JP2023024507A - Copolymer, curable polymer composition, cured product, and laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable polymer composition that can give a cured product a matte tone and anti-fouling properties.

SOLUTION: A curable polymer composition has a copolymer (A) having a unit based on a monomer (x) having an active group to generate a radical by irradiation with active energy rays and a unit based on a monomer (f) having a fluorine atom or a silicon atom, and a polyfunctional compound (B) having two or more radical-polymerizable groups in one molecule.

SELECTED DRAWING: None

COPYRIGHT: (C)2023,JPO&INPIT

Description

TECHNICAL FIELD 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 comprising the cured product.

BACKGROUND ART In order to impart a matte property and the like to construction materials such as wallpaper, members for displays, decorative films, etc., the surface of a base material may be provided with fine unevenness. In addition, these members are sometimes required to have antifouling properties.
In Patent Document 1, decorative sheets for building materials, various parts of home electric appliances such as refrigerators and washing machines, various parts of OA products such as personal computers, and film for transfer foil when manufacturing packaging containers by molding are subjected to hairline processing. , sandblasting, satin finishing, and the like are disclosed.
Patent Document 2 discloses a method of dispersing acrylic particles in a resin binder as a method of forming unevenness on the surface of a light diffusion film used in a backlight unit of a liquid crystal display.

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

However, the unevenness forming method described in Patent Document 1 cannot provide a sufficient matting effect. Also, in sandblasting, sand left in the film can cause quality problems. Since the surface is still polished, it is difficult to impart antifouling properties.
Further, in the method described in Patent Document 2, the acrylic particles fall off during use, which may hinder the visibility of the display.
To solve these problems, the present invention provides a polymer capable of imparting matting properties and antifouling properties to a cured product, a curable polymer composition containing the polymer, and a cured product of the curable polymer composition. and a layer comprising the cured product.

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

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

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic cross section which shows an example of the laminated body of this invention. FIG. 3 is a schematic cross-sectional view showing another example of the laminate of the present invention;

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail.
In the present invention, "(meth)acrylate" is a generic term for acrylate or methacrylate. "(Meth)acryl" is a generic term for acryl and methacryl.
"~" indicating a numerical range means that the numerical values before and after it are included as lower and upper limits.

<Curable polymer composition>
The curable polymer composition comprises units based on a monomer (x) having an active group that generates radicals upon exposure to active energy rays (hereinafter also simply referred to as an active group), and a monomer having a fluorine atom or a silicon atom ( It includes a copolymer (A) having units based on f) and a polyfunctional compound (B) having two or more radically polymerizable groups per molecule.
When the curable polymer composition is irradiated with an active energy ray, radicals are generated from the active groups of the copolymer (A), and the generated radicals are used as starting points to cause a reaction between the radically polymerizable groups of the polyfunctional compound (B). progresses and the entire curable polymer composition is cured. For example, when a coating film of a curable polymer composition is formed and this coating film is irradiated with active energy rays, the surface side of the coating film is first cured to form a cured film. After that, when the inside of the coating film is cured, the cured coating film on the surface side buckles to form a cured product having wrinkle-like unevenness on the surface (hereinafter also referred to as “uneven layer”). When the surface of the cured product becomes uneven, functions such as matte properties can be obtained. A method for forming the uneven layer will be described later in detail.
The curable polymeric composition can further contain an organic solvent, if desired.
The curable polymer composition can further contain other components than those mentioned above, if necessary.

<Copolymer (A)>
[monomer (x)]
Examples of the monomer (x) include compounds having an active group and a radically polymerizable group.
Any active group may be used as long as it has a structure that generates radicals upon irradiation with active energy rays (a structure having photopolymerization initiation properties). As the structure having photopolymerization initiation properties, various known structures can be employed, and examples thereof include a hydrogen abstraction type, an electron transfer type, and an intramolecular cleavage type.
Specific examples of active groups include a benzophenone group, an acetophenone group, a benzoin group, an α-hydroxyketone group (for example, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-methylpropanone “2 -group obtained by removing one hydrogen atom from "hydroxyl group in hydroxyethoxy"), α-aminoketone group, α-diketone group, α-diketone dialkylacetal group, anthraquinone group, thioxanthone group, phosphine oxide group, and the like. Among these, a benzophenone group, an acetophenone group, and an α-hydroxyketone group are preferable because they are less susceptible to oxygen inhibition during curing and have good surface curability when forming an uneven layer.

The radically polymerizable group of the monomer (x) includes a functional group containing a radically polymerizable unsaturated bond (carbon-carbon double bond, etc.), and specific examples thereof include a (meth)acryloyl group and a vinyl group. be done.
As the monomer having an active group, a (meth)acrylic acid ester having an active group is preferable from the viewpoint of ease of synthesis of the polymer (A) and ease of adjustment of the introduction amount of the active group.
Monomers having active groups include, for example, 4-methacryloyloxybenzophenone and 2-[4-(2-hydroxy-2-methyl-1-oxopropyl)phenoxy]ethyl methacrylate.

[Monomer (f)]
Examples of the monomer (f) include compounds having a fluorine atom or silicon atom and a radically polymerizable group. The radically polymerizable group is the same as described above.
The unit based on the monomer (f) imparts at least one of water repellency and oil repellency to the cured product and contributes to the antifouling property of the cured product.
Further, if the copolymer (A) has 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 on 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 the surface of the cured product can be efficiently imparted with antifouling properties.

In addition, the segregation of the copolymer (A) on the surface side of the coating film increases the concentration of the active groups on the surface side of the coating film, and when the active energy ray is irradiated, the surface side of the coating film cures first. A cured film is then formed, after which the inside of the coating film is cured. When the inside of the coating film is cured, the cured film on the surface is buckled to develop wrinkle-like unevenness.
At this time, there is a tendency that the shorter the curing time inside the coating film, the shorter the period of irregularities on the surface of the uneven layer, and the longer the curing time, the larger the period of irregularities on the surface of the uneven layer. This curing time can be adjusted by the amount of radically polymerizable groups in the curable polymer composition, the amount of active groups (the amount of the copolymer (A) and the photopolymerization initiator), the amount of active energy ray irradiation, and the like. .
Furthermore, if the copolymer (A) segregates on the surface side of the coating film, the curing reaction inside the coating film (on the substrate layer side) is less likely to be inhibited by oxygen, and curing can be performed with a low exposure dose. , even thin films that tend to be susceptible to oxygen inhibition can be cured successfully.

The monomer (f) preferably contains one or more selected from the group consisting of compounds having a fluoroalkyl group and a radically polymerizable group and compounds having a polydimethylsiloxane chain and a radically polymerizable group.
More preferably, the monomer (f) contains one or more 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.

A (meth)acrylic acid ester containing a fluorine atom is more preferably a (meth)acrylic acid ester having a perfluoroalkyl group. The perfluoroalkyl group preferably has 3 or more carbon atoms. (Meth)acrylic esters containing a fluorine atom include, for example, 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 (Osaka Organic Chemical Industrial Co., Ltd., Viscoat 8FM), 1H, 1H, 2H, 2H-tridecafluorooctyl acrylate (Osaka Organic Chemical Industry Co., Ltd., Viscoat 13F), 1H, 1H, 2H, 2H-nonafluorohexyl acrylate (Unimatec Co., Ltd. Company, CHEMINOX FAAC-4), 1H, 1H, 2H, 2H-nonafluorohexyl methacrylate (UNIMATEC Co., CHEMINOX FAMAC-4), 1H, 1H, 2H, 2H-tridecafluorooctyl methacrylate (Unimatec Co., Ltd. , CHEMINOX FAMAC-6) are commercially available.
Specific examples of (meth)acrylic acid esters having a polydimethylsiloxane chain include polydimethylsiloxane having a molecular weight of 500 to 50,000 and having a (meth)acryloyl group substituted on one end. The molecular weight is preferably 1,000 to 30,000, more preferably 1,500 to 20,000. (Meth) acrylic acid esters having a polydimethylsiloxane chain, for example, "FM-0711", "FM-0721", "FM-0725" (all manufactured by JNC Co., Ltd.) and "X-24-8201". , “X-22-174DX” and “X-22-2426” (both from Shin-Etsu Chemical Co., Ltd.) are commercially available.

[Monomer (r)]
From the viewpoint of more effectively segregating the copolymer (A) on the surface of the coating film, the copolymer (A) has a number of carbon atoms in addition to units based on the monomer (x) and units based on the monomer (f). It is preferred to have one or more units based on monomers (r) having 4 or more alkyl groups.

The alkyl group having 4 or more carbon atoms may be linear, branched or cyclic. Cyclic alkyl groups 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, from the viewpoint of more effectively segregating the copolymer (A) on the surface of the coating film. It is more preferably in the range of 12-18.

Examples of the monomer (r) include compounds having an alkyl group having 4 or more carbon atoms and a radically polymerizable group, and ease of synthesis of the compound and ease of adjustment of the introduction amount of the alkyl group having 4 or more carbon atoms. from the viewpoint of (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, ) acrylate, decyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)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 ) acrylate, adamantyl (meth)acrylate and the like.
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 straight-chain alkyl group having 4 or more carbon atoms, those in which the number of carbon atoms in the alkyl group is within the preferred range described above are preferable. - Ethylhexyl (meth)acrylate, octyl (meth)acrylate, dodecyl (meth)acrylate, and stearyl (meth)acrylate are more preferred, and stearyl (meth)acrylate is particularly preferred.
These (meth)acrylic acid esters may be used alone or in combination of two or more.

[Monomer (h)]
The copolymer (A) may, if necessary, further have units based on the monomer (h) having a hydrogen-donating functional group.
In particular, when the monomer (x) has a hydrogen abstraction type active group, it preferably contains units based on the monomer (h). When the polymer (A) has this unit, it is possible to effectively cure the coating film of the curable polymer composition from the surface thereof, thereby facilitating the formation of irregularities.
Hydrogen-donating functional groups include a hydroxyl group, an amino group, a mercapto group, an amide group, and the like. Among these, a hydroxyl group, an amino group, or an amide group is preferable from the viewpoint that the curing reaction can proceed particularly efficiently and unevenness can be easily formed.

Examples of the monomer having a hydrogen-donating functional group include compounds having a hydrogen-donating functional group and a radically polymerizable group, and ease of synthesis of the compound and ease of adjustment of the introduction amount of the hydrogen-donating functional group. (Meth)acrylic acid esters and (meth)acrylamides having a hydrogen-donating functional group are preferable.
Monomers having a hydrogen-donating functional group include, for example, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8 - hydroxyl group-containing monomers such as hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, monobutylhydroxyl fumarate, monobutylhydroxyitaconate; N,N-dimethyl ( meth)acrylamide, N,N-diethyl (meth)acrylamide, N-vinylcaprolactam, N-vinylpyrrolidone, N-isopropyl (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-dimethyl aminopropyl (meth)acrylate, N,N-diethylaminopropyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylamide, (meth)acryloylmorpholine, vinylacetamide, etc. and amino group- or amide group-containing monomers. 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 preferable, and N,N-diethylaminoethyl (meth)acrylate is more preferable in that unevenness is easily increased. These compounds may be used singly or in combination of two or more.

The copolymer (A) may further have units based on monomers other than those described above, if necessary. Other monomers include, for example, compounds having a radically polymerizable group and not having an active group, an alkyl group having 4 or more carbon atoms, a fluorine atom, a silicon atom and a hydrogen-donating functional group.
Other monomers include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, citraconic acid, and salts thereof; methyl (meth) acrylate, ethyl (meth) acrylate. , (meth)acrylates such as propyl (meth)acrylate; nitrogen-containing monomers such as (meth)acrylonitrile; styrene compounds such as styrene, α-methylstyrene, divinylbenzene, and vinyltoluene; vinyls such as vinyl propionate and vinyl acetate esters; phosphorus-containing vinyl-based monomers; vinyl halides such as vinyl chloride and pyridene chloride; and conjugated dienes such as butadiene.

The active group may be present at the end of the main chain of the copolymer (A), or may be present in units based on the monomers constituting the copolymer (A).
Copolymer (A) preferably has a plurality of active groups in the molecule. As a result, the concentration of active groups in the vicinity of the surface of the coating film can be increased, and unevenness such as a wrinkle-like structure can be easily developed on the surface after curing.
The content of active groups per gram of the copolymer (A) is preferably 0.1 to 3.5 mmol/g, more preferably 0.5 to 2.5 mmol/g, still more preferably 0.8 to 2 .0 mmol/g. When the content of the active group is at least the lower limit of the above range, the curability is more excellent, and unevenness can be formed more effectively. Storage stability of a curable composition is more excellent in it being below an upper limit.

The ratio of units based on the monomer (x) to the total mass of all units constituting the copolymer (A) is preferably 1 to 90% by mass, more preferably 10 to 80% by mass, and still more preferably 20 to 70%. % by weight, particularly preferably in the range from 30 to 60% by weight. When the ratio of the units based on the monomer (x) is at least the lower limit of the above range, the curability is more excellent, and unevenness can be formed more effectively. Storage stability of a curable composition is more excellent in it being below an upper limit.

The ratio of the units based on the monomer (f) to the total mass of all units constituting the copolymer (A) is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, and still more preferably 15 to 50%. It is in the range of % by mass. If the proportion of units based on the monomer (f) is at least the lower limit of the above range, unevenness can be formed more effectively. In addition, the antifouling property of the cured product is more excellent. When it is at most the upper limit, the compatibility between the copolymer (A) and the polyfunctional compound (B) is excellent.

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

The ratio of units based on the monomer (h) to the total mass of all units constituting the copolymer (A) is preferably 80% by mass or less, more preferably 1 to 60% by mass, and still more preferably 3 to 50% by mass. %, particularly preferably in the range from 5 to 40% by weight. If the ratio of units based on the 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, still more preferably 3,000 to 60,000. . When Mw is at least the lower limit of the above range, unevenness can be formed more effectively. When it is at most the upper limit, the coatability of the curable polymer composition is more excellent.
The Mw of the copolymer (A) is a standard polystyrene-equivalent value measured by gel permeation chromatography (GPC). Detailed measurement conditions are as described in the examples below.

The glass transition temperature (Tg) of the copolymer (A) is preferably -30 to 180°C, more preferably 0 to 150°C, still more preferably 25 to 100°C. When Tg is at least the lower limit of the above range, unevenness can be formed more effectively, and the matting property is more excellent. When it is at most the upper limit, the compatibility between the copolymer (A) and the polyfunctional compound (B) is excellent.

Copolymer (A) is obtained, for example, by polymerizing a monomer component containing monomer (x) and monomer (f). The monomer component may further contain any one or more of the monomer (r), the monomer (h) and other monomers, if necessary.
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 them, solution polymerization is preferable in terms of simple operation and high productivity.

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

The bifunctional polyfunctional (meth)acrylates are not particularly limited, and examples include 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, (Meth)acrylate, alkanediol di(meth)acrylate such as 1,9-nonanediol di(meth)acrylate, tricyclodecanedimethylol di(meth)acrylate, bisphenol A ethylene oxide-modified di(meth)acrylate, bisphenol F Bisphenol-modified di(meth)acrylates such as ethylene oxide-modified di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, urethane di(meth)acrylate, epoxy di(meth)acrylate and the like can be mentioned.

Trifunctional or higher polyfunctional (meth)acrylates are not particularly limited, but for example, dipentaerythritol hexa(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, penta isocyanuric acid-modified tri(meth)acrylates such as erythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, isocyanuric acid ethylene oxide-modified 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>
An organic solvent is used as necessary for the purpose of improving the workability when applying the curable polymer composition onto a substrate.
Organic solvents include aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone; diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and diethylene glycol dimethyl ether. Ether solvents such as , diethylene glycol diethyl ether, propylene glycol monomethyl ether, anisole, and phenetol; Ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate, and ethylene glycol diacetate; Dimethylformamide, diethylformamide, N-methylpyrrolidone, etc. amide solvents; cellosolve solvents such as methyl cellosolve, ethyl cellosolve and butyl cellosolve; alcohol solvents such as methanol, ethanol, propanol, isopropanol and butanol; halogen solvents such as dichloromethane and chloroform; 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 because they tend to improve workability in coating.

<Photoinitiator (C)>
The curable polymer composition may further contain one or more photopolymerization initiators (excluding copolymer (A)).
For example, a photopolymerization initiator (C) that is a non-polymer having an active group that generates a radical upon irradiation with an active energy ray can be used. 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, benzyldiphenyl disulfide, dibenzyl, diacetyl, anthraquinone, naphthoquinone, 3,3′-dimethyl-4- Methoxybenzophenone, benzophenone, p,p'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, pivaloin ethyl ether, benzyldimethylketal, 1,1-dichloroacetophenone, pt-butyl dichloroacetophenone, 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, tribromophenylsulfone, tribromomethylphenylsulfone and the like. 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 leveling agents include acrylic leveling agents, silicone leveling agents, and fluorine leveling agents. These leveling agents may be used alone or in combination of two or more.

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 matting property of the uneven layer.
The particles may be organic particles or inorganic particles, and two or more of them may be used in combination. The inorganic particles may be particles surface-modified with a silane coupling agent having a reactive group such as a (meth)acryloyl group.
For surface-modified particles, for example, a silane coupling agent and inorganic particles are reacted at 25° C. to 120° C. for about 1 hour to 24 hours in the presence of an acid, a base, or a silane coupling reaction catalyst such as aluminum acetylacetonate. obtained by the method.

A curable polymer composition can be added with a monofunctional (meth)acrylate having one radically polymerizable group in one molecule for adjustment of viscosity and adjustment of curing speed by active energy rays.
The monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl acrylate, hexyl acrylate, heptyl (meth)acrylate, and octyl (meth)acrylate. acrylates, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, benzyl (meth) acrylate, cresol (meth) acrylate, di Cyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, 7-amino-3,7-dimethyloctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate ) 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 ) acrylates and the like.

The curable polymer composition contains 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 a range that does not impair the effects of the present invention. may contain.

The content of the copolymer (A) in the curable polymer composition is such that the content of active groups derived from the copolymer (A) per 100 g of the non-volatile content of the curable polymer composition is 0.1 to 20 mmol/100 g, more preferably 0.5 to 15 mmol/100 g, still more preferably 1 to 12 mmol/100 g, particularly preferably 1.5 to 10 mmol/100 g. When the content of the active group is at least the lower limit of the above range, the curability is more excellent, the unevenness can be formed more effectively, and the matting property is more excellent. The storage stability of a curable composition is excellent in it being below an upper limit.

The ratio of the copolymer (A) to the nonvolatile content of the curable polymer composition is preferably 0.5 to 50% by mass, more preferably 1 to 20% by mass, and still more preferably 1.5 to 5% by mass. Range. Curability is more excellent as it is more than the lower limit of the said range. Moreover, antifouling property is more excellent. When it is at most the upper limit, unevenness with excellent mattness is likely to be 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. measured by the change in thickness.

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

The ratio of the organic solvent to 100 parts by mass of the non-volatile content of the curable polymer composition is preferably 10 parts by mass or more and 1900 parts by mass or less, and preferably 40 parts by mass or more and 400 parts by mass or less, from the viewpoint of improving the operability in the coating operation. more preferred.

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, and 10% by mass. Less than is more preferable, and less than 5% by mass is even more preferable. Curability will be more excellent in it being more than the lower limit of the said range. When it is at most the upper limit, unevenness with excellent mattness is likely to be formed.

<Cured product>
The cured product of the curable polymer composition is obtained by coating the curable polymer composition on the surface of a substrate or an article to form a coating film, drying if necessary, and applying active energy rays to the coating film. It can be formed by irradiation.
The method of applying the curable polymer composition is not particularly limited. For example, it can be applied by known methods such as dip coating, air knife coating, curtain coating, spin coating, roller coating, bar coating, wire bar coating, gravure coating, and spray coating.

When the curable polymer composition contains an organic solvent, it is preferable to heat and dry in advance before irradiating the active energy ray. By drying by heating in advance, 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, causing wrinkles on the surface of the cured product. unevenness is likely to occur.
The drying temperature of heat drying is preferably 30° C. or higher and 200° C. or lower, more preferably 40° C. or higher and 150° C. or lower. The drying time is preferably 0.01 to 30 minutes, more preferably 0.1 to 10 minutes.

Examples of active energy rays include ultraviolet rays, α rays, β rays, γ rays, and the like. Among them, ultraviolet rays are preferable.
The irradiation amount of the active energy ray can be appropriately selected according to the active energy ray to be irradiated.
When ultraviolet rays are used, irradiation is preferably carried out so that the cumulative amount of irradiation is 100 mJ/cm ² or more and 3000 mJ/cm ² or less, 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, medium-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, electrodeless lamp, metal halide lamp, or high-pressure mercury lamp, ultra-high-pressure mercury lamp, low-pressure mercury lamp, etc., such as an electron beam using a scanning or curtain-type electron beam acceleration path shall be used. can be done.

The surface of the cured product is an uneven surface (non-smooth surface) having unevenness. Thereby, the cured product has a matting property.
A cured product of the curable polymer composition has antifouling properties. It preferably has water repellency and oil repellency.
A cured product of the curable polymer composition is suitable as a coating layer having antifouling properties and matting properties.

The thickness of the cured product (uneven layer) is preferably 0.1 to 20 μm, more preferably 0.2 to 10 μm, still 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 mattness.
The thickness of the cured product indicates the maximum thickness of the concavo-convex layer, and is obtained by cross-sectional observation with an electron microscope.

The surface roughness of the cured product is preferably 10 nm or more, more preferably 20 to 500 nm, still more preferably 50 to 400 nm. When it is at least the lower limit of the above range, the matting property is excellent, and when it is at most the upper limit, the scratch resistance is excellent. The surface roughness is measured by the method described in Examples below.

The cured product has a haze of usually 0.5% or more, preferably 1% or more, more preferably 5% or more, still more preferably 10% or more, particularly The range is preferably 20% or more, most preferably 30% or more, and the upper limit is, for example, 99%. When the haze is at least the above lower limit, it is easy to obtain good matte properties.
The cured product preferably has a 60° gloss (60° specular glossiness) of less than 50, more preferably less than 20, measured by the method described in Examples below. When it is equal to or less than the above upper limit value, the matting property is excellent.
The cured product preferably has transparency. The total light transmittance measured by the method described in Examples below is preferably in the range of 40 to 100%, more preferably 60 to 99%, and still more preferably 80 to 98%. When it is at least the lower limit value of the above range, the transparency is excellent, and when it is at most the upper limit value, the matte property is excellent.

The water contact angle of the cured product is preferably 100 to 150°, more preferably 102 to 140°, still more preferably 105 to 130°. When it is at least the lower limit value of the above range, the antifouling property is excellent, and when it is at most the upper limit value, the durability of the antifouling property is improved. The water contact angle of the cured product is measured by the method described in Examples below.
The hardness of the cured product is preferably higher than F, more preferably higher than 2H, in terms of pencil hardness measured by the method described in Examples below.

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

1 and 2 are schematic cross-sectional views showing examples of the laminate. The dimensional ratios in FIGS. 1 and 2 are for convenience of explanation and are different from the actual ones.
The laminate 10 in the example of FIG. 1 includes a substrate layer 1, an uneven layer 2 provided on one surface 1a of the substrate layer 1, and a and a primer layer 3 .
The laminate 10 in the example of FIG. 2 includes a substrate layer 1, an uneven layer 2 provided on one surface 1a of the substrate layer 1, and a It has a primer layer 3 and a back surface functional layer 5 provided on the surface 1 b of the substrate layer 1 opposite to the uneven layer 2 side.

(Base material layer)
As the base material layer, a known one can be used, and examples thereof include a resin base material, a metal base material, and a paper base material. Among these, a resin substrate is preferable from the viewpoint of workability.
The resin base material may have a single layer structure or a multilayer structure of two or more layers, and is not particularly limited. It is preferable that the resin base material has a multi-layered structure of two or more layers and that each layer has its own characteristic to achieve multi-functionality.

Various resin films (sheets) can be used as the resin base material. A polyvinyl alcohol film, a nylon film, etc. are mentioned.
Polyester film, poly(meth)acrylate film, polyolefin film, polycarbonate film, polyimide film, and triacetyl cellulose film are preferable when the present laminate is used for displays. Among these, polyester films, poly(meth)acrylate films, and polyolefin films are preferred for antiglare applications, and polyester films are more preferred in consideration of transparency, moldability, and versatility.
The polyester film may be a non-stretched film or a stretched film, preferably a stretched film. Among them, a uniaxially stretched film or a biaxially stretched film 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 substrate layer may be homopolyester or copolymer polyester.
The homopolyester is preferably obtained by polycondensation of an aromatic dicarboxylic acid and an aliphatic glycol. Examples of aromatic dicarboxylic acids include terephthalic acid and 2,6-naphthalenedicarboxylic acid. Aliphatic glycols include ethylene glycol, diethylene glycol, 1,4-cyclohexanedimethanol and the like. Aromatic dicarboxylic acids and aliphatic glycols may be used alone or in combination of two or more.
The dicarboxylic acid component of the copolymerized polyester includes isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, oxycarboxylic acid and the like. Glycol components include ethylene glycol, diethylene glycol, propylene glycol, butanediol, 4-cyclohexanedimethanol, neopentyl glycol and the like. Each of the dicarboxylic acid component and the glycol component may be used alone or in combination of two or more.
Representative polyesters include polyethylene terephthalate and polyethylene naphthalate.

As the polyester film, considering the mechanical strength and heat resistance, among the above, films formed from polyethylene terephthalate and polyethylene naphthalate are more preferable, and are easy to manufacture and easy to handle as a surface protection film. Considering , a film formed from polyethylene terephthalate is more preferred.

As the poly(meth)acrylate constituting the poly(meth)acrylate film that can be used as the base material layer, any poly(meth)acrylate having units based on (meth)acrylate can be used, and various acrylic resins can be used. (Meth)acrylates include alkyl (meth)acrylates having an alkyl group having 1 to 4 carbon atoms, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate; Examples thereof include alkyl (meth)acrylates having alkyl groups with a large number of carbon atoms.
Poly(meth)acrylate is preferably composed mainly of units based on alkyl(meth)acrylate having an alkyl group having 1 to 4 carbon atoms in consideration of transparency, workability, and chemical resistance. More preferably, at least one selected from the group consisting of meth)acrylate-based units and ethyl (meth)acrylate-based units is the main component, and methyl (meth)acrylate-based units are particularly the main component. preferable.
Poly(meth)acrylates may contain units based on (meth)acrylates other than alkyl(meth)acrylates or units based on other monomers to impart properties such as flexibility.
The ratio of units based on alkyl (meth)acrylate having an alkyl group having 1 to 4 carbon atoms to the total mass of poly(meth)acrylate is preferably 50% by mass or more, more preferably 80% by mass or more.

The base material layer can contain particles for the purpose of imparting lubricity, preventing scratching in each step, and improving anti-blocking properties.
The type of particles can be appropriately selected depending on 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, acrylic resin, styrene resin, urea resin, and phenol. Examples include organic particles such as resins, epoxy resins, and benzoguanamine resins. Furthermore, when the substrate layer includes a polyester film, deposited particles obtained by depositing a part of a metal compound such as a catalyst in the polyester production process can also be used. Among these, silica particles and calcium carbonate particles are preferable because they are particularly effective even in small amounts.
The shape of the particles is not particularly limited, and may be spherical, massive, rod-like, flat, or the like. Moreover, there are no particular restrictions on its hardness, specific gravity, color, and the like.
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, still more preferably 0.01 to 3 μm. If the average particle diameter is 10 μm or less, problems due to a decrease in transparency of the base material layer are less likely to occur.
The average particle diameter of particles is the value of 50% of the cumulative (mass basis) in the equivalent spherical distribution measured by a centrifugal sedimentation particle size distribution analyzer.

When the base material layer contains particles, the content of the particles in the base material layer cannot be generalized due to the balance with the average particle size of the particles. It is preferably 5% by mass or less, more preferably in the range of 0.0003 to 3% by mass, still more preferably in the range of 0.0005 to 1% by mass. If the content of the particles is 5% by mass or less, problems such as falling off of the particles and deterioration of the transparency of the substrate layer are less likely to occur.

The base material layer can contain additives other than the particles described above, if necessary. Known additives such as ultraviolet absorbers, antioxidants, antistatic agents, heat stabilizers, lubricants, dyes and pigments can be used as additives.

The thickness of the base material layer is not particularly limited as long as it is within a film-forming range, preferably 2 to 350 μm, more preferably 5 to 250 μm, further preferably 10 to 100 μm.

(primer layer)
The primer layer is provided to provide various functions between the substrate layer and the uneven layer.
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 serve as an antistatic layer.

In one preferred embodiment, the primer layer is an adhesion improving layer. If the adhesion between the substrate layer and the uneven layer is insufficient, the laminate may not be usable depending on the application. By having the adhesion improving layer, the adhesion between the substrate layer and the uneven layer is improved, and the laminate can be used for various purposes.
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 cross-linking agent from the viewpoint of improving adhesion between the substrate layer and the uneven layer.

In another preferred embodiment, the primer layer is an antistatic layer. If the primer layer is an antistatic layer, adhesion of dust due to separation electrification or triboelectrification to the outermost surface of the laminate, particularly to the outermost surface on the side of the substrate layer where the uneven layer is present, can be reduced.
To use the primer layer as an antistatic layer, for example, the primer layer may contain an antistatic agent.

Conventionally known resins can be used as the resin. Specific examples of the resin include polyester resin, acrylic resin, urethane resin, polyvinyl resin (polyvinyl alcohol, vinyl chloride-vinyl acetate copolymer, etc.), and the like. Among these resins, polyester resins, acrylic resins, and urethane resins are preferable in consideration of adhesion performance and coatability.
When the substrate layer is a resin film, the resin of the substrate layer is preferably the same resin as that of the resin film from the viewpoint of 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.

Examples of polyester resins include those composed mainly of polyvalent carboxylic acid and polyvalent hydroxy compound.
Polyvalent carboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, 4,4′-diphenyldicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid and 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 salts 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, poly Tetramethylene oxide glycol, dimethylolpropionic acid, glycerin, trimethylolpropane, sodium dimethylolethylsulfonate, potassium dimethylolpropionate and the like.
One or more of these compounds may be appropriately selected, and a polyester resin may be synthesized by a conventional polycondensation reaction.

An acrylic resin is a polymer of polymerizable monomers including (meth)acrylic monomers.
Examples of acrylic resins include homopolymers and copolymers of (meth)acrylic monomers, copolymers of (meth)acrylic monomers and polymerizable monomers other than (meth)acrylic monomers, and the like.
Acrylic resins may be copolymers of these polymers with other polymers (eg, polyester, polyurethane, etc.). Such copolymers are, for example, block copolymers, graft copolymers. Alternatively, a polymer obtained by polymerizing a polymerizable monomer in a polyester solution or dispersion (sometimes a mixture of polymers) is also included. Also included are polymers (optionally mixtures of polymers) obtained by polymerizing polymerizable monomers in polyurethane solutions or dispersions. Also included are polymers (possibly polymer mixtures) obtained by polymerizing polymerizable monomers in solutions or dispersions of other polymers.

The polymerizable monomer is 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 these salts of; hydroxyl group-containing monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, monobutyl hydroxyl fumarate, monobutyl hydroxy itaconate; methyl ( Alkyl (meth)acrylates such as meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate; (meth)acrylamide, Nitrogen-containing monomers such as diacetone acrylamide, N-methylolacrylamide and (meth)acrylonitrile; styrene compounds such as styrene, α-methylstyrene, divinylbenzene and vinyltoluene; vinyl esters such as vinyl propionate and vinyl acetate; Silicon-containing monomers such as methacryloxypropyltrimethoxysilane and vinyltrimethoxysilane; phosphorus-containing vinyl monomers; vinyl halides such as vinyl chloride and pyridene chloride; and conjugated dienes such as butadiene.

A urethane resin is a polymer compound having urethane bonds in its molecule, and is typically synthesized by reacting a polyol and a polyisocyanate. A chain extender may be used when synthesizing the urethane resin.
Polyols used to obtain urethane resins include polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, and the like. These compounds may be used alone or in combination of two or more.

A polycarbonate polyol is obtained by a reaction (dealcoholization reaction) between a polyhydric alcohol and a carbonate compound. Polyhydric alcohols include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol and 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, 3,3-dimethylolheptane, and the like. Examples of carbonate compounds include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate and the like.
Specific examples of polycarbonate polyols include poly(1,6-hexylene) carbonate and poly(3-methyl-1,5-pentylene) carbonate.

Polyether polyols include polyethylene glycol, polypropylene glycol, polyethylene propylene glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol and the like.

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 polycarboxylic acids include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, terephthalic acid, and isophthalic acid.
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, alkyldialkanolamine, lactonediol and the like.

Polyester polyols and polycarbonate polyols are preferred as polyols, and polyester polyols are particularly preferred, in consideration of adhesion performance.

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 aromatic rings such as tetramethylxylylene diisocyanate; aliphatic diisocyanates such as methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate; cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane alicyclic diisocyanates such as diisocyanate and isopropylidene dicyclohexyl diisocyanate; These may be used individually by 1 type, or may use 2 or more types together.

The chain extender is not particularly limited as long as it has two or more active groups that react with an isocyanate group. Generally, chain extenders having two hydroxyl groups or two amino groups can be mainly used. .
Examples of chain extenders having two hydroxyl groups include aliphatic glycols such as ethylene glycol, propylene glycol and butanediol; aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene; and esters such as neopentyl glycol hydroxypivalate. Glycol compounds such as glycol can be mentioned.
Examples of chain extenders having two amino groups include aromatic diamines such as tolylenediamine, xylylenediamine and diphenylmethanediamine, ethylenediamine, propylenediamine, hexanediamine, and 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, 1,10-decanediamine aliphatic diamines such as 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, dicyclohexylmethanediamine, isopropylitincyclohexyl-4,4′-diamine, 1,4-diaminocyclohexane, 1,3 - Alicyclic diamines such as bisaminomethylcyclohexane.

Urethane resins are typically used in the form of dispersions or solutions. The medium for the dispersion or solution may be a solvent, but water is preferred.
Aqueous dispersions or aqueous solutions of urethane resin include 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, and a water-based type. In particular, a self-emulsifying type in which an ionic group is introduced into the structure of a urethane resin to form an ionomer is preferable because it is excellent in the storage stability of the liquid and the water resistance and transparency of the resulting primer layer.

As the ionic group introduced into the structure of the urethane resin, various groups such as a carboxyl group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group and a quaternary ammonium group can be mentioned, but a carboxyl group is preferred.
A carboxyl group is preferably in the form of a salt neutralized with a neutralizing agent such as ammonia, amine, alkali metals or inorganic alkalis. Particularly preferred neutralizing agents are ammonia, trimethylamine and triethylamine. A urethane resin having carboxyl groups neutralized with a neutralizing agent can use the carboxyl groups removed from the neutralizing agent in the drying process after coating as crosslinking reaction sites with a crosslinking agent. As a result, the stability of the liquid state before coating is excellent, and the durability, solvent resistance, water resistance, blocking resistance, etc. of the resulting primer layer can be further improved.

As a method for introducing a carboxyl group into a urethane resin, various methods can be adopted in each stage of the polymerization reaction. For example, there is a method of using a resin having a carboxyl group as a copolymerization component when synthesizing a prepolymer, and a method of using a component having a carboxyl group as one component such as a polyol, polyisocyanate, or chain extender. In particular, a method of using a carboxyl group-containing diol and introducing a desired amount of carboxyl groups depending on the charged amount of this component is preferred. For example, a carboxyl group-containing diol can be copolymerized with a polyol used for synthesizing a urethane resin.
Carboxyl group-containing diols include dimethylolpropionic acid, dimethylolbutanoic acid, bis-(2-hydroxyethyl)propionic acid, bis-(2-hydroxyethyl)butanoic acid, and their carboxyl groups are neutralized with a neutralizing agent. and the like.

The primer layer preferably contains a compound derived from a cross-linking agent in order to strengthen the primer layer and improve performance such as adhesion.
As the cross-linking agent, known materials can be used, for example, melamine compounds, oxazoline compounds, isocyanate compounds, epoxy compounds, carbodiimide compounds, silane coupling compounds, hydrazide compounds, aziridine compounds and the like. Among them, melamine compounds, isocyanate compounds, epoxy compounds, oxazoline compounds, carbodiimide compounds, and silane coupling compounds are preferred. From the viewpoint of further improving adhesion and durability, melamine compounds, oxazoline compounds, and isocyanate compounds are preferred. and epoxy compounds are more preferred, and oxazoline compounds and isocyanate compounds are particularly preferred. These crosslinking agents may be used alone or in combination of two or more. By using two or more kinds together, the adhesion and durability may be further improved and become favorable in some cases.

A melamine compound is a compound having a melamine skeleton in the compound. mixtures. 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 polymer of dimers or higher, or a mixture thereof. Further, melamine may be partially co-condensed with urea or the like, and a catalyst may be used to increase the reactivity of the melamine compound.
As the melamine compound, those having a hydroxyl group are preferable in consideration of reactivity with various compounds.

The isocyanate-based compound is a compound having an isocyanate derivative structure represented by isocyanate or blocked isocyanate.
Examples of isocyanates include aromatic isocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate; Aliphatic isocyanates; aliphatic isocyanates such as methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, and hexamethylene diisocyanate; and alicyclic isocyanates. Polymers and derivatives of these isocyanates, such as buret products, isocyanurate products, uretdione products, and carbodiimide modified products, are also included. These may be used individually by 1 type, or may use 2 or more types together. 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 blocked isocyanates include those obtained by blocking the isocyanate groups of the above isocyanate compounds with a blocking agent. Examples of blocking agents 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, dimethyl malonate, diethyl malonate, active methylene compounds such as methyl isobutanoylacetate, methyl acetoacetate, ethyl acetoacetate and acetylacetone; mercaptan compounds such as butyl mercaptan and dodecyl mercaptan; lactam compounds such as ε-caprolactam and δ-valerolactam; Examples include amine compounds such as ethyleneimine, acid amide compounds such as acetanilide and acetic acid amide, and oxime compounds such as formaldehyde, acetaldoxime, acetone oxime, methyl ethyl ketone oxime, and cyclohexanone oxime. These may be used individually by 1 type, or may use 2 or more types together.
As the blocked isocyanate, an isocyanate blocked with an active methylene compound is preferable from the viewpoint that the primer layer is less likely to be destroyed.

The isocyanate compound may be used alone, or may be used as a mixture or combination with various polymers. From the viewpoint of improving the dispersibility and crosslinkability of the isocyanate compound, it is preferable to use a mixture or combination with a polyester resin or a urethane resin.

An oxazoline compound is a compound having an oxazoline group in its molecule.
As the oxazoline compound, a polymer containing an oxazoline group is preferable. A polymer containing an oxazoline group can be obtained by polymerization of an addition polymerizable oxazoline group-containing monomer alone or with another monomer.
Examples of addition polymerizable oxazoline group-containing monomers include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, and 2-isopropenyl-2-oxazoline. , 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline and the like. These may be used individually by 1 type, or may use 2 or more types together. Among these, 2-isopropenyl-2-oxazoline is suitable because it is easily available industrially.
Other monomers are not particularly limited as long as they are monomers copolymerizable with addition-polymerizable oxazoline group-containing monomers. isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group); acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, styrene Unsaturated carboxylic acids such as sulfonic acids and salts thereof (sodium salts, potassium salts, ammonium salts, tertiary amine salts, etc.); Unsaturated nitriles such as acrylonitrile and methacrylonitrile; ) acrylamide, N,N-dialkyl (meth)acrylamide, (as alkyl groups, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group , cyclohexyl group, etc.); 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; and α,β-unsaturated aromatic monomers such as styrene and α-methylstyrene. These may be used individually by 1 type, or may use 2 or more types together.

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

An epoxy compound is a compound having an epoxy group in its 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.), polyepoxy compounds, diepoxy compounds, There are monoepoxy compounds, glycidylamine compounds, and the like. 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, trimethylolpropane. Polyglycidyl ethers are mentioned. 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. glycidyl ether, polytetramethylene glycol diglycidyl ether; Examples of monoepoxy compounds include allyl glycidyl ether, 2-ethylhexyl glycidyl ether, and phenyl glycidyl ether. Examples of glycidylamine compounds include N,N,N',N'-tetraglycidyl-m-xylylenediamine and 1,3-bis(N,N-diglycidylamino)cyclohexane.

A carbodiimide-based compound is a compound having one or more carbodiimide structures or carbodiimide derivative structures in the molecule.
As the carbodiimide-based compound, a polycarbodiimide-based compound having two or more carbodiimide structures or carbodiimide derivative structures in the molecule is more preferable for better strength of the primer layer.

A carbodiimide-based compound can be synthesized by a known technique, and generally a condensation reaction of diisocyanate is used. The diisocyanate is not particularly limited, and both aromatic and aliphatic can be used. Specifically, tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexyl diisocyanate, dicyclohexylmethane diisocyanate and the like.

In order to improve the water-solubility and water-dispersibility of the polycarbodiimide-based compound, a surfactant may be added, or a polyalkylene oxide or a quaternary ammonium salt of a dialkylaminoalcohol may be added as long as the effects of the present invention are not lost. , hydroxyalkylsulfonates, and other hydrophilic monomers may be added.

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

As the silane coupling compound, among the above compounds, from the viewpoint of the strength of the primer layer, epoxy group-containing silane coupling compounds, double bond-containing silane coupling compounds such as vinyl groups and (meth)acrylic groups, amino group-containing Silane coupling compounds are more preferred.

These cross-linking agents react during the drying process and the film-forming process to improve the performance of the primer layer. It can be inferred that unreacted products of the cross-linking agent, compounds after the reaction, or mixtures thereof are present as compounds derived from the cross-linking agent in the primer layer to be formed.

The antistatic agent to be contained in the primer layer is not particularly limited, and known antistatic agents can be used. For example, compounds having an ammonium group, polyether compounds, compounds having a sulfonic acid group, betaine compounds, conductive organic polymers, and the like.
As the antistatic agent, a polymer type antistatic agent is preferable because it has good heat resistance and moist heat resistance.

A compound having an ammonium group is a compound having an ammonium group in the molecule, and examples thereof include ammonium compounds of aliphatic amines, alicyclic amines, and aromatic amines.
The compound having an ammonium group is preferably a compound having a polymer type ammonium group.
In a polymer-type compound having an ammonium group, the ammonium group is preferably incorporated into the main chain or side chain of the polymer rather than as a counterion. Examples of such a compound include, for example, an ammonium group or an addition-polymerizable monomer having an ammonium group precursor group such as an amine is polymerized, and if necessary, the ammonium group precursor group is converted to an ammonium group, A high molecular compound having an ammonium group can be mentioned. The addition-polymerizable monomers containing an ammonium group or an ammonium group precursor group may be polymerized singly, or two or more of them may be copolymerized, or may be copolymerized with other monomers. may

As a compound having an ammonium group, a compound having a pyrrolidinium ring is also preferable from the viewpoint of excellent antistatic properties and heat resistance stability.
The two substituents bonded to the nitrogen atom of the pyrrolidinium ring-containing compound are each independently an alkyl group, a phenyl group, or the like, and even if these alkyl groups and phenyl groups are substituted with groups shown below, good. Substitutable groups are, for example, hydroxyl groups, amide groups, ester groups, alkoxy groups, phenoxy groups, naphthoxy groups, thioalkoxy groups, thiophenoxy groups, cycloalkyl groups, trialkylammoniumalkyl groups, cyano groups, halogens. In addition, the two substituents bonded to the nitrogen atom may be chemically bonded, and examples of the group in which the 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 pyrrolidinium ring-containing compound is preferably a pyrrolidinium ring-containing polymer.
A polymer having a pyrrolidinium ring can be obtained, for example, by cyclopolymerizing a diallylamine derivative using a radical polymerization catalyst. A diallylamine derivative and a compound having a polymerizable carbon-carbon unsaturated bond may be used as a copolymerization component. Polymerization is carried out in a polar solvent (water, methanol, ethanol, isopropanol, formamide, dimethylformamide, dioxane, acetonitrile, etc.) using a polymerization initiator such as hydrogen peroxide, benzoyl peroxide, tertiary butyl peroxide, etc., using a known method, but is not limited to this.

Examples of the anion that serves as a counter ion for the ammonium group of the compound having an ammonium group include ions such as halogen ions, sulfonates, phosphates, nitrates, alkylsulfonates, and carboxylates.

The compound having an ammonium group preferably has a number average molecular weight of 1,000 to 500,000, more preferably 2,000 to 350,000, still more preferably 5,000 to 200,000. When the number average molecular weight is 1000 or more, the strength and heat resistance of the coating film are more excellent. 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 handleability and coating properties are good.

Polyether compounds include, for example, polyethylene oxide, polyether ester amide, acrylic resins having polyethylene glycol in side chains, and the like.

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, compounds having a plurality of sulfonic acid groups in the molecule, such as polystyrene sulfonic acid and salts thereof, are preferred.

As the conductive organic polymer, known materials can be used, and examples thereof include polythiophenes, polyanilines, polypyrroles, polyacetylenes, polyphenylene sulfides, and the like. Among these, polythiophene-based materials (polythiophene or polythiophene derivatives) are preferable because they have both high transparency and high conductivity, are difficult to be colored, and are easy to exhibit performance by coating. Among polythiophenes, a compound obtained by combining poly(3,4-ethylenedioxythiophene) with polystyrenesulfonic acid is particularly preferable from the viewpoint of conductive performance.
A conductive organic polymer is preferable in that it exhibits high conductivity, is less dependent on humidity, and can be expected to be used in various applications.

The primer layer may contain particles for blocking and improving slipperiness.
The primer layer may optionally contain antifoaming agents, coatability improvers, thickeners, organic lubricants, ultraviolet absorbers, antioxidants, foaming agents, dyes, Additives such as pigments may be contained.

The ratio of the 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 still more preferably 30 to 90% by mass. If the proportion of the resin is within the above range, the adhesion performance and the appearance of the primer layer are more excellent.

The ratio of the compound derived from the cross-linking 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, further preferably 5 to 40% by mass. Range. If the ratio of the compound derived from the cross-linking agent is within the above range, the adhesion performance and the strength of the primer layer are more excellent.

When the primer layer is an antistatic layer containing an antistatic agent, the ratio of the antistatic agent in 100% by mass of the primer layer depends on the type of the antistatic agent, so it is not general, but for example 80% by mass or less. , preferably 0.5 to 70% by mass, more preferably 1 to 50% by mass. When the proportion of the antistatic agent is within the above range, it is easy to impart a sufficient antistatic function to the primer layer, and even after forming the uneven layer on the primer layer, the antistatic performance is likely to be exhibited.

The thickness of the primer layer depends on the material used for the primer layer and the performance to be developed, and cannot be generalized. 02 to 1 μm.
A primer layer can be formed by a well-known method.

(back functional layer)
The back surface functional layer is provided in order to impart various functions to the surface of the substrate layer opposite to the uneven layer side.
Examples of the back functional layer include an adhesive layer, an antistatic layer, a refractive index adjusting layer, an antiblocking layer and the like.
The adhesive layer is provided for bonding the laminate to various adherends. The antistatic layer is provided on the outermost surface of the laminate, particularly on the outermost surface of the substrate layer opposite to the uneven layer side, to prevent adhesion of surrounding dust due to peel electrification or triboelectrification, and the resulting defects. be provided. The refractive index adjusting layer is provided, for example, to improve the total light transmittance of the laminate. An anti-blocking layer is provided to reduce blocking of the laminate.

As the adhesive for forming the adhesive layer, a known one can be used, and examples thereof include acrylic, polyester, urethane, rubber, and the like. Among them, the acrylic type is preferable in consideration of versatility.
The antistatic layer and the refractive index adjusting layer are the same as the antistatic layer and the refractive index adjusting layer as surface functional layers, respectively.

The thickness of the back functional layer depends on the material used for the back functional layer and the performance to be developed, so it cannot be said unconditionally, but it 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.
A back surface functional layer can be formed by a well-known method.

[EXAMPLES] Hereafter, although an Example demonstrates this invention further in detail, this invention is not limited to the following Examples, unless the gist is exceeded.
The measurement methods 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: "e2695" manufactured by Waters,
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: 0.5 mL/min,
Injection volume: 10 μL,
Concentration: 0.2% by mass,
Calibration sample: monodisperse polystyrene,
Calibration method: polystyrene conversion.

(2) Total Light Transmittance/Haze A laminate obtained by forming an uneven layer on a PET film was measured. The total light transmittance and haze are determined according to JIS Z8722Z (geometrical conditions for irradiation and light reception of transparent objects), JIS K7361-1 (plastics-testing method for total light transmittance of transparent materials), and JIS K7136 (plastics-haze of transparent materials). The value at a wavelength of 550 nm was measured using a haze meter "SH7000" manufactured by Nippon Denshoku Industries Co., Ltd.
In addition, the haze of the laminate is 0.044 rad (2.0 rad) from the incident light due to forward scattering in the transmitted light that enters the substrate layer from the outermost surface on the side where the uneven layer exists and passes through the laminate. 5°) is the percentage of transmitted light (ratio of diffuse transmittance to total light transmittance).

(3) 60° Gloss/Matte Properties A laminate obtained by forming an uneven layer on a PET film was used as an object of measurement. The 60° gloss (60° specular glossiness) was measured according to JIS Z 8741 using a gloss meter "VG2000" manufactured by Nippon Denshoku Industries Co., Ltd. The lower the 60° gloss value, the better the mattness. The matting property was evaluated according to the following criteria.
The principle of specular glossiness measurement is to measure the specularly reflected light flux φs from the sample surface with respect to a specified incident angle θ (60° for 60° specular glossiness).
A: The 60° gloss is less than 20.
B: The 60° gloss is 20 or more and less than 50.
C: 60° gloss of 50 or more.

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

(5) Evaluation of pen writability (oil repellency / antifouling property) After writing on the uneven layer with an oil-based black marker “Mackie Fine” manufactured by Zebra Co., Ltd., it is visually observed, and A is when the ink is repelled. , and B when the ink was not repelled. Ink repellency is evaluated as superior oil repellency (antifouling property).

(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 Coating Film-Section 4: Scratch Hardness (Pencil Method). Evaluation was made according to the following criteria.
A: 2H or more.
B: F-H.
C: HB or less.

(7) Flexibility A laminate obtained by forming an uneven layer on a PET film was used as an object of measurement. According to JIS K5600-5-1 (general test methods for paints-Part 5: mechanical properties of coating film), the flexibility of the uneven layer was confirmed by a mandrel test. Specifically, the laminate was wound around the mandrel so that the uneven layer was on the mandrel side, and the state of the cured layer was visually observed. The mandrel was evaluated while decreasing the diameter of the mandrel as follows, and the minimum diameter of the mandrel at which cracks did not occur in the concavo-convex layer was determined. The smaller the minimum diameter, the better the bendability. Evaluation was made according to the following criteria.
Mandrel diameter: 32mm, 25mm, 16mm, 12mm, 10mm, 8mm, 6mm, 5mm, 4mm, 3mm, 2mm.
A: Minimum diameter less than 3 mm.
B: The minimum diameter is 3 mm or more and less than 5 mm.
C: The minimum diameter is 5 mm or more.

(8) Leveling property The surface (10 cm x 10 cm) of the uneven layer was visually observed, and the number of cissing and pitting defects was examined. Evaluation was made according to the following criteria.
A: The total number of cissing and spot defects is less than 10.
B: The total number of cissing and spot defects is 10 or more.

(9) Surface roughness Using a surface shape measurement system (“Vert Scan” (registered trademark) VS1330 manufactured by Hitachi High-Tech Science), the uneven shape of the surface is measured for a 703.12 μm × 937.42 μm area on the surface of the uneven layer. Interferometry was performed, imputed and baseline corrected, and data read. The magnification of the objective lens at the time of measurement was set to 5 times.

A copolymer having the composition shown in Table 1 was produced. The monomers in the table are as follows.
<Monomer (x)>
x-1: 4-methacryloyloxybenzophenone.
x-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 Co., 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 Kasei Kogyo Co., Ltd.) was distilled under reduced pressure, and fractions with a purity of 99.8% or more were collected to obtain a distillate of methacrylic anhydride. The vacuum distillation was carried out by gradually raising the temperature from room temperature to 90° C. at a pressure of 30 pa.
Separately, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-methylpropanone (manufactured by Tokyo Chemical Industry Co., Ltd.) 22.4 g (0.1 mol), and triethylamine (Tokyo Chemical Industry Co., Ltd. Co., Ltd.) was dissolved in 500 mL of methylene chloride (manufactured by Tokyo Chemical Industry Co., Ltd.). 23.1 g (0.15 mol) of the distillate of methacrylic anhydride was added dropwise thereto at room temperature and stirred for 12 hours.
After washing the resulting reaction solution with 500 mL of ion-exchanged water three times, the organic phase was concentrated and the solvent was distilled off. 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 obtained compound was 2-[4-(2-hydroxy-2-methyl-1-oxopropyl)phenoxy]ethyl methacrylate.
¹ H NMR (300 MHz, chloroform-d): δ 8.06 (d, J = 9.0 Hz, 2H), 6.96 (d, J = 9.0 Hz, 2H), 6.13 (d, J = 0 .6 Hz, 1 H), 5.59 (s, 1 H), 4.50 (d, J = 5.1 Hz, 2 H), 4.29 (dd, J = 5.5, 4.1 Hz, 3 H), 1 .94 (dd, J=1.6, 1.0 Hz, 3H), 1.61 (s, 6H).

(Production Example 1: Production of copolymer (A-1))
In a flask equipped with a stirrer, a condenser and a thermometer, 70 parts of methyl isobutyl ketone (hereinafter referred to as MIBK) was placed, then the inside of the flask was replaced with nitrogen and the temperature was raised to 65 ° C., and the monomer (x-2 ) 40 parts by mass, monomer (r-1) 10 parts by mass, monomer (r-2) 20 parts by mass, monomer (f-1) 30 parts by mass, 1-dodecanethiol as a chain transfer agent 3 parts by mass, polymerization initiator A mixed solution of 1 part by mass of 2,2′-azobis(2,4-dimethylvaleronitrile) and 78 parts by mass of MIBK was added dropwise over 2 hours. After 2 hours, 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 in order to increase the polymerization rate. Thereafter, the reaction solution was cooled to 40° C. to obtain a copolymer MIBK solution (A-1). Hereinafter, the solid content in solution (A-1) is referred to as copolymer (A-1).
The solid content (non-volatile content) of the solution (A-1) was 40% by mass. Table 1 shows the weight average molecular weight (Mw) of the copolymer (A-1) and the content of active groups per 1 g of the copolymer (A-1).

(Production Example 2: Production of polymer (H-1))
In Production Example 1, the composition of the mixed solution was 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), Monomer (h-2) 10 parts by weight, 0.8 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) as a polymerization initiator, and MIBK 78 parts by weight were changed to the same as in Production Example 1. A copolymer MIBK solution (H-1) was obtained under the conditions. 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. Table 1 shows the weight average molecular weight (Mw) of copolymer (H-1) and the content of active groups per 1 g of copolymer (H-1).

(Example 1, Reference Example 1, Comparative Example 1: Production of coating liquid (curable polymer composition))
Each material shown in Table 2 was mixed so as to have a ratio (parts by mass) shown in Table 2 in terms of non-volatile content. After that, a mixed solvent of propylene glycol monomethyl ether (hereinafter referred to as PGM) and methyl ethyl ketone (hereinafter referred to as MEK) (PGM:MEK (mass ratio) 7:3) was added so that the solid content concentration was 40% by mass, and the mixture was uniformly mixed. to obtain a coating liquid (curable polymer composition).
Table 2 shows the active group content per 100 g of the non-volatile content of the curable polymer composition in the coating liquid.

The materials in Table 2 are as follows.
A-1: MIBK solution of copolymer (A-1) obtained in Production Example 1.
H-1: MIBK solution of 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 resulting coating liquid is applied to a PET film (“T602E50” manufactured by Mitsubishi Chemical Corporation) having a thickness of 50 μm with a bar coater No. 8, and dried for 60 seconds with a hot air dryer heated to 70° C. to volatilize the solvent. Then, ultraviolet rays were irradiated from a high-pressure mercury lamp in an air atmosphere at an integrated light amount of 250 mJ/cm ² and an illuminance of 100 mW/cm ² to form an uneven layer (cured product) having a thickness of 2.5 μm. As a result, a laminate was obtained in which a layer made of the cured product was laminated on the substrate layer made of the PET film.
For the irradiation of ultraviolet rays, a UV conveyor of Eyegraphics high output UV device (model: US5-X1802-X1202) was used. The integrated amount of light is a value obtained by measuring the integrated amount of light at a wavelength of 300 to 390 nm with an illuminometer manufactured by Iwasaki Electric Co., Ltd. (I UV illuminance meter "UVPF-A1", "PD-365").
Regarding the obtained laminate, the items shown in Table 2 were measured or evaluated by the methods described above. Table 2 shows the results.

As shown in the results of Table 2, Example 1 containing the polymer (A-1) has an uneven layer and has matting properties. The uneven layer has excellent transparency, antifouling properties, and excellent hardness.
On the other hand, the uneven layer of Reference Example 1 using the polymer (H-1) instead of the polymer (A-1) has substantially the same transparency, hardness, and mattness as those of Example 1, No antifouling property was obtained.
Further, the layer made of the cured product of Comparative Example 1 using a general photopolymerization initiator (non-polymer having an active group) (C-1) instead of the polymer (A-1) has transparency. and hardness were almost the same as those of Example 1, but the surface was almost smooth, and neither matting nor antifouling properties were obtained.

DESCRIPTION OF SYMBOLS 1... Base material layer 2... Concavo-convex layer 3... Primer layer 5... Back surface functional layer 10... Laminate

Claims (10)

A copolymer having units based on a monomer (x) having an active group that generates a radical upon irradiation with an active energy ray and units based on a monomer (f) having a fluorine atom or a silicon atom. the active group is a 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 dialkylacetal group, an anthraquinone group, a thioxanthone group, and a phosphine oxide group; The copolymer according to claim 1, which is one or more selected from. 3. The copolymer according to claim 1, wherein the content of said active groups per gram of said copolymer is 0.1 to 3.5 mmol/g. The monomer (f) contains one or more 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, claims 1- 4. The copolymer according to any one of 3. The copolymer according to any one of claims 1 to 4, wherein the content of units based on the monomer (f) is 5 to 70% by mass with respect to the total mass of all units constituting the copolymer. . 6. The copolymer according to any one of claims 1 to 5, further comprising a unit based on a monomer (r) having an alkyl group having 4 or more carbon atoms. A curable polymer composition comprising the copolymer (A) according to any one of claims 1 to 6 and a polyfunctional compound (B) having two or more radically polymerizable groups per molecule. 8. The curable polymer composition according to claim 7, wherein the content of said copolymer (A) is 0.5 to 50% by mass based on the non-volatile content of said curable polymer composition. A cured product of the curable polymer composition according to claim 7 or 8. A laminate comprising a substrate layer and a layer comprising the cured product according to claim 9 .

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