Hardening components, hardened substances and lamellae

Abstract

To provide a laminate having a low gloss and good mattness, consisting of a curable composition laminated on a base material, wherein the curable composition forms an uneven structure upon curing, and the base material has a surface roughness with an arithmetic average roughness (Ra) of 0.10 μm or more.SOLUTION: A laminate comprises the following layer (1) and layer (2). The layer (1): a curable composition comprising a polymer (A) with an active group to generate radicals upon irradiation with active energy rays; and the layer (2): a base material having a surface roughness with an arithmetic average roughness (Ra) of 0.10 μm or more.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a laminate formed by laminating a cured material having an uneven surface structure on a substrate. [Background technology]

[0002] By forming a fine, uneven surface on the substrate, the color changes depending on the viewing angle. As a method to impart iridescence or matte finishes and improve design and visibility, for example, A method of curing a curable composition containing dispersed particles by coating it onto a substrate, and a method of depositing a thin metal film onto a substrate. A method for causing this, which involves applying a curable composition to a substrate and curing it to produce a cured product with fine wrinkles on its surface. A method for making it appear is known. For example, Patent Document 1 describes a method of applying a curable composition to a substrate and irradiating it with active energy rays to cure it. A technology that creates a fine uneven surface structure on the hardened material, thereby exhibiting iridescence and matte finish. It is stated. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2019-131717 [Overview of the project] [Problems that the invention aims to solve]

[0004] However, the laminate of the curable composition used in the method described in Patent Document 1 has a relatively high 60° gloss. It was difficult to use in applications requiring a high level of matte finish, almost completely non-reflective. The present invention relates to a curable composition that forms an uneven structure upon curing, wherein the arithmetic mean roughness (Ra) is 0 By laminating onto a substrate with a surface roughness of 0.10 μm or more, it is possible to achieve low gloss and excellent matte finish. The objective is to provide a laminated material. [Means for solving the problem]

[0005] [1] A laminate containing the following layers (1) and (2). Layer (1): Polymer having active groups that generate radicals upon irradiation with active energy rays ( A) Curable composition Layer (2): Substrate having a surface roughness of 0.10 μm or more with an arithmetic mean roughness (Ra). [2] The polymer (A) is a constituent unit derived from an (meth)acrylic acid ester having an active group. The laminate described in [1], which includes [1]. [3] The active group that generates radicals upon irradiation with the active energy ray is benzophenone Group, acetophenone group, benzoin group, α-hydroxyketone group, α-aminoketone group, α-diketone group, α-diketone dialkylacetal group, anthraquinone group, thioxane One or more selected from the group consisting of a ton group and a phosphine oxide group [1] or [ The laminate described in [2]. [4] The polymer (A) is an alkyl group having 4 or more carbon atoms, a fluoroalkyl group, and a polymer (Meta) Having one or more chain-like structures selected from the group consisting only of dimethylsiloxane chains Laminate according to any one of [1] to [3], comprising constituent units derived from acrylic acid esters . [5] The weight-average molecular weight of the polymer (A) is 1,000 to 500,000. [1] to [4] A laminate as described in any one of the items in ]. [6] The layer (1) contains polymer (A) as well as (meth)acrylate (B) [1]~[ A laminate as described in any one of item 5]. [7] The (meth)acrylate (B) contains a bifunctional or more (meth)acrylate [1 A laminate as described in any one of items [6]. [8] The laminate according to any one of [1] to [7], comprising a cured product obtained by curing the curable composition of the layer (1). described above. [9] The laminate according to [8], wherein the cured product is a film having an uneven structure on its surface.

Advantages of the Invention

[0006] In the present invention, a curable composition that forms an uneven structure upon curing is laminated on a substrate having a surface roughness with an arithmetic mean roughness (Ra) of 0.10 μm or more, whereby a laminate with low gloss and excellent matting properties can be provided.

Embodiments for Carrying Out the Invention

[0007] Hereinafter, embodiments of the present invention will be described in detail. However, the following description is merely an example of the embodiments of the present invention, and the present invention is not limited to the following description as long as it does not exceed the gist thereof. In the present invention, “(meth)acrylate” is a general term for acrylate or methacrylate. “(meth)acrylic” is a general term for acrylic and methacrylic. The “~” indicating a numerical range means that the numerical values described before and after it are included as the lower limit value and the upper limit value .

[0008] The present invention relates to a laminate including the following layer (1) and layer (2). Layer (1): A curable composition containing a polymer ( A) having an active group that generates radicals upon irradiation with active energy rays Layer (2): A substrate having a surface roughness with an arithmetic mean roughness (Ra) of 0.10 μm or more

[0009] (Curable composition) The layer (1) of the present invention has an active group that generates radicals upon irradiation with active energy rays ​​This is a curable composition containing polymer (A) (hereinafter referred to as polymer (A)). It may contain (meth)acrylate (B). The curable composition may, if necessary, It may contain other ingredients not listed above.

[0010] (Polymer (A)) Polymer (A) is an active group that generates radicals upon irradiation with active energy rays (hereinafter referred to as active It has (called an active group). An active group is one that generates radicals when irradiated with active energy rays. It is a group having a structure, in other words, a structure that initiates photopolymerization. Examples of structures include hydrogen abstraction type, electron transfer type, and intramolecular cleavage type. In the clear, radicals generated from the active group are found in the polymer (A) itself and the (meth)acrylate (B). It reacts with other elements to form a cross-linked structure. (active group) Examples of active groups include benzophenone group, acetophenone group, benzoin group, α- Hydroxyketone group (e.g., 1-[4-(2-hydroxyethoxy)-phenyl]-2 - From the "hydroxyl group in 2-hydroxyethoxy" of hydroxymethylpropanone, hydrogen atoms (a group with one element removed), α-aminoketone group, α-diketone group, α-diketonedialkylase Examples include tar groups, anthraquinone groups, thioxanthone groups, and phosphine oxide groups. Among these, those that are less susceptible to oxygen inhibition during curing and have good surface hardening properties when forming an uneven layer Benzophenone groups, acetophenone groups, and α-hydroxyketone groups are preferred for their favorable properties. It's nice.

[0011] The active group may be located at the end of the main chain of polymer (A), and may be a monomer constituting polymer (A). It may be present in constituent units derived from the body. Polymer (A) can increase the concentration of active groups near the surface of the coating film, and inhibits oxygen. This makes it less susceptible to damage, resulting in improved curability, and the appearance of uneven structures such as wrinkles on the surface after curing. It is preferable to have multiple active groups in the molecule, as this makes it easier to achieve.

[0012] The polymer (A) having multiple active groups is composed of elements derived from the monomer (a) having active groups. Polymers having units are preferred.

[0013] (monomer (a)) Examples of monomers (a) include compounds having an active group and a radical polymerizable group. Dical polymerizable groups include functionalities containing radically polymerizable unsaturated bonds such as carbon-carbon double bonds. The basis is cited. The monomer (a) is chosen for its ease of synthesis of polymer (A) and ease of adjusting the amount of active group introduced. From the viewpoint of fiber content, (meth)acrylic acid esters are preferred. Such (meth)acrylic Examples of acid esters include 4-methacryloyloxybenzophenone, 2-[4-( 2-Hydroxy-2-methyl-1-oxopropyl)phenoxy]ethyl methacrylate These are some examples.

[0014] The ratio of constituent units derived from monomer (a) to the total mass of all units constituting polymer (A) The mixture is preferably 1 to 90% by mass, more preferably 5 to 80% by mass, and even more preferably 1 The percentage is in the range of 5 to 70% by mass, particularly preferably 30 to 60% by mass. Therefore, the hardening properties can be improved, and an uneven structure can be effectively formed.

[0015] (monomer (b)) Polymer (A) has a chain-like structure in addition to the constituent units derived from monomer (a) which has an active group. It is preferable that the monomer (b) has constituent units derived from monomer (b). Monomer (b) has 4 or fewer carbon atoms. The above alkyl or fluoroalkyl group and polydimethylsiloxane chains alone Examples include compounds having one or more chain-like structures and radical polymerizable groups selected from the group. Radical polymerizable groups include radical polymerizable unsaturated bonds such as carbon-carbon double bonds. Functional groups are one example. As for monomer (b), the ease of synthesis of polymer (A) and the adjustment of the amount of chain structure introduced are important. From the standpoint of ease, (meth)acrylic acid esters are preferred. Polymer (A) is this unit If present, when a coating film of the curable composition is formed, the polymer (A) will be biased toward the surface side of the coating film. This makes segregation easier. Due to this segregation, the curing reaction inside the coating film (on the substrate side) is inhibited by oxygen. This reduces the risk of oxidation and improves curing properties. For example, it can be cured with low exposure and oxygen inhibition. It can cure even thin coatings that tend to be susceptible to damage.

[0016] Alkyl groups with 4 or more carbon atoms may be linear, branched, monocyclic, or polycyclic. The formula may include a cyclic structure. This allows polymer (A) to be more effectively segregated on the surface of the coating film. From this viewpoint, the alkyl group is preferably linear. The number of carbon atoms in alkyl groups with 4 or more carbon atoms allows polymer (A) to more effectively segregate on the surface of the coating film. From the viewpoint of enabling this, preferably in the range of 4 to 30, more preferably in the range of 6 to 20, even more preferably The range is 12 to 18.

[0017] Monomers having an alkyl group with 4 or more carbon atoms include alkyl groups with 4 or more carbon atoms and radiates. Examples of such compounds include those having a CAL polymerizable group. (T) Alkyl acrylate, dialkyl fumarate, dialkyl maleate Examples include esters and aliphatic olefins. They are easy to synthesize and have alkyl groups with 4 or more carbon atoms. From the viewpoint of ease of adjusting the amount introduced, alkyl (meth)acrylate is preferred. .

[0018] Examples of such alkyl (meth)acrylates include butyl(meth)acrylate. acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cycloacrylate Xyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, octyl(meth)acrylate Acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate, Nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate Rate, Isodecyl (meth)acrylate, Dodecyl (meth)acrylate, Myristyl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate Isostearyl (meth)acrylate, tridecyl (meth)acrylate, dicyclopene Thenyloxyethyl (meth)acrylate, Tricyclodecane (meth)acrylate, Dicyclopentanyl (meth)acrylate, isobornyl (meth)acrylate, Adamantine Examples include methyl (meth)acrylate. Among these, (meth)acrylates having a linear alkyl group with 4 or more carbon atoms are particularly important. It is preferable to include a kill ester. (Meta) having a linear alkyl group with 4 or more carbon atoms. )As alkyl acrylates, the number of carbon atoms of the alkyl group is within the preferred range described above. It is preferable to use 2-ethylhexyl(meth)acrylate, and considering ease of manufacture, etc. Rate, Octyl(meth)acrylate, Dodecyl(meth)acrylate, Stearyl( Meth)acrylate is more preferred, and stearyl (meth)acrylate is particularly preferred. These alkyl (meth)acrylates may be used individually or in combination of two or more. You may use them in combination.

[0019] Polymer (A) is composed of carbon, from the viewpoint of more effectively segregating polymer (A) on the surface of the coating film. In addition to constituent units derived from monomers having 4 or more alkyl groups, or alkyl groups having 4 or more carbon atoms Instead of constituent units derived from monomers having a kill group, fluoroalkyl groups or polydimethyl groups are used. It may have constituent units derived from monomers containing siloxane chains.

[0020] Monomers containing fluoroalkyl groups include (meth )Acrylic acid esters are preferred, and (meth)acrylic acid having a perfluoroalkyl group is preferred. Esters are more preferable. (Meth)acrylic acid esters having a perfluoroalkyl group 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 (Osaka Organic Manufactured by Chemical Industry Co., Ltd., Viscoat 8F), 1H,1H,5H-Octafluoropentylmethionine Tacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., Viscoat 8FM), 1H,1H,2H, 2H-Tridecafluorooctyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., visco (T13F), 1H,1H,2H,2H-nonafluorohexyl acrylate (unimate) K Corporation, CHEMINOX FAAC-4), 1H, 1H, 2H, 2H-non-fluorine Rohexyl methacrylate (Unimatec Corporation, CHEMINOX FAMAC- 4) 1H,1H,2H,2H-Tridecafluorooctyl methacrylate (Unimate Products such as those from CHEMINOX FAMAC-6 are commercially available. The number of carbon atoms in the ruoroalkyl group is preferably 3 or more.

[0021] Monomers containing polydimethylsiloxane chains contain polydimethylsiloxane chains (Meth)acrylic acid esters are preferred. (Meth)acrylic acid esters having polydimethylsiloxane chains are preferred. Specific examples of acrylic acid esters include those with a molecular weight of 500 to 50,000 (meth-a). Examples include cashloyl group-substituted polydimethylsiloxanes. The molecular weight is 1,000 to 30. 0,000 is preferred, and 1,500 to 20,000 is more preferred. Polydimethylsiloxane (Meth)acrylic acid esters having a chain include, for example, "FM-0711" and "FM-0 "721", "FM-0725" (both manufactured by JNC Corporation), and "X-24-8201" "X-22-174DX", "X-22-2426" (all manufactured by Shin-Etsu Chemical Co., Ltd.) Companies such as [company name] can commercially obtain it.

[0022] The ratio of monomer (b) to the total mass of all units constituting polymer (A) is preferably is 80% by mass or less, more preferably 1 to 55% by mass, even more preferably 5 to 50% by mass. Particularly preferred is a range of 8 to 40% by mass. If this ratio is within the above range, the curing properties It can be improved and an uneven structure can be effectively formed.

[0023] (Monomers having hydrogen-donating functional groups) Polymer (A) optionally contains constituent units derived from monomers having hydrogen-donating functional groups. It is permissible to do so. In particular, if the active group includes a hydrogen abstraction type, hydrogen donor It is preferable that the polymer (A) contains constituent units derived from monomers having active groups. If done so, the coating film of the curable composition will harden effectively from the surface, improving the curability, This makes it easier to form an uneven structure. Examples of hydrogen-donating functional groups include hydroxyl groups, amino groups, mercapto groups, and amide groups. This can be achieved. Among these, those that allow the curing reaction to proceed particularly efficiently and improve curability, or From the viewpoint of easily forming an uneven structure, hydroxyl groups, amino groups, or amide groups are preferred. stomach.

[0024] Monomers having hydrogen-donating functional groups include those with hydrogen-donating functional groups and radical polymerizable groups. Examples of compounds include those possessing this feature, and the ease of synthesis of the compound and the adjustment of the amount of hydrogen-donating functional group introduced are important. From the viewpoint of ease of use, (meth)acrylic acid esters having hydrogen-donating functional groups are preferred. . Examples of monomers having hydrogen-donating functional groups include 2-hydroxyethyl(meth)a acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth (T) Acrylate, 6-Hydroxyhexyl (meth)acrylate, 8-Hydroxy 10-Hydroxydecyl(meth)acrylate, 12-Hydroxydecyl(meth)acrylate, 12-Hydroxydecyl(meth)acrylate Roxylauryl (meth)acrylate, monobutylhydrocylfumalate, monobutylhi Hydroxyl group-containing monomers such as hydroxyitaconate; N,N-dimethyl(meth)acrylamide N,N-diethyl(meth)acrylamide, N-vinylcaprolactam, N-vinyl Loridone, N-isopropyl(meth)acrylamide, N,N-dimethylaminoethyl( Meth)acrylate, 2-[(butylamino)carbonyl]oxy]ethyl (meth)acrylate Relate, N,N-dimethylaminopropyl(meth)acrylamide, N,N-diethyl Aminopropyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylamide N,N-dimethylaminopropyl (meth)acrylate, N,N-diethylamine Nopropyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylamine D, N,N-diethylaminoethyl(meth)acrylamide, (meth)acryloylmol Examples include monomers containing amino groups or amide groups, such as phorin and vinylacetamide. Among them, 2-hydroxyethyl( Meth)acrylate, 3-hydroxypropyl(meth)acrylate, 4-hydroxypropyl (Meth)acrylate, (N,N-dimethylacrylamide, N,N-dimethylam Noethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate Preferably, in terms of easily creating a large uneven structure, N,N-diethylaminoethyl(meth Acrylates are more preferred. These compounds can be used individually or in combination of two or more. You may do so.

[0025] (Other monomers) Polymer (A) may further have constituent units derived from other monomers other than those mentioned above, as needed. It may be present. Other monomers include those having a radical polymerizable group, an active group, and a carbon atom with 4 or more carbon atoms. Examples include compounds that do not have a lukyl group, a fluorine atom, a silicon atom, or a hydrogen-donating functional group. ru. Other monomers include, for example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, Carboxyl group-containing monomers such as fumaric acid, maleic acid, and citraconic acid, and their salts; Ethyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate (Meth)acrylates such as (meth)acrylates; nitrogen-containing monomers such as (meth)acrylonitrile; styrene , styrene compounds such as α-methylstyrene, divinylbenzene, vinyltoluene; pro Vinyl esters such as vinyl pionicate and vinyl acetate; γ-methacryloxypropyl trimeth Silicon-containing monomers such as xysilane and vinyltrimethoxysilane; phosphorus-containing vinyl monomers; salts Examples include vinyl halogens such as vinyl compounds and pyridene chloride; and conjugated dienes such as butadiene. .

[0026] A monomer having a hydrogen-donating functional group relative to the total mass of all units constituting polymer (A) The proportion of derived constituent units is preferably 80% by mass or less, more preferably 1 to 40% by mass. More preferably, the range is 3 to 35% by mass, and particularly preferably 5 to 30% by mass. If the mixture is within the above range, the curing properties can be improved, and an uneven structure can be effectively formed.

[0027] (Weight average molecular weight) The weight-average molecular weight (Mw) of polymer (A) is preferably 1,000 to 500,000, more Preferably in the range of 3000 to 300000, and more preferably in the range of 5000 to 200000. Yes. If Mw is within the above range, the applicability and curability of the curable composition will be further improved, and the recess will be concave. The ease of forming convex structures tends to improve. The Mw of polymer (A) was measured by gel permeation chromatography (GPC). This is the value equivalent to the standard polystyrene. Detailed measurement conditions are described in the examples below. It is a cage.

[0028] The content of active groups per gram of polymer (A) is preferably 0.1 to 3.5 mmol / g, more preferably 0.3 to 3.0 mmol / g, even more preferably 0.5 to 2.7 mm The amount of active group is ol / g, particularly preferably in the range of 1.0 to 2.5 mmol / g. Within the above range, the curing properties are superior, and the uneven surface can be formed more effectively.

[0029] (Glass transition temperature) The glass transition temperature (Tg) of polymer (A) is preferably -30 to 150°C, more preferably The temperature range is 0 to 120°C, more preferably 25 to 100°C. If present, it tends to improve hardening properties and the ease of forming uneven structures.

[0030] (Production of polymer (A)) Polymer (A) is typically produced by polymerizing starting monomers in the presence of a polymerization initiator. Yes, it is possible. During polymerization, a chain transfer agent may be used in combination as needed. Examples of polymerization methods include: Examples include solution polymerization, suspension polymerization, bulk polymerization, and emulsion polymerization, and among these, the one that is easiest to operate and produces Solution polymerization is preferred due to its high productivity.

[0031] (Content of polymer (A)) The amount of polymer (A) in the curable composition of the present invention determines the imparting of an uneven surface structure to the cured product. Furthermore, in terms of providing good active energy ray curability, 0.5% by mass or more and 25.0% by mass or less is appropriate. Preferably, 0.7% by mass or more and 20.0% by mass or less; more preferably, 1.0% by mass or more and 15% by mass or less. A concentration of 0.0% by mass or less is more preferable, and a concentration of 2.0% by mass or more and 12.0% by mass or less is particularly preferable. The most preferred range is 3.0% by mass or more and 10.0% by mass or less. The non-volatile content of a curable composition refers to the total mass of components other than the solvent, such as organic solvents. The proportion of non-volatile content in a curable composition can be measured by conventionally known methods, for example, 1 The weight obtained when the organic solvent is evaporated by spreading out a composition of g and heating it at 100°C for 1 hour. It can be calculated from the changes in [the variable].

[0032] ((meth)acrylate(B)) Layer (1) may contain (meth)acrylate (B) in addition to polymer (A). (T) Acrylate (B) is not particularly limited as long as it is a methacrylic acid ester, monofunctional meth Whether it is a methacrylate, a bifunctional methacrylate, or a polyfunctional methacrylate with three or more functions It is also acceptable to include one or more methacrylate esters as (meth)acrylate (B). It is also possible to use commercially available active energy ray curable resin materials. Methacrylate (B) facilitates the formation of uneven surfaces on the cured product and improves scratch resistance. Furthermore, it is a component that contributes to improving hardness.

[0033] The monofunctional (meth)acrylate is not particularly limited, but for example, methyl (meth)acrylate, n-butyl(meth)acrylate, 2-ethylhexyl(meth) Acrylate, Lauryl (meth)acrylate, Stearyl (meth)acrylate, Secret Alkyl(meth)acrylate, isobornyl(meth)acrylate, etc. (T) Acrylate, Hydroxyethyl (meth)acrylate, Hydroxypropyl (meth) ) Acrylate, hydroxybutyl (meth)acrylate, etc. hydroxyalkyl (meth) Acrylate, Methoxyethyl (meth)acrylate, Ethoxyethyl (meth)acrylate Methoxypropyl (meth)acrylate, ethoxypropyl (meth)acrylate, etc. Alkoxyalkyl (meth)acrylate, benzyl (meth)acrylate, phenoxy Aromatic (meth)acrylates such as cyethyl (meth)acrylate, diaminoethyl (meth)acrylate ) Amino group-containing (meth) acrylates, diethylaminoethyl (meth)acrylates, etc. Acrylate, methoxyethylene glycol (meth)acrylate, phenoxyethylene Lengril (meth)acrylate, phenylphenol ethylene oxide modified (meth )Ethylene oxide-modified (meth)acrylates such as acrylates, glycidyl (meth) Acrylates, tetrahydrofurfuryl (meth)acrylates, (meth)acrylic acid, etc. It can be listed.

[0034] The difunctional (meth)acrylate is not particularly limited, but for example, 1,4 -Butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate 1,6-Hexanediol di(meth)acrylate, 1,9-nonanediol di( Alka such as meth)acrylate, tricyclodecane dimethylol di(meth)acrylate Diol di(meth)acrylate, bisphenol A ethylene oxide modified di(meth)acrylate ) Acrylates, bisphenol F ethylene oxide-modified di(meth)acrylates, etc. Bisphenol-modified di(meth)acrylate, polyethylene glycol di(meth)acrylate Polypropylene glycol di(meth)acrylate, urethane di(meth)acrylate Examples include acrylates, epoxy di(meth)acrylates, etc. Among these, the structure without branching is preferable considering the ease with which wrinkled, uneven structures can be formed. Preferably, alkyldiol di(meth)acrylate is preferred, and having 4 carbon atoms. Alkyl diol di(meth)acrylates with a coefficient of ~18 are even more preferred.

[0035] While there are no particular limitations on polyfunctional (meth)acrylates with three or more functions, For example, dipentaerythritol hexa(meth)acrylate, pentaerythritol tetra La(meth)acrylate, ditrimethylolpropanetetra(meth)acrylate, pen Taerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate Relate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate , ethylene oxide-modified pentaerythritol tetra(meth)acrylate and other ethylene Ethylene oxide-modified (meth)acrylate, isocyanurate ethylene oxide-modified tri( Meth-acrylate, ε-caprolactone-modified tris(acrooxyethyl) isocyanure Isocyanuric acid-modified tri(meth)acrylates such as methyl acrylate, pentaerythritol tri(meth)acrylate (T) Acrylate hexamethylene diisocyanate urethane prepolymer, pentaerythritol Litol tri(meth)acrylate toluene diisocyanate urethane prepolymer, di Pentaerythritol penta(meth)acrylate hexamethylene diisocyanate urea Examples include urethane (meth)acrylates such as tanprepolymers. Among these, Considering the ease with which wrinkled, uneven structures can be formed, ethylene oxide modified types, for example Pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate ) Trifunctional (meth)acrylates such as acrylates are preferred. The (meth)acrylates mentioned above may be used alone or in combination of two or more types.

[0036] The content of (meth)acrylate (B) in the curable composition of the present invention is such that good curability is achieved. From this perspective, a concentration of 0.5% by mass or more and 70.0% by mass or less relative to the nonvolatile content of the curable composition is preferred. More preferably 0.7% by mass or more and 65.0% by mass or less, and 1.0% by mass or more and 60.0% by mass or less. More preferably less than or equal to mass%, particularly preferably 2.0% by mass or more and 50.0% by mass or less, 3 The most preferable concentration is 0.0% by mass or more and 40.0% by mass or less. Using this range results in a matte finish. It can form an uneven structure suitable for exhibiting properties. In addition, the hardness of the cured product is sufficient. This improves scratch resistance.

[0037] (organic solvent) The curable composition of the present invention may contain an organic solvent. By including an organic solvent, the present invention The workability of applying the curable composition of the invention to a substrate is improved. Examples of organic solvents include aromatic solvents such as toluene and xylene; methyl ethyl keto Ketone solvents such as acetone, methyl isobutyl ketone, and cyclohexanone; diethyl Ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glyco Didimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether Diethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl Lu ether, propylene glycol monomethyl ether acetate, anisole, phenoxyethanol Ether solvents such as Thor; ethyl acetate, butyl acetate, isopropyl acetate, ethylene glycol Ester solvents such as chol diacetate; dimethylformamide, diethylformamide amide solvents such as N-methylpyrrolidone; methyl cellosolve, ethyl cellosolve, buty Cellosolve-based solvents such as Lucerosolve; methanol, ethanol, propanol, isopropyl alcohol Alcoholic solvents such as panol and butanol; halogens such as dichloromethane and chloroform Examples include solvents of the ion type. One organic solvent may be used alone, or two or more may be used in combination. That's fine. Of these solvents, ester-based solvents and ether-based solvents offer improved workability during coating. A solvent, alcoholic solvent, and ketone solvent are preferred.

[0038] The content of organic solvents in the curable composition of the present invention improves operability during the coating operation. Therefore, a ratio of 10 parts by mass or more to less than 1900 parts by mass per 100 parts by mass of nonvolatile content of the curable composition is preferred. More preferably, the amount is 40 parts by mass or more and less than 400 parts by mass.

[0039] (Photopolymerization initiator) The curable composition of the present invention, when irradiated with active energy rays, exhibits the active groups of polymer (A). Since radicals are generated from it, it has photocurability even without containing a separate photopolymerization initiator, but hard A photopolymerization initiator may be included to promote polymerization. A photopolymerization initiator with a molecular weight of 10 Compounds with a pH of less than 00 are preferred. Examples of photopolymerization initiators include benzoin, benzoin Methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzo In-n-butyl ether, benzoinphenyl ether, benzyl diphenyl disulfide D, dibenzyl, diacetyl, anthraquinone, 2-ethylanthraquinone, naphthoquinone Benzophenone, consisting of 2,4-diethylthioxanthone, benzophenone and its derivatives Phenones, 1-hydroxy-cyclohexyl-phenyl-ketones [e.g., trade name "Om Nirad (registered trademark) 184, manufactured by IGM, 2-hydroxy-1-{4-[4-( 2-Hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propionyl Ropan-1-on [For example, product name "Omnirad(registered trademark) 127", 2,2-j Methoxy-1,2-diphenylethane-1-one [For example, trade name "Omnirad (registered [Registered Trademark 651], manufactured by IGM, 2,4,6-trimethylbenzoyl-diphenyl- Fosphing oxide [For example, the product name "Omnirad(registered trademark) TPO H", I [Manufactured by GM] Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxa Id [for example, product name "Omnirad(registered trademark) 819", manufactured by IGM], 2-methyl Lu-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one [Example Product name "Omnirad(registered trademark) 907", manufactured by IGM, 2-benzyl-2- Dimethylamino-1-(4-morpholinophenyl)-butanone-1 [For example, trade name " Omnirad(registered trademark) 369, 2-hydroxy-2-methyl-1-phenylpropyl Pan-1-On [For example, product name "Omnirad(registered trademark) 1173", manufactured by IGM] These photopolymerization initiators can be used individually or in combination of two or more. It may be present. Among these, benzophenone compounds with excellent surface hardening properties are preferred. Examples of such compounds include benzophenone.

[0040] The photopolymerization initiator should be added in a manner that does not cause curing, prioritizing it over the polymer (A). The amount of photopolymerization initiator added per 100 parts by mass of nonvolatile content of the chemical composition is preferably 3% by mass or less. More preferably 2% by mass or less, even more preferably 1% by mass or less, and 0.5% by mass or less. The bottom one is particularly preferable.

[0041] (Leveling agent) The curable composition of the present invention contains an appropriate amount of a leveling agent to improve the appearance of the cured product. It is also possible to use leveling agents such as acrylic leveling agents and silicone leveling agents. Examples include ringing agents and fluorine-based leveling agents. Leveling agents can be used individually. Often, two or more types can be used in combination.

[0042] (Inorganic particles) The curable composition of the present invention contains an appropriate amount of inorganic particles to further improve the matte finish of the cured product. It may contain. The average primary particle size of the inorganic particles is preferably 0.01 to 10 μm. Inorganic particles The child was surface-modified with a silane coupling agent having a reactive group such as a (meth)acryloyl group. Particles are also acceptable. Surface-modified particles may have reactive groups such as (meth)acryloyl groups. The silane coupling agent and inorganic particles are subjected to acids, bases, aluminum acetylacetone, etc. The reaction is carried out at 25-120°C for about 1-24 hours in the presence of a silane coupling reaction catalyst. They can be manufactured by law. Examples of inorganic particles include silica, alumina, and zirconia. Among them, silica is preferred.

[0043] (Other ingredients) The curable composition of the present invention may contain, for example, thiol groups, to the extent that it does not impair the effects of the present invention. Polymerization accelerators, antistatic agents, plasticizers, surfactants, antioxidants, ultraviolet rays, and other compounds containing these substances. It may contain an absorbent.

[0044] (Method for manufacturing curable compositions) The curable composition of the present invention comprises a polymer (A) and, if necessary, (meth)acrylate ( B) Mixing organic solvents, photopolymerization initiators, leveling agents, inorganic particles, and other components. It can be manufactured by [method].

[0045] (cured product) The cured product of the present invention is obtained, for example, by applying a curable composition to a substrate, then drying the coating film, and then... It is obtained by irradiation with active energy rays. The surface side of the coating film before curing is polymer (A). Because the concentration of the polymer tends to be high, when activated energy rays are irradiated from the surface side, polymer (A A radical is generated from the active group of ), and the generated radical becomes the starting point for radical polymerization. As the reaction between the methacrylate (B) molecules proceeds, the surface of the coating hardens first. A film is formed. Subsequently, the inside of the coating reacts and hardens, causing shrinkage stress. It is thought that the hardened coating buckles further, resulting in the appearance of a wrinkled, uneven structure. Typically, the surface of the resulting film-like cured material (hereinafter also referred to as the cured film) has a wrinkled, uneven structure (non It has a smooth structure, and therefore has a matte finish.

[0046] The thickness of the cured film (textured layer) is preferably 0.1 to 100 μm, more preferably 0.2 to 20 μm, more preferably 0.3 to 10 μm, and particularly preferably in the range of 0.3 to 7 μm Yes. If the thickness of the cured material is within the above range, it achieves a matte finish with sufficiently little reflection of external light. It is easy. The thickness of the cured film indicates the maximum thickness of the uneven layer, and cross-sectional observation with an electron microscope reveals the result. It is required.

[0047] (Method of manufacturing a cured product) The method for applying the curable composition to the substrate is not particularly limited, but for example, the dip-coat method. , air knife coating method, curtain coating method, spin coating method, roller coating method, bar Coating methods, wire bar coating method, gravure coating method, spray coating method, etc. can be mentioned.

[0048] The curable composition applied to the substrate is preferably dried before being irradiated with active energy rays for curing. When drying, the drying temperature is preferably 30 to 200 °C, more preferably 40 to 15 0 °C. Also, the drying time is preferably 0.01 to 30 minutes, more preferably 0.1 to 10 minutes. By drying in advance, the solvent in the coating film can be effectively removed, and the concentration of the polymer (A) on the surface side of the coating film becomes high, so that an uneven structure is likely to appear on the surface of the cured product.

[0049] Examples of the active energy rays include ultraviolet rays, α rays, β rays, and γ rays. Among them ultraviolet rays are preferred. The irradiation amount of the active energy rays can be appropriately selected according to the type of the active energy rays to be irradiated. When using ultraviolet rays, the integrated light amount of irradiation is 100 mJ / cm , 2 , , 2 , , 2 , 2 , 2 , , or more and 3000 mJ / cm 2 or less is preferred, and 200 mJ / cm 2 or more and 2000 mJ / cm 2 or less is more preferred. Also, the illuminance is preferably 50 mW / cm 2 or more and 600 mW / cm 2 [[ID=4K]]or less is preferred, 75 mW / c m 2 or more and 450 mW / cm2 or less is more preferred, and 100 mW / cm 2 or more and 300 mW / cm 2 or less is even more preferred. Examples of the light source include, for example, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, electrodeless lamps, metal halide lamps, scanning-type or curtain-type electron beam acceleration paths Examples include high-voltage mercury lamps and low-voltage mercury lamps that use electron beams.

[0050] When curing by irradiating with active energy rays, the concentration of polymer (A) on the surface of the coating film is increased beforehand. If left untreated, the surface of the coating hardens first, forming a hardened film. After that, the inside of the coating hardens. During hardening, shrinkage occurs, and the resulting shrinkage stress causes the hardened coating to buckle, creating a wrinkled, uneven structure. It is thought that...

[0051] The arithmetic mean roughness (Ra) of the surface uneven structure decreases when the curing time inside the coating film is shortened. The curing time increases, and the size increases with longer curing time. (B) The amount of photopolymerization initiator and the intensity of the active energy rays can be adjusted. ru.

[0052] (base material) The layer (2) of the present invention has a surface roughness having an arithmetic mean roughness (Ra) of 0.10 μm or more. It is a material. Examples of such base materials include films, plates, and other forms of various polymers. Examples of molded articles include those in the shape of a polymer film, such as triacetylcellulose (T AC film, polyethylene terephthalate (PET) film, diacetylene cellulose Cellulose film, acetate butyrate cellulose film, polyethersulfone film Polyacrylic polymer film, polyurethane polymer film, polycarbonate Film, polysulfone film, polyether film, polymethylpentene film , polyetherketone film, polyvinyl chloride (PVC) film, (meth)acrylo Examples include nitrile films and cycloolefin polymer (COP) films. Examples of sheets and polymer molded articles include acrylic, triacetylcellulose, and polyethylene. Polyester phthalate, diacetylene cellulose, acetate butyrate cellulose, polyethylene Polysulfone, polyurethane, polycarbonate, polysulfone, polyether, poly Examples include plates and molded bodies made of methylpentene, polyether ketone, and (meth)acrylonitrile. It can be done. In addition, inorganic materials such as glass can be used as the base material. To impart surface roughness, one means of forming a fine uneven pattern is, for example, sand Blasting, nanoimprinting, or incorporating fine particles as fillers into the substrate. Methods can be mentioned. When incorporating fine particles, the type of particles to be incorporated depends on the surface roughness. The particles that can be imparted are not particularly limited; for example, silica. Calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate Inorganic particles such as magnesium phosphate, kaolin, aluminum oxide, and titanium dioxide, Lyl resin, styrene resin, urea resin, phenol resin, epoxy resin, benzoguanamine Examples include organic particles such as resins. Among these, the fact that they are particularly effective even in small amounts is noteworthy. Silica particles, calcium carbonate particles, and acrylic resin particles are preferred.

[0053] Furthermore, there are no particular restrictions on the shape of the particles used; they can be spherical, lumpy, or rod-shaped. Any shape, such as flattened or otherwise, may be used. Furthermore, there are no particular restrictions on its hardness, specific gravity, color, etc. No. These series of particles may be used in combination of two or more types as needed.

[0054] Furthermore, the average particle size of the particles used is in the range of 0.01 to 10 μm, in order to impart surface roughness. Preferably, it is in the range of 0.05 to 8 μm, and more preferably 0.1 to 6 It is more preferable that the range be in μm, and particularly preferable that it be in the range of 0.15 to 5 μm. It's nice.

[0055] The thickness of the base material can be selected as appropriate depending on the application, but generally it is 10 to 100. Materials with a thickness of approximately 00 μm are used.

[0056] (Laminated structure) The laminate of the present invention comprises a layer made of a substrate and a layer (uneven layer) made of a cured film of a curable composition. The laminate may further have a primer layer between the substrate and the cured film. The substrate may have a functional layer on the surface opposite to the cured film side. If none is present, a surface functional layer may be provided on the surface opposite to the substrate of the cured film.

[0057] (Primer layer) The primer layer is appropriately constructed between the substrate and the cured film (textured layer) to impart various functions. The primer layer may have one or more functions in a single layer, or multiple layers may be used. It may be composed of such elements.

[0058] In a preferred embodiment, the primer layer is an adhesion-enhancing layer. Adhesion between the substrate and the uneven layer If the adhesion is insufficient, the laminate may not be usable depending on the application. This improves the adhesion between the substrate and the uneven layer, allowing the laminate to be used in a variety of applications. From the perspective of improvement, the adhesion-enhancing layer may contain either one or both of the following compounds: resin and crosslinking agent. It is preferable that it contains [the specified ingredient].

[0059] In another preferred embodiment, the primer layer is an antistatic layer. If it is a protective layer, it is applied to the outermost surface of the laminate, especially the outermost surface on the side where the uneven layer exists relative to the substrate. This reduces the adhesion of dust and other particles due to peeling charge and triboelectric charge. To make the primer layer an antistatic layer, for example, an antistatic agent can be incorporated into the primer layer. That's all you need to do.

[0060] Conventionally known resins can be used as the resin included in the primer layer. Specific examples include polyester resin, acrylic resin, urethane resin, and polyvinyl resin. Examples include polyvinyl alcohol, vinyl chloride-vinyl acetate copolymer, etc. However, considering adhesion performance and coating properties, polyester resin, acrylic resin, urethane A resin is preferred. When the substrate is a resin film, from the viewpoint of affinity with the substrate, the primer layer contains The resin is preferably the same type as the resin film. For example, if the base material is a polyester film. The primer layer preferably contains polyester resin. In the case of a relate film, it is preferable that the primer layer contains an acrylic resin.

[0061] There are no particular restrictions on the antistatic agent to be included in the primer layer; any known antistatic agent is acceptable. It can be used, for example, compounds having an ammonium group, polyether compounds Examples include substances, compounds having sulfonic acid groups, betaine compounds, and conductive organic polymers.

[0062] The primer layer may contain particles for blocking or improving lubricity. The primer layer may contain, as necessary, an antifoaming agent and a coating agent, to the extent that it does not impair the spirit of the present invention. Fabric modifiers, thickeners, organic lubricants, UV absorbers, antioxidants, foaming agents, dyes, pigments, etc. It may contain the following additives.

[0063] The proportion of resin in 100% by mass of the primer layer is, for example, 5% by mass or more, preferably 10%. 99% by mass, more preferably 20-95% by mass, and even more preferably 30-90% by mass Within the specified range, the adhesion performance and appearance of the primer layer will be superior. ru.

[0064] The thickness of the primer layer depends on the material used for the primer layer and the performance to be achieved. It is difficult to say definitively, but preferably 0.001 to 10 μm, more preferably 0.01 to 4 μm. The size is μm, more preferably in the range of 0.02 to 1 μm. The primer layer can be formed by known methods.

[0065] (Surface functional layer) The surface functional layer is used to impart various functions to the side of the cured film (textured layer) opposite to the substrate layer. This is a layer provided on the surface. Examples of surface functional layers include an anti-fouling layer, an antistatic layer, and a refractive index adjustment layer. Examples include layers (anti-reflective layer, low-reflection layer, etc.), infrared absorption layer, ultraviolet absorption layer, and color correction layer. The surface functional layer may have one or more functions in a single layer, or may be composed of multiple layers. That's fine.

[0066] The antifouling layer is provided to improve the antifouling performance by imparting water-repellent and oil-repellent properties to the hardened film. Materials used in the antifouling layer include silicone compounds, fluorine compounds, and long Conventional known compounds such as alkyl chain-containing compounds can be used. Among these, For strong antifouling performance, silicone compounds and fluorine compounds are preferred, and the antifouling layer From the perspective of not contaminating the object it comes into contact with, fluorine compounds and long-chain alkyl group-containing compounds are considered. It is preferable.

[0067] When forming an antistatic layer as a surface functional layer, conventionally known antistatic agents are used. Various antistatic agents can be used. Also, for example, compounds having an ammonium group. Another preferred method involves introducing a double bond, such as an acryloyl group, and allowing the reaction to occur at the double bond site.

[0068] Examples of refractive index adjustment layers include high refractive index layers, low refractive index layers, and laminates thereof. It can be done.

[0069] The thickness of the surface functional layer shall be no more than five times the height from the recess to the protrusion of the uneven structure of the cured film. This ratio is preferable, and 3 times or less is more preferable. The smaller this ratio, the lower the matte performance of the cured film. It tends to become more difficult to remove. The thickness of the surface functional layer is measured from the recessed parts to the convex parts of the uneven structure of the cured film. It is difficult to say definitively as it depends on the height, but it is usually 0.001 to 3 μm, preferably 0.005 ~2 μm, more preferably 0.01~1 μm, even more preferably 0.02~0.5 μm, Particularly preferred is a range of 0.03 to 0.2 μm. By using within the above range, surface machine This makes it possible to achieve both the functional properties of the functional layer and the matte finish of the cured film. The surface functional layer can be formed by known methods.

[0070] (Reverse side functional layer) The functional layer on the back side is used to impart various functions to the side opposite to the cured film (uneven layer) of the substrate layer. This is a layer provided on the back surface. Examples of back surface functional layers include an adhesive layer, an antistatic layer, and a refractive index adjuster. Examples include layers and antiblocking layers. The back-side functional layer has one or more functions in a single layer. It may be structured in a single layer, and it may also be composed of multiple layers. The adhesive layer is provided to bond the laminate to various adherends. The antistatic layer is provided to the laminate Exfoliation and triboelectric charging occur on the outermost surface, particularly on the surface opposite to the uneven layer of the substrate layer. It is provided to prevent the adhesion of dust and other debris, and the resulting defects. The refractive index adjustment layer is, for example, The antiblocking layer is provided to improve the total light transmittance of the laminate. It is designed to reduce body blocking.

[0071] Examples of adhesives that form the adhesive layer include acrylic, polyester, and urethane adhesives. Examples include known rubber-based adhesives. Among these, acrylic-based adhesives are considered to have versatility. An adhesive is preferred. The components forming the antistatic layer and the refractive index adjusting layer are as described in the respective sections of the surface functional layer. It is similar to that.

[0072] The thickness of the functional layer on the back side depends on the material used for the functional layer and the performance it is intended to achieve. It's difficult to generalize, but for example, it's between 0.001 and 30 μm. This is the case when the functional layer on the back surface is an adhesive layer. The thickness is preferably 0.01 to 30 μm, more preferably 0.1 to 20 μm. (Back surface function) If the layer is an antistatic layer, it is preferably 0.001 to 10 μm, more preferably 0.0 The size is 1-5 μm. The back surface functional layer can be formed by known methods.

[0073] (Formation of surface functional layer and back functional layer) The surface functional layer and the back functional layer are formed, for example, by using the above-mentioned series of components as a solution or dispersion in a solvent. Then, a liquid with a solid content concentration of approximately 0.1 to 80% by mass is coated onto the designated surface. It can be formed by drying and hardening.

[0074] Coating methods include, for example, gravure coating, reverse roll coating, and Icoat, Air Doctor Coat, Blade Coat, Rod Coat, Bar Coat, Curtain Coat, knife coat, transfer coat, squeeze coat, impregnation coat, kiss Conventional known coating methods such as coating, spray coating, calender coating, and extrusion coating. These are some examples.

[0075] The drying and curing conditions when forming the surface functional layer and the back functional layer are not particularly limited. However, regarding the drying of solvents such as water used in the coating solution, it is usually 50-150 The temperature is in the range of °C, preferably 80 to 130 °C, and more preferably 90 to 120 °C. The approximate time range is 3 to 200 seconds, preferably 5 to 120 seconds. Also, the surface To improve the strength of the functional layer and the back functional layer, after drying, it is usually heated to 150-270°C, preferably... Heat treatment in the range of 170-230°C, more preferably 180-210°C, is performed. Preferred. The heat treatment time is approximately 3 to 200 seconds, preferably in the range of 5 to 120 seconds. This type of heat treatment is suitable when the laminate is a film.

[0076] (Characteristics of laminates) The arithmetic mean roughness (Ra) of the surface of the laminate is preferably 0.10 μm or more, more preferably The particle size is 0.30 μm or larger, more preferably 0.50 μm or larger, and particularly preferably 0.60 μm. The most preferred range is 0.80 μm or more, and there is no particular upper limit, but it is preferable. The thickness is 5 μm. Within this range, excellent matte finish is achieved.

[0077] The haze of the laminate measured by the method described in the examples below is high. There is a tendency for the matte finish to improve. The haze is preferably 40% or more, more preferably 50% or more, and even more preferably 60%. The above range is particularly preferably 80% or more, most preferably 90% or more, and as an upper limit For example, it is 99%. In applications where a matte finish is important, a higher haze in the laminate is preferable. It is desirable. Within the above range, it will have excellent matte finish.

[0078] The 60° gloss of the laminate surface measured by the method described in the examples below (60° mirror) The surface gloss is preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less. The range is preferably 10 or less, most preferably 5 or less, and the lower the value, the less matte the finish. There is a tendency for improvement. Similarly, the 20° gloss is preferably 20 or less, more preferably 15 or less, and further Preferably in the range of 10 or less, particularly preferably 5 or less, and most preferably 1 or less. This is preferable. Within the above range, the matte finish will be excellent.

[0079] The laminate preferably has light transmittance. The total light transmittance is preferably 50% or more, more preferably 60% or more. The range is 70% or more, particularly preferably 80% or more, and most preferably 90% or more. A higher value is preferable in terms of permeability (the upper limit is 100%).

[0080] The laminate obtained by the present invention, by utilizing its matte properties, can be used for building materials, interiors of vehicles, etc. It can be used for glass decoration and to improve the design of housings for electrical and electronic equipment. [Examples]

[0081] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these. It is not something that can be determined. The measurement and evaluation methods used in this invention are as follows.

[0082] <Weight average molecular weight> The weight-average molecular weight of polymer (A) can be measured under the following measurement conditions. (GPC measurement conditions) Columns: "TSK-gel superHZM-M", "TSK-gel HZMM" "TSK-gel HZ2000" Eluent:THF Flow rate: 0.35mL / min Injection volume: 10μL Column temperature: 40℃ Detector: UV-8020

[0083] <Total light transmittance / haze> The measurement target was a laminate in which a cured film was formed on a substrate. Total light transmittance and haze were measured using JIS standards. S Z8722:2009 (Geometric conditions for illumination and reception of light from a penetrating object) and JIS K736 1-1:1997 (Plastics - Test method for total light transmittance of transparent materials) JIS K71 In accordance with 36:2000 (Plastics - Method for determining haze of transparent materials), manufactured by Nippon Denshoku Industries Co., Ltd. The measurement was taken using the SH7000 haze meter. Regarding haze, measure the haze of the substrate only and subtract it from the haze measurement of the laminate. This allowed us to evaluate the haze of only the uneven layer (hardened film).

[0084] <20° and 60° Gross> Laminates with a cured film formed on a substrate were used as the measurement target. 20° and 60° gloss (20° (and 60° specular gloss) in accordance with JIS Z 8741-1997, Nippon Denshoku Industries Co., Ltd. The measurement was taken using the "VG2000" gloss meter. A lower gloss value indicates a matte finish. To be excellent.

[0085] <Arithmetic mean roughness (Ra) of surface texture> The arithmetic mean roughness (Ra) of the surface irregularity structure of a cured product is determined by a surface shape measurement system (Hitachi Hi-Tech). Measurements were taken using a scanning white light interference microscope (VS1330) manufactured by KScience Co., Ltd. The magnification of the objective lens was set to 20x. On the surface of the uneven layer, 236.87 μm × The surface topography in the 177.60 μm region was measured using optical interferometry, and the resulting composite and base data were used. Line correction was performed, and the arithmetic mean roughness (Ra) of the uneven cross-section was calculated.

[0086] (Synthesis Example 1: Synthesis of monomer (i-1)) Methacrylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) is distilled under reduced pressure to obtain a distillate with a purity of 99.8% or higher. The fraction was recovered to obtain the distillate of methacrylic anhydride. Vacuum distillation was performed at a pressure of 30 Pa from room temperature. The method involved gradually increasing the temperature to 90°C. Separately, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy -2-Methyl-1-propan-1-one (manufactured by Tokyo Chemical Industry Co., Ltd.) 22.4g (0.1mol) ), and triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) 30.4g (0.3mol) are mixed with methyl chloride. It was dissolved in 500 mL of ethylene (manufactured by Tokyo Chemical Industry Co., Ltd.). The above methacrylic anhydride was then vaporized. 23.1 g (0.15 mol) of the residue was added dropwise at room temperature, and the mixture was stirred for 12 hours. The resulting reaction solution was washed three times with 500 mL of deionized water, then the organic phase was concentrated, and the solvent was removed. The residue was removed by distillation. The residue was collected by column chromatography (ethyl acetate / hexane = 10 / 90 (volume)). The compound was purified using a ratio of 21.6 g to obtain 21.6 g of the target compound (yield 74%). ¹H-NMR analysis revealed that the obtained compound was 2-[4-(2-hydroxy-2-methyl It was confirmed to be -1-oxopropyl)phenoxy]ethyl methacrylate. 1H NMR(300MHz,chloroform-d):δ8.06(d,J=9 .0Hz,2H),6.96(d,J=9.0Hz,2H),6.13(d,J=0.6 Hz,1H),5.59(s,1H),4.50(d,J=5.1Hz,2H),4.2 9(dd,J=5.5,4.1Hz,3H),1.94(dd,J=1.6,1.0Hz ,3H),1.61(s,6H).

[0087] [A polymer (A) having active groups that generate radicals upon irradiation with active energy rays] (Synthesis Example 2: Synthesis of Polymer A-1) In a flask equipped with a stirrer, condenser, and thermometer, methyl isobutyl ketone (hereinafter, M 75.0 parts of IBK were added and stirred. Then, the flask was purged with nitrogen and heated to 65°C. Heat and add 40.0 parts of 4-methacryloyloxybenzophenone (manufactured by Shinryo Co., Ltd.) and stearyl phosphate. Methacrylate (manufactured by Mitsubishi Chemical Corporation, product name: Acrylic Ester (registered trademark) S) 10. 0 parts, N,N-diethylaminoethyl methacrylate (manufactured by Mitsubishi Chemical Corporation, product name: Aqua 10.0 parts of ester DE, 2-ethylhexyl methacrylate (manufactured by Mitsubishi Chemical Corporation, Product name: Acryester EH) 30.0 parts, 2-hydroxyethyl methacrylate (Mitsubishi Chemical Co., Ltd., Product name: Acryester HO) 10.0 parts, Azobis(2,4-dimethylba Leronitrile (manufactured by Wako Pure Chemical Industries, Ltd., product name: V-65) 0.8 parts, MIBK 75.9 parts The mixed solution was added dropwise over 2 hours. After another 2 hours, in order to increase the polymerization rate, azobis( 2,4-Dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd., product name: V-65) 0.5 parts, M Add 1.0 part IBK of the mixture and hold for 5 hours. Then, cool the reaction solution to 40°C. A polymer (A) having an active group that generates radicals upon irradiation with active energy rays. Compound 1 (hereinafter referred to as A-1) was polymerized. The non-volatile content of A-1 is 40%, and the weight-average molecular weight is 40%. The quantity (Mw) was 16,700. The composition and evaluation results are shown in Table 1.

[0088] (Synthesis Example 3: Synthesis of Polymer A-2) In a flask equipped with a stirrer, condenser, and thermometer, propylene glycol monomethyl ester - 89.2 parts of methylacetate (hereinafter referred to as PMA), monomer obtained in Synthesis Example 1 (i -1) 26.6 parts, 2-(perfluorohexyl)ethyl methacrylate (Daikin Industries) (Manufactured by [Company Name], Product Name: C6SFMA monomer) 31.5 parts, 2-hydroxyethyl methacrylate (Mitsubishi Chemical Corporation, product name: Acryester HO) 7.0 parts, Glycidyl Methacrylate Acryester G (manufactured by Mitsubishi Chemical Corporation, product name: Acryester G) 4.9 parts, Azobis (2,4-dimethyl Add 0.4 parts of tilvaleronitrile (manufactured by Wako Pure Chemical Industries, Ltd., product name: V-65) and stir. Next, the inside of the flask was purged with nitrogen and the temperature was raised to 90°C to obtain the monomer (i) obtained in Synthesis Example 1. -1) 11.4 parts, 2-(perfluorohexyl)ethyl methacrylate (Daikin Industries) (Manufactured by [Company Name], Product Name: C6SFMA monomer) 13.5 parts, 2-hydroxyethyl methacrylate (Mitsubishi Chemical Corporation, product name: Acryester HO) 3.0 parts, Glycidyl Methacrylate A mixture of 2.1 parts of acrylic acid (manufactured by Mitsubishi Chemical Corporation, product name: Acryester G) and 7.1 parts of PMA5. The combined solution was added dropwise over 4 hours. After another 2 hours, in order to increase the polymerization rate, azobis(2, 4-Dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd., product name: V-65) 1.1 parts, PMA A 6.0 - part mixture was introduced and held for 5 hours. Then, the reaction solution was cooled to 40 °C, and 84.5 parts of PMA was added and stirred to polymerize a polymer (A)-2 having reactive groups that generate radicals by irradiation with active energy rays (hereinafter referred to as A-2). The non - volatile content of A-2 was 30%, and the weight - average molecular weight (Mw) was 110900. The composition and evaluation results are shown in Table 1 as described below.

[0089]

Table 1

[0090] 〔(Meth)acrylate (B)〕 The following commercially available products were used as (meth)acrylate (B).

[0091] <00009​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​• Aronix M-930 manufactured by Toagosei Co., Ltd. A mixture of glycerin diacrylate and glycerin triacrylate.

[0096] [Base material] The following films were used as substrates. The evaluation results for the substrates only are shown in Table 2.

[0097] Acrylic film (F-1) [Adjustment Example 1] Acrylic rubber particles (I) that exhibit a matte finish Place 171.3 parts of deionized water and sodium formaldehyde sulfohydrate in a container equipped with a stirrer. A mixture containing 0.20 parts silate, 0.0001 parts ferrous sulfate, and 0.0003 parts EDTA. A mixture was prepared. The mixture was heated to 74°C while being stirred under a nitrogen atmosphere, and then further 72.9 parts methyl methacrylate, 7 parts methyl acrylate, 1 part n-butyl acrylate 4.4 parts, 1.2 parts 1,3-butylene glycol dimethacrylate, allyl methacrylate A monomer component consisting of 0.4 parts of t, 0.05 parts of cumene hydroperoxide, and n-octa 0.25 parts of thiol, and the emulsifier phosphanol RS-610NA (manufactured by Toyo Chemical Co., Ltd.) 1. Add 3 parts dropwise over 90 minutes, then allow the reaction to continue for 60 minutes to develop a matte finish. A polymer latex of acrylic rubber particles (I) was obtained. The polymer latex was treated with calcium acetate. The material was salted out in an aqueous solution containing 3.5 parts of sodium, washed with water, recovered, dried, and measured for an average particle size of 0. A powder of acrylic rubber particles (I) with a size of 4 μm was obtained.

[0098] [Manufacturing Example 1] 25 parts of the acrylic rubber particles (I) that exhibit the aforementioned matte finish are mixed with thermoplastic polymer methacrylic acid Alkyl-alkyl acrylate copolymer (manufactured by Mitsubishi Chemical Corporation; product name: Acrypet) After adding to 75 parts of VH, it was mixed using a Henschel mixer, and a die head with a T-die was attached. Using an inventive single-screw extruder, an acrylic film F-1 was formed under the conditions of a cylinder temperature of 200 - 240 °C and a T-die temperature of 245 °C. The thickness of the obtained acrylic film F-1 was 40 μm, and the arithmetic mean roughness (Ra) was 0.68 μm.

[0099] Acrylic film (F-2) [Adjustment Example 2] Production of acrylic rubber particles (II) that exhibit matting properties In a container equipped with a stirrer, a mixture was prepared by adding 200 parts of deionized water, 0.20 parts of sodium formaldehyde sulfoxylate, 0.0001 parts of ferrous sulfate, and 0.0003 parts of EDTA. The mixture was heated to 74 °C while stirring under a nitrogen atmosphere, and then further added with 63 parts of methyl methacrylate, 8.8 parts of methyl acrylate, 27 parts of n-butyl acrylate, 1.2 parts of 1,3-butylene glycol dimethacrylate, 0.4 parts of allyl methacrylate, a monomer component consisting of, 0.05 parts of cumene hydroperoxide, 0.2 parts of n-octyl mercaptan, and 1.1 parts of emulsifier Phosphanol RS-610NA (manufactured by Toyo Chemical Co., Ltd.) were added dropwise over 90 minutes, and then the reaction was continued for 60 minutes to obtain a polymer latex of acrylic rubber particles (II) that exhibit matting properties. The polymer latex was salting out in an aqueous solution containing 3.5 parts of calcium acetate, washed with water and recovered, and then dried to obtain a powder of acrylic rubber particles (II) with an average particle size of 0.2 μm. 1.2 parts of 1,3-butylene glycol dimethacrylate, 0.4 parts of allyl methacrylate, a monomer component consisting of, 0.05 parts of cumene hydroperoxide, 0.2 parts of n-octyl mercaptan, and 1.1 parts of emulsifier Phosphanol RS-610NA (manufactured by Toyo Chemical Co., Ltd.) were added dropwise over 90 minutes, and then the reaction was continued for 60 minutes to obtain a polymer latex of acrylic rubber particles (II) that exhibit matting properties. The polymer latex was salting out in an aqueous solution containing 3.5 parts of calcium acetate, washed with water and recovered, and then dried to obtain a powder of acrylic rubber particles (II) with an average particle size of 0.2 μm. a monomer component consisting of, 0.05 parts of cumene hydroperoxide, 0.2 parts of n-octyl mercaptan, and 1.1 parts of emulsifier Phosphanol RS-610NA (manufactured by Toyo Chemical Co., Ltd.) were added dropwise over 90 minutes, and then the reaction was continued for 6 minutes to obtain a polymer latex of acrylic rubber particles (II) that exhibit matting properties. The polymer latex was salting out in an aqueous solution containing 3.5 parts of calcium acetate, washed with water and recovered, and then dried to obtain a powder of acrylic rubber particles (II) with an average particle size of 0.2 μm. a monomer component consisting of, 0.05 parts of cumene hydroperoxide, 0.2 parts of n-octyl mercaptan, and 1.1 parts of emulsifier Phosphanol RS-610NA (manufactured by Toyo Chemical Co., Ltd.) were added dropwise over 90 minutes, and then the reaction was continued for 60 minutes to obtain a polymer latex of acrylic rubber particles (II) that exhibit matting properties. The polymer latex was salting out in an aqueous solution containing 3.5 parts of calcium acetate, washed with water and recovered, and then dried to obtain a powder of acrylic rubber particles (II) with an average particle size of 0.2 μm. The polymer latex was salting out in an aqueous solution containing 3.5 parts of calcium acetate, washed with water and recovered, and then dried to obtain a powder of acrylic rubber particles (II) with an average particle size of 0.2 μm. The polymer latex was salting out in an aqueous solution containing 3.5 parts of calcium acetate, washed with water and recovered, and then dried to obtain a powder of acrylic rubber particles (II) with an average particle size of 0.2 μm. The polymer latex was salting out in an aqueous solution containing 3.5 parts of calcium acetate, washed with water and recovered, and then dried to obtain a powder of acrylic rubber particles (II) with an average particle size of 0.2 μm.

[0100] [Production Example 2] The acrylic rubber particles (I) that exhibit matting properties described in Production Example 1 were used as acrylic rubber particles (II) The film was manufactured in the same manner as in Manufacturing Example 1, except that it was replaced with ). The resulting acrylic film F-2 The thickness was 40 μm, and the arithmetic mean roughness (Ra) was 0.35 μm.

[0101] Film mat (F-3) A flexible PVC film (manufactured by Neschen) with a thickness of 80 μm and a Ra of 0.42 μm.

[0102] The polyester resins used in the manufacture of the polyester film are as follows: • Polyester resin a Polyester resin made from polyethylene terephthalate (intrinsic viscosity: 0.9 dl / g) • Polyester resin b Polyethylene terephthalate is blended with spherical silica particles with an average particle size of 4.1 μm. Polyester resin composition (intrinsic viscosity: 0.6 dl / g) • Polyester resin c Polyethylene terephthalate is blended with spherical silica particles with an average particle size of 2.7 μm. Polyester resin composition (intrinsic viscosity: 0.6 dl / g)

[0103] Polyester film (F-4) [Manufacturing Example 3] The aforementioned polyester resin a and polyester resin b are mixed to obtain a particle concentration of 2.2% by mass. The mixed raw materials are then supplied to a vented twin-screw extruder, where they are melted at 285°C and co-extruded. The material is extruded from the die and then placed on a cooling roll with a surface temperature set to 22°C using an electrostatic application adhesion method. The film was then cooled and solidified to obtain an unstretched sheet. Next, the film temperature was increased by utilizing the difference in roll peripheral speed. After being stretched 3.3 times in the vertical direction at ℃, it is guided into a tenter and stretched 4.0 times in the horizontal direction at 140℃. Then, after heat treatment at a temperature of 235°C in the main crystallization zone, it is relaxed by 10% in the lateral direction, and biaxially. A stretched polyester film F-4 was fabricated. The thickness of the obtained polyester film F-4 was determined. The particle size was 25 μm, and the Ra value was 0.42 μm.

[0104] Polyester film (F-5) [Manufacturing Example 4] Except for using a mixed raw material with a particle concentration of 0.1% by mass as described in Manufacturing Example 3, this is the same as Manufacturing Example 3. The same method was used to produce a biaxially oriented polyester film F-5. The thickness of Stellfilm F-5 was 25 μm, and its Ra value was 0.16 μm.

[0105] Polyester film (F-6) [Manufacturing Example 5] In Manufacturing Example 3, polyester resin b is replaced with polyester resin c, and the particle concentration is reduced to 0. The same method as in Production Example 3 was used, except that a mixed raw material of 4% by mass was used, and biaxially oriented poly Ester film F-6 was fabricated. The thickness of the obtained polyester film F-6 was 50 The particle size was μm, and Ra was 0.01 μm.

[0106] [Table 2]

[0107] [Example 1] In a flask equipped with a stirring bar, an active energy beam is used to generate radicals. As a polymer (A) having a group, 7.5 parts by mass of A-1 in terms of nonvolatile content, and (meth)acrylate (B) consists of 70.0 parts by mass of B-1, 30.0 parts by mass of B-2, and methyl as an organic solvent. 45.0 parts by mass of ethyl ketone (hereinafter referred to as MEK), propylene glycol monomethyl After adding 105.0 parts by mass of ether (hereinafter referred to as PGM), stir until homogenized. Next, a curable composition was prepared.

[0108] The resulting curable composition is applied to a substrate having an arithmetic mean roughness (Ra) of 0.68 μm. The paint was applied to F1 with a #8 bar coater, and the resulting coating was dried in a hot air dryer heated to 70°C. The solvent was evaporated by drying for 60 seconds. Next, Iwasaki Electric's UV conveyor The US5-X0401 was used to evaluate coatings that had been cured in air under high-pressure mercury lamp conditions. The valency sample was used. The curing was performed using an integrated light quantity with a wavelength of 300-390 nm, manufactured by Iwasaki Electric Co., Ltd. When measured with an illuminance meter (Eye UV Integrated Illuminance Meter "UVPF-A1, PD-365"), 3 00 mJ / cm 2 (150mW / cm 2 Adjust the settings so that it is approximately 2 seconds long, and irradiate twice (6 00 mJ / cm 2 ) was carried out to produce a laminate in which a cured film of a curable composition was laminated on a substrate. The evaluation results of the obtained laminates are shown in Table 3.

[0109] [Example 2] The hardening process was carried out in the same manner as in Example 1, except that the substrate was F-2, which has a surface roughness of Ra of 0.35 μm. A chemical composition was prepared, and a laminate was manufactured. The evaluation results of the obtained cured product are shown in Table 3.

[0110] [Example 3] The hardening process was carried out in the same manner as in Example 1, except that the substrate was F-3, which has a surface roughness of Ra of 1.04 μm. A chemical composition was prepared, and a laminate was manufactured. The evaluation results of the obtained cured product are shown in Table 3.

[0111] [Example 4] The hardening process was carried out in the same manner as in Example 1, except that the substrate was F-4, which has a surface roughness of Ra of 0.42 μm. A chemical composition was prepared, and a laminate was manufactured. The evaluation results of the obtained cured product are shown in Table 3.

[0112] [Example 5] The hardening process was carried out in the same manner as in Example 1, except that the substrate was F-5 with a surface roughness of Ra of 0.16 μm. A chemical composition was prepared, and a laminate was manufactured. The evaluation results of the obtained cured product are shown in Table 3.

[0113] [Example 6] In a flask equipped with a stirring bar, add 12.5 parts by mass of polymer (A) A-2, based on its non-volatile content. , 15.0 parts by mass of B-3 and 35.0 parts by mass of B-4 as (meth)acrylate (B) 50.0 parts by mass of B-5, 41.8 parts by mass of MEK as an organic solvent, and 97.8 parts by mass of PGM. After adding the material, the mixture was stirred until homogeneous to prepare a curable composition. The resulting curable composition was applied to a substrate F-3 having a surface roughness of Ra = 1.04 μm. Except for the above, the laminate was manufactured in the same manner as in Example 1. The evaluation results of the obtained cured product are shown in Table 3. .

[0114] [Example 7] In a flask equipped with a stirring bar, add 12.5 parts by mass of polymer (A) A-2, based on its non-volatile content. , 80.0 parts by mass of B-3 and 10.0 parts by mass of B-4 as (meth)acrylate (B) , 10.0 parts by mass of B-5, 1.8 parts by mass of MEK as an organic solvent, 7.8 parts by mass of PGM After adding the material, the mixture was stirred until homogeneous to prepare a curable composition. The resulting curable composition was applied to a substrate F-4 having a surface roughness of Ra = 0.42 μm. Except for the above, the laminate was manufactured in the same manner as in Example 1. The evaluation results of the obtained cured product are shown in Table 3. .

[0115] [Comparative Example 1] Instead of A-1, use 3.0 parts by mass of the photopolymerization initiator benzophenone and MEK4 as the organic solvent. A curable composition was prepared in the same manner as in Example 1, except that it contained 6.4 parts by mass of PGM and 8.2 parts by mass of PGM. The material was prepared, and a laminate was manufactured. The evaluation results of the cured product of the obtained coating solution are shown in Table 4.

[0116] [Comparative Example 2] Instead of A-1, use the photopolymerization initiator 2-hydroxy-1-{4-[4-(2-hydroxy- 2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one (Omnirad127D, manufactured by IGM) 3.0 parts by mass, with MEK 46.4 as an organic solvent. A curable composition was prepared in the same manner as in Example 6, except that the amounts were parts by mass of PGM108.2 parts by mass. A laminate was manufactured. The evaluation results of the cured product of the obtained coating solution are shown in Table 4.

[0117] [Comparative Example 3] Instead of A-1, use the photopolymerization initiator 2-hydroxy-1-{4-[4-(2-hydroxy- 2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one (Omnirad127D, manufactured by IGM) 3.0 parts by mass, with MEK 46.4 as an organic solvent. A curable composition was prepared in the same manner as in Example 7, except that the amounts were parts by mass of PGM108.2 parts by mass. A laminate was manufactured. The evaluation results of the cured product of the obtained coating solution are shown in Table 4.

[0118] [Comparative Example 4] The hardness was the same as in Comparative Example 1, except that the substrate was F-6 with a surface roughness of Ra of 0.01 μm. A chemical composition was prepared, and a laminate was manufactured. The evaluation results of the obtained cured product are shown in Table 4.

[0119] [Comparative Example 5] The hardening process was carried out in the same manner as in Example 7, except that the substrate was F-6, which has a surface roughness of Ra of 0.01 μm. A chemical composition was prepared, and a laminate was manufactured. The evaluation results of the obtained cured product are shown in Table 4.

[0120] [Table 3]

[0121] [Table 4]

[0122] Examples 1 to 7 are curable compositions comprising polymer A-1 or A-2 in layer (1), and layer (2) The laminate is made using substrates F-1 to F-5 having a surface roughness of Ra of 0.10 μm or more. In all cases, a laminate with excellent matte finish and a 60° gloss of less than 10% was obtained. On the other hand, the laminates of Comparative Examples 1-4 that do not contain polymer A-1 or A-2, and Ra is 0 The laminates of Comparative Examples 4-5, using substrate F-6 with a thickness of less than 0.10 μm, had a 60° gloss of less than 10%. The result was that it was expensive and had poor matte finish.

Claims

1. A laminate comprising the following layers (1) and (2): Layer (1): A curable product obtained by curing a curable composition containing a polymer (A) and a (meth)acrylate (B) having active groups that generate radicals upon irradiation with active energy rays (excluding radical polymerizable groups), wherein the curable product is a film-like cured product having an uneven structure on the surface opposite to the surface facing layer (2). Layer (2): A substrate having a surface roughness of 0.10 μm or more, with an arithmetic mean roughness (Ra) of the surface facing Layer (1). The polymer (A) contains one or more chain-like structures derived from (meth)acrylic acid esters, selected from the group consisting only of alkyl groups, fluoroalkyl groups, and polydimethylsiloxane chains having four or more carbon atoms. A laminate in which the (meth)acrylate (B) comprises a bifunctional or more (meth)acrylate.

2. The laminate according to claim 1, wherein the polymer (A) comprises a constituent unit derived from the (meth)acrylic acid ester having the active group.

3. The laminate according to claim 1 or 2, wherein the active group that generates radicals upon irradiation with the active energy ray is one or more selected from the group consisting of a benzophenone group, an acetophenone group, an α-hydroxyacetophenone group, a benzoin group, an α-hydroxyketone group, an α-aminoketone group, an α-diketone group, an α-diketone dialkylacetal group, anthraquinone group, a thioxanthone group, and a phosphine oxide group.

4. The laminate according to any one of claims 1 to 3, wherein the polymer (A) comprises one or more structural units derived from a (meth)acrylic acid ester having a chain structure selected from alkyl groups having 4 or more carbon atoms.

5. The laminate according to any one of claims 1 to 4, wherein the weight-average molecular weight of the polymer (A) is 1,000 to 500,000.

6. The laminate according to any one of claims 1 to 5, wherein the content of the polymer (A) in the curable composition is 0.5% by mass or more and 25.0% by mass or less.

7. The laminate according to any one of claims 1 to 6, wherein the content of the (meth)acrylate (B) in the curable composition is 0.5% by mass or more and 70.0% by mass or less relative to the nonvolatile content of the curable composition.

8. The laminate according to any one of claims 1 to 7, wherein the arithmetic mean roughness (Ra) of the surface having an uneven structure of layer (1) is 0.10 μm or more.

9. The laminate according to any one of claims 1 to 8, wherein the 20° gloss of the surface of the laminate is 20 or less.

10. A laminate according to any one of claims 1 to 9, wherein the haze is 40% or more.

11. A laminate according to any one of claims 1 to 10, wherein the haze is 90% or more.

12. The laminate according to any one of claims 1 to 11, wherein the 60° gloss of the surface of the laminate is 30 or less.

13. The laminate according to any one of claims 1 to 12, wherein the 60° gloss of the surface of the laminate is 10 or less.

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