a radical polymerizable group. The radical polymerizable group is the same as described above.
The units based on monomer (f) impart at least one of water repellency and oil repellency to the cured product, and contribute to the stain resistance of the cured product.
Furthermore, if the copolymer (A) contains this unit, when a coating film of the curable polymer composition is formed, the copolymer (A) tends to segregate on the surface side of the coating film.
When the copolymer (A) segregates to the surface side of the coating film, the concentration of units based on the monomer (f) on the surface side of the coating film increases, and antifouling properties can be efficiently imparted to the surface of the cured product.

In addition, the copolymer (A) segregates on the surface side of the coating film, so that the concentration of active groups on the surface side of the coating film increases, and when the coating film is irradiated with active energy rays, the surface side of the coating film cures first to form a cured coating film, and then the inside of the coating film cures. As the inside of the coating film cures, the cured coating film on the surface buckles, resulting in the appearance of wrinkle-like unevenness.
In this case, the shorter the curing time inside the coating film, the smaller the period of the concave-convex pattern on the surface of the concave-convex layer, and the longer the curing time, the larger the period of the concave-convex pattern on the surface of the concave-convex layer. This curing time can be adjusted by the amount of radical polymerizable groups in the curable polymer composition, the amount of active groups (the amount of copolymer (A) and photopolymerization initiator), the amount of active energy radiation, etc.
Furthermore, if the copolymer (A) segregates to the surface side of the coating film, the curing reaction inside the coating film (on the substrate layer side) is less susceptible to oxygen inhibition, and the coating film can be cured with a low exposure dose, and even a thin film that tends to be easily inhibited by oxygen can be cured well.

It is preferable that the monomer (f) contains at least one member selected from the group consisting of a compound having a fluoroalkyl group and a radically polymerizable group, and a compound having a polydimethylsiloxane chain and a radically polymerizable group.
It is more preferable that the monomer (f) contains at least one member selected from the group consisting of a (meth)acrylic acid ester having a fluoroalkyl group and a (meth)acrylic acid ester having a polydimethylsiloxane chain.

The fluorine atom-containing (meth)acrylic acid ester is more preferably a (meth)acrylic acid ester having a perfluoroalkyl group, the number of carbon atoms of which is preferably 3 or more. Examples of the (meth)acrylic acid ester containing a fluorine atom include 2,2,2-trifluoroethyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., Viscoat 3F), 2,2,3,3-tetrafluoropropyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., Viscoat 4F), 1H,1H,5H-octafluoropentyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., Viscoat 8F), 1H,1H,5H-octafluoropentyl methacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., Viscoat 8FM), 1H,1H,2H,2H-tridecafluorooctyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., Viscoat 13F), 1H,1H,2H,2H-nonafluorohexyl acrylate (manufactured by Unimatec Co., Ltd., CHEMINOX FAAC-4), and 1H,1H,2H,2H-nonafluorohexyl methacrylate (manufactured by Unimatec Co., Ltd., CHEMINOX FAAC-4). FAMAC-4), 1H,1H,2H,2H-tridecafluorooctyl methacrylate (Unimatec Co., Ltd., CHEMINOX FAMAC-6), and the like are commercially available.
Specific examples of (meth)acrylic acid esters having a polydimethylsiloxane chain include polydimethylsiloxanes substituted with a (meth)acryloyl group at one end and having a molecular weight of 500 to 50,000. The molecular weight is preferably 1,000 to 30,000, and more preferably 1,500 to 20,000. Examples of (meth)acrylic acid esters having a polydimethylsiloxane chain include commercially available products such as "FM-0711", "FM-0721", and "FM-0725" (all manufactured by JNC Corporation), and "X-24-8201", "X-22-174DX", and "X-22-2426" (all manufactured by Shin-Etsu Chemical Co., Ltd.).

[Monomer (r)]
From the viewpoint of more effectively segregating the copolymer (A) on the surface of the coating film, the copolymer (A) preferably has, in addition to units based on the monomer (x) and units based on the monomer (f), one or more units based on the monomer (r) having an alkyl group having 4 or more carbon atoms.

The alkyl group having 4 or more carbon atoms may be linear, branched, or cyclic. The cyclic alkyl group may be monocyclic or polycyclic. From the viewpoint of more effectively segregating the copolymer (A) on the surface of the coating film, the alkyl group is preferably linear.
The number of carbon atoms in the alkyl group having 4 or more carbon atoms is preferably in the range of 4 to 30, more preferably in the range of 6 to 20, and even more preferably in the range of 12 to 18, from the viewpoint of more effectively segregating the copolymer (A) on the surface of the coating film.

Examples of the monomer (r) include compounds having an alkyl group having 4 or more carbon atoms and a radical polymerizable group. From the viewpoints of ease of synthesis of the compound and ease of adjusting the amount of the alkyl group having 4 or more carbon atoms to be introduced, a (meth)acrylic acid alkyl ester having an alkyl group having 4 or more carbon atoms is preferred.
Examples of the monomer (r) include butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, and isodecyl (meth)acrylate. Examples of the acrylates include butyl acrylate, dodecyl (meth)acrylate, myristyl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, tridecyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, tricyclodecane (meth)acrylate, dicyclopentanyl (meth)acrylate, isobornyl (meth)acrylate, and adamantyl (meth)acrylate.
Among these, it is preferable to include a (meth)acrylic acid alkyl ester having a linear alkyl group having 4 or more carbon atoms. As the (meth)acrylic acid alkyl ester having a linear alkyl group having 4 or more carbon atoms, it is preferable that the number of carbon atoms in the alkyl group is within the above-mentioned preferred range, and taking into consideration ease of production, etc., 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, dodecyl (meth)acrylate, and stearyl (meth)acrylate are more preferable, and stearyl (meth)acrylate is particularly preferable.
These (meth)acrylic acid esters may be used alone or in combination of two or more kinds.

[Monomer (h)]
The copolymer (A) may further contain units based on a monomer (h) having a hydrogen donor functional group, if necessary.
In particular, when the monomer (x) has a hydrogen abstraction type active group, it is preferable that the polymer (A) contains a unit based on the monomer (h). When the polymer (A) contains this unit, curing from the surface of the coating film of the curable polymer composition can be effectively performed, and unevenness can be easily formed.
Examples of the hydrogen donating functional group include a hydroxyl group, an amino group, a mercapto group, an amide group, etc. Among these, a hydroxyl group, an amino group, or an amide group is preferred from the viewpoint of efficiently proceeding with the curing reaction and facilitating the formation of unevenness.

Examples of the monomer having a hydrogen donor functional group include compounds having a hydrogen donor functional group and a radical polymerizable group. From the viewpoints of ease of synthesis of the compound and ease of adjustment of the amount of hydrogen donor functional group to be introduced, (meth)acrylic acid esters and (meth)acrylamides having a hydrogen donor functional group are preferred.
Examples of monomers having a hydrogen donating functional group include hydroxyl group-containing monomers such as 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, monobutyl hydroxyl fumarate, and monobutyl hydroxy itaconate; N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-vinyl caprolactam, N-vinyl pyrrolidone, and N-isopropyl (meth)acrylamide. Examples of the monomers include amino group- or amide group-containing monomers such as N,N-dimethylaminoethyl (meth)acrylamide, N,N-dimethylaminoethyl (meth)acrylate, 2-[(butylamino)carbonyl]oxy]ethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylamide, N,N-diethylaminopropyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N,N-diethylaminopropyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylamide, (meth)acryloylmorpholine, and vinylacetamide. Among these, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, (N,N-dimethylacrylamide, N,N-dimethylaminoethyl (meth)acrylate, and N,N-diethylaminoethyl (meth)acrylate are preferred because they have an excellent curing acceleration effect when used in combination with an active group, and N,N-diethylaminoethyl (meth)acrylate is more preferred because it is easy to increase the unevenness. These compounds may be used alone or in combination of two or more.

The copolymer (A) may further contain units based on other monomers other than those mentioned above, as necessary. Examples of the other monomers include compounds having a radical polymerizable group but not having an active group, an alkyl group having 4 or more carbon atoms, a fluorine atom, a silicon atom, or a hydrogen donor functional group.
Examples of the other monomers include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, and citraconic acid, and salts thereof; (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, and propyl (meth)acrylate; nitrogen-containing monomers such as (meth)acrylonitrile; styrene-based compounds such as styrene, α-methylstyrene, divinylbenzene, and vinyl toluene, and vinyl esters such as vinyl propionate and vinyl acetate; phosphorus-containing vinyl monomers; vinyl halides such as vinyl chloride and vinylidene chloride; and conjugated dienes such as butadiene.

The active group may be present at the terminal of the main chain of the copolymer (A), or may be present in a unit based on a monomer constituting the copolymer (A).
The copolymer (A) preferably has a plurality of active groups in the molecule, which can increase the concentration of active groups near the surface of the coating film and facilitate the appearance of unevenness such as wrinkled structures on the surface after curing.
The content of active groups per 1 g of copolymer (A) is preferably in the range of 0.1 to 3.5 mmol/g, more preferably 0.5 to 2.5 mmol/g, and even more preferably 0.8 to 2.0 mmol/g. When the content of active groups is equal to or more than the lower limit of the above range, the curability is excellent and the unevenness can be formed more effectively. When the content is equal to or less than the upper limit, the storage stability of the curable composition is excellent.

The ratio of units based on monomer (x) to the total mass of all units constituting copolymer (A) is preferably in the range of 1 to 90 mass%, more preferably 10 to 80 mass%, even more preferably 20 to 70 mass%, and particularly preferably 30 to 60 mass%. When the ratio of units based on monomer (x) is equal to or greater than the lower limit of the above range, the curability is superior and unevenness can be formed more effectively. When it is equal to or less than the upper limit, the storage stability of the curable composition is superior.

The ratio of units based on monomer (f) to the total mass of all units constituting copolymer (A) is preferably in the range of 5 to 70 mass%, more preferably 10 to 60 mass%, and even more preferably 15 to 50 mass%. When the ratio of units based on monomer (f) is equal to or greater than the lower limit of the above range, unevenness can be formed more effectively. In addition, the stain resistance of the cured product is more excellent. When it is equal to or less than the upper limit, the compatibility between copolymer (A) and polyfunctional compound (B) is more excellent.

The ratio of units based on monomer (r) to the total mass of all units constituting copolymer (A) is preferably 80% by mass or less, more preferably 1 to 70% by mass, even more preferably 5 to 60% by mass, and particularly preferably 8 to 50% by mass. If the ratio of units based on monomer (r) is within the above range, unevenness can be formed more effectively.

The ratio of units based on monomer (h) to the total mass of all units constituting copolymer (A) is preferably 80% by mass or less, more preferably 1 to 60% by mass, even more preferably 3 to 50% by mass, and particularly preferably 5 to 40% by mass. If the ratio of units based on monomer (h) is within the above range, unevenness can be formed more effectively.

The weight average molecular weight (Mw) of the copolymer (A) is preferably in the range of 1,000 to 500,000, more preferably 2,000 to 100,000, and even more preferably 3,000 to 60,000. When the Mw is equal to or greater than the lower limit of the above range, the unevenness can be formed more effectively. When the Mw is equal to or less than the upper limit, the coatability of the curable polymer composition is more excellent.
The Mw of the copolymer (A) is a value calculated in terms of standard polystyrene as measured by gel permeation chromatography (GPC). The detailed measurement conditions are as described in the Examples below.

The glass transition temperature (Tg) of the copolymer (A) is preferably in the range of -30 to 180°C, more preferably 0 to 150°C, and even more preferably 25 to 100°C. If the Tg is equal to or greater than the lower limit of the above range, the unevenness can be formed more effectively, and the matte properties are more excellent. If the Tg is equal to or less than the upper limit, the compatibility between the copolymer (A) and the polyfunctional compound (B) is more excellent.

The copolymer (A) can be obtained, for example, by polymerizing a monomer component including the monomer (x) and the monomer (f). The monomer component may further include at least one of the monomer (r), the monomer (h) and other monomers, as necessary.
The polymerization is typically carried out in the presence of a polymerization initiator. If necessary, a chain transfer agent may be used in combination during the polymerization.
Examples of the polymerization method include known methods such as solution polymerization, suspension polymerization, bulk polymerization, and emulsion polymerization. Among these, solution polymerization is preferred in terms of ease of operation and high productivity.

<Polyfunctional compound (B)>
The polyfunctional compound (B) may be any compound having two or more radical polymerizable groups in one molecule, and various known compounds may be used. Polyfunctional (meth)acrylates are preferred. The compound (B) may be used alone or in combination of two or more kinds.

Examples of bifunctional polyfunctional (meth)acrylates include, but are not limited to, alkanediol di(meth)acrylates such as 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, tricyclodecanedimethylol di(meth)acrylate, bisphenol-modified di(meth)acrylates such as bisphenol A ethylene oxide-modified di(meth)acrylate and bisphenol F ethylene oxide-modified di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, urethane di(meth)acrylate, and epoxy di(meth)acrylate.

The trifunctional or higher polyfunctional (meth)acrylate is not particularly limited, but examples thereof include dipentaerythritol hexa(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, isocyanuric acid modified tri(meth)acrylate such as ethylene oxide-modified isocyanuric acid tri(meth)acrylate, ε-caprolactone modified tris(acryloxyethyl)isocyanurate, urethane acrylates such as pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, pentaerythritol triacrylate toluene diisocyanate urethane prepolymer, and dipentaerythritol pentaacrylate hexamethylene diisocyanate urethane prepolymer. Among these, dipentaerythritol hexa(meth)acrylate is preferred.

<Organic Solvent>
The organic solvent is used, if necessary, for the purpose of improving workability when applying the curable polymer composition onto a substrate.
Examples of organic solvents include aromatic solvents such as toluene and xylene; ketone-based solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone; ether-based solvents such as diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, anisole, and phenetole; ester-based solvents such as ethyl acetate, butyl acetate, isopropyl acetate, and ethylene glycol diacetate; amide-based solvents such as dimethylformamide, diethylformamide, and N-methylpyrrolidone; cellosolve-based solvents such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve; alcohol-based solvents such as methanol, ethanol, propanol, isopropanol, and butanol; halogen-based solvents such as dichloromethane and chloroform; and the like. These organic solvents may be used alone or in combination of two or more. Among these organic solvents, ester-based solvents, ether-based solvents, alcohol-based solvents and ketone-based solvents are preferred in that they can easily improve workability during coating.

<Photopolymerization initiator (C)>
The curable polymer composition may further contain one or more photopolymerization initiators (other than the copolymer (A)).
For example, a photopolymerization initiator (C) that is a non-polymer having an active group that generates radicals by irradiation with active energy rays can be mentioned. The molecular weight of the photopolymerization initiator (C) is preferably 1000 or less. Specific examples include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin phenyl ether, benzyl diphenyl disulfide, dibenzyl, diacetyl, anthraquinone, naphthoquinone, 3,3'-dimethyl-4-methoxybenzophenone, benzophenone, p,p'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, pivaloin ethyl ether, benzyl dimethyl ketal, 1,1-dichloroacetophenone, p-t-butyl dichloroacetophenone, and the like. Examples of the photopolymerization initiator include phenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-diethylthioxanthone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-dichloro-4-phenoxyacetophenone, phenyl glyoxylate, α-hydroxyisobutylphenone, dibenzosparone, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl-1-propanone, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, tribromophenyl sulfone, tribromomethylphenyl sulfone, etc. These photopolymerization initiators may be used alone or in combination of two or more.

<Other ingredients>
The curable polymer composition may further contain a leveling agent to improve the appearance of the cured product.
Examples of the leveling agent include acrylic leveling agents, silicone leveling agents, fluorine-based leveling agents, etc. These leveling agents may be used alone or in combination of two or more kinds.

The curable polymer composition may further contain particles having an average primary particle size of 0.01 μm or more and 10 μm or less in order to further improve the matte property provided by the uneven layer.
The particles may be organic particles or inorganic particles, or two or more kinds may be used in combination. The inorganic particles may be particles whose surfaces have been modified with a silane coupling agent having a reactive group such as a (meth)acryloyl group.
The surface-modified particles can be obtained, for example, by reacting a silane coupling agent with inorganic particles in the presence of a silane coupling reaction catalyst such as an acid, a base, or aluminum acetylacetonate at 25° C. to 120° C. for about 1 hour to 24 hours.

To the curable polymer composition, a monofunctional (meth)acrylate having one radically polymerizable group per molecule can be added in order to adjust the viscosity or the curing rate with active energy rays.
Examples of the monofunctional (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl acrylate, hexyl acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, benzyl (meth)acrylate, cresol (meth)acrylate, and dicyclopentenyl (meth)acrylate. acrylate, dicyclopentenyloxyethyl (meth)acrylate, phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, 7-amino-3,7-dimethyloctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, ethyl diethylene glycol (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, lauryl (meth)acrylate, polyurethane mono(meth)acrylate, polyepoxy mono(meth)acrylate, polyester mono(meth)acrylate, and the like.

The curable polymer composition may contain a polymerization accelerator such as a compound containing a thiol group, an antistatic agent, a plasticizer, a surfactant, an antioxidant, an ultraviolet absorber, etc., within the scope of the invention.

The content of copolymer (A) in the curable polymer composition is an amount such that the content of active groups derived from copolymer (A) per 100 g of nonvolatile matter of the curable polymer composition is in the range of 0.1 to 20 mmol/100 g, more preferably 0.5 to 15 mmol/100 g, even more preferably 1 to 12 mmol/100 g, and particularly preferably 1.5 to 10 mmol/100 g. When the content of active groups is equal to or greater than the lower limit of the above range, the curability is superior, unevenness can be formed more effectively, and matte properties are superior. When the content is equal to or less than the upper limit, the storage stability of the curable composition is superior.

The ratio of the copolymer (A) to the non-volatile content of the curable polymer composition is preferably in the range of 0.5 to 50 mass%, more preferably 1 to 20 mass%, and even more preferably 1.5 to 5 mass%. When it is equal to or more than the lower limit of the above range, the curability is more excellent. Also, the antifouling property is more excellent. When it is equal to or less than the upper limit, unevenness with excellent matte property is easily formed.
The non-volatile content of the curable polymer composition is the total mass of components other than the organic solvent. The non-volatile content of the curable polymer composition can be measured by a conventionally known method, for example, by measuring the change in weight when 1 g of the composition is spread and heated at 100° C. for 1 hour to volatilize the organic solvent.

The ratio of the polyfunctional compound (B) to the non-volatile content of the curable polymer composition is preferably in the range of 50 to 99.5% by mass, more preferably 70 to 99% by mass, and even more preferably 80 to 98.5% by mass. Within the above range, unevenness with excellent curability and excellent matte properties is easily formed.

From the viewpoint of improving operability in the coating operation, the ratio of the organic solvent to 100 parts by mass of the nonvolatile content of the curable polymer composition is preferably 10 parts by mass or more and 1,900 parts by mass or less, and more preferably 40 parts by mass or more and 400 parts by mass or less.

When the photopolymerization initiator (C) is contained in the curable polymer composition, the ratio of the photopolymerization initiator (C) to the non-volatile content of the curable polymer composition is preferably less than 15% by mass, more preferably less than 10% by mass, and even more preferably less than 5% by mass. If it is equal to or greater than the lower limit of the above range, the curability is more excellent. If it is equal to or less than the upper limit, unevenness with excellent matte properties is easily formed.

<Cured Product>
A cured product of the curable polymer composition can be formed by applying the curable polymer composition onto the surface of a substrate or an article to form a coating film, drying it as necessary, and then irradiating the coating film with active energy rays.
The method for applying the curable polymer composition is not particularly limited, and may be a known method such as dip coating, air knife coating, curtain coating, spin coating, roller coating, bar coating, wire bar coating, gravure coating, or spray coating.

When the curable polymer composition contains an organic solvent, it is preferable to heat-dry the composition before irradiating it with active energy rays. By heating-drying the composition beforehand, the organic solvent in the coating film can be effectively removed. When the copolymer (A) segregates on the surface side of the coating film, removing the organic solvent increases the concentration of the copolymer (A) on the surface side of the coating film, and wrinkle-like unevenness is likely to appear on the surface of the cured product.
The drying temperature of the heat drying is preferably from 30° C. to 200° C., and more preferably from 40° C. to 150° C. The drying time is preferably from 0.01 to 30 minutes, and more preferably from 0.1 to 10 minutes.

Examples of the active energy ray include ultraviolet rays, α rays, β rays, γ rays, etc. Among these, ultraviolet rays are preferred.
The amount of irradiation with active energy rays can be appropriately selected depending on the active energy rays to be irradiated.
When ultraviolet light is used, it is preferable to irradiate so that the cumulative amount of irradiation is 100 mJ/cm ² or more and 3000 mJ/cm ² or less, and more preferably 200 mJ/cm ² or more and 2000 mJ/cm ² or less. The illuminance is preferably 50 mW/cm ² or more and 600 mW/cm ² or less, more preferably 75 mW/cm ² or more and 450 mW/cm ² or less, and even more preferably 100 mW/cm ² or more and 300 mW/cm ² or less. As the light source, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra-high pressure mercury lamp, an electrodeless lamp, a metal halide lamp, or an electron beam by a scanning type or curtain type electron beam acceleration path, a high pressure mercury lamp, an ultra-high pressure mercury lamp, a low pressure mercury lamp, etc. can be used.

The surface of the cured product is an uneven surface (non-smooth surface) having projections and recesses, and therefore the cured product has a matte finish.
The cured product of the curable polymer composition has antifouling properties, and preferably has water repellency and oil repellency.
The cured product of the curable polymer composition is suitable as a coating layer having antifouling properties and matte properties.

The thickness of the cured product (uneven layer) is preferably in the range of 0.1 to 20 μm, more preferably 0.2 to 10 μm, and even more preferably 0.3 to 7 μm. If the thickness of the cured product is within the above range, it is easy to achieve the desired matte properties.
The thickness of the cured product indicates the maximum thickness of the uneven layer, and is determined by observing a cross section with an electron microscope.

The surface roughness of the cured product is preferably 10 nm or more, more preferably 20 to 500 nm, and even more preferably in the range of 50 to 400 nm. If it is equal to or greater than the lower limit of the above range, it will have excellent matte properties, and if it is equal to or less than the upper limit, it will have excellent scratch resistance. The surface roughness is measured by the method described in the examples below.

The haze of the cured product, measured by the method described in the Examples below, is usually 0.5% or more, preferably 1% or more, more preferably 5% or more, even more preferably 10% or more, particularly preferably 20% or more, and most preferably 30% or more, with the upper limit being, for example, 99%. If the haze is equal to or more than the lower limit, the matte property is easily improved.
The 60° gloss (60° specular gloss) of the cured product, measured by the method described in the Examples below, is preferably less than 50, more preferably less than 20. When it is equal to or less than the above upper limit, the matte property is excellent.
The cured product preferably has transparency. The total light transmittance measured by the method described in the Examples below is preferably in the range of 40 to 100%, more preferably 60 to 99%, and even more preferably 80 to 98%. When it is equal to or higher than the lower limit of the above range, the transparency is excellent, and when it is equal to or lower than the upper limit, the matte finish is excellent.

The water contact angle of the cured product is preferably in the range of 100 to 150°, more preferably 102 to 140°, and even more preferably 105 to 130°. When the angle is equal to or greater than the lower limit of the above range, the antifouling properties are excellent, and when the angle is equal to or less than the upper limit, the durability of the antifouling properties is improved. The water contact angle of the cured product is measured by the method described in the examples below.
The hardness of the cured product is preferably a pencil hardness of harder than F, and more preferably harder than 2H, as measured by the method described in the Examples section below.

<Laminate>
The laminate of the present invention (hereinafter also referred to as "the laminate") has a base layer and a layer (uneven layer) made of a cured product of a curable polymer composition. The laminate may further have one or more layers selected from the group consisting of a primer layer provided between the base layer and the uneven layer, and a back functional layer provided on the surface of the base layer opposite the uneven layer. In addition, the laminate may have a surface functional layer provided on the surface of the uneven layer opposite the base layer, as long as it does not impair the effects of the present invention.

1 and 2 are schematic cross-sectional views showing an example of the present laminate. The dimensional ratios in Figs. 1 and 2 are for the convenience of explanation and differ from the actual ones.
The laminate 10 of the example in Figure 1 has a base layer 1, a concave-convex layer 2 provided on one surface 1a of the base layer 1, and a primer layer 3 provided between the base layer 1 and the concave-convex layer 2.
The laminate 10 in the example of Figure 2 has a base layer 1, an uneven layer 2 provided on one surface 1a of the base layer 1, a primer layer 3 provided between the base layer 1 and the uneven layer 2, and a back surface functional layer 5 provided on the surface 1b of the base layer 1 opposite the uneven layer 2.

(Base layer)
The substrate layer may be a known one, for example a resin substrate, a metal substrate, or a paper substrate. Among these, the resin substrate is preferred from the viewpoint of processability.
The resin substrate may be a single layer or a multi-layer structure of two or more layers, and is not particularly limited. It is preferable that the resin substrate is a multi-layer structure of two or more layers, each of which has its own characteristics, and is multifunctional.

As the resin substrate, various resin films (sheets) can be used, such as a polyester film, a poly(meth)acrylate film, a polyolefin film, a polycarbonate film, a polyimide film, a triacetyl cellulose film, a polystyrene film, a polyvinyl chloride film, a polyvinyl alcohol film, and a nylon film.
When the laminate is used for a display, polyester films, poly(meth)acrylate films, polyolefin films, polycarbonate films, polyimide films, and triacetyl cellulose films are preferred. Among these, polyester films, poly(meth)acrylate films, and polyolefin films are preferred for anti-glare applications, and polyester films are more preferred in terms of transparency, formability, and versatility.
The polyester film may be a non-stretched film or a stretched film, and a stretched film is preferable. Among them, a uniaxially stretched film stretched in one direction or a biaxially stretched film stretched in two directions is preferable, and a biaxially stretched film is more preferable from the viewpoint of excellent balance of mechanical properties and flatness.

The polyester constituting the polyester film that can be used as the base layer may be either a homopolyester or a copolymer polyester.
The homopolyester 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. The aromatic dicarboxylic acid and the aliphatic glycol may each be used alone or in combination of two or more kinds.
Examples of the dicarboxylic acid component of the copolymer polyester include isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, oxycarboxylic acid, etc. Examples of the glycol component include ethylene glycol, diethylene glycol, propylene glycol, butanediol, 4-cyclohexanedimethanol, neopentyl glycol, etc. The dicarboxylic acid component and the glycol component may each be used alone or in combination of two or more kinds.
Representative examples of polyester include polyethylene terephthalate and polyethylene naphthalate.

When considering mechanical strength and heat resistance, among the above polyester films, films formed from polyethylene terephthalate and polyethylene naphthalate are more preferable, and when considering ease of production and ease of handling for applications such as surface protection films, films formed from polyethylene terephthalate are more preferable.

The poly(meth)acrylate constituting the poly(meth)acrylate film that can be used as the base layer may be any poly(meth)acrylate having a unit based on (meth)acrylate, and various acrylic resins can be used. Examples of the (meth)acrylate include alkyl (meth)acrylates having an alkyl group with 1 to 4 carbon atoms, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate, and alkyl (meth)acrylates having an alkyl group with a larger number of carbon atoms.
In consideration of transparency, processability, and chemical resistance, the poly(meth)acrylate preferably contains as a main component a unit based on an alkyl(meth)acrylate having an alkyl group having 1 to 4 carbon atoms, more preferably contains as a main component at least one selected from the group consisting of units based on methyl(meth)acrylate and units based on ethyl(meth)acrylate, and particularly preferably contains as a main component a unit based on methyl(meth)acrylate.
It is also possible to impart properties such as flexibility to the poly(meth)acrylate by incorporating units based on (meth)acrylates other than alkyl (meth)acrylates or units based on other monomers.
The proportion of units based on alkyl (meth)acrylate having an alkyl group having 1 to 4 carbon atoms relative to the total mass of the poly(meth)acrylate is preferably 50% by mass or more, more preferably 80% by mass or more.

The base layer may contain particles for the purposes of imparting easy slippage, preventing scratches during each process, and improving blocking resistance.
The type of particles can be appropriately selected according to the purpose, and is not particularly limited. Specific examples include inorganic particles such as silica, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, magnesium phosphate, kaolin, aluminum oxide, zirconium oxide, and titanium oxide, and organic particles such as acrylic resin, styrene resin, urea resin, phenol resin, epoxy resin, and benzoguanamine resin. Furthermore, when the base layer includes a polyester film, precipitated particles obtained by precipitating a part of a metal compound such as a catalyst during the polyester manufacturing process can also be used. Among these, silica particles and calcium carbonate particles are preferred because they are particularly effective in small amounts.
The shape of the particles is not particularly limited, and any of spherical, block, rod-like, flat, etc. is acceptable. In addition, there is no particular limit to the hardness, specific gravity, color, etc.
Two or more kinds of these particles may be used in combination, if necessary.

The average particle size of the particles is preferably 10 μm or less, more preferably 0.01 to 5 μm, and even more preferably 0.01 to 3 μm. If the average particle size is 10 μm or less, problems due to a decrease in the transparency of the base layer are unlikely to occur.
The average particle size of the particles is the cumulative 50% (mass basis) value in the equivalent sphericity distribution measured by a centrifugal sedimentation type particle size distribution measuring device.

When the base layer contains particles, the content of the particles in the base layer cannot be generalized because it depends on the average particle size of the particles, but it is preferably 5% by mass or less, more preferably in the range of 0.0003 to 3% by mass, and even more preferably in the range of 0.0005 to 1% by mass, relative to the total mass of the layer containing the particles in the base layer. If the particle content is 5% by mass or less, problems such as particle dropout and reduced transparency of the base layer are unlikely to occur.

The base layer may contain additives other than the above-mentioned particles as necessary. Examples of additives that can be used include known additives such as ultraviolet absorbers, antioxidants, antistatic agents, heat stabilizers, lubricants, dyes, and pigments.

The thickness of the substrate layer is not particularly limited as long as it is within the range in which a film can be formed, but is preferably in the range of 2 to 350 μm, more preferably 5 to 250 μm, and even more preferably 10 to 100 μm.

(Primer layer)
The primer layer is provided between the base layer and the irregularity layer in order to impart various functions.
Examples of the primer layer include an adhesion improving layer and an antistatic layer.
The primer layer may have multiple functions. For example, the adhesion improving layer may also function as an antistatic layer.

In a preferred embodiment, the primer layer is an adhesion improving layer. If the adhesion between the base layer and the uneven layer is insufficient, the laminate may not be usable for some applications. By having the adhesion improving layer, the adhesion between the base layer and the uneven layer is improved, and the laminate can be used for various applications.
When the primer layer is an adhesion improving layer, the primer layer preferably contains either one or both of a resin and a compound derived from a crosslinking agent from the viewpoint of improving adhesion between the base layer and the uneven layer.

In another preferred embodiment, the primer layer is an antistatic layer. When the primer layer is an antistatic layer, adhesion of dust and the like due to peeling electrification or frictional electrification can be reduced to the outermost surface of the laminate, particularly to the outermost surface on the side where the uneven layer is present relative to the base layer.
In order to make the primer layer an antistatic layer, for example, an antistatic agent may be contained in the primer layer.

As the resin, a conventionally known resin can be used. Specific examples of the resin include polyester resin, acrylic resin, urethane resin, polyvinyl resin (polyvinyl alcohol, vinyl chloride-vinyl acetate copolymer, etc.), etc. Among them, polyester resin, acrylic resin, and urethane resin are preferred in consideration of adhesion performance and coating property.
When the substrate layer is a resin film, the resin of the substrate layer is preferably the same type of resin as the resin of the resin film from the viewpoint of the affinity between the primer layer and the substrate layer. For example, when the substrate layer is a polyester film, the primer layer preferably contains a polyester resin. When the substrate layer is a poly(meth)acrylate film, the primer layer preferably contains an acrylic resin.

The polyester resin may be one whose main components are a polyvalent carboxylic acid and a polyvalent hydroxy compound.
Examples of polyvalent carboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, 4,4'-diphenyldicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2-potassium sulfoterephthalic acid, 5-sodium sulfoisophthalic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, glutaric acid, succinic acid, trimellitic acid, trimesic acid, pyromellitic acid, trimellitic anhydride, phthalic anhydride, trimellitic acid monopotassium salt, and ester-forming derivatives thereof.
Examples of polyhydric hydroxy compounds include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 2-methyl-1,5-pentanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, p-xylylene glycol, bisphenol A-ethylene glycol adduct, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polytetramethylene oxide glycol, dimethylolpropionic acid, glycerin, trimethylolpropane, sodium dimethylolethylsulfonate, and potassium dimethylolpropionate.
One or more of these compounds may be appropriately selected and subjected to a conventional polycondensation reaction to synthesize a polyester resin.

The acrylic resin is a polymer of polymerizable monomers including a (meth)acrylic monomer.
Examples of the acrylic resin include homopolymers and copolymers of (meth)acrylic monomers, and copolymers of (meth)acrylic monomers and polymerizable monomers other than (meth)acrylic monomers.
The acrylic resin may be a copolymer of such a polymer with another polymer (e.g., polyester, polyurethane, etc.). Such a copolymer is, for example, a block copolymer or a graft copolymer. Alternatively, a polymer (or a mixture of polymers, as the case may be) obtained by polymerizing a polymerizable monomer in a solution or dispersion of a polyester is also included. Similarly, a polymer (or a mixture of polymers, as the case may be) obtained by polymerizing a polymerizable monomer in a solution or dispersion of a polyurethane is also included. Similarly, a polymer (or a mixture of polymers, as the case may be) obtained by polymerizing a polymerizable monomer in a solution or dispersion of another polymer is also included.

The above-mentioned polymerizable monomers are not particularly limited, but particularly representative compounds include, for example, carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, and citraconic acid, and their salts; hydroxyl group-containing monomers such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, monobutyl hydroxyl fumarate, and monobutyl hydroxy itaconate; methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethyl Examples include alkyl (meth)acrylates such as hexyl (meth)acrylate and lauryl (meth)acrylate; nitrogen-containing monomers such as (meth)acrylamide, diacetone acrylamide, N-methylol acrylamide and (meth)acrylonitrile; styrene-based compounds such as styrene, α-methylstyrene, divinylbenzene and vinyl toluene; vinyl esters such as vinyl propionate and vinyl acetate; silicon-containing monomers such as γ-methacryloxypropyltrimethoxysilane and vinyltrimethoxysilane; phosphorus-containing vinyl monomers; vinyl halides such as vinyl chloride and vinylidene chloride; and conjugated dienes such as butadiene.

The urethane resin is a polymeric compound having a urethane bond in the molecule, and is typically synthesized by reacting a polyol with a polyisocyanate. A chain extender may be used when synthesizing the urethane resin.
Examples of polyols used to obtain the urethane resin include polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, etc. These compounds may be used alone or in combination of two or more.

Polycarbonate polyols are obtained by reacting polyhydric alcohols with carbonate compounds (dealcoholization reaction). Examples of polyhydric alcohols include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, and 3,3-dimethylolheptane. Examples of carbonate compounds include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, and ethylene carbonate.
Specific examples of polycarbonate polyols include poly(1,6-hexylene) carbonate, poly(3-methyl-1,5-pentylene) carbonate, and the like.

Examples of polyether polyols include polyethylene glycol, polypropylene glycol, polyethylene propylene glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol, etc.

Examples of polyester polyols include those obtained by reacting a polyvalent carboxylic acid or an acid anhydride thereof with a polyhydric alcohol, and those having a derivative unit of a lactone compound such as polycaprolactone.
Examples of the polyvalent carboxylic acid include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, terephthalic acid, and isophthalic acid.
Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 2-methyl-2-propyl-1,3-propanediol, 1 ,8-octanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-butyl-2-hexyl-1,3-propanediol, cyclohexanediol, bishydroxymethylcyclohexane, dimethanolbenzene, bishydroxyethoxybenzene, alkyldialkanolamines, lactonediols, and the like.

As polyols, polyester polyols and polycarbonate polyols are preferred in terms of adhesion performance, with polyester polyols being particularly preferred.

Examples of polyisocyanates used to obtain urethane resins include aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, and tolidine diisocyanate; aliphatic diisocyanates having an aromatic ring such as α,α,α',α'-tetramethyl xylylene diisocyanate; aliphatic diisocyanates such as methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, and hexamethylene diisocyanate; and alicyclic diisocyanates such as cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and isopropylidenedicyclohexyl diisocyanate. These may be used alone or in combination of two or more.

There are no particular limitations on the chain extender as long as it has two or more active groups that react with an isocyanate group, and generally, a chain extender having two hydroxyl groups or two amino groups can be mainly used.
Examples of chain extenders having two hydroxyl groups include glycol compounds such as aliphatic glycols such as ethylene glycol, propylene glycol, and butanediol; aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene; and ester glycols such as neopentyl glycol hydroxypivalate.
Examples of chain extenders having two amino groups include aromatic diamines such as tolylenediamine, xylylenediamine, and diphenylmethanediamine; aliphatic diamines such as ethylenediamine, propylenediamine, hexanediamine, 2,2-dimethyl-1,3-propanediamine, 2-methyl-1,5-pentanediamine, trimethylhexanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,8-octanediamine, 1,9-nonanediamine, and 1,10-decanediamine; and alicyclic diamines such as 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, dicyclohexylmethanediamine, isopropylidincyclohexyl-4,4'-diamine, 1,4-diaminocyclohexane, and 1,3-bisaminomethylcyclohexane.

The urethane resin is typically used in the form of a dispersion or solution. The medium for the dispersion or solution may be a solvent, but is preferably water.
The aqueous dispersion or solution of the urethane resin may be a forced emulsification type using an emulsifier, a self-emulsification type in which a hydrophilic group is introduced into the structure of the urethane resin, or a water-soluble type, etc. In particular, a self-emulsification type in which an ionic group is introduced into the structure of the urethane resin to form an ionomer is preferred, since it has excellent storage stability of the liquid and excellent water resistance and transparency of the resulting primer layer.

Examples of the ionic group to be introduced into the structure of the urethane resin include a carboxyl group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a quaternary ammonium salt group, and the like, with the carboxyl group being preferred.
The carboxyl group is preferably in the form of a salt neutralized with a neutralizing agent such as ammonia, amines, alkali metals, inorganic alkalis, etc. Particularly preferred neutralizing agents are ammonia, trimethylamine, and triethylamine. In the urethane resin having a carboxyl group neutralized with a neutralizing agent, the carboxyl group from which the neutralizing agent is removed in the drying process after application can be used as a crosslinking reaction point with a crosslinking agent. This not only provides excellent stability in the liquid state before coating, but also makes it possible to further improve the durability, solvent resistance, water resistance, blocking resistance, etc. of the obtained primer layer.

Various methods can be used to introduce carboxyl groups into urethane resins at each stage of polymerization reaction. For example, there is a method of using a resin having carboxyl groups as a copolymerization component during prepolymer synthesis, or a method of using a component having carboxyl groups as one component of polyol, polyisocyanate, chain extender, etc. In particular, a method of using a carboxyl group-containing diol and introducing a desired amount of carboxyl groups by the amount of this component is preferred. For example, a carboxyl group-containing diol can be copolymerized with the polyol used in synthesizing the urethane resin.
Examples of the carboxyl group-containing diol include dimethylolpropionic acid, dimethylolbutanoic acid, bis-(2-hydroxyethyl)propionic acid, bis-(2-hydroxyethyl)butanoic acid, and salts of these acids in which the carboxyl group has been neutralized with a neutralizing agent.

The primer layer preferably contains a compound derived from a crosslinking agent in order to make the primer layer stronger and improve performance such as adhesion.
As the crosslinking agent, a known material can be used, for example, a melamine compound, an oxazoline compound, an isocyanate compound, an epoxy compound, a carbodiimide compound, a silane coupling compound, a hydrazide compound, an aziridine compound, etc. are listed. Among them, a melamine compound, an isocyanate compound, an epoxy compound, an oxazoline compound, a carbodiimide compound, and a silane coupling compound are preferred, and from the viewpoint of further improving adhesion and durability, a melamine compound, an oxazoline compound, an isocyanate compound, and an epoxy compound are more preferred, and an oxazoline compound and an isocyanate compound are particularly preferred. These crosslinking agents may be used alone or in combination of two or more. By using two or more types in combination, adhesion and durability may be further improved and become good.

The melamine compound is a compound having a melamine skeleton in the compound, and examples thereof include alkylolated melamine derivatives, compounds obtained by reacting an alkylolated melamine derivative with an alcohol to partially or completely etherify the same, and mixtures thereof. Examples of alcohols used for etherification include methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butanol, isobutanol, and the like. The melamine compound may be either a monomer or a dimer or higher polymer, or a mixture thereof. Furthermore, a product obtained by co-condensing a part of melamine with urea or the like may be used, and a catalyst may be used to increase the reactivity of the melamine compound.
As the melamine compound, those having a hydroxyl group are preferred in consideration of reactivity with various compounds.

The isocyanate compound is a compound having an isocyanate or an isocyanate derivative structure, such as a blocked isocyanate.
Examples of the isocyanate include aromatic isocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate; aliphatic isocyanates having an aromatic ring such as α,α,α',α'-tetramethylxylylene diisocyanate; aliphatic isocyanates such as methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, and hexamethylene diisocyanate; and alicyclic isocyanates such as cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, methylene bis(4-cyclohexyl isocyanate), and isopropylidenedicyclohexyl diisocyanate. Further, polymers and derivatives such as biuretized products, isocyanurate products, uretdione products, and carbodiimide modified products of these isocyanates are also included. These may be used alone or in combination of two or more. Among the above isocyanates, aliphatic isocyanates or alicyclic isocyanates are more preferable than aromatic isocyanates from the viewpoint of avoiding yellowing due to ultraviolet rays.

Examples of the blocked isocyanate include those in which the isocyanate group of the isocyanate compound is blocked with a blocking agent. Examples of the blocking agent include bisulfites, phenolic compounds such as phenol, cresol, and ethylphenol, alcoholic compounds such as propylene glycol monomethyl ether, ethylene glycol, benzyl alcohol, methanol, and ethanol, active methylene compounds such as dimethyl malonate, diethyl malonate, methyl isobutanoyl acetate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone, mercaptan compounds such as butyl mercaptan and dodecyl mercaptan, lactam compounds such as ε-caprolactam and δ-valerolactam, amine compounds such as diphenylaniline, aniline, and ethyleneimine, acid amide compounds such as acetanilide and acetic acid amide, and oxime compounds such as formaldehyde, acetaldoxime, acetoneoxime, methyl ethyl ketoneoxime, and cyclohexanoneoxime. These may be used alone or in combination of two or more.
As the blocked isocyanate, an isocyanate blocked with an active methylene compound is preferred from the viewpoint that the primer layer is less likely to be destroyed.

The isocyanate compound may be used alone or as a mixture or bond with various polymers. In order to improve the dispersibility and crosslinking properties of the isocyanate compound, it is preferable to use a mixture or bond with a polyester resin or a urethane resin.

The oxazoline compound is a compound having an oxazoline group in the molecule.
The oxazoline compound is preferably a polymer containing an oxazoline group. The polymer containing an oxazoline group can be obtained by polymerization of an addition-polymerizable oxazoline group-containing monomer alone or with other monomers.
Examples of the addition-polymerizable oxazoline group-containing monomer include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, and 2-isopropenyl-5-ethyl-2-oxazoline. These may be used alone or in combination of two or more. Among these, 2-isopropenyl-2-oxazoline is preferred because it is easily available industrially.
The other monomer is not particularly limited as long as it is a monomer that is copolymerizable with the addition-polymerizable oxazoline group-containing monomer, and examples thereof include (meth)acrylates such as alkyl (meth)acrylates (the alkyl group is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, a 2-ethylhexyl group, and a cyclohexyl group); unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, styrenesulfonic acid, and salts thereof (sodium salts, potassium salts, ammonium salts, tertiary amine salts, and the like); unsaturated nitriles such as acrylonitrile and methacrylonitrile; (meth)acrylonitrile; Examples of such unsaturated amides include unsaturated amides such as N-alkyl(meth)acrylamides, N,N-dialkyl(meth)acrylamides (alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl, and cyclohexyl groups); vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; α-olefins such as ethylene and propylene; halogen-containing α,β-unsaturated monomers such as vinyl chloride, vinylidene chloride, and vinyl fluoride; and α,β-unsaturated aromatic monomers such as styrene and α-methylstyrene. These may be used alone or in combination of two or more.

The amount of oxazoline groups per 1 g of oxazoline compound is preferably in the range of 0.5 to 10 mmol/g, more preferably 1 to 9 mmol/g, even more preferably 3 to 8 mmol/g, and particularly preferably 4 to 6 mmol/g. If the amount of oxazoline groups is within the above range, the durability of the coating film is improved and the adhesion can be easily adjusted.

An epoxy compound is a compound having an epoxy group in the molecule.
Examples of epoxy compounds include condensates of epichlorohydrin and compounds having a hydroxyl group or an amino group (ethylene glycol, polyethylene glycol, glycerin, polyglycerin, bisphenol A, etc.), and include polyepoxy compounds, diepoxy compounds, monoepoxy compounds, glycidylamine compounds, etc. Examples of polyepoxy compounds include sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, triglycidyl tris(2-hydroxyethyl)isocyanate, glycerol polyglycidyl ether, and trimethylolpropane polyglycidyl ether. Examples of diepoxy compounds include neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, resorcinol diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and polytetramethylene glycol diglycidyl ether. Examples of the monoepoxy compound include allyl glycidyl ether, 2-ethylhexyl glycidyl ether, and phenyl glycidyl ether. Examples of the glycidylamine compound include N,N,N',N'-tetraglycidyl-m-xylylenediamine and 1,3-bis(N,N-diglycidylamino)cyclohexane.

The carbodiimide compound is a compound having one or more carbodiimide structures or carbodiimide derivative structures in the molecule.
As the carbodiimide compound, in order to obtain a better strength of the primer layer, a polycarbodiimide compound having two or more carbodiimide structures or carbodiimide derivative structures in the molecule is more preferable.

Carbodiimide compounds can be synthesized by known techniques, and generally, a condensation reaction of diisocyanate is used. There are no particular limitations on the diisocyanate, and either aromatic or aliphatic diisocyanates can be used. Specific examples include tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexyl diisocyanate, dicyclohexylmethane diisocyanate, etc.

To improve the water solubility and water dispersibility of the polycarbodiimide compound, a surfactant may be added, or a hydrophilic monomer such as a polyalkylene oxide, a quaternary ammonium salt of a dialkylamino alcohol, or a hydroxyalkylsulfonate may be added, as long as the effect of the present invention is not lost.

The silane coupling compound is an organosilicon compound having an organic functional group and a hydrolyzable group such as an alkoxy group in one molecule.
Examples of the silane coupling compound include epoxy group-containing compounds such as 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; vinyl group-containing compounds such as vinyltrimethoxysilane and vinyltriethoxysilane; styryl group-containing compounds such as p-styryltrimethoxysilane and p-styryltriethoxysilane; (meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, and 3-(meth)acryloxypropylmethyldiethoxysilane; (meth)acryloyl group-containing compounds such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane and other amino group-containing compounds; isocyanurate group-containing compounds such as tris(trimethoxysilylpropyl)isocyanurate and tris(triethoxysilylpropyl)isocyanurate; mercapto group-containing compounds such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropylmethyldiethoxysilane.

Among the above-mentioned compounds, the silane coupling compounds are more preferably epoxy group-containing silane coupling compounds, double bond-containing silane coupling compounds such as vinyl groups and (meth)acrylic groups, and amino group-containing silane coupling compounds, from the viewpoint of the strength of the primer layer.

These crosslinking agents react during the drying and film-forming processes, improving the performance of the primer layer. It can be assumed that the crosslinking agent-derived compounds present in the formed primer layer include unreacted crosslinking agents, reacted compounds, or mixtures thereof.

The antistatic agent contained in the primer layer is not particularly limited, and any known antistatic agent can be used. Examples of the antistatic agent include compounds having an ammonium group, polyether compounds, compounds having a sulfonic acid group, betaine compounds, and conductive organic polymers.
As the antistatic agent, a polymer type antistatic agent is preferred because it has good heat resistance and moist heat resistance.

The compound having an ammonium group is a compound having an ammonium group in the molecule, and examples of the compound include ammonium compounds of aliphatic amines, alicyclic amines, and aromatic amines.
The compound having an ammonium group is preferably a polymeric type compound having an ammonium group.
In the compound having a polymer type ammonium group, it is preferable that the ammonium group is incorporated in the main chain or side chain of the polymer, not as a counter ion. Such a compound can be, for example, a polymer compound having an ammonium group, which is obtained by polymerizing an addition polymerizable monomer having an ammonium group or a precursor group of an ammonium group such as an amine, and converting the precursor group of the ammonium group to an ammonium group as necessary. The addition polymerizable monomer containing an ammonium group or a precursor group of an ammonium group may be polymerized alone, or may be copolymerized with two or more kinds, or may be copolymerized with other monomers.

As the compound having an ammonium group, a compound having a pyrrolidinium ring is also preferred in terms of excellent antistatic properties and heat resistance stability.
The two substituents bonded to the nitrogen atom of the compound having a pyrrolidinium ring are each independently an alkyl group, a phenyl group, or the like, and these alkyl groups and phenyl groups may be substituted with the groups shown below. Examples of the substitutable groups are a hydroxyl group, an amide group, an ester group, an alkoxy group, a phenoxy group, a naphthoxy group, a thioalkoxy group, a thiophenoxy group, a cycloalkyl group, a trialkylammonium alkyl group, a cyano group, and a halogen. The two substituents bonded to the nitrogen atom may be chemically bonded, and examples of groups in which two substituents are chemically bonded include -(CH ₂ ) _m - (m = an integer of 2 to 5), -CH(CH ₃ )CH(CH ₃ )-, -CH=CH-CH=CH-, -CH=CH-CH=N-, -CH=CH-N=C-, -CH ₂ OCH ₂ -, -(CH ₂ ) ₂ O(CH ₂ ) ₂ -, and the like.

The compound having a pyrrolidinium ring is preferably a polymer having a pyrrolidinium ring.
The polymer having a pyrrolidinium ring can be obtained, for example, by cyclic polymerization of a diallylamine derivative using a radical polymerization catalyst. A compound having a diallylamine derivative and a polymerizable carbon-carbon unsaturated bond may be used as a copolymerization component. The polymerization can be carried out by a known method using a polymerization initiator such as hydrogen peroxide, benzoyl peroxide, or tertiary butyl peroxide in a polar solvent (water, methanol, ethanol, isopropanol, formamide, dimethylformamide, dioxane, acetonitrile, etc.), but is not limited thereto.

Examples of anions that serve as counter ions to the ammonium group of the above-mentioned ammonium group-containing compounds include halogen ions, sulfonates, phosphates, nitrates, alkylsulfonates, and carboxylates.

The number average molecular weight of the compound having an ammonium group is preferably 1,000 to 500,000, more preferably 2,000 to 350,000, and even more preferably 5,000 to 200,000. If the number average molecular weight is 1,000 or more, the strength and heat resistance stability of the coating film are superior. If the number average molecular weight is 500,000 or less, the viscosity of the coating liquid for forming the primer layer is low, and the handling and coating properties are good.

Examples of polyether compounds include polyethylene oxide, polyether ester amide, and acrylic resins having polyethylene glycol in the side chain.

In the compound having a sulfonic acid group, the sulfonic acid group may be neutralized with a neutralizing agent to form a salt. As the compound having a sulfonic acid group, a compound having multiple sulfonic acid groups in the molecule, such as polystyrene sulfonic acid and its salts, is preferable.

Known materials can be used as the conductive organic polymer, and examples thereof include polythiophenes, polyanilines, polypyrroles, polyacetylenes, polyphenylene sulfides, etc. Among these, polythiophenes (polythiophenes or polythiophene derivatives) are preferred because they combine high transparency and high conductivity, are less likely to be colored, and are easily able to exhibit performance through coating. Among polythiophenes, a compound in which poly(3,4-ethylenedioxythiophene) is combined with polystyrene sulfonic acid is particularly preferred from the viewpoint of conductive performance.
Conductive organic polymers are preferred in that they exhibit high conductivity, are less dependent on humidity, and can be expected to be used in a wide variety of applications.

The primer layer may contain particles to improve blocking and slip properties.
The primer layer may contain additives such as antifoaming agents, coatability improvers, thickeners, organic lubricants, ultraviolet absorbers, antioxidants, foaming agents, dyes, and pigments, as necessary, within the scope of the present invention.

The proportion of resin in 100% by mass of the primer layer is, for example, 5% by mass or more, preferably 10 to 99% by mass, more preferably 20 to 95% by mass, and even more preferably 30 to 90% by mass. If the proportion of resin is within the above range, the adhesion performance and the appearance of the primer layer will be superior.

The proportion of the compound derived from the crosslinking agent in 100% by mass of the primer layer is, for example, 80% by mass or less, preferably 0.5 to 65% by mass, more preferably 3 to 50% by mass, and even more preferably 5 to 40% by mass. If the proportion of the compound derived from the crosslinking agent is within the above range, the adhesion performance and strength of the primer layer will be superior.

When the primer layer is an antistatic layer containing an antistatic agent, the proportion of the antistatic agent in 100% by mass of the primer layer is not generalized as it depends on the type of antistatic agent, but is, for example, 80% by mass or less, preferably 0.5 to 70% by mass, and more preferably 1 to 50% by mass. If the proportion of the antistatic agent is within the above range, it is easy to impart sufficient antistatic function to the primer layer, and it is easy to exhibit antistatic performance even after a roughness layer is formed on the primer layer.

The thickness of the primer layer depends on the material used in the primer layer and the performance to be achieved, so cannot be generally determined, but is preferably in the range of 0.001 to 10 μm, more preferably 0.01 to 4 μm, and even more preferably 0.02 to 1 μm.
The primer layer can be formed by a known method.

(Back functional layer)
The back surface functional layer is provided on the surface of the base layer opposite to the uneven layer side in order to impart various functions.
Examples of the back surface functional layer include an adhesive layer, an antistatic layer, a refractive index adjusting layer, and an antiblocking layer.
The adhesive layer is provided to bond the laminate to various adherends. The antistatic layer is provided to prevent adhesion of surrounding dirt and the like due to peeling electrification or frictional electrification to the outermost surface of the laminate, particularly the outermost surface of the base layer opposite to the uneven layer side, and to prevent defects and the like caused thereby. The refractive index adjustment layer is provided, for example, to improve the total light transmittance of the laminate. The antiblocking layer is provided to reduce blocking of the laminate.

The adhesive for forming the adhesive layer may be a known adhesive, such as an acrylic adhesive, a polyester adhesive, a urethane adhesive, a rubber adhesive, etc. Among these, an acrylic adhesive is preferred in view of versatility.
The antistatic layer and the refractive index adjusting layer are similar to the antistatic layer and the refractive index adjusting layer as the surface functional layer, respectively.

The thickness of the back functional layer depends on the material used in the back functional layer and the performance to be achieved, and cannot be generally determined, but is, for example, 0.001 to 30 μm. When the back functional layer is an adhesive layer, the thickness is preferably 0.01 to 30 μm, more preferably 0.1 to 20 μm. When the back functional layer is an antistatic layer, the thickness is preferably 0.001 to 10 μm, more preferably 0.01 to 5 μm.
The back surface functional layer can be formed by a known method.

The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to the following examples as long as it does not depart from the gist of the present invention.
The measurement and evaluation methods used in the present invention are as follows.

(1) Weight average molecular weight (Mw)
The weight average molecular weight of the copolymer was measured by GPC under the following conditions.
Equipment: Waters "e2695"
Column: "TSKgel Super H3000+H4000+H6000" manufactured by Tosoh Corporation,
Detector: Differential refractive index detector (RI detector/built-in),
Solvent: tetrahydrofuran,
Temperature: 40° C.
Flow rate: 0.5mL/min,
Injection volume: 10 μL,
Concentration: 0.2% by mass,
Calibration sample: monodisperse polystyrene,
Calibration method: polystyrene equivalent.

(2) Total light transmittance and haze A laminate having an uneven layer formed on a PET film was measured. The total light transmittance and haze were measured at a wavelength of 550 nm using a haze meter "SH7000" manufactured by Nippon Denshoku Industries Co., Ltd., in accordance with JIS Z8722Z (geometric conditions of irradiation and reception of a transparent object), JIS K7361-1 (test method for total light transmittance of plastic-transparent materials), and JIS K7136 (method of determining haze of plastic-transparent materials).
The haze of the laminate is the percentage of transmitted light that deviates from the incident light by 0.044 rad (2.5°) or more due to forward scattering, out of the transmitted light that is incident on the outermost surface on the side where the uneven layer is present relative to the base layer and passes through the laminate (the ratio of diffuse transmittance to total light transmittance).

(3) 60° Gloss and Matte Property A laminate having an uneven layer formed on a PET film was used as the measurement subject. The 60° gloss (60° specular gloss) was measured using a gloss meter "VG2000" manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS Z 8741. The lower the 60° gloss value, the better the matte property. The matte property was evaluated according to the following criteria.
The principle of measuring specular gloss is to measure the specular reflected light beam φs from a sample surface at a specified angle of incidence θ (60° for 60° specular gloss).
A: 60° gloss is less than 20.
B: 60° gloss is 20 or more and less than 50.
C: 60° gloss is 50 or more.

(4) Water contact angle (water repellency/stain resistance)
The water contact angle of the uneven layer (liquid volume 2 μL) was measured using a contact angle meter ("Drop Master 500" manufactured by Kyowa Interface Science Co., Ltd.) The larger the water contact angle value, the more excellent the water repellency (antifouling property) was evaluated.

(5) Evaluation of pen writability (oil repellency and stain resistance) After writing on the uneven layer with a black oil-based marker "Mackie Fine" manufactured by Zebra Corporation, the layer was visually observed, and a rating of A was given if the ink was repelled, and a rating of B if the ink was not repelled. Note that a layer that repels ink is rated as having excellent oil repellency (stain resistance).

(6) Pencil hardness The pencil hardness of the uneven layer was measured according to JIS K5600-5-4 General test methods for paints - Part 5: Mechanical properties of coatings - Section 4: Scratch hardness (pencil method). It was evaluated according to the following criteria.
A: 2 hours or more.
B: F to H.
C: Below HB.

(7) Flexibility A laminate having a concave-convex layer formed on a PET film was used as the measurement subject. In accordance with JIS K5600-5-1 (General test method for coating materials - Part 5: Mechanical properties of coating film), the flexibility of the concave-convex layer was confirmed by a mandrel test. Specifically, the laminate was wrapped around a mandrel so that the concave-convex layer was on the mandrel side, and the state of the cured layer was visually observed. Evaluation was performed while decreasing the diameter of the mandrel as follows, and the minimum diameter of the mandrel at which no cracks were generated in the concave-convex layer was obtained. The smaller the minimum diameter, the better the flexibility. Evaluation was performed according to the following criteria.
Mandrel diameter: 32mm, 25mm, 16mm, 12mm, 10mm, 8mm, 6mm, 5mm, 4mm, 3mm, 2mm.
A: The minimum diameter is less than 3 mm.
B: The minimum diameter is 3 mm or more and less than 5 mm.
C: Minimum diameter is 5 mm or more.

(8) Leveling Ability The surface of the uneven layer (10 cm x 10 cm) was visually observed to check the number of repelling and bump defects. The leveling ability was evaluated according to the following criteria.
A: The total number of repelling and bump defects is less than 10.
B: The total number of repelling and bump defects is 10 or more.

(9) Surface Roughness Using a surface profile measurement system (Hitachi High-Tech Science Corporation's "Vert Scan" (registered trademark) VS1330), the surface profile of the uneven layer was measured by optical interference over an area of 703.12 μm × 937.42 μm, and the data was read after interpolation and baseline correction. The magnification of the objective lens during the measurement was set to 5 times.

A copolymer was produced according to the composition shown in Table 1. The monomers in the table are as follows:
<Monomer (x)>
x-1: 4-methacryloyloxybenzophenone.
x-2: 2- [4-(2-hydroxy-2-methyl-1-oxopropyl)phenoxy]ethyl methacrylate obtained in Synthesis Example 1 below.
<Monomer (r)>
r-1: Stearyl methacrylate.
r-2: 2-ethylhexyl methacrylate.
<Monomer (f)>
f-1: 1H,1H,2H,2H-tridecafluorooctyl acrylate ("Viscoat 13F" manufactured by Osaka Organic Chemical Industry Ltd.).
<Monomer (h)>
h-1: 2-hydroxyethyl methacrylate.
h-2: Diethylaminoethyl methacrylate.

(Synthesis Example 1: Synthesis of Monomer (x-2))
Methacrylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was distilled under reduced pressure, and a fraction with a purity of 99.8% or more was collected to obtain a distillate of methacrylic anhydride. The reduced pressure distillation was carried out by gradually increasing the temperature from room temperature to 90° C. at a pressure of 30 Pa.
Separately, 22.4 g (0.1 mol) of 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-methylpropanone (manufactured by Tokyo Chemical Industry Co., Ltd.) and 30.4 g (0.3 mol) of triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 500 mL of methylene chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) to which 23.1 g (0.15 mol) of the above-mentioned distillate of methacrylic anhydride was added dropwise at room temperature and stirred for 12 hours.
The reaction solution was washed three times with 500 mL of ion-exchanged water, and then the organic phase was concentrated to remove the solvent. The residue was purified by column chromatography (ethyl acetate/hexane = 10/90 (volume ratio)) to obtain 21.6 g of the target compound (yield 74%).
¹ H-NMR analysis confirmed that the resulting compound was 2-[4-(2-hydroxy-2-methyl-1-oxopropyl)phenoxy]ethyl methacrylate.
^1H NMR (300MHz, chloroform-d): δ8.06 (d, J = 9.0Hz, 2H), 6.96 (d, J = 9.0Hz, 2H), 6.13 (d, J = 0.6Hz, 1H), 5.59 (s, 1H), 4.50 (d, J = 5.1H) z, 2H), 4.29 (dd, J=5.5, 4.1Hz, 3H), 1.94 (dd, J=1.6, 1.0Hz, 3H), 1.61 (s, 6H).

(Production Example 1: Production of Copolymer (A-1))
In a flask equipped with a stirrer, a cooling tube and a thermometer, 70 parts of methyl isobutyl ketone (hereinafter referred to as MIBK) was placed, and then the flask was replaced with nitrogen and heated to 65 ° C., and a mixed solution of 40 parts by mass of monomer (x-2), 10 parts by mass of monomer (r-1), 20 parts by mass of monomer (r-2), 30 parts by mass of monomer (f-1), 3 parts by mass of 1-dodecanethiol as a chain transfer agent, 1 part by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator, and 78 parts by mass of MIBK was dropped over 2 hours. After another 2 hours, in order to increase the polymerization rate, a mixed solution of 0.5 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 0.6 parts by mass of MIBK was added and held for 5 hours. Thereafter, the reaction solution was cooled to 40 ° C. to obtain a copolymer MIBK solution (A-1). Hereinafter, the solid content in the solution (A-1) will be referred to as copolymer (A-1).
The solid content (non-volatile content) of the solution (A-1) was 40% by mass. The weight average molecular weight (Mw) of the copolymer (A-1) and the content of active groups per gram of the copolymer (A-1) are shown in Table 1.

(Production Example 2: Production of Polymer (H-1))
An MIBK solution (H-1) of a copolymer was obtained under the same conditions as in Production Example 1, except that the composition of the mixed solution in Production Example 1 was changed to 40 parts by mass of monomer (x-1), 10 parts by mass of monomer (r-1), 30 parts by mass of monomer (r-2), 10 parts by mass of monomer (h-1), 10 parts by mass of monomer (h-2), 0.8 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) as a polymerization initiator, and 78 parts by mass of MIBK. Hereinafter, the solid content in solution (H-1) is referred to as copolymer (H-1).
The solid content (non-volatile content) of the solution (H-1) was 40% by mass. The weight average molecular weight (Mw) of the copolymer (H-1) and the content of active groups per gram of the copolymer (H-1) are shown in Table 1.

(Example 1, Reference Example 1, Comparative Example 1: Production of Coating Liquid (Curable Polymer Composition))
The materials shown in Table 2 were mixed to obtain the ratio (parts by mass) calculated as the nonvolatile content shown in Table 2. Then, a mixed solvent of propylene glycol monomethyl ether (hereinafter, PGM) and methyl ethyl ketone (hereinafter, MEK) (PGM:MEK (mass ratio) 7:3) was added so that the solid content concentration became 40 mass%, and the mixture was stirred until it became uniform, thereby obtaining a coating liquid (curable polymer composition).
Table 2 shows the content of active groups per 100 g of the nonvolatile matter of the curable polymer composition in the coating liquid.

The materials in Table 2 are as follows:
A-1: MIBK solution of the copolymer (A-1) obtained in Production Example 1.
H-1: MIBK solution of the copolymer (H-1) obtained in Production Example 2.
B-1: A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate ("KAYARAD DPHA" manufactured by Nippon Kayaku Co., Ltd.).
B-2: Pentaerythritol triacrylate ("Viscoat V#300" manufactured by Osaka Organic Chemical Industry Co., Ltd.).
C-1: Benzophenone.

The obtained coating liquid was applied to a 50 μm-thick PET film ("T602E50" manufactured by Mitsubishi Chemical Corporation) using a bar coater No. 8, dried for 60 seconds in a hot air dryer heated to 70° C. to volatilize the solvent, and irradiated with ultraviolet light from a high-pressure mercury lamp in an air atmosphere at an integrated light quantity of 250 mJ/cm ² and an illuminance of 100 mW/cm ² to form a 2.5 μm-thick uneven layer (cured product). This resulted in a laminate in which a layer made of the cured product was laminated on a substrate layer made of a PET film.
The UV conveyor of an Eye Graphics high-output UV device (model: US5-X1802-X1202) was used for UV irradiation. The integrated light amount was measured using an illuminometer (Eye UV integrated illuminometer "UVPF-A1" and "PD-365") manufactured by Iwasaki Electric Co., Ltd., measuring the integrated light amount at wavelengths of 300 to 390 nm.
The obtained laminate was measured or evaluated by the above-mentioned methods for the items shown in Table 2. The results are shown in Table 2.

As shown in the results in Table 2, Example 1 containing the polymer (A-1) has a concave-convex layer and has a matte finish. The concave-convex layer has excellent transparency, antifouling properties, and hardness.
On the other hand, the uneven layer of Reference Example 1, in which the polymer (H-1) was used instead of the polymer (A-1), had almost the same transparency, hardness, and matte property as Example 1, but did not obtain antifouling properties.
In addition, the layer made of the cured product of Comparative Example 1, in which a general photopolymerization initiator (non-polymer having an active group) (C-1) was used instead of the polymer (A-1), had almost the same transparency and hardness as those of Example 1, but the surface was almost smooth and did not provide matte properties or antifouling properties.

Reference Signs List 1: Base material layer 2: Irregular layer 3: Primer layer 5: Back surface functional layer 10: Laminate

Claims (7)

a unit based on a monomer (x) which is a (meth)acrylic acid ester having an active group that generates radicals when irradiated with active energy rays;
units based on monomer (f) which is a (meth)acrylic acid ester having a perfluoroalkyl group having 3 or more carbon atoms ;
a copolymer having a unit based on a monomer (r) which is an alkyl (meth)acrylate having an alkyl group of 6 to 18 carbon atoms, the alkyl group including a linear alkyl group having 4 or more carbon atoms ,
A copolymer, wherein the content of units based on the monomer (x) is 30 to 60 mass%, the content of units based on the monomer (f) is 10 to 60 mass%, and the content of units based on the monomer (r) is 1 to 70 mass%, relative to the total mass of all units constituting the copolymer. The copolymer according to claim 1, wherein the active group is at least one selected from the group consisting of a benzophenone group, an acetophenone group, a benzoin group, an α-hydroxyketone group, an α-aminoketone group, an α-diketone group, an α-diketone dialkyl acetal group, an anthraquinone group, a thioxanthone group, and a phosphine oxide group. The copolymer according to claim 1 or 2, wherein the content of the active group per 1 g of the copolymer is 0.1 to 3.5 mmol/g. A curable polymer composition comprising the copolymer (A) according to any one of claims 1 to 3 , and a polyfunctional compound (B) having two or more radically polymerizable groups in one molecule. The curable polymer composition according to claim 4 , wherein the content of the copolymer (A) is 0.5 to 50 mass % based on the non-volatile content of the curable polymer composition. A cured product of the curable polymer composition according to claim 4 or 5 . A laminate comprising a substrate layer and a layer made of the cured product according to claim 6 .

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