Curable composition, cured product, and laminate

Abstract

To provide a curable composition that enables both formation of a fine irregular surface structure on a cured product and expression of matte properties, as well as improvement of uniformity in the cured product, and to provide a cured product of the curable composition and a laminate including a layer composed of the cured product.SOLUTION: A curable composition comprises a polymer having an active group that generates radicals upon irradiation with active energy rays, particles, and a (meth)acrylate.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a curable composition, a cured product of the curable composition, and a laminate having a layer made of the cured product. It relates to a laminate having the same.

Background Art

[0002] As a method of imparting a matte property and improving the design and visibility by forming a fine uneven structure on the surface of a substrate, for example, a curable composition in which fine particles are dispersed is applied to the substrate and cured, a method of depositing a thin metal film on the substrate, and a method of expressing fine wrinkles on the surface of a cured product obtained by applying a curable composition to the substrate and curing it are known. For example, Patent Document 1 describes a technique of forming a fine uneven structure on the surface of a cured product obtained by applying a curable composition to a substrate and irradiating it with active energy rays to develop a matte property. For example, Patent Document 1 describes a technique of forming a fine uneven structure on the surface of a cured product obtained by applying a curable composition to a substrate and irradiating it with active energy rays to develop a matte property. It is described.

[0003] It is described.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, in the case of the method of Patent Document 1, due to variations in curing depending on the composition, the appearance (mura) deteriorates, and it may be difficult to use it for optical applications. There were cases where it was difficult to use for optical applications.

[0006] The present invention has been made to improve the above problems, and has a fine uneven structure on the surface of the cured product. To form a cured product that exhibits matting properties and has good uniformity, and to provide a curable composition for this purpose. For the purpose of providing.

Means for Solving the Problems

[0007] The present invention has the following aspects. [1] A curable composition containing a polymer having an active group that generates radicals upon irradiation with active energy rays, particles , and (meth)acrylate. [2] The active group that generates radicals upon irradiation with the active energy rays is one or more selected from the group consisting of an α-hydroxy ketone group, a benzophenone group, an acetophenone group, a benzoin group, an α-aminoketone group , an α-diketone group, an α-diketone dialkyl acetal group, an anthraquinone group, a thioxanthone group , and a phosphine oxide group. The curable composition of the above [1 . [3] The polymer having an active group that generates radicals upon irradiation with the active energy rays has , an alkyl group having 4 or more carbon atoms, or a structural unit derived from an alkyl (meth)acrylate having a perfluoroalkylene group. The curable composition of the above [1] or [2]. [4] The weight average molecular weight of the polymer having an active group that generates radicals upon irradiation with the active energy rays is 1,000 to 500,000. The curable composition of the above [1] to [3] [5] The curable composition of the above [1] to [4], wherein the particles are organic particles. [6] The average particle diameter of the particles is 1 nm to 50 μm. The curable composition of the above [1] to [5] [7] The curable composition of the above [1] to [6], wherein the (meth)acrylate has a functionality of 3 or more. [8] The (meth)acrylate contains any one or more of urethane acrylate, (meth)acrylate of a hyperbranched body, or glycerin-containing (meth)acrylate, and the curable composition of [1] to [7] above. [9] A cured product obtained by curing the curable composition of [1] to [8] above.

[10] The cured product of [9] above, wherein the cured product is a film-like material having an uneven structure on the surface.

[11] The cured product of [9] or

[10] above, wherein the haze of the cured product is 5% or more.

[12] The cured product according to [9] to

[11] above, wherein the 20° gloss of the cured product is 80 or less.

[13] The cured product according to [9] to

[0012] above, wherein the arithmetic mean roughness (Ra) of the cured product is 0.02 μm or more.

[14] A method for producing a cured product, which forms a coating film of a curable composition containing a polymer having an active group that generates radicals by irradiation with active energy rays, particles, and (meth)acrylate, and irradiates the coating film with active energy rays.

[15] A laminate in which the cured products of [9] to

[13] above are laminated on the surface of a substrate. [Advantages of the Invention]

[0008] According to the present invention, it is possible to provide a curable composition that forms a fine uneven structure on the surface of a cured product, exhibits matting properties, and has a cured product with good uniformity, a cured product obtained by curing the curable composition, and a laminate in which the cured product is laminated on the surface of a substrate. [Embodiments for Carrying Out the Invention]

[0009] Hereinafter, embodiments of the present invention will be described in detail. In the present invention, "(meth)acrylate" is a general term for acrylate or methacrylate. ​​​​​​​​The "~" indicating a numerical range includes the numerical values described before and after it as the lower limit value and the upper limit value. That is what it means. The numerical ranges disclosed in this specification can be combined arbitrarily with their lower limit values and upper limit values to form new numerical ranges.

[0010] <Curable composition> The curable composition of the present invention contains a polymer having an active group that generates radicals upon irradiation with active energy rays, particles, and (meth)acrylate.

[0011] <Polymer having an active group that generates radicals upon irradiation with active energy rays> The active group in the polymer having an active group that generates radicals upon irradiation with active energy rays is a group having a structure that generates radicals upon irradiation with active energy rays, in other words, a structure having photopolymerization initiation properties. Examples of the structure having photopolymerization initiation properties include, for example, hydrogen abstraction type, electron transfer type, and intramolecular cleavage type. In the present invention, the radicals generated from the active group react with (meth)acrylate to form a crosslinked structure.

[0012] Examples of the active group include, for example, an α-hydroxy ketone group (e.g., the group obtained by removing one hydrogen atom from the "hydroxyl group in 2-hydroxyethoxy" of 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-methylpropanone), benzophenone group, acetophenone group, benzoin group, α-amino ketone group, α-diketone group, α-diketone dialkyl acetal group, anthraquinone group, thioxanthone group, and phosphine oxide group. Among these, the α-hydroxy ketone group, benzophenone group, and acetophenone group are preferred in that they are less susceptible to oxygen inhibition during curing and have good surface curability when forming the uneven layer. for this reason. Yes.

[0013] The active group may be present at the end of the main chain of the polymer or in the constituent units derived from the monomers constituting the polymer. It may be present in the unit. The polymer can increase the concentration of the active group near the coating film surface and is less susceptible to oxygen inhibition, so it is preferable to have a plurality of active groups in the molecule because it can improve the curability and easily develop an uneven structure such as a wrinkled structure on the surface after curing. Since it becomes difficult to occur, it is preferable to have a plurality of active groups in the molecule. From the above, it is preferable to have a plurality of active groups in the molecule.

[0014] As the polymer having a plurality of active groups, a polymer having a constituent unit derived from a monomer having an active group is preferable. As the monomer having an active group, a compound having an active group and a radical polymerizable group can be mentioned. Examples of the radical polymerizable group include functional groups containing a radical polymerizable unsaturated bond such as a carbon-carbon double bond, and specific examples include (meth)acryloyl group, (meth)acrylamide group, vinyl group, etc. As the monomer having an active group, a compound having an active group and a radical polymerizable group can be mentioned. Examples of the radical polymerizable group include functional groups containing a radical polymerizable unsaturated bond such as a carbon-carbon double bond, and specific examples include (meth)acryloyl group, (meth)acrylamide group, vinyl group, etc. As the radical polymerizable group, a functional group containing a radical polymerizable unsaturated bond such as a carbon-carbon double bond can be mentioned, and specific examples include (meth)acryloyl group, (meth)acrylamide group, vinyl group, etc. As the radical polymerizable group, a functional group containing a radical polymerizable unsaturated bond such as a carbon-carbon double bond can be mentioned, and specific examples include (meth)acryloyl group, (meth)acrylamide group, vinyl group, etc. As the radical polymerizable group, a functional group containing a radical polymerizable unsaturated bond such as a carbon-carbon double bond can be mentioned, and specific examples include (meth)acryloyl group, (meth)acrylamide group, vinyl group, etc.

[0015] As the monomer having an active group, (meth)acrylate is preferable from the viewpoints of ease of polymer synthesis and ease of adjusting the introduction amount of the active group. For example, 2-[4-(2-hydroxy-2-methyl-1-oxopropyl)phenoxy]ethyl methacrylate, 4-methacryloyloxybenzophenone, etc. can be mentioned. As the monomer having an active group, (meth)acrylate is preferable from the viewpoints of ease of polymer synthesis and ease of adjusting the introduction amount of the active group. For example, 2-[4-(2-hydroxy-2-methyl-1-oxopropyl)phenoxy]ethyl methacrylate, 4-methacryloyloxybenzophenone, etc. can be mentioned. As the monomer having an active group, (meth)acrylate is preferable from the viewpoints of ease of polymer synthesis and ease of adjusting the introduction amount of the active group. For example, 2-[4-(2-hydroxy-2-methyl-1-oxopropyl)phenoxy]ethyl methacrylate, 4-methacryloyloxybenzophenone, etc. can be mentioned. As the monomer having an active group, (meth)acrylate is preferable from the viewpoints of ease of polymer synthesis and ease of adjusting the introduction amount of the active group. For example, 2-[4-(2-hydroxy-2-methyl-1-oxopropyl)phenoxy]ethyl methacrylate, 4-methacryloyloxybenzophenone, etc. can be mentioned.

[0016] The ratio of the constituent unit derived from the monomer having an active group to the total mass of all the units constituting the polymer is preferably in the range of 1 to 90% by mass, more preferably 5 to 80% by mass, still more preferably 15 to 70% by mass, and particularly preferably 30 to 60% by mass. If this ratio is within the above range, the curability can be improved and the uneven structure can be effectively formed. The ratio of the constituent unit derived from the monomer having an active group to the total mass of all the units constituting the polymer is preferably in the range of 1 to 90% by mass, more preferably 5 to 80% by mass, still more preferably 15 to 70% by mass, and particularly preferably 30 to 60% by mass. The ratio of the constituent unit derived from the monomer having an active group to the total mass of all the units constituting the polymer is preferably in the range of 1 to 90% by mass, more preferably 5 to 80% by mass, still more preferably 15 to 70% by mass, and particularly preferably 30 to 60% by mass. If this ratio is within the above range, the curability can be improved and the uneven structure can be effectively formed.

[0017] In a polymer having an active group that generates radicals upon irradiation with active energy rays, in addition to the structural unit derived from a monomer having an active group, it preferably has a structural unit derived from a monomer having an alkyl group having 4 or more carbon atoms or a perfluoroalkylene group. Considering the current environmental problems, an alkyl group having 4 or more carbon atoms is more preferable. If the polymer has this unit, when forming a coating film of the curable composition, the polymer tends to segregate to the surface side of the coating film. Due to such segregation, the curing reaction inside the coating film (substrate side) is less likely to be inhibited by oxygen, and the curability is improved. For example, it can be cured with a low irradiation amount, and even a thin coating film that tends to be susceptible to oxygen inhibition can be cured well. As the monomer having an alkyl group having 4 or more carbon atoms, it may be linear, branched, or cyclic. The cyclic alkyl group may be monocyclic or polycyclic. From the viewpoint of more effectively segregating the copolymer to the surface of the coating film, the alkyl group is preferably linear. The carbon number of the alkyl group having 4 or more carbon atoms is preferably in the range of 4 to 30, more preferably in the range of 6 to 20, and even more preferably in the range of 12 to 18 from the viewpoint of more effectively segregating the polymer to the surface of the coating film. As the monomer, a compound having an alkyl group having 4 or more carbon atoms and a radical polymerizable group can be mentioned. From the viewpoints of ease of synthesizing the compound and ease of adjusting the introduction amount of the alkyl group having 4 or more carbon atoms, an alkyl (meth)acrylate having an alkyl group having 4 or more carbon atoms is preferable.

[0018]

[0019]

[0020] ​​​​​​​​​​​​​​​For example, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth )acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, dec yl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acry late, decyl (meth)acrylate, isodecyl (meth)acrylate, dodecyl (meth )acrylate, myristyl (meth)acrylate, cetyl (meth)acrylate, ste aryl (meth)acrylate, isostearyl (meth)acrylate, tridecyl (meth )acrylate, dicyclopentenyl oxyethyl (meth)acrylate, tricyclode cane (meth)acrylate, dicyclopentanyl (meth)acrylate, isobornyl ([[]] meth)acrylate, adamantyl (meth)acrylate, etc. may be mentioned. Among these, it is preferable to contain an (meth)acrylic acid al kyl ester having a linear alkyl group with 4 or more carbon atoms. As the (meth)acrylic acid alkyl ester having a linear alkyl group with 4 or more carbon atoms, those having the carbon number of the alkyl group within the above-mentioned preferable range are preferable. Considering ease of production and the like, 2-ethylhexyl (meth)acry late, octyl (meth)acrylate, dodecyl (meth)acrylate, stearyl ([[]] meth)acrylate are more preferable, and stearyl (meth)acrylate is particularly preferable. These (meth)acrylic acid esters may be used alone or in combination of two or more. As the perfluoroalkylene group, conventionally known compounds can be used. Effect

[0021] ​​For the formation of effective concavo-convex structures, the number of carbon atoms in the perfluoroalkylene group is preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, and most preferably 6 or more. The upper limit is not particularly limited, but preferably 30.

[0022] In addition, from the perspective of forming the surface concavo-convex structure, the perfluoroalkylene group is preferably a terminal structure rather than an internal structure. Compared with an internal structure, a terminal structure can be unevenly distributed on the surface when it becomes a cured product, and a more effective concavo-convex structure can be formed.

[0023] The terminal of the perfluoroalkylene group includes a hydrogen atom or a halogen atom. Among them, a hydrogen atom or a fluorine atom is preferable, and a fluorine atom (i.e., a perfluoro alkyl group) is more preferable. By using a perfluoroalkyl group, all atoms bonded to carbon become fluorine atoms, so it is likely to be unevenly distributed on the surface, and the compatibility with other materials may also decrease, making it excellent for forming a surface concavo-convex structure. Also, it can be made more excellent in antifouling properties and liquid repellency.

[0024] In addition, the perfluoroalkylene group may be linear, or may have a branched chain such as a perfluoroisopropyl group. From the perspective of being excellent in forming the surface concavo-convex structure, a linear chain is preferable.

[0025] That is, as the optimal structure of the perfluoroalkylene group, it is a perfluoroalkylene group with 6 or more carbon atoms, such as a perfluorohexylene group or a perfluorohexyl group. In addition, these perfluoroalkylene groups may be used alone or in combination of two or more. ​

[0026] For example, in the case of (meth)acrylic acid esters having a fluoroalkyl group, 1H ,1H,7H-dodecafluoromethyl methacrylate (manufactured by Daikin Industries, Ltd.) 2, 2,3,3-tetrafluoropropyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., Bis Coat 4F), 1H,1H,5H-octafluoropentyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., Bis Coat 8F), 1H,1H,5H-octafluoropentyl methac rylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., Bis Coat 8FM), 1H,1H,2H,2H -tridecafluorooctyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., Bis Coat 1 3F), 1H,1H,2H,2H-nonafluorohexyl acrylate (manufactured by Unimatech Co., Ltd., CHEMINOX FAAC-4), 1H,1H,2H,2H-nonafluoro hexyl methacrylate (manufactured by Unimatech Co., Ltd., CHEMINOX FAMAC-4) , 1H,1H,2H,2H-tridecafluorooctyl methacrylate (manufactured by Unimatech Co., Ltd., CHEMINOX FAMAC-6), etc. are commercially available.

[0027] The ratio of the constituent unit derived from a monomer having an alkyl group having 4 or more carbon atoms or a perfluoroalkylene group to the total mass of all the constituent units constituting the polymer having an active group that generates radicals by irradiation with active energy rays is preferably 80% by mass or less, more preferably 1 ~70% by mass, still more preferably 5~60% by mass, particularly preferably in the range of 10~55% by mass. If this ratio is within the above range, a surface uneven structure can be effectively formed.

[0028] ​​​Also, the monomer having a perfluoroalkylene group or an alkyl group having 4 or more carbon atoms Instead of or in addition to the conventional structural units, the compound has structural units derived from monomers containing silicon atoms. The silicon atom-containing monomer may be a silicon atom-containing (meta) Acrylic acid esters are preferred, and (meth)acrylic acid having a polydimethylsiloxane chain is preferred. Esters are more preferred. (Meth)acrylic acid esters having polydimethylsiloxane chains Specific examples of the copolymer include those having a molecular weight of 500 to 50,000 and a (meth)acryloyl group at one end. The molecular weight of the siloxane is preferably 1,000 to 30,000. It is preferable that the number of the sieving members is 1,500 to 20,000.

[0029] The polymer having an active group that generates radicals upon irradiation with active energy rays is, if necessary, In some cases, the copolymer may have a structural unit derived from a monomer having a hydrogen donor functional group. When the hydrogen-abstraction type is included as the hydrogen-donating functional group, the structure derived from the monomer having the hydrogen-donating functional group is When the polymer has this unit, the coating film of the curable composition is Since the curing is effective from the surface, the curability is improved and the uneven structure can be easily formed. Examples of the hydrogen donating functional group include a hydroxyl group, an amino group, a mercapto group, and an amide group. Among these, the curing reaction proceeds particularly efficiently, and the curing property is improved, or From the viewpoint of facilitating the formation of a concave-convex structure, a hydroxyl group, an amino group, or an amide group is preferred. stomach.

[0030] The monomer having a hydrogen donating functional group is a monomer having a hydrogen donating functional group and a radical polymerizable group. The compounds are easy to synthesize and have the advantage of being easy to adjust the amount of hydrogen-donating functional groups introduced. From the viewpoint of ease of use, (meth)acrylate esters having a hydrogen-donating functional group are preferred. 。 Examples of monomers having a hydrogen-donating functional group include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, monobutylhydroxyfumarate, monobutylhydroxyitaconate and other hydroxyl group-containing monomers; 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-dimethylaminopropyl (meth)acrylate, N,N-diethylaminopropyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylamide, (meth)acryloylmorpholine, vinylacetamide and other amino group- or amide group-containing monomers. Among these, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate are excellent in the curing acceleration effect when used in combination with active groups. Among these, in terms of excellent curing acceleration effect when used in combination with active groups, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, Chloromethyl (meth)acrylate, (N,N-dimethylacrylamide, N,N-dimethylamino ethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate are preferred, and N,N-diethylaminoethyl (meth )acrylate is more preferred in that it is easier to increase the uneven structure. These compounds may be used alone or in combination of two or more.

[0031] The ratio of the constituent units derived from the monomer having a hydrogen-donating functional group to the total mass of all the units constituting the polymer is preferably 80% by mass or less, more preferably 1 to 40% by mass, still more preferably 3 to 35% by mass, and particularly preferably 5 to 30% by mass. If this ratio is within the above range, the curability can be improved and the uneven structure can be effectively formed.

[0032] The polymer having an active group that generates radicals by irradiation with active energy rays may further have constituent units derived from other monomers other than the above, if necessary. Examples of other monomers include compounds having a radically polymerizable group and not having an active group, a perfluoroalkylene group, an alkyl group having 4 or more carbon atoms, a silicon atom, or a hydrogen-donating functional group. Examples of other monomers include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, citraconic acid and their salts; methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, etc. (meth)acrylate; nitrogen-containing monomers such as (meth)acrylonitrile; styrene-based compounds such as styrene, α-methylstyrene, divinylbenzene, vinyltoluene; vinyl esters such as vinyl propionate, vinyl acetate; γ-methacryloxypropyltrimeth oxysilane, etc.​​​​​​​​​​ Silicon-containing monomers such as xylylsilane and vinyltrimethoxysilane; phosphorus-containing vinyl monomers; salts Vinyl halides such as vinyl chloride and vinylidene chloride; conjugated dienes such as butadiene can be mentioned .

[0033] The weight average molecular weight (Mw) of the polymer having an active group that generates radicals upon irradiation with active energy rays is preferably in the range of 1,000 to 500,000, more preferably 3,000 to 50,000, and even more preferably 5,000 to 30,000. If Mw is within the above range, the coatability and curability of the curable composition are further improved, and the formation of the uneven structure is more likely to be improved. The Mw of the polymer is a value in terms of standard polystyrene measured by gel permeation chromatography (GPC). The detailed measurement conditions are as described in the examples below . The content of active groups per gram of the polymer having an active group that generates radicals upon irradiation with active energy rays 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 mmol / g, and particularly preferably 1 .0 to 2.5 mmol / g. If the content of active groups is within the above range, the curability

[0034] is more excellent, and the unevenness can be formed more effectively. The polymer having an active group that generates radicals upon irradiation with active energy rays can typically be produced by polymerizing a monomer as a raw material in the presence of a polymerization initiator. During the polymerization, if necessary , a chain transfer agent may be used in combination. Examples of the polymerization method include solution polymerization, suspension polymerization , etc.

[0035] Typically, it can be produced by polymerizing the monomer as a raw material in the presence of a polymerization initiator. During the polymerization, if necessary , a chain transfer agent may be used in combination. Examples of the polymerization method include, for example, solution polymerization, suspension polymerization ​Examples include bulk polymerization and emulsion polymerization. Among these, solution polymerization is preferred in terms of simple operation and high productivity.

[0036] <Particle> It has been found that by incorporating particles into the curable composition, the appearance (non-uniformity) is improved. The me chanism is not clear, but it is speculated that it may be because the particles serve as starting points and buckling is likely to occur. Speculate. As the particles, conventionally known materials can be used, for example, organic particles and inorganic particles can be mentioned. From the viewpoint of improving non-uniformity, organic particles are preferred. Since there is little electrostatic interaction due to the charge with the compounds in the curable composition, or because they are compatible with each other as organic substances, it is speculated that they have good compatibility. Speculate.

[0037] Examples of the organic particles include acrylic particles, styrene particles, urea particles, phenol formaldehyde particles, epoxy particles, melamine particles, benzoguanamine particles, urethane particles and the like. Among them, from the viewpoint of being less likely to deform and maintaining the particle size even as a cured product, a cross-linked type is preferred. For example, cross-linked acrylic particles, cross-linked acrylic-styrene particles, cross-linked styrene particles and the like can be mentioned. Among them, from the viewpoint of good appearance, cross-linked acrylic particles and cross-linked acrylic-styrene particles are preferred.

[0038] Examples of the inorganic particles include silica, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, magnesium phosphate, kaolin, aluminum oxide, zirconium oxide, titanium oxide and the like.

[0039] The average particle diameter of the particles is preferably 1 nm to 50 μm, more preferably 0.1 to 3 It is in the range of 0 μm, more preferably 0.5 to 20 μm. Further, in order to improve the appearance it is in the range of more than 1 μm and 10 μm or less, more preferably 8 μm or less. By using within the above range, it is easy to adjust optical properties such as haze, and it also leads to improvement in appearance (non-uniformity). The average particle diameter can be measured by observing with an optical microscope, an electron microscope, etc.

[0040] <(meth)acrylate> (Meth)acrylate is not particularly limited, and one or more of monofunctional (meth)acrylate, difunctional (meth)acrylate, and polyfunctional (meth)acrylate having three or more functional groups mixed, those commercially available as curable resin materials, or those obtained by further adding other components within a range that does not impair the object of this embodiment can be used. Among these, from the viewpoint of excellent curability, polyfunctional (meth)acrylate having three or more functional groups is preferable, and polyfunctional (meth)acrylate

[0041] having six or more functional groups is more preferable. Examples of monofunctional (meth)acrylate include methyl (meth)acrylate, ethyl (meth) acrylate, butyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, morpholyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl ([[]] (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycidyl (meth) Acrylates, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth )acrylate, tricyclodecane (meth)acrylate, polyethylene glycol mo no (meth)acrylate, cyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, isobornyl (meth)acrylate, allyl (meth)acryle te, 2-ethoxyethyl (meth)acrylate, benzyl (meth)acrylate, phen oxyethyl (meth)acrylate, phenyl (meth)acrylate and other mono (meth)a crylates, adducts of phthalic anhydride and 2-hydroxyethyl (meth)acrylate, etc. mono (meth)acrylate compounds and the like can be mentioned.

[0042] As the bifunctional and polyfunctional (meth)acrylates, although not particularly limited, for example 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth) acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanedi ol di(meth)acrylate, tricyclodecane dimethylol di(meth)acrylate and the like alkane diol di(meth)acrylates, bisphenol A ethylene oxide modified di(meth)acrylate, bisphenol F ethylene oxide modified di(meth)acry ate and other bisphenol modified di(meth)acrylates, polyethylene glycol di(meth )acrylate, polypropylene glycol di(meth)acrylate, urethane di(meth )acrylate, epoxy di(meth)acrylate and the like can be mentioned.

[0043] The polyfunctional (meth)acrylate having three or more functional groups is not particularly limited, but for example, dipentaerythritol hexa(meth)acrylate, pentaerythritol tetra (meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethyl olpropane tetra(meth)acrylate, pentaerythritol tri(meth)acry late, trimethylolpropane tri(meth)acrylate, glycerin triacrylate and other glycerin-containing polyfunctional (meth)acrylates, ethylene oxide-modified dipentaery thritol hexa(meth)acrylate, ethylene oxide-modified pentaerythritol tetra(meth)acrylate, ethylene oxide-modified pentaerythritol tri(meth )acrylate and other ethylene oxide-modified (meth)acrylates, ethylene oxide-modified isocyanuric acid tri(meth)acrylate, ε-caprolactone-modified tris(acryloxyethyl)isocyanurate and other isocyanuric acid-modified tri(meth)acrylates, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepoly mer, pentaerythritol triacrylate toluene diisocyanate urethane prepoly mer, dipentaerythritol pentaacrylate hexamethylene diisocyanate u rethane prepolymer and other urethane (meth)acrylates can be mentioned. Among these, the (meth)acrylate having six or more functional groups is preferable from the viewpoint of hardness, and further, it is preferable that it is urethane (meth) acrylate from the viewpoint of adhesion to the substrate. Also, from the viewpoint that the uneven structure becomes fine and it becomes easy to adjust optical properties such as haze, glycerin-containing (meth )acrylate is preferable.

[0044] ​​​ Furthermore, hyperbranched (meth)acrylates can also be mentioned as polyfunctional (meth)acrylates. Although it is presumed that the mechanism is due to the random structure, it has also been found that the use of hyperbranched (meth)acrylates can reduce the appearance (non-uniformity) of the cured film.

[0045] In addition, it is also possible to use active energy ray-curable compounds other than (meth)acrylates in the curable composition. For example, vinyl compounds such as styrene, vinyl halide, and vinyl acetate, and diene compounds such as vinylidene halide, 1,3-butadiene, isoprene, and chloroprene can be mentioned.

[0046] The curable composition may contain various polymers for adjusting the hardness when cured. For example, acrylic polymers, polyesters, polyurethanes, etc. can be mentioned.

[0047] In addition, the curable composition may contain an ultraviolet absorber to improve the weather resistance when cured. For example, organic ultraviolet absorbers and inorganic ultraviolet absorbers can be mentioned. From the viewpoints of transparency and compatibility, organic ultraviolet absorbers are preferred. The organic ultraviolet absorbers are not particularly limited, but for example, triazine-based, benzotriazole-based, benzophenone-based, cyclic iminoester-based, salicylic acid ester-based, cyanoacrylate-based, etc. can be mentioned. Among these, from the viewpoints of weather resistance and durability, triazine-based, benzotriazole-based, benzophenone-based, and cyclic iminoester-based are more preferred, and triazine-based is even more preferred. These ultraviolet absorbers may be used alone or in combination of two or more. Furthermore, these compounds may be incorporated into polymers. It is also possible to use

[0048] Similarly, the curable composition may contain a light stabilizer to improve the weather resistance of the cured product. The light stabilizer is not particularly limited, but for example, an amine-based light stabilizer may be used. light stabilizers, phenolic light stabilizers, phosphorus light stabilizers, and thioether light stabilizers. Among these, amine-based light stabilizers, phenol-based light stabilizers, and phosphorus-based light stabilizers are preferred. In particular, amine-based light stabilizers are more preferable in terms of preventing yellowing. The fixing agent may be used alone or in combination of two or more kinds. It is also possible to use these compounds incorporated into polymers.

[0049] The curable composition may further contain a leveling agent to improve the appearance of the cured product. The leveling agents include acrylic leveling agents, silicone leveling agents, Fluorine-based leveling agents and the like can be used. These leveling agents can be used alone or in combination. More than one species may be used in combination.

[0050] The curable composition may further contain a non-polymeric photopolymerization initiator, Contains polymerization accelerators, antistatic agents, plasticizers, antioxidants, UV absorbers, and infrared absorbers. It may be possible.

[0051] Furthermore, when the curable composition is applied onto a substrate, in order to improve workability, It is preferable to use an organic solvent depending on the circumstances. Organic solvents include aromatic solvents such as toluene and xylene; methyl ethyl ketone, acetonitrile, etc. - ketone solvents such as methyl isobutyl ketone and cyclohexanone; diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether l, diethylene glycol diethyl ether, propylene glycol monomethyl ether , anisole, phenetole and other ether solvents; ethyl acetate, butyl acetate, isopropyl acetate , ethylene glycol diacetate and other ester solvents; dimethylformamide, diethylformamide, N-methylpyrrolidone and other amide solvents; methyl cellosolve, ethyl cellosolve, butyl cellosolve and other cellosolve solvents; methanol, ethanol, propanol, isopropanol, butanol and other alcohol solvents; dichloromethane, chloroform and other halogen solvents; etc. These organic solvents may be used alone or in combination of two or more. Among these organic solvents, ester solvents, ether solvents, alcohol solvents and ketone solvents are preferred in terms of being easy to improve workability in coating. The content of the active group in the curable composition is such that the content of the active group derived from the copolymer per 100 g of the non-volatile content of the curable composition is 0.1 to 100 mmol / 100 g, more preferably 0.5 to 70 mmol / 100 g, still more preferably 1.5 to 50 mmol / 100 g, particularly preferably 2.0 to 40 mmol / 100 g, most preferably 4.0 to 30 mmol / 10

[0052] 0 g. By setting the range as above, an effective curing reaction can be expected while ensuring storage stability, and effective surface unevenness can be expressed. ​​​​​Incidentally, the content of the active group can be estimated by analytical methods such as NMR and GCMS after separating and purifying the curable composition. It is possible to estimate.

[0053] The content of the polymer having an active group that generates radicals by irradiation of active energy rays in the curable composition is 0.1% by mass or more, preferably 0.5 to 30% by mass, in terms of imparting an uneven structure to the surface of the cured product and improving the active energy ray curability, based on the non-volatile content. more preferably 1 to 25% by mass, still more preferably 3 to 20% by mass, and particularly preferably 5 to 15% by mass. Incidentally, the non-volatile content of the curable composition is the total mass of components other than solvents such as organic solvents. The ratio of the non-volatile content in the curable composition can be measured by a conventionally known method. For example, when 1 g of the composition is spread out and heated at 100 °C for 1 hour to volatilize the organic solvent, it can be calculated from the change in weight.

[0054] The content of the particles in the curable composition is 0.1% by mass or more, preferably 0.5 to 50% by mass, more preferably 1 to 40% by mass, still more preferably 3 to 35% by mass and particularly preferably 5 to 30% by mass, based on the non-volatile content. By setting the range as above, it is possible to improve the unevenness while maintaining optical properties such as haze.

[0055] The content of (meth)acrylate in the curable composition is 0.1 to 99.8% by mass, preferably 10 to 99% by mass in terms of good curability, based on the non-volatile content of the curable composition. more preferably 30 to 98% by mass, still more preferably 50 to 94% by mass, and particularly preferably 60 to 90% by mass. By using it in the above range, the hardness of the cured product is sufficient. ​​This results in improved scratch resistance. Particularly when it is desired to increase the hardness of the cured product, the (meth)acrylate having 6 or more functional groups is preferably 30% by mass or more, more preferably 40% by mass or more, even more preferably in the range of 50% by mass or more. Also, particularly when it is desired to improve the appearance, the (meth)acrylate of the hyperbranched polymer is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably in the range of 15% by mass or more. In addition, when it is desired to adjust the haze, the glycerin-containing (meth)acrylate is preferably in the range of 3 to 50% by mass, more preferably 5 to 30% by mass. The solid content concentration of the curable composition can be appropriately changed according to the application, but from the viewpoint of improving the operability in the coating operation, it is preferably 1 to 100%, more preferably 5 to 90% even more preferably 10 to 80%, particularly preferably 20 to 70%.

[0056] <Cured product> The cured product of the curable composition can be formed, for example, by applying the curable composition onto the surface of a substrate or an article to form a coating film, drying if necessary, and then irradiating the coating film with active energy rays.

[0057] When forming a cured product (cured film) by coating, the coating method of the curable 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, spray coating. When the curable composition contains an organic solvent, it is preheated and dried before irradiating with active energy rays.

[0058] ​​​​​​​It is preferable to heat and dry the coating film in advance to effectively remove the organic solvent from the coating film. The drying temperature for the heat drying is preferably 30 to 200° C., more preferably 40 The drying temperature is preferably from 0.01 to 30 minutes. It is preferable, and 0.1 to 10 minutes is more preferable.

[0059] Examples of active energy rays include ultraviolet rays, electron beams, visible light, infrared rays, and X-rays. Among these, ultraviolet rays and electron beams are preferred from the viewpoints of curing property and prevention of deterioration of the substrate. In addition, the amount of irradiation of the active energy ray is preferably adjusted according to the amount of the active energy ray to be irradiated. The appropriate selection can be made.

[0060] For example, when using ultraviolet light, the total cumulative light intensity is 50 to 3,000 mJ / c. m 2 It is preferable to irradiate so that the irradiation temperature is 100 to 2,000 mJ / cm 2 is more preferred 200~1,000mJ / cm 2 More preferably, the illuminance is 50 to 6 00mW / cm 2 is preferable, and 75 to 450 mW / cm 2 More preferably, 100 to 30 0mW / cm 2 As the light source, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra-high pressure mercury lamp, Lamps, electrodeless lamps, metal halide lamps, or scanning or curtain type electron beam acceleration paths Electron beams, high pressure mercury lamps, ultra-high pressure mercury lamps, low pressure mercury lamps, etc. can be used.

[0061] The thickness of the cured product (cured film) is preferably 0.1 to 20 μm, more preferably 0.2 to 1 The thickness of the cured product is preferably in the range of 0.0 μm, and more preferably in the range of 0.3 to 7 μm. If so, it is easy to realize a desired surface uneven structure. In addition, the thickness of the cured product is determined by cross-sectional observation using an electron microscope or the like.

[0062] The haze of the cured product measured by the method described in the examples below has an optimum value depending on various applications, and cannot be generally stated. Preferably, it is 5% or more, more preferably 10% or more, even more preferably 20% or more, particularly preferably 30% or more, and most preferably 40% or more. The range is not particularly limited as the upper limit, but for example, it is 99%. For example, in applications that require strong anti-glare properties or strong anti-reflection properties (anti-glare film, etc.), it is preferably 50% or more, more preferably 60% or more, and even more preferably 80% or more in some cases where high values are required.

[0063] The cured product preferably has transparency. The total light transmittance measured by the method described in the examples below is preferably in the range of 40 to 100%, more preferably 60 to 99%, and even more preferably 80 to 98%. When it is equal to or higher than the lower limit value of the above range, it has excellent transparency and is suitable for various optical applications, for example. When it is equal to or lower than the upper limit value, it has excellent anti-glare properties.

[0064] The 20° gloss (20° specular glossiness) of the cured product measured by the method described in the examples below has an optimum value depending on various applications and cannot be generally stated. Preferably, it is 80 or less, more preferably 60 or less, and even more preferably 50 or less. There is no particular limitation as the lower limit, but for example, it is 0.1 or more. For example, in applications that require strong anti-glare properties or strong anti-reflection properties (anti-glare film, etc.), it is preferably 20 or less, more preferably 10 or less, ​​In some cases, a low value of preferably 5 or less may be required. Similarly, at 60° gloss, there are optimal values depending on various applications, and it cannot be generally stated, but preferably it is 120 or less, more preferably 100 or less, still more preferably 80 or less, and there is no particular limitation on the lower limit, but for example, it is 0.1 or more. For example, in applications that require strong anti-glare properties or strong anti-reflection properties (such as anti-glare films), a low value of preferably 50 or less, more preferably 30 or less, still more preferably 20 or less may be required in some cases.

[0065] The surface of the cured product is a concavo-convex surface (non-smooth surface) having irregularities. As a result, the cured product has anti-glare properties, anti-reflection properties, and anti-blocking properties. The arithmetic mean roughness (Ra) of the cured product measured by the method described in the examples below has optimal values depending on various applications, and it cannot be generally stated, but preferably it is 0.02 μm or more, more preferably 0.05 μm or more, still more preferably 0.10 μm or more, and there is no particular limitation on the upper limit, but for example, it is in the range of 2 μm or less. For example, in applications that require strong anti-glare properties or strong anti-reflection properties such as anti-glare films, a high value of preferably 0.15 μm or more, more preferably 0.20 μm or more, still more preferably 0.30 μm or more may be required in some cases.

[0066] The inclination angle (inner angle) (θα) of the protrusions of the surface irregularities of the cured product affects the anti-glare properties and anti-reflection properties of the cured product, and the higher the angle, the higher the anti-glare properties and anti-reflection properties. The angle (θα) of the cured product measured by the method described in the examples below has optimal values depending on various applications, and it cannot be generally stated, but preferably it is 0.5° or more, more preferably 1.0° or more, still more preferably it is 41 ​Preferably, it is 2.0° or more, and there is no particular limitation on the upper limit. For example, it is in the range of 30° or less. For example, in applications that require strong anti-glare properties and strong anti-reflection properties (such as anti-glare films), it is preferably 3.0° or more, more preferably 5.0° or more, and even more preferably 1 0° or more, and high values may be required in some cases.

[0067] <Laminate> The laminate of the present invention (hereinafter, also referred to as "the present laminate") has a base material layer and a layer composed of a cured product (cured film) of a curable composition. The present laminate further has a primer layer provided between the base material layer and the cured product, and one or more layers selected from the group consisting of a back surface functional layer provided on the surface of the base material layer opposite to the cured product side. Further, as long as the effects of the present invention are not impaired, a surface functional layer provided on the surface of the cured product opposite to the base material layer side may be provided.

[0068] (Base material layer) As the base material layer, known ones can be used, such as resin base materials, metal base materials, paper base materials, glass base materials, etc. Among these, from the viewpoint of processability, a resin base material is preferable. The resin base material may be a single-layer structure or a multi-layer structure of two or more layers, and is not particularly limited. It is preferable to make the resin base material into a multi-layer structure of two or more layers, give each layer characteristics, and achieve multi-functionality.

[0069] As the resin base material, various resin films (sheets) can be used, such as triacetyl cellulose films, polyester films, poly(meth)acrylate films, polyolefin films, polycarbonate films, polyimide films, polystyrene films Examples include rum, polyvinyl chloride film, polyvinyl alcohol film, nylon film, and polyurethane film. When this laminate is applied to display applications, triacetyl cellulose film, polyester film, poly(meth)acrylate film, polyolefin film, polycarbonate film, and polyimide film are preferred. Among these, triacetyl cellulose film, polyester film, poly( (meth)acrylate film, and polyolefin film are preferred because of their excellent mechanical properties. Further, considering transparency, moldability, and versatility, triacetyl cellulose film or polyester film is more preferred.

[0070] The base material layer can also contain particles for the purpose of imparting slipperiness, preventing scratches from occurring in each process, and improving blocking resistance properties, or can contain an ultraviolet absorber to improve weather resistance. Further, if necessary, additives other than the above-mentioned particles and ultraviolet absorber can be included. As the additives, known additives such as antioxidants, antistatic agents, heat stabilizers, lubricants, plasticizers, dyes, and pigments can be used.

[0071] The thickness of the base material layer is not particularly limited. For example, if it is in the form of a film, it is preferably in the range of 2 to 350 μm, more preferably 5 to 250 μm, and even more preferably 10 to 100 μm.

[0072] Further, the base material layer may be subjected to corona treatment or plasma treatment in order to improve the adhesion to the cured product of the curable composition.

[0073] (Primer layer) ​The primer layer is provided to impart various functions between the base material layer and the cured product layer. Examples of the primer layer include an adhesion improvement layer and an antistatic layer. The primer layer may have a plurality of functions. For example, the adhesion improvement layer may also serve as an antistatic layer.

[0074] In a preferred embodiment, the primer layer is an adhesion improvement layer. If the adhesion between the base material layer and the cured product is insufficient, the laminate may not be usable depending on the application. By having an adhesion improvement layer, the adhesion between the base material layer and the cured product is improved, and the laminate can be used for various applications. Examples of the components constituting the primer layer include polyester resin, acrylic resin, urethane resin, polyvinyl resin (such as polyvinyl alcohol and vinyl chloride-vinyl acetate copolymer), etc.

[0075] In another preferred embodiment, the primer layer is an antistatic layer. If the primer layer is an antistatic layer, adhesion of dust and the like due to peeling charge or friction charge to the outermost surface of the laminate, particularly the outermost surface on the side where the cured product exists with respect to the base material layer, can be reduced. To make the primer layer an antistatic layer, for example, an antistatic agent may be contained in the primer layer. Also, the primer layer can be formed by a known method.

[0076] (Back surface functional layer) The back surface functional layer is provided to impart various functions to the surface of the base material layer opposite to the cured product layer. Examples of the back surface functional layer include an adhesive layer, an antistatic layer, a refractive index adjustment layer, an antiblocking layer, etc. The adhesive layer is provided to bond the laminate to various adherends. The antistatic layer is for the laminate ​​​​​​​For the outermost surface, particularly for the outermost surface on the side opposite to the cured product layer of the base material layer, it is provided to prevent adhesion of surrounding dust and the like caused by peeling electrification or frictional electrification, and defects caused thereby. The refractive index adjustment layer is , for example, provided to improve the total light transmittance of the laminate. The anti-blocking layer is provided to reduce blocking of the laminate. The back surface functional layer can be formed by a known method.

[0077] (Surface functional layer) The surface functional layer can be provided to impart various functions on the surface on the side opposite to the base material layer side of the cured product layer (cured film). Examples of the surface functional layer include an antifouling layer, an antistatic layer, a refractive index adjustment layer (antireflection layer, low reflection layer, etc.), an infrared absorption layer, an ultraviolet absorption layer, a color correction layer, and the like. The surface functional layer can be formed by a known method.

[0078] It is also possible to provide it in order to further improve the performance of the cured product of the present invention. For example, by forming a surface functional layer having a high content ratio of a fluorine compound, higher antifouling properties and liquid repellency can be imparted. It is also a preferable form to make it a curable surface functional layer in order to impart durability, and further, by making the fluorine compound contain an active energy ray curable site , it is also possible to make a surface functional layer having higher performance.

Examples

[0079] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. The measurement methods and evaluation methods used in the present invention are as follows.

[0080] (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 + H" manufactured by Tosoh Corporation, 6000", 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 mass%, Calibration sample: Monodisperse polystyrene, Calibration method: Polystyrene conversion.

[0081] (2) Evaluation method for the appearance (non-uniformity) of the cured product The laminate with a cured layer formed on a triacetyl cellulose film was used as the evaluation object. Under a fluorescent lamp, the non-uniformity situation was observed by reflected light from the side with the cured layer, and the evaluation was conducted as follows. Non-uniformity is preferably slight, and in applications where appearance is strict such as optical applications, those with a B rank or above can be evaluated as good. A: No non-uniformity is observed. B: The area where slight non-uniformity is observed is 50% or less. C: The area where slight non-uniformity is observed exceeds 50%, or the area where distinct non-uniformity is observed is 20% or less. D: The area where distinct non-uniformity is observed exceeds 20% and is 50% or less. E: The area where distinct non-uniformity is observed exceeds 50%.

[0082] (3) Measurement of total light transmittance and haze The laminate with a cured layer formed on a triacetyl cellulose film was used as the measurement object. The total light transmittance and haze were measured in accordance with JIS Z 8722 (Geometric conditions for irradiation and light reception of transparent objects), JIS K 7361-1 (Plastics - Test Method for Total Light Transmittance of Transparent Materials) and J IS K 7136 (Plastics - Method for Determining 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. The haze of the laminate is the percentage of the transmitted light that is scattered forward by more than 0.044 rad (2.5°) from the incident light among the transmitted light that enters from the outermost surface on the side where the cured layer exists with respect to the base material layer and passes through the laminate (the ratio of the diffuse transmittance to the total light transmittance). When it is desired to evaluate the haze of the cured product itself, it can be obtained by subtracting the haze value of the base material without the cured product from the haze value of the laminate with the cured product laminated. Specifically, it can be obtained by subtracting the haze value of Comparative Example 1.

[0083] (4) Measurement of 20° and 60° Gloss The laminate with the cured film formed on the base material was used as the measurement object. The 20° and 60° gloss (20° and 60° specular glossiness) was measured in accordance with JIS Z 8741-1997 using a gloss meter "VG2000" manufactured by Nippon Denshoku Industries Co., Ltd.

[0084] (5) Measurement of the Arithmetic Mean Roughness (Ra) and the Inclination Angle (Inner Angle) (θα) of the Surface Uneven Structure The arithmetic mean roughness (Ra) and the inclination angle (inner angle) (θα) of the surface uneven structure of the cured product were measured using a surface shape measurement system (scanning white light interference microscope "VS1330" manufactured by Hitachi High-Technologies Corporation). The magnification of the objective lens at the time of measurement was set to 20 times. The surface uneven structure of the uneven layer surface in a region of 236.87 μm × 177.60 μm was measured by the optical interference method, complementation and baseline correction were performed, and the arithmetic mean roughness Ra of the uneven cross-section was ​​​​​​​​​​​​ The calling angle θα was calculated.

[0085] (Synthesis Example 1: Synthesis of 2-[4-(2-hydroxy-2-methyl-1-oxopropyl)phenoxy ethyl methacrylate) Methacrylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was distilled under reduced pressure, and the fraction with a purity of 99.8% or more was collected to obtain a distillate of methacrylic anhydride. The distillation under reduced pressure was carried out by gradually raising the temperature from room temperature to 90 °C at a pressure of 30 Pa. Separately, 22.4 g (0.1 mol ) of 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy -2-methyl-1-propan-1-one (manufactured by Tokyo Chemical Industry Co., Ltd.) and 30.4 g (0.3 mol) of triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 500 mL of methylene chloride (manufactured by Tokyo Chemical Industry Co., Ltd.). To this, 23.1 g (0.15 mol) of the above-mentioned distillate of methacrylic anhydride was added dropwise at room temperature, and the mixture was stirred for 12 hours. -2-methyl-1-propan-1-one (manufactured by Tokyo Chemical Industry Co., Ltd.) 22.4 g (0.1 mol ) and triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) 30.4 g (0.3 mol) were dissolved in methylene chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) 500 mL. To this, the above-mentioned distillate of methacrylic anhydride 23.1 g (0.15 mol) was added dropwise at room temperature and stirred for 12 hours. -2-methyl-1-propan-1-one (manufactured by Tokyo Chemical Industry Co., Ltd.) 22.4 g (0.1 mol) and triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) 30.4 g (0.3 mol) were dissolved in methylene chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) 500 mL. To this, the above-mentioned distillate of methacrylic anhydride 23.1 g (0.15 mol) was added dropwise at room temperature and stirred for 12 hours. The obtained reaction solution was washed three times with 500 mL of ion-exchanged water, and then the organic phase was concentrated to remove the solvent. The residue was purified by column chromatography (ethyl acetate / hexane = 10 / 90 (volume ratio)) to obtain 21.6 g of the target compound (yield 74%). ratio)) to obtain 21.6 g of the target compound (yield 74%). ratio)) to obtain 21.6 g of the target compound (yield 74%). 1 By 1H-NMR analysis, it was confirmed that the obtained compound was 2-[4-(2-hydroxy-2-methyl -1-oxopropyl)phenoxy]ethyl methacrylate. 1 1H NMR (300 MHz, chloroform-d): δ8.06 (d, J = 9 .0 Hz, 2H), 6.96 (d, J = 9.0 Hz, 2H), 6.13 (d, J = 0.6 Hz, 1H), 5.59 (s, 1H), 4.50 (d, J = 5.1 Hz, 2H), 4.2 9 (dd, J = 5.5, 4.1 Hz, 3H), 1.94 (dd, J = 1.6, 1.0 Hz , 3H), 1.61 (s, 6H).

[0086] (Production Example 1: Production of Polymer ( A) Having an Active Group that Generates Radicals upon Irradiation with Active Energy Rays) Into a flask equipped with a stirrer, a cooling tube, and a thermometer, 70 parts of methyl isobutyl ketone (hereinafter referred to as M IBK) was placed. Next, the inside of the flask was purged with nitrogen and heated to 65°C. Then, 2- [4-(2-Hydroxy-2-methyl-1-oxopropyl)phenoxy]ethyl meth acrylate 25 parts by mass, 4-methacryloyloxybenzophenone 25 parts by mass, stearyl acrylate 10 parts by mass, 2-ethylhexyl methacrylate 30 parts by mass, N,N-di ethylaminoethyl methacrylate 10 parts by mass, 1-dodecanethiol ( nDM) 3 parts by mass as a chain transfer agent, 2,2'-azobis(2,4-dimethylvalero nitrile) (AMBN) 0.8 parts by mass as a polymerization initiator, and a mixed solution of 78 parts by mass of MIBK were added dropwise over 2 hours. After another 2 hours, to increase the polymerization rate, a mixed solution of 0.5 parts by mass of 2,2'-azobis(2,4-dimethyl valeronitrile) and 0.6 parts by mass of MIBK was added and held for 5 hours. Thereafter, the reaction solution was cooled to 40°C to obtain a MIBK solution (A) of the polymer. Hereinafter , the solid content in solution (A) is referred to as polymer (A). The solid content (non-volatile content) of solution (A) was 40% by mass. Also, the content of active groups per gram of polymer (A) was 1.77 mmol / g. Also, the weight average molecular weight (Mw) was 19,800.

[0087] (Production of Curable Composition (Coating Solution)) ​The respective materials shown in Table 1 were mixed so as to be in the ratios (parts by mass) shown in Table 1 on a nonvolatile content basis. After that, a mixed solvent of propylene glycol monomethyl ether (hereinafter, PGM), methyl isobutyl ketone (hereinafter, MIBK), and diisobutyl ketone (hereinafter, DIBK) (PMA:MIBK:DIBK (mass ratio) of 7:2:1) was added so that the solid content concentration became 40% by mass, and the mixture was stirred until uniform to obtain a curable composition (coating solution). · Particles Crosslinked acrylic particles (manufactured by Sekisui Chemical Co., Ltd., MBX-2H, average particle diameter 2.5 μm ): B1 Crosslinked acrylic particles (manufactured by Soken Chemical & Engineering Co., Ltd., MX-500L, average particle diameter 5 μm): B2 · (Meth)acrylate Hexafunctional urethane (meth)acrylate: manufactured by Mitsubishi Chemical Corporation, Shinsei (registered trademark) UV-1700B: C1 Hexafunctional hyperbranched (meth)acrylate: Sartomer (registered trademark) CN2303: C2 manufactured by ARKEMA Trifunctional glycerin triacrylate: manufactured by Toagosei Co., Ltd., Aronix (registered trademark ) M-930: C3 Trifunctional trimethylolpropane trimethacrylate: C4 · Photoinitiator Benzophenone: D1 2-Hydroxy-2-methyl-1-phenylpropanone: D2

[0088] [Example 1] The obtained curable composition was applied to a triacetyl cellulose film (manufactured by Fuji Film Co., Ltd., TD80UL) with a thickness of 80 μm so that the film thickness after drying became 5 μm, and the obtained coating film was dried for 60 seconds with a hot air dryer heated to 70 °C to volatilize the solvent, and in an air atmosphere it was irradiated with a high-pressure mercury lamp so that the integrated light quantity became 100 mJ / cm in the air atmosphere.2 、 At an illuminance of 100 mW / cm 2 ultraviolet light was irradiated 6 times (600 mJ / cm 2 ), and a laminate in which a layer made of a cured product was laminated on a film substrate was obtained. For the obtained laminate, the items shown in Table 2 were measured or evaluated by the above method. The results are as shown in Table 2. The unevenness was good, and the haze, gloss, Ra, and θα also showed good results.

[0089] [Examples 2 to 9] In Example 1, a laminate having a cured film was obtained in the same manner as in Example 1, except that the coating liquid composition was changed to the coating liquid composition shown in Table 1. The characteristics of the obtained laminate are shown in Table 2 below.

[0090] [Comparative Example 1] In Example 1, a triacetyl cellulose film (manufactured by Fuji Film Co., Ltd., TD80UL) was evaluated without laminating a cured film. The characteristics are shown in Table 2 below. [Comparative Examples 2 to 7] In Example 1, a laminate having a cured film was obtained in the same manner as in Example 1, except that the coating liquid composition was changed to the coating liquid composition shown in Table 1. The characteristics of the obtained laminate are shown in Table 2 below. In Comparative Examples 2 and 3, since no particles were contained in the composition, the unevenness of the appearance was poor. In Comparative Examples 4 to 7, since a non-polymeric photoinitiator was used instead of the polymer (A) having an active group that generates radicals by irradiation with active energy rays, the matting property was insufficient.

[0091]

Table 1

[0092]

Table 2

Claims

1. A curable composition containing a polymer having an active group that generates radicals upon irradiation with active energy rays, particles, and (meth)acrylate.

2. The curable composition according to Claim 1, wherein the active group that generates radicals upon irradiation with the active energy rays is one or more selected from the group consisting of an α-hydroxy ketone group, a benzophenone group, an acetophenone group, a benzoin group, an α-amino ketone group, an α- diketone group, an α-diketone dialkyl acetal group, an anthraquinone group, a thioxanthone group, and a phosphine oxide group.

3. The curable composition according to Claim 1, wherein the polymer having an active group that generates radicals upon irradiation with the active energy rays contains a structural unit derived from an alkyl (meth)acrylate having an alkyl group having 4 or more carbon atoms or a perfluoroalkylene group.

4. The curable composition according to Claim 3, wherein the weight average molecular weight of the polymer having an active group that generates radicals upon irradiation with the active energy rays is 1,000 to 500,000.

5. The curable composition according to Claim 1, wherein the particles are organic particles.

6. The curable composition according to Claim 1, wherein the average particle diameter of the particles is 1 nm to 50 μm.

7. The curable composition according to Claim 1, wherein the (meth)acrylate is trifunctional or higher.

8. The curable composition according to Claim 7, wherein the (meth)acrylate contains any one or more of urethane acrylate, (meth)acrylate of a hyperbranched body, or glycerin-containing (meth)acrylate.

9. A cured product obtained by curing the curable composition according to Claim 1 or 5.

10. The cured product according to Claim 9, wherein the cured product is a film-like material having an uneven structure on the surface.

11. The cured product according to Claim 10, wherein the haze of the cured product is 5% or more.

12. The cured product according to Claim 10, wherein the 20° gloss of the cured product is 80 or less.

13. The cured product according to Claim 10, wherein the arithmetic mean roughness (Ra) of the cured product is 0.02 μm or more.

14. A method for producing a cured product, comprising forming a coating film of a curable composition containing a polymer having an active group that generates radicals upon irradiation with active energy rays, particles, and (meth)acrylate, and irradiating the coating film with active energy rays.

15. A laminate obtained by laminating the cured product according to Claim 9 on a substrate surface. ​ ​ ​ ​ ​ ​ ​ ​

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