JP6973031B2 - Active energy ray curable resin composition, decorative sheet, and molded product - Google Patents

Description

The present invention relates to an active energy ray-curable resin composition, a decorative sheet, and a molded product.

Conventionally, the surface of plastic housings used in various fields such as mobile phones such as smartphones, electronic devices such as notebook PCs including mobile PCs, interior and exterior parts for automobiles, and building materials are printed and painted. High design (design, texture, appearance, etc.) is given (decorated) by the processing of. Further, in many cases, a protective layer (hard coat layer) is further provided for the purpose of protecting such a decorative body or the soft plastic itself.

In recent years, in the manufacturing for decorating such plastics, in order to reduce the environmental load, productivity and cost, and to cope with complicated product shapes, the conventional method of directly attaching to the housing is used to attach films and sheets. The replacement with transfer decoration technology is in progress. That is, a decorative sheet in which a design layer for producing the above-mentioned design and a hard coat layer for protection are laminated is bonded to a base material such as plastic. A conventional decorative sheet may be configured by laminating a single layer or a multilayer on a sheet base material, but the outermost layer after the final molding process is configured to be a protective layer (hard coat layer). Has been done.

Decorative sheets provided with a protective layer on such films and sheet-like substrates can be obtained by various methods such as vacuum forming, compressed air forming, membrane press forming, in-mold molding, insert molding, insert molding, and overlay vacuum forming. It is molded. In either case, the decorative sheet is stretched or bent according to the shape of the object to be decorated (plastic housing) or the shape of the mold.

In the molding process, heat of several tens to several hundreds of degrees is generally applied to the sheet. The main reason is that the decorative sheet required in the process and the decorative body (plastic housing) are joined by heat, and the stretchability of the decorative sheet is improved by heating. However, if the hard coat layer does not have sufficient flexibility and extensibility, the moldability is poor, whitening, scratches, cracks, peeling, etc. occur, which greatly impairs the design, which is not desirable. (Patent Document 1)

As a method generally used in a method of forming a hard coat layer on a film or a sheet-like substrate, for example, in the invention described in Patent Document 2, a photosensitive coating composition is formed on a film to form an active energy ray. A hard coat layer is formed by photocuring (crosslinking) by irradiation. By using a polyfunctional photocrosslinkable monomer in the composition, a hard coat property is obtained by improving the degree of crosslinkage after light irradiation. However, a film with a viaduct degree is hard and brittle, and therefore lacks flexibility and extensibility. Therefore, it is extremely difficult for the conventional technique for obtaining a hard coat layer to cope with processing such as bending and stretching performed according to various product shapes in the molding process of a decorative sheet.

In response to the above-mentioned extremely high technical problems, materials having both curability and flexibility, such as urethane acrylate oligomers, have been proposed in the past, but at a very high level required for decorative films in recent years. It is difficult to achieve both hard coat properties and flexibility / extensibility.

In addition, technical problems are avoided by devising the entire manufacturing process including the decorative sheet and the molding process using the decorative sheet. For example, Patent Document 3 proposes a method of semi-curing a photosensitive composition with active energy rays to ensure the extensibility required for molding, and further irradiating the photosensitive composition with active energy rays to obtain a hard coat layer. However, it is difficult to control the light irradiation conditions to obtain a semi-cured state, and the difference between the UV irradiator and the lamp has a great influence, and the active energy ray irradiation device required for back-photocrosslinking is burdened by the processor. There are big disadvantages such as. Further, Patent Document 4 proposes to improve the hard coat property by performing thermal cross-linking as post-processing after molding by using a heat-crosslinkable composition in combination with the photosensitive composition. In order to obtain sufficient hard coatability, a long heat cross-linking time is required, and there are major disadvantages such as burdening the processor with the heating device required for heat cross-linking.

Further, Patent Document 5 proposes a hard coat agent composition for a decorative sheet in which a thermoplastic resin and an ionizing radiation resin are combined. Since the thermoplastic resin acts as an inactive component, it exhibits extensibility by suppressing the degree of cross-linking. As a result, although it shows a certain degree of moldability, it is insufficient to the level required in recent years. Further, due to the adverse effect of the non-curable component, the hard coat property such as curability and chemical resistance is insufficient.

In each case, the key is to control the degree of cross-linking of the cross-linked film in order to cope with the molding process, but the technical difficulty of the cross-linking control is high, and there is a big demerit in that the process becomes complicated. Therefore, in the prior art, a decorated molded product can be obtained by a simple process from the formation of the crosslinked film to the molding process, for example, the hardcourt property is lost as a result of forming a soft crosslinked film in order to obtain moldability. It's difficult. Therefore, the current situation is that it is handled by a complicated method.

Therefore, there is a need for a crosslinkable composition that has both hard-coating properties and moldability required for a decorative sheet and enables a molded product to be obtained in a simpler process.

Furthermore, the use of plastic products in various applications is increasing, and the extensibility, scratch resistance, adhesion to a base material, and chemical resistance of the product are universally required. Patent Document 6 proposes an active energy ray-curable resin composition in which a resin having a ring structure in a main chain is used as a main polymer. However, the active energy ray-curable resin composition described in this patent cannot obtain the levels of extensibility, chemical resistance, scratch resistance, and substrate adhesion required in recent years. Further, even if an inorganic filler is added to impart scratch resistance, there is a problem that the active energy ray-curable resin composition has poor stability over time and the inorganic filler settles over time. Furthermore, since it is water-based, it is difficult to handle in hard coat applications, which are mainly solvent-based.

Patent No. 5704929 Patent No. 5524455 Japanese Unexamined Patent Publication No. 2015-54886 Patent No. 5389904 Japanese Unexamined Patent Publication No. 2007-290392 Japanese Unexamined Patent Publication No. 2016-180081

The present invention has been made in view of the above-mentioned current situation, and provides an active energy ray-curable resin composition having excellent stability over time. In addition, we provide a new composition to obtain a protective layer that has both hard coatability, extensibility, moldability, and substrate adhesion required for an excellent decorative sheet that can be used for various molding processes at a high level. do. Further, a composition for obtaining a decorative sheet that does not require a step such as photo-curing after the molding process is provided.

As a result of diligent studies, the present inventors have found that a resin (A) having an aliphatic ring structure and a hydroxyl group in the main chain, an active energy ray-curable compound (B), and an inorganic filler (in the active energy ray-curable composition). It has been found that the above-mentioned problems can be solved by including C) and the organic solvent (D), and the present invention has been completed.

The present invention is an active energy ray-curable composition containing a resin (A), an active energy ray-curable compound (B), an inorganic filler (C) and an organic solvent (D).
The resin (A) is a copolymer containing 25 to 99% by weight of the structural unit (a) having an aliphatic cyclic structure in the main chain and 1 to 75% by weight of the structural unit (b) having a hydroxyl group. It relates to a characteristic active energy ray curable resin composition.

（一般式（１）中、Ｒ₁は水素原子または炭素数１〜３０の有機残基、Ｒ₂は直接結合、メチレン基、またはエチレン基、Ｒ₃は直接結合、メチレン基、またはエチレン基、Ｒ₄は水素原子、炭素数１〜４のアルキル基、フェニル基、カルボキシル基、エステル基またはシアノ基、Ｒ₅は直接結合、メチレン基、またはエチレン基、ＸおよびＹはそれぞれ独立して炭素数１〜４のアルキル基を有していてもよいメチレン基、イミノ基、カルボニル基、酸素原子またはイオウ原子、Ｚは直接結合、炭素数１〜４のアルキル基を有していてもよいメチレン基、イミノ基、カルボニル基、酸素原子またはイオウ原子を示し、Ｘ、ＹおよびＺのうちの少なくとも１つの基は互いに隣接しない酸素原子、イオウ原子またはイミノ基である） The active energy ray-curable resin according to claim 1, wherein the structural unit (a) having an aliphatic cyclic structure in the main chain has a structure represented by the following general formula (1). Regarding the composition.
General formula (1)

(In the general formula (1), R ₁ is a hydrogen atom or an organic residue having 1 to 30 carbon atoms, R ₂ is a direct bond, a methylene group, or an ethylene group, and R ₃ is a direct bond, a methylene group, or an ethylene group. R ₄ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, a carboxyl group, an ester group or a cyano group, R ₅ is a direct bond, a methylene group or an ethylene group, and X and Y are independent carbon atoms. A methylene group which may have an alkyl group of 1 to 4, an imino group, a carbonyl group, an oxygen atom or a sulfur atom, Z is a direct bond, and a methylene group which may have an alkyl group having 1 to 4 carbon atoms. , Imino group, carbonyl group, oxygen atom or sulfur atom, and at least one group of X, Y and Z is an oxygen atom, sulfur atom or imino group which is not adjacent to each other)

（一般式（２）中、Ｒ₆は、水素原子、置換または無置換のアルキル基、置換または無置換のアリール基を表し、Ｒ₇は水素原子、炭素数１〜４のアルキル基、カルボキシル基、エステル基またはシアノ基、Ｒ₈は直接結合またはメチレン基を表し、Ｒ_９は直接結合またはメチレン基を示す。） The present invention relates to the active energy ray-curable resin composition, wherein the structural unit (a) having an aliphatic cyclic structure in the main chain is represented by the following general formula (2).
General formula (2)

(In the general formula (2), R ₆ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and R ₇ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a carboxyl group. , Esther group or cyano group, R ₈ represents a direct bond or a methylene group, and R ₉ represents a direct bond or a methylene group.)

The present invention relates to the active energy ray-curable composition, wherein the resin (A) has a weight average molecular weight of 500 or more and less than 100,000.

The present invention relates to the active energy ray-curable resin composition, wherein the inorganic filler (C) is at least one selected from the group consisting of alumina, silica, titanium oxide, and zirconium oxide.

The present invention relates to a decorative sheet having a cured film formed from the active energy ray-curable resin composition on a substrate.

The present invention relates to a molded product formed from the decorative sheet.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide an active energy ray-curable resin composition having excellent stability over time. In addition, we provide a new composition to obtain a protective layer that has both hard coatability, extensibility, moldability, and substrate adhesion required for an excellent decorative sheet that can be used for various molding processes at a high level. Can be done. Further, it is possible to provide a composition for obtaining a decorative sheet that does not require a step such as photocuring after the molding process.

In addition, in this application, especially when it is described as "(meth) acryloyl", "(meth) acrylic", "(meth) acrylic acid", "(meth) acrylate", and "(meth) acryloyloxy". Unless otherwise stated, "acryloyl and / or methacryloyl", "acrylic and / or methacrylic", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", and "acryloyloxy and / or methacryloyloxy", respectively. ".

Further, in the present specification, the curability (hard coat property) includes scratch resistance, chemical resistance and the like. Further, the moldability means that the molding process does not cause problems such as whitening, scratches, cracks, and peeling that greatly impair the design. Weather resistance means that the state of the coating film does not change even when exposed to light, heat, water, air pollutants, etc. for a long period of time.

Each component of the invention will be described. The active energy ray-curable resin composition of the present invention contains the resin (A), the active energy ray-curable compound (B), the inorganic filler (C) and the organic solvent (D), so that it has scratch resistance and chemical resistance. , Moldability, adhesion, and dispersion stability can be realized.

<Active energy ray curable resin composition>
The active energy ray-curable resin composition of the present invention contains a resin (A), an active energy ray-curable compound (B), an inorganic filler (C) and an organic solvent (D).

<Resin (A)>
The resin (A) is characterized by having a structural unit (a) having an aliphatic cyclic structure in the main chain and a structural unit (b) having a hydroxyl group. An acrylic polymer is preferable. As used herein, the main chain means a carbon chain that forms the main skeleton of the resin (A).

The structural unit (a) having an aliphatic cyclic structure in the main chain is not particularly limited, but is preferably a structure represented by the following general formula (1) in terms of availability, manufacturing cost and performance. It is preferably a structure represented by the following general formula (2). Further, as the structural unit (a) having an aliphatic cyclic structure in the main chain, one type may be used alone or two or more types may be used in combination.

（一般式（１）中、Ｒ₁は水素原子または炭素数１〜３０の有機残基、Ｒ₂は直接結合、メチレン基、またはエチレン基、Ｒ₃は直接結合、メチレン基、またはエチレン基、Ｒ₄は水素原子、炭素数１〜４のアルキル基、フェニル基、カルボキシル基、エステル基またはシアノ基、Ｒ₅は直接結合、メチレン基、またはエチレン基、ＸおよびＹはそれぞれ独立して炭素数１〜４のアルキル基を有していてもよいメチレン基、イミノ基、カルボニル基、酸素原子またはイオウ原子、Ｚは直接結合、炭素数１〜４のアルキル基を有していてもよいメチレン基、イミノ基、カルボニル基、酸素原子またはイオウ原子を示し、Ｘ、ＹおよびＺのうちの少なくとも１つの基は互いに隣接しない酸素原子、イオウ原子またはイミノ基である） General formula (1)

(In the general formula (1), R ₁ is a hydrogen atom or an organic residue having 1 to 30 carbon atoms, R ₂ is a direct bond, a methylene group, or an ethylene group, and R ₃ is a direct bond, a methylene group, or an ethylene group. R ₄ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, a carboxyl group, an ester group or a cyano group, R ₅ is a direct bond, a methylene group or an ethylene group, and X and Y are independent carbon atoms. A methylene group which may have an alkyl group of 1 to 4, an imino group, a carbonyl group, an oxygen atom or a sulfur atom, Z is a direct bond, and a methylene group which may have an alkyl group having 1 to 4 carbon atoms. , Imino group, carbonyl group, oxygen atom or sulfur atom, and at least one group of X, Y and Z is an oxygen atom, sulfur atom or imino group which is not adjacent to each other)

_{Examples of the organic group having 1 to 30 carbon atoms in R 1} of the general formula (1) include a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, an unsaturated hydrocarbon group, and a cyclic ether having 2 to 30 carbon atoms. Groups can be mentioned, but are not limited to these. Some or all of the hydrogen atoms of these organic groups are substituted at least one selected from the group consisting of alkoxy groups having 1 to 30 carbon atoms, hydroxyl groups, halogen atoms, or cyclic ether groups substituted with halogen atoms. It may be substituted with a group.

Substituted or unsubstituted alkyl groups include linear, branched, monocyclic or condensed polycyclic alkyl groups having 1 to 30 carbon atoms, or optionally one or more -O- having 2 to 30 carbon atoms. Examples include linear, branched, monocyclic or condensed polycyclic alkyl groups interrupted by. Specific examples of linear and branched alkyl groups having 1 to 30 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, amyl group, hexyl group, heptyl group, octyl group and nonyl group. , Decyl group, dodecyl group, octadecyl group, capryl group, undecyl group, lauryl group, tridecyl group, myristyl group, pentadecyl group, cetyl group, heptadecyl group, stearyl group, nonadecyl group, eicosyl group, ceryl group, mesilyl group, isopropyl Group, isobutyl group, isopentyl group, sec-butyl group, tert-butyl group, sec-pentyl group, tert-pentyl group, sec-amyl group, tert-amyl group, sec-hexyl group, sec-octyl group, tert- Octyl group, neopentyl group, 2-ethylhexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group, 4-methylcyclohexyl group, 4-tert-butylcyclohexyl group, tricyclodecanyl group, isobornyl group, Examples thereof include, but are not limited to, a dicyclopentadienyl group, a norbornyl group, a boronyl group, a 4-decylcyclohexyl group, and the like. Specific examples of linear and branched alkyl groups having 2 to 30 carbon atoms and being interrupted by one or more of -O- are -CH ₂ -O-CH ₃ and -CH _{2. -CH 2 -O-CH 2 -CH 3} , -CH 2 -CH 2 -CH 2 -O-CH 2 -CH 3, - (CH 2 -CH 2 -O) k -CH 3 ( where k is 1 from a _14), - _(CH 2 is _{-CH 2 -CH 2 -O) l -CH} 3 ( wherein l is 10 _{1), - CH 2 - (} O-CH 2 -CH 2) m - OCH ₂ -CH ₃ (here m is from 1 to _{14), - CH 2 -CH (} CH 3) -O-CH 2 -CH 3 -, - CH 2 -CH- (OCH 3) 2 , etc. However, it is not limited to these.

A part or all of hydrogen atoms of an organic group having 1 to 30 carbon atoms may be substituted with at least one substituent selected from the group consisting of hydroxyl groups and halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like. Specific examples thereof include, but are not limited to, a fluoroethyl group, a difluoroethyl group, a chloroethyl group, a dichloroethyl group, a bromoethyl group, and a dibromoethyl group.

Specifically, as the unsaturated hydrocarbon group, a chain unsaturated hydrocarbon group having 2 to 30 carbon atoms such as a vinyl group, an allyl group, a metallicyl group, a crotyl group, and a propagyl group, and a part of the hydrogen atom thereof have a carbon number of carbon atoms. Examples thereof include, but are not limited to, 1 to 30 alkoxy groups, chain unsaturated hydrocarbon groups substituted with hydroxyl groups or halogen atoms.

_{Examples of the substituted or unsubstituted aryl group in R 1} of the general formula (1) include a monocyclic or condensed polycyclic aryl group having 6 to 24 carbon atoms, and specific examples thereof include a phenyl group, a methylphenyl group, and a dimethyl group. Phenyl group, trimethylphenyl group, 4-tert-butylphenyl group, benzyl group, diphenylmethyl group, diphenylethyl group, triphenylmethyl group, cinnamyl group, anthranil group, 1-naphthyl group, 2-naphthyl group, 1-anthrill group , 9-Anthril group, 2-Phenyltril group, 3-Phenyltril group, 9-Phenyltril group, 1-Pyrenyl group, 5-Naphthalsenyl group, 1-Indenyl group, 2-Azrenyl group, 1-Acenaphthyl group, 2-Fluorenyl group , 9-Fluorenyl group, 3-Perylenyl group, o-tryl group, m-tryl group, p-tolyl group, 2,3-kisilyl group, 2,5-kisilyl group, mesityl group, p-cumenyl group, p- Dodecylphenyl group, p-cyclohexylphenyl group, 4-biphenyl group, o-fluorophenyl group, m-chlorophenyl group, p-bromophenyl group, p-hydroxyphenyl group, m-carboxyphenyl group, o-mercaptophenyl group, Examples thereof include, but are not limited to, a p-cyanophenyl group, an m-nitrophenyl group, and an m-azidophenyl group.

_{R 1} of the general formula (1) may be a cyclic ether group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms partially substituted with a hydrogen atom thereof, a cyclic ether group in which a hydroxyl group or a halogen atom is substituted, and the like. Specifically, glycidyl group, β-methylglycidyl group, 3,4-epoxycyclohexylmethyl group, tetrahydrofurfuryl group, furfuryl group, 3-methyl-3-oxetanylmethyl group, 3-ethyl-3-oxetanylmethyl group. However, it is not limited to these.

Here, from the viewpoint of obtaining raw materials and the physical properties of copolymerization, R ₁ is a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms (a part of the hydrogen atom having 1 to 18 carbon atoms is substituted with an alkoxy group or a hydroxyl group). Or an alkoxy group having 1 to 18 carbon atoms (a part of the hydrogen atom having 1 to 18 carbon atoms may be replaced with an alkoxy group or a hydroxyl group) is preferable, and more preferably the number of carbon atoms. It is a substituted or unsubstituted alkyl group of 1 to 18 (a part of a hydrogen atom having 1 to 18 carbon atoms may be substituted with an alkoxy group or a hydroxyl group), and more preferably, it has 1 to 5 carbon atoms. It is an unsubstituted or substituted linear alkyl group (a part of a hydrogen atom having 1 to 5 carbon atoms may be substituted with a hydroxyl group).

Examples of R ₂ include a direct bond, a methylene group and an ethylene group. Here, from the viewpoint of obtaining raw materials and physical properties of copolymerization, R ₂ is preferably a direct bond or a methylene group, and more preferably a methylene group.

Examples of R ₃ include a direct bond, a methylene group and an ethylene group. Here, from the viewpoint of obtaining raw materials and physical properties of copolymerization, R ₃ is preferably a direct bond or a methylene group, and more preferably a direct bond.

Examples of R ₄ include a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, a carboxyl group, an ester group or a cyano group. Here, from the viewpoint of obtaining raw materials and physical properties of copolymerization, R ₄ is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a carboxyl group, an ester group or a cyano group, and more preferably a hydrogen atom or 1 carbon atom. It is an alkyl group of ~ 4.

Examples of R ₅ include a direct bond, a methylene group and an ethylene group. Here, from the viewpoint of obtaining raw materials and physical properties of copolymerization, R ₂ is preferably a direct bond or a methylene group, and more preferably a methylene group.

Examples of X and Y include a methylene group, an imino group, a carbonyl group, an oxygen atom or a sulfur atom, which may independently have an alkyl group having 1 to 4 carbon atoms. From the viewpoint of physical properties, each of X and Y is preferably a methylene group, a carbonyl group or an oxygen atom which may independently have an alkyl group having 1 to 4 carbon atoms, and more preferably 1 to 1 carbon atoms. It is a methylene group, a carbonyl group or an oxygen atom which may have an alkyl group of 4, and more preferably a methylene group.

Examples of Z include a methylene group, an imino group, a carbonyl group, an oxygen atom or a sulfur atom which are directly bonded and may have an alkyl group having 1 to 4 carbon atoms. Here, from the viewpoint of obtaining raw materials and physical properties of copolymerization, a methylene group and a carbonyl group which may have an alkyl group having 1 to 4 carbon atoms are preferable.

At least one group of X, Y and Z is an oxygen atom, sulfur atom or imino group, and these oxygen atom, sulfur atom or imino group are not adjacent to each other. Here, oxygen atoms are preferable from the viewpoint of obtaining raw materials and physical properties of copolymerization.

（一般式（２）中、Ｒ₆は、水素原子、置換または無置換のアルキル基、置換または無置換のアリール基を表し、Ｒ₇は水素原子、炭素数１〜４のアルキル基、カルボキシル基、エステル基またはシアノ基、Ｒ₈は直接結合またはメチレン基を表し、Ｒ_９は直接結合またはメチレン基を示す。） General formula (2)

(In the general formula (2), R ₆ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and R ₇ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a carboxyl group. , Esther group or cyano group, R ₈ represents a direct bond or a methylene group, and R ₉ represents a direct bond or a methylene group.)

_{The substituted or unsubstituted alkyl group in R 6} in the general formula (2) may be a linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms, or 2 to 18 carbon atoms. Included are linear, branched, monocyclic or condensed polycyclic alkyl groups optionally interrupted by one or more —O—s. Specific examples of linear and branched alkyl groups having 1 to 18 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group. , Dodecyl group, octadecyl group, isopropyl group, isobutyl group, isopentyl group, sec-butyl group, tert-butyl group, sec-pentyl group, tert-pentyl group, tert-octyl group, neopentyl group, cyclopropyl group, cyclobutyl group. , Cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, 4-decylcyclohexyl group and the like, but are not limited thereto. Specific examples of linear and branched alkyl groups having 2 to 18 carbon atoms and optionally interrupted by one or more of -O- are -CH ₂ -O-CH ₃ and -CH _{2. -CH 2 -O-CH 2 -CH 3} , -CH 2 -CH 2 -CH 2 -O-CH 2 -CH 3, - (CH 2 -CH 2 -O) k-CH 3 ( where k is 1 from a _{8), -} (CH 2 is _{-CH 2 -CH 2 -O) l-} CH 3 ( where l is 5 _{1), - CH 2 -CH (} CH 3) -O-CH 2 - CH ₃ −, −CH ₂ −CH− (OCH ₃ ) _{2, and the} like can be mentioned, but the present invention is not limited thereto.

_{Examples of the substituted or unsubstituted aryl group in R 6} of the general formula (2) include a monocyclic or fused polycyclic aryl group having 6 to 24 carbon atoms, and specific examples thereof include a phenyl group and a 1-naphthyl group. 2-naphthyl group, 1-anthryl group, 9-anthrill group, 2-phenanthryl group, 3-phenanthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azulenyl group, 1-acenaphtyl group, 2-fluorenyl group, 9-fluorenyl group, 3-perylenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,3-kisilyl group, 2,5-xylyl group, mesityl Group, p-cumenyl group, p-dodecylphenyl group, p-cyclohexylphenyl group, 4-biphenyl group, o-fluorophenyl group, m-chlorophenyl group, p-bromophenyl group, p-hydroxyphenyl group, m-carboxy Examples thereof include, but are not limited to, a phenyl group, an o-mercaptophenyl group, a p-cyanophenyl group, an m-nitrophenyl group, and an m-azidophenyl group.

Here, from the viewpoint of obtaining raw materials and physical properties of copolymerization, R ₆ is preferably an alkyl group, more preferably a linear alkyl group having 1 to 5 carbon atoms.

_{Examples of R 7} in the general formula (2) include a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a carboxyl group, an ester group or a cyano group. Here, from the viewpoint of obtaining raw materials and the physical properties of copolymerization, R ₇ is preferably an alkyl group having 1 to 4 carbon atoms, a carboxyl group, an ester group or a cyano group, and more preferably a hydrogen atom or an alkyl having 1 to 4 carbon atoms. It is a group.

R ₈ in the general formula (2) can be mentioned a direct bond or a methylene group. Wherein, R ₈ in view of the physical properties of the availability of raw materials and copolymer is a direct bond are preferred.

_{R 9} in the general formula (2) represents a direct bond or a methylene group. Here, a methylene group is preferable for _{R 9} from the viewpoint of obtaining raw materials and physical properties of copolymerization.

The method for introducing the structural unit (a) having an aliphatic cyclic structure in the main chain of the resin (A) is not particularly limited, but can be obtained by acrylic polymerization of the diene structure-containing monomer (c). This is possible, and the polymerization proceeds by the mechanism described in JP2013-216736.

Regarding the method for introducing the structural unit (a) having an aliphatic cyclic structure in the main chain of the resin (A), when the structural unit (a) is introduced by advancing the polymerization by the mechanism described in JP2013-216736, R _{4 in the general formula (1) is introduced.} When is a hydrogen atom, _{it is preferable that R 3} is a direct bond and R ₅ is a methylene group. On the other hand, when R ₄ is an alkyl group having 1 to 4 carbon atoms, a phenyl group, a carboxyl group, an ester group or a cyano group, _{it is preferable that R 3} is a methylene group and R ₅ is a direct bond.

Regarding the method for introducing the structural unit (a) having an aliphatic cyclic structure in the main chain of the resin (A), when the introduction is carried out by advancing the polymerization by the mechanism described in JP2013-216736, R _{7 in the general formula (2) is introduced.} When is a hydrogen atom, _{it is preferable that R 8} is a direct bond and R ₉ is a methylene group. On the other hand, when R ₇ is an alkyl group, a carboxyl group, an ester group and a cyano group having 1 to 4 carbon atoms, it is preferable that _{R 8} is a methylene group and R _{9 is a direct bond.}

The diene structure-containing monomer (c) is not particularly limited, but is preferably a structure represented by the following general formula (3) from the viewpoint of availability, manufacturing cost and performance, and more preferably. , The structure according to the general formula (4).

（一般式（３）中のＲ_１、Ｒ_４、Ｘ、Ｙ、Ｚは前記と同じである。） General formula (3)

_{(R 1} , R ₄ , X, Y, Z in the general formula (3) are the same as described above.)

（一般式（４）中のＲ_６、Ｒ_７は前記と同じである。） General formula (4)

_{(R 6} and R ₇ in the general formula (4) are the same as described above.)

The structural unit (b) having a hydroxyl group is not particularly limited, and specific examples thereof include structures derived from the following monomers having a hydroxyl group and an ethylenically unsaturated bond group. However, the structural unit (b) having a hydroxyl group does not include the structural unit (a) having an aliphatic cyclic structure in the main chain.

Examples of hydroxyacrylates having a monofunctional hydroxyl group:
2-Hydroxyethyl acrylate, 2-Hydroxypropyl acrylate, 3-Hydroxypropyl (meth) acrylate, 4-Hydroxybutyl acrylate, 4-Hydroxyvinylbenzene, 2-Hydroxy-3-chloropropyl acrylate, 2-Hydroxy-3-phenoxy Propyl acrylate, 2-hydroxy-3-allyloxypropyl acrylate, -2-hydroxy-3-allyloxypropyl acrylate, 2-acryloyloxyethyl-2-hydroxypropylphthalate or caprolactone adducts of these monomers (additional number of moles) Acrylate having a hydroxyl group such as 1 to 5). Polyalkylene glycols such as polyethylene glycol acrylates and polypropylene glycol acrylates, polyethylene glycol acrylates, and polypropylene glycol acrylates having a polyoxyalkylene chain having a hydroxyl group at the molecular end, and polyalkylene glycol having an acrylic acid and a polyoxyalkylene chain having a hydroxyl group. Monohydroxyethyl Acrylate Acrylate, Monohydroxyethyl Tetrahydrophthalate Acrylate, Monohydroxypropyl Tetrahydrophthalate Acrylate, Monohydroxyethyl 5-Methyl-1,2-Cyclohexanedicarboxylic Acid Monohydroxyethyl Acrylate, Monohydroxyethyl Acrylate Acrylate, Monohydroxyphthalate Propyl acrylate, monohydroxyethyl acrylate acrylate, hydroxypropyl acrylate maleate, monohydroxybutyl acrylate tetrahydrophthalate, etc.

Examples of hydroxymethacrylates having a monofunctional hydroxyl group:
2-Hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 4-hydroxyvinylbenzene, 2-hydroxy-3-chloropropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-Hydroxy-3-allyloxypropyl methacrylate, 2-methacryloyloxyethyl-2-hydroxypropylphthalate or methacrylates having a hydroxyl group such as a caprolactone adduct of these monomers (additional number of moles is 1 to 5). Esterides of polyalkylene glycol having a polyoxyalkylene chain having a hydroxyl group at the molecular end such as polyethylene glycol methacrylate and polypropylene glycol methacrylate, polyethylene glycol methacrylate and polypropylene glycol methacrylate, and methacrylic acid, monohydroxyethyl methacrylate and tetrahydro oxalate. Monohydroxyethyl methacrylate phthalate, monohydroxypropyl methacrylate tetrahydrophthalate, monohydroxyethyl methacrylate 5-methyl-1,2-cyclohexanedicarboxylic acid, monohydroxyethyl methacrylate phthalate, monohydroxypropylmethacrylate phthalate, monohydroxyethyl maleate Methacrylate, hydroxypropyl methacrylate maleate, monohydroxybutyl methacrylate tetrahydrophthalate, etc.

Examples of hydroxy (meth) acrylates having bifunctional or higher hydroxyl groups:
Glycerin mono (meth) acrylate, trimethylol propane mono (meth) acrylate, pentaerythritol mono (meth) acrylate, diglycerin mono (meth) acrylate, ditrimethylol propane mono (meth) acrylate, dipentaerythritol mono (meth) acrylate, Mono (meth) acrylate of trimethylolpropane alkylene oxide adduct, mono (meth) acrylate of glycerin alkylene oxide adduct, mono (meth) acrylate of isocyanuric acid alkylene oxide adduct, mono (meth) of pentaerythritol alkylene oxide adduct. Acrylate, mono (meth) acrylate of ditrimethylolpropane alkylene oxide adduct, mono (meth) acrylate of diglycerin alkylene oxide adduct, mono (meth) acrylate of dipentaerythritol alkylene oxide adduct, and the like.

Preferred are 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and glycerin mono (meth) acrylate.

As the resin (A), other monomers can be used depending on the required physical characteristics. As the other monomer, only one kind may be used, or two or more kinds may be used at an arbitrary ratio.

Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) Acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, cetyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, tridecyl (meth) acrylate, isomyristyl (meth). ) Linear or branched alkyl (meth) acrylates such as acrylates, lauryl (meth) acrylates, stearyl (meth) acrylates, isostearyl (meth) acrylates, benzyl (meth) acrylates, isobornyl (meth) acrylates and adamantyl (meth) acrylates. Kind;

Cyclohexyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, Cyclic alkyl (meth) acrylates such as dicyclopentenyl (meth) acrylates, dicyclopentenyloxyethyl (meth) acrylates, and isobornyl (meth) acrylates or cyclic alkenyl (meth) acrylates;

2-Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 2 -Hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3-allyloxypropyl (meth) acrylate, -2-hydroxy-3-allyloxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl -2-Hydroxypropyl phthalate, glycerin mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, 4-hydroxyvinylbenzene, polypropylene glycol mono (meth) acrylate, and caprolactone adducts of these monomers (additional moles are 1 to 1). (Meta) acrylates having a hydroxyl group such as 5);

(2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H-hexafluoroisopropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (Meta) Acrylate, 1H, 1H, 2H, 2H-Heptadecafluorodecyl (meth) Acrylate, 2,6-dibromo-4-butylphenyl (meth) Acrylate, 2,4,6-Tribromophenoxyethyl (Meta) Fluoroalkyl (meth) acrylates such as acrylates, 2,4,6-tribromophenol 3EO-added (meth) acrylates, and perfluorooctylethyl (meth) acrylates;

Tetrahydrofurfuryl (meth) acrylate, dioxolan (meth) acrylate, acryloylfurfuryl (meth) acrylate, 2-isocyanatoethyl (meth) acrylate-modified furfuryl alcohol, 2-isocyanatoethyl (meth) acrylate-modified furfurylamine, 2, -(Meta) acrylates having a heterocycle such as bromofuran EO-added (meth) acrylate and 3-methyl-3-oxetanyl (meth) acrylate;

Benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, paracumylphenoxyethyl (meth) acrylate, paracumylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, etc. (Meta) acrylates having an aromatic ring of

2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, n-butoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, 1,3-butylene glycol methyl ether (meth) acrylate, methoxytri Ethylene glycol (meth) acrylate, methoxypolyethylene glycol mono (meth) acrylate, methoxypolyethylene glycol # 400 (meth) acrylate, methoxypolyethylene glycol # 100 (meth) acrylate, methoxypolyethylene glycol # 1000 (meth) acrylate, methoxypolyethylene glycol # 4000 (meth) acrylate, methoxypolyethylene glycol # 200 (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, ethyl Carbitol (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, cresil polyethylene Glycol (meth) acrylate, -2- (vinyloxyethoxy) ethyl (meth) acrylate, p-nonylphenoxyethyl (meth) acrylate, p-nonylphenoxypolyethylene glycol (meth) acrylate, glycidyl (meth) acrylate, β- Carboxyethyl (meth) acrylate, mono (meth) succiloyloxyethyl ester, ω-carboxypolycaprolactone mono (meth) acrylate, 2- (meth) acryloyloxyethyl hydrogenphthalate, 2- (meth) acryloyloxypropylhydrogenphthalate , 2- (meth) acryloyloxypropyl hexahydrohydrogenphthalate, 2- (meth) acryloyloxypropyltetrahydrohydrogenphthalate, octoxypolyethylene glycol polypropylene glycol mono (meth) acrylate, lauroxypolyethylene glycol mono (meth) acrylate, stearoxy Polyethylene glycol No (meth) acrylate, phenoxypolyethylene glycol mono (meth) acrylate, phenoxypolyethylene glycol polypropylene glycol mono (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate, nonylphenoxypolyethylene glycol mono (meth) acrylate, nonylphenoxypolypropylene glycol mono (Meta) acrylates having ether groups such as (meth) acrylate, nonylphenoxypolyethylene glycol polypropylene glycol mono (meth) acrylate, n-butoxyethyl (meth) acrylate, and 2-ethoxyethyl (meth) acrylate;

3- (Acryloyloxymethyl) 3-methyloxetane, 3- (methacryloyloxymethyl) 3-methyloxetane, 3- (acryloyloxymethyl) 3-ethyloxetane, 3- (methacryloyloxymethyl) 3-ethyloxetane, 3- Oxetanyl groups such as (acryloyloxymethyl) 3-butyloxetane, 3- (methacryloyloxymethyl) 3-butyloxetane, 3- (acryloyloxymethyl) 3-hexyloxetane, and 3- (methacryloyloxymethyl) 3-hexyloxetane. (Methyl) acrylates with

Styrene, α-methylstyrene, p-hydroxystyrene, p-chlorostyrene, p-bromostyrene, p-methylstyrene, p-methoxystyrene, pt-butoxystyrene, pt-butoxycarbonylstyrene, pt -Vinyls such as butoxycarbonyloxystyrene, 2,4-diphenyl-4-methyl-1-pentenevinyl acetate, vinyl (meth) acrylate, and allyl (meth) acrylate;

(Meta) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N , N-dimethylaminopropylacrylamide, morpholinoethyl (meth) acrylate, N-methylol (meth) acrylamide, diacetone (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N -(Meta) acrylamides such as isopropyl (meth) acrylamide, diacetone (meth) acrylamide, and (meth) acryloylmorpholin;

(Meta) Nitriles such as acrylonitrile;

Vinyl ethers having an ether group such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether;

Fluoroalkyl (meth) acrylates such as trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, or tetrafluoropropyl (meth) acrylate;

Product name "Silaplane FM-0711" (manufactured by JNC Co., Ltd.), Product name "Silaplane FM-0721" (manufactured by JNC Co., Ltd.) Product name "Silaplane FM-0725" (manufactured by JNC Co., Ltd.) , Product name "X-22-174DX" (manufactured by Shinetsu Silicone) "X-22-2426" (manufactured by Shinetsu Silicone), product name "X-22-174ASX" (manufactured by Shinetsu Silicone), etc. Polysiloxane (meth) acrylates;

(Meta) acrylates having an isocyanate group such as 2-isocyanate ethyl methacrylate, 2-isocyanate ethyl acrylate, 4-isocyanate butyl methacrylate, and 4-isocyanate butyl acrylate;

The isocyanate group also includes a blocked isocyanate group and can be used. The blocked isocyanate group can suppress the reactivity of the isocyanate group by protecting the isocyanate group with another functional group under normal conditions, while deprotecting the isocyanate group by heating to regenerate the active isocyanate group. Indicates an isocyanate block body.

Commercially available products of (meth) acrylates having such a blocked isocyanate group include, for example, 2-[(3,5-dimethylpyrazolyl) carboxyamino] ethyl methacrylate (Carens MOI-BP, manufactured by Showa Denko); methacrylic acid. 2- (0- [1'methylprovideneamino] carboxyamino) ethyl (Carens MOI-BM, manufactured by Showa Denko) and the like can be mentioned.

Other polymerizable monomers include vinyl acetate, monochloroacetate, vinyl benzoate, vinyl pivalate, vinyl butyrate, vinyl laurate, vinyl 2-ethylhexanoate, N-vinylcarbazole, N-vinylpyrrolidone and the like. However, it is not limited to these.

When other polymerizable monomers are contained, linear or branched alkyl (meth) acrylates, (meth) acrylamides, and polysiloxane (meth) acrylates are preferable, and linear or branched having 1 to 5 carbon atoms is preferable. Alkyl (meth) acrylates, (meth) acryloylmorpholine, N-isopropyl (meth) acrylamide, and polysiloxane (meth) acrylates are more preferred, but are not limited thereto.

When other polymerizable monomers are contained, the content thereof is preferably 1 to 50% by weight, preferably 1 to 35% by weight.

From the viewpoint of various physical properties, the structural unit (a) having an aliphatic cyclic structure in the main chain is preferably 25 to 99% by weight, more preferably 40 to 99% by weight, out of 100% by weight of the resin (A). More preferably, it is 40 to 80% by weight.

From the viewpoint of various physical properties when the resin (A) is used as a decorative sheet, the structural unit (b) having a hydroxyl group is preferably 1 to 75% by weight in 100% by weight of the resin (A). It is more preferably 1 to 60% by weight, still more preferably 20 to 60% by weight.

The resin (A) is preferably synthesized by using acrylic polymerization from the viewpoint of introducing the polymerization units of the general formulas (1) and (2) and controlling the amount. Further, it may have a polymerization unit based on other monomers if necessary such as physical properties.

The resin (A) of the present invention can be obtained by a known radical polymerization method. Further, known methods such as free radical polymerization and living radical polymerization can be used.

In the living radical polymerization method, side reactions that occur in general radical polymerization are suppressed, and further, the growth of polymerization occurs uniformly, so that a block polymer or a resin having a uniform molecular weight can be easily synthesized.

Among them, the atom transfer radical polymerization method using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst can be applied to a wide range of monomers and has a polymerization temperature applicable to existing equipment. It is preferable in that it can be adopted. The atom transfer radical polymerization method can be carried out by the method described in References 1 to 8 below.

(Reference 1) Fukuda et al., Prog. Polym. Sci. 2004, 29, 329
(Reference 2) Matyjaszewski et al., Chem. Rev. 2001,101,
2921
(Reference 3) Mattyjaszewski et al., J. Mol. Am. Chem. Soc. 1995, 117, 5614
(Reference 4) Macromolecules 1995, 28, 7901, Science, 1996, 272,866
(Reference 5) WO96 / 034211
(Reference 6) WO97 / 018247
(Reference 7) Japanese Patent Application Laid-Open No. 9-208616 (Reference 8) Japanese Patent Application Laid-Open No. 8-411117

The polymerization temperature is preferably adjusted appropriately according to the type of the polymerization initiator used and the boiling point of the solvent, but is preferably 20 ° C to 150 ° C, more preferably 40 ° C to 120 ° C, and even more preferably 50 ° C to 50 ° C. It is 100 ° C.

The reaction time is preferably adjusted as appropriate depending on the type of polymerization initiator and monomer used, but is preferably 2 to 30 hours, more preferably 3 to 15 hours.

Regarding the environment in which the polymerization is carried out, it is desirable to carry out the polymerization in an inert gas atmosphere for the purpose of reducing coloration and preventing the deactivation of the polymerization initiator, and nitrogen gas is preferable from the viewpoint of availability and cost. Not limited to.

As the polymerization initiator, an azo compound and an organic peroxide can be used. Examples of azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane1-carbonitrile), 2 , 2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), 2,2'-azobis (4-methoxy-2,4- Dimethylvaleronitrile), dimethyl 2,2'-azobis (2-methylpropionate), 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis (2-hydroxymethylpropionitrile) ), 2,2'-Azobis [N- (2-propenyl) -2-methylpropionamide], 2,2'-azobis (N-butyl-2-methylpropionamide), dimethyl 1,1'-azobis ( 1-Cyclohexanecarboxylate) and 2,2'-azobis [2- (2-imidazolin-2-yl) propane] and the like, but are not limited thereto.

Examples of organic peroxides are benzoyl peroxide, t-butylperbenzoate, cumenehydroperoxide, diisopropylperoxydicarbonate, di-n-propylperoxydicarbonate, di (2-ethoxyethyl) peroxy. Dicarbonate, t-butylperoxy2-ethylhexanoate, t-butylperoxyneodecanoate, t-butylperoxy-2-ethylhexanoate, dilauroxyperooxide, peroxyneodecanoate, Examples include, but are not limited to, t-butylperoxyvivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, diacetyl peroxide and the like.

These polymerization initiators can be used alone or in combination of two or more, and the amount used is 0.001 to 20% by weight based on the total amount of the monomers used in the polymerization (total 100 parts by weight). It can be adjusted arbitrarily within the range of the part.

At the time of polymerization, a chain transfer agent may be used for the purpose of adjusting the molecular weight. As the amount to be used, 0.001 to 15 parts by mass of the chain transfer agent can be optionally used with respect to the total amount of the monomers used in the polymerization (100 parts by weight in total).

The chain transfer agent is not particularly limited as long as it is a compound capable of adjusting the molecular weight, and known chain transfer agents can be used. for example,
Octyl mercapto, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercapto, mercaptoethanol, 1-thioglycerol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 2 -Ethylhexyl-3-mercaptopropionate, n-octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, stearyl-3-mercaptopropionate, trimethylolpropanetris (3-mercaptopropionate) Nate), Tris-[(3-mercaptopropionyloxy) -ethyl] -isosianurate, pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), dipentaerythritol hexakiss (3-Mercaptopropionate), thioapple acid, octyl thioglycolate, octyl 3-mercaptopropionate, 2-mercaptoethanol sulfonic acid, mercaptans such as butylthioglycolate;
Disulfides such as dimethylxanthogen disulfide, diethylxantogen disulfide, diisopropylxanthigen disulfide, tetramethylthium disulfide, tetraethylthium disulfide, tetrabutyltiuram disulfide; carbon tetrachloride, methylene chloride, bromoform, bromotrichloroethane, carbon tetrabromide, bromide. Halogenized hydrocarbons such as ethylene;
Secondary alcohols such as isopropanol and glycerin;
Sodium bisulfite, hypophosphite, and salts thereof (sodium bisulfite, potassium hypophosphite, etc.), sulfite, hydrogen sulfite, dithionic acid, metabisulfite, and salts thereof (sodium bisulfite). , Sodium bisulfite, sodium bisulfite, potassium bisulfite, sodium metabisulfite, potassium metabisulfite, etc.), lower oxides and salts thereof; and allyl alcohol, 2-ethylhexylthioglycolate, α -Methylstyrene dimer, tarpinolene, α-terpinen, γ-terpinen, dipentene, anisole and the like can be mentioned, but are not limited thereto. These may be used alone or in combination of two or more.

Further, at the time of polymerization, an organic solvent can be used as the polymerization solvent. Examples of the organic solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, n-propyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, diethoxydiethylene glycol, and the like. 3-Methyl-1-butanol and the like are used, but the present invention is not particularly limited thereto. Two or more kinds of these polymerization solvents may be mixed and used, but the solvent used in the final use is preferable.

From the viewpoint of moldability and the like, the weight average molecular weight of the resin (A) of the present invention is preferably 500 or more and less than 100,000, more preferably 10,000 or more and less than 100,000, and further preferably 30,000 or more and less than 100,000. More preferred. As used herein, the weight average molecular weight refers to a polystyrene-equivalent molecular weight measured by gel permeation chromatography.

The resin (A) is 1 to 99 parts by weight out of a total of 100 parts by weight of the solid content of the active energy ray-curable resin composition from the viewpoint of hard coatability and processability of the active energy ray-curable resin composition. It is preferably used in an amount, more preferably 20 to 80 parts by weight.

From the viewpoint of moldability and the like, the glass transition temperature (Tg) of the resin (A) of the present invention is preferably 30 ° C. or higher and 120 ° C. or lower.

From the viewpoint of moldability, chemical resistance and the like, the hydroxyl value of the resin (A) of the present invention is preferably 1-350 mgKOH / g, more preferably 1-330 mgKOH / g, still more preferably 100 to 100. It is 330 mgKOH / g.

<Active energy ray-curable compound (B)>
Next, as the active energy ray-curable compound (B), a compound having a polymerizable group can be used in order to improve the curability associated with the reaction. The compound having a polymerizable group in the present invention means a compound having at least one polymerizable skeleton in the molecule (however, the resin (A) is not included). In addition, all of these have chemical forms of liquid or solid monomers, oligomers, or polymers at normal temperature and pressure.

Preferred examples of the active energy ray-curable compound (B) include polymerizable oligomers and polymerizable monomers. The polymerizable oligomer can impart resistance, flexibility, and curability to the surface protective layer, and those having a number average molecular weight (measured by gel permeation chromatography (GPC); hereinafter the same) of 100 or more are preferable. Used for.

Examples of such polymerizable compounds include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid and maleic acid, salts thereof, esters, acid amides, acid anhydrides and the like. Furthermore, (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, acrylic (meth) acrylate, ester (meth) acrylate, ester (meth) acrylate acrylonitrile, ether (meth) acrylate, styrene derivative, Examples thereof include, but are not limited to, various unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, and unsaturated polyurethanes. Specific examples of the radically polymerizable compound in the present invention are given below.

Examples of acrylates:
Examples of monofunctional alkyl acrylates, monofunctional cyclic alkyl acrylates, or monofunctional cyclic alkenyl acrylates:
Methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, tert-butyl acrylate, amyl acrylate, isoamyl acrylate, neopentyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, decyl acrylate, lauryl acrylate, Stearyl acrylate, isobornyl acrylate, cyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, benzyl acrylate, cyclohexyl acrylate, lauryl acrylate, stearyl acrylate.

Examples of monofunctional hydroxy acrylates:
2-Hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-3-chloropropyl acrylate, N- (2-hydroxyethyl) acrylamide, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-allyloxy Propyl acrylate, -2-hydroxy-3-allyloxypropyl acrylate, 2-acryloyloxyethyl-2-hydroxypropylphthalate.

Examples of monofunctional halogen-containing acrylates:
2,2,2-Trifluoroethyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, 1H-hexafluoroisopropyl acrylate, 1H, 1H, 5H-octafluoropentyl acrylate, 1H, 1H, 2H, 2H- Heptadecafluorodecyl acrylate, 2,6-dibromo-4-butylphenyl acrylate, 2,4,6-tribromophenoxyethyl acrylate, 2,4,6-tribromophenol 3EO-added acrylate.

Examples of monofunctional ether-containing ether group acrylates:
2-methoxyethyl acrylate, 1,3-butylene glycol methyl ether acrylate, butoxyethyl acrylate, methoxytriethylene glycol acrylate, methoxypolyethylene glycol # 400 acrylate, methoxydipropylene glycol acrylate, methoxytripropylene glycol acrylate, methoxypolypropylene glycol acrylate, Ethoxydiethylene glycol acrylate, ethylcarbitol acrylate, 2-ethylhexylcarbitol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxypolyethylene glycol acrylate, cresylpolyethylene glycol acrylate, -2- (vinyloxyethoxy) acrylate Ethyl, p-nonylphenoxyethyl acrylate, p-nonylphenoxypolyethylene glycol acrylate, glycidyl acrylate.

Examples of monofunctional-containing carboxyl acrylates:
β-carboxyethyl acrylate, succinic acid monoacryloyloxyethyl ester, ω-carboxypolycaprolactone monoacrylate, 2-acryloyloxyethylhydrogenphthalate, 2-acryloyloxypropylhydrogenphthalate, 2-acryloyloxypropylhexahydrohydrogenphthalate, 2- Acryloyloxypropyltetrahydrohydrogenphthalate.

Examples of other monofunctional acrylates:
N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate, morpholinoethyl acrylate, trimethylsiloxyethyl acrylate, diphenyl-2-acryloyloxyethyl phosphate, 2-acryloyloxyethyl acid phosphate, caprolactone-modified -2-acryloyl Oxyethyl acid phosphate, 2-hydroxy-1-acryloxy-3-methacryloxypropane.

Examples of bifunctional acrylates:
1,4-Butanediol diacrylate, 1,6-hexanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 200 diacrylate, polyethylene glycol # 300 Diacrylate, Polyethylene Glycol # 400 Diacrylate, Polyethylene Glycol # 600 Diacrylate, Dipropylene Glycol Diacrylate, Tripropylene Glycol Diacrylate, Tetrapropylene Glycol Diacrylate, Polypropylene Glycol # 400 Diacrylate, Polypropylene Glycol # 700 Diacrylate, Neo Pentyl glycol diacrylate, neopentyl glycol PO modified diacrylate, hydroxypivalate neopentyl glycol ester diacrylate, hydroxypivalate neopentyl glycol ester caprolactone adduct diacrylate, 1,6-hexanediol bis (2-hydroxy-3) -Acryloyloxypropyl) ether, bis (4-acryloxypolyethoxyphenyl) propane, 1,9-nonanediol diacrylate, pentaerythritol diacrylate, pentaerythritol diacrylate monostearate, pentaerythritol diacrylate monobenzoate, bisphenol A Diacrylate, EO modified bisphenol A diacrylate, PO modified bisphenol A diacrylate, hydride bisphenol A diacrylate, EO modified hydride bisphenol A diacrylate, PO modified hydride bisphenol A diacrylate, bisphenol F diacrylate, EO modified bisphenol F-diacrylate, PO-modified bisphenol F-diacrylate, EO-modified tetrabromobisphenol A-diacrylate, tricyclodecanedimethylol diacrylate, isocyanuric acid EO-modified diacrylate, ethoxylated isocyanuric acid diacrylate, 2-hydroxy-1,3- Diacryloxypropane, pentaerythritol diacrylate.

Examples of trifunctional acrylates:
Glycerin PO-modified triacrylate, trimethylolpropane triacrylate, trimethylolpropane EO-modified triacrylate, trimethylolpropane PO-modified triacrylate, isocyanuric acid EO-modified triacrylate, ethoxylated isocyanuric acid triacrylate, isocyanuric acid EO-modified ε-caprolactone-modified Triacrylate, 1,3,5-triacryloylhexahydro-s-triazine, pentaerythritol triacrylate, dipentaerythritol triacrylate tripropionate.

Examples of tetrafunctional or higher acrylates:
Pentaerythritol tetraacrylate, acrylate in which two molecules of ethoxylated isocyanuric acid diacrylate are linked with hexamethylene diisocyanate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate monopropionate, dipentaerythritol hexaacrylate, dipentaerythritol ε-caprolactone Modified hexaacrylate, dipentaerythritol EO modified hexaacrylate, tetramethylolmethanetetraacrylate, oligoestertetraacrylate, pentaerythritol tetraacrylate, tris (acryloyloxy) phosphate.

Examples of methacrylates:
Examples of monofunctional alkyl methacrylates, monofunctional cyclic alkyl methacrylates, or monofunctional cyclic alkenyl methacrylates:
Methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, amyl methacrylate, neopentyl methacrylate, isoamyl methacrylate, hexyl methacrylate, 2-hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, decyl Methacrylate, lauryl methacrylate, stearyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, lauryl methacrylate, stearyl methacrylate.

Examples of monofunctional hydroxymethacrylates:
2-Hydroxyethyl methacrylate, 2-Hydroxypropyl methacrylate, 2-Hydroxy-3-chloropropylmethacrylate, 2-Hydroxy-3-phenoxypropylmethacrylate, 2-Hydroxy-3-allyloxypropylmethacrylate, 2-methacryloyloxyethyl-2 -Hydroxypropyl phthalate.

Examples of monofunctional halogen-containing methacrylates:
2,2,2-Trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 1H-hexafluoroisopropyl methacrylate, 1H, 1H, 5H-octafluoropentyl methacrylate, 1H, 1H, 2H, 2H- Heptadecafluorodecyl methacrylate, 2,6-dibromo-4-butylphenyl methacrylate, 2,4,6-tribromophenoxyethyl methacrylate, 2,4,6-tribromophenol 3EO-added methacrylate.

Examples of monofunctional ether-containing methacrylates:
2-methoxyethyl methacrylate, 1,3-butylene glycol methyl ether methacrylate, butoxyethyl methacrylate, methoxytriethylene glycol methacrylate, methoxypolyethylene glycol # 400 methacrylate, methoxydipropylene glycol methacrylate, methoxytripropylene glycol methacrylate, methoxypolyethylene glycol methacrylate, -2- (Binyloxyethoxy) ethyl methacrylate, ethoxydiethylene glycol methacrylate, 2-ethylhexyl carbitol methacrylate, tetrahydrofurfuryl methacrylate, phenoxyethyl methacrylate, phenoxydiethylene glycol methacrylate, phenoxypolyethylene glycol methacrylate, cresylpolyethylene glycol methacrylate, p-nonyl Phenoxyethyl methacrylate, p-nonylphenoxypolyethylene glycol methacrylate, glycidyl methacrylate.

Examples of monofunctional carboxyl-containing carboxyl methacrylates:
β-carboxyethyl methacrylate, succinic acid monomethacryloyloxyethyl ester, ω-carboxypolycaprolactone monomethacrylate, 2-methacryloyloxyethylhydrogenphthalate, 2-methacryloyloxypropylhydrogenphthalate, 2-methacryloyloxypropylhexahydrohydrogenphthalate, 2- Methacryloyloxypropyltetrahydrohydrogenphthalate.

Examples of other monofunctional methacrylates:
Didimethylaminomethylmethacrylate, N, N-dimethylaminoethyl methacrylate, N, N-dimethylaminopropyl methacrylate, morpholinoethyl methacrylate, trimethylsiloxyethyl methacrylate, diphenyl-2-methacryloyloxyethyl phosphate, 2-methacryloyloxyethyl acid phosphate, caprolactone Modified-2-methacryloyloxyethyl acid phosphate, etc.

Examples of bifunctional methacrylates:
1,4-Butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol # 200 dimethacrylate, polyethylene glycol # 300. Dimethacrylate, polyethylene glycol # 400 dimethacrylate, polyethylene glycol # 600 dimethacrylate, dipropylene glycol dimethacrylate, tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate, polypropylene glycol # 400 dimethacrylate, polypropylene glycol # 700 dimethacrylate, neo Pentyl glycol dimethacrylate, neopentyl glycol PO modified dimethacrylate, hydroxypivalic acid neopentyl glycol ester dimethacrylate, hydroxypivalate neopentyl glycol ester caprolactone adhydrate dimethacrylate, 1,6-hexanediol bis (2-hydroxy-3) -Methattylene Oyloxypropyl) Ether, 1,9-Nonanediol Dimethacrylate, Pentaerythritol Dimethacrylate, Pentaerythritol Dimethacrylate Monostearate, Pentaerythritol Dimethacrylate Monobenzoate, 2,2-Bis (4-Methyloxypolyethoxyphenyl) Propane, Bisphenol A Dimethacrylate, EO Modified Bisphenol A Dimethacrylate, PO Modified Bisphenol A Dimethacrylate, Hydrogenated Bisphenol A Dimethacrylate, EO Modified Hydrogenated Bisphenol A Dimethacrylate, PO Modified Hydrogenated Bisphenol A Dimethacrylate, Bisphenol F Dimethacrylate , EO-modified bisphenol F dimethacrylate, PO-modified bisphenol F dimethacrylate, EO-modified tetrabromobisphenol A dimethacrylate, tricyclodecanedimethylol dimethacrylate, isocyanuric acid EO-modified dimethacrylate, 2-hydroxy-1,3-dimethacrylate Propane, tricyclodecanedimethanol diacrylate.

Examples of trifunctional methacrylates:
Glycerin PO-modified trimethacrylate, trimethylolethanetrimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane EO-modified trimethacrylate, trimethylolpropane PO-modified trimethacrylate, isocyanuric acid EO-modified trimethacrylate, isocyanuric acid EO-modified ε-caprolactone-modified bird Methacrylate, 1,3,5-trimethacrylhexahydro-s-triazine, pentaerythritol trimethacrylate, dipentaerythritol trimethacrylate tripropionate.

Examples of tetrafunctional or higher chromates:
Pentaerythritol tetramethacrylate, dipentaerythritol pentamethacrylate monopropionate, dipentaerythritol hexamethacrylate, dipentaerythritol ε-caprolactone-modified hexamethacrylate, dipentaerythritol EO-modified hexamethacrylate, tetramethylolmethanetetramethacrylate, oligoestertetramethacrylate, Tris (methacryloyloxy) phosphate and ε-lactone-modified compounds thereof.

Examples of allylate:
Allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, isocyanuric acid trialilate.

Examples of acid amides:
Acrylamide, N-methylolacrylamide, diacetoneacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-isopropylacrylamide, acryloylmorpholine, methacrylamide, N-methylolmethacrylamide, diacetonemethacrylamide, N, N -Dimethylmethacrylamide, N, N-diethylmethacrylamide, N-isopropylmethacrylamide, methacryloylmorpholin.

Examples of styrenes:
Styrene, p-hydroxystyrene, p-chlorostyrene, p-bromostyrene, p-methylstyrene, p-methoxystyrene, pt-butoxystyrene, pt-butoxycarbonylstyrene, pt-butoxycarbonyloxystyrene , 2,4-Diphenyl-4-methyl-1-pentene.

Examples of other vinyl compounds:
Vinyl acetate, monochloroacetate, vinyl benzoate, vinyl pivalate, vinyl butyrate, vinyl laurate, divinyl adipate, vinyl methacrylate, vinyl crotonic acid, vinyl 2-ethylhexanoate, N-vinylcarbazole, N-vinylpyrrolidone etc.

The above radically polymerizable compound can be easily obtained as a commercially available product of the following manufacturers. For example, "Light Acrylate", "Light Ester", "Epoxy Ester", "Urethane Acrylate" and "Highly Functional Monomer" series manufactured by Kyoei Co., Ltd., "Light Ester" manufactured by Shin-Nakamura Chemical Co., Ltd. "NK Ester" and "NK Oligo" series, "Funkril" series manufactured by Hitachi Kasei Kogyo Co., Ltd., "Aronix M" series manufactured by Toa Synthetic Chemical Co., Ltd., manufactured by Daihachi Kagaku Kogyo Co., Ltd. "Functional Monomer" series, "Special Acrylic Monomer" series manufactured by Osaka Organic Chemical Industry Co., Ltd., "Acrylate" and "Diabeam oligomer" series manufactured by Mitsubishi Rayon Co., Ltd., Nippon Kayaku Co., Ltd. "Kayarad" and "Kayamar" series manufactured by Nippon Catalyst Co., Ltd., "Acrylic acid / methacrylic acid ester monomer" series manufactured by Nippon Catalyst Co., Ltd., "NICHIGO-UV purple light urethane acrylate oligomer" manufactured by Nippon Synthetic Chemical Industry Co., Ltd. Examples include the "carboxylic acid vinyl ester monomer" series manufactured by Shinetsu Vinyl Acetate Co., Ltd., and the "functional monomer" series manufactured by Kojin Co., Ltd.

Further, the cyclic compounds shown below are also mentioned as radically polymerizable compounds.
Example of three-membered ring compound:
Journal of Polymer Science Polymer Chemistry Edition (J.Polym.Sci.Polym.Chem.Ed.), Vol. 17, p. 3169 (1979), Vinyl Cyclopropanes, Macromolecular Chemie. 1-Phenyl-2-vinylcyclopropanes, Journal of Polymer Science Polymer Chemistry Edition (Makromol. Chem. Rapid Commun.), Vol. 5, p. 63 (1984). J.Polym.Sci.Polym.Chem.Ed.), Vol. 23, p. 1931 (1985) and Journal of Polymer Science Polymer Letter Edition (J.Polym.Sci.Polym.Lett.Ed) .), Vol. 21, p. 4331 (1983), 2-phenyl-3-vinyloxylans, Proceedings of the 50th Annual Meeting of the Chemical Society of Japan, p. 1564 (1985), 2,3-divinyl. Oxylans.

Examples of annular ketene acetals:
Journal of Polymer Science Polymer Chemistry Edition (J.Polym.Sci.Polym.Chem.Ed.), Vol. 20, p. 3021 (1982) and Journal of Polymer Science Polymer Letter. -Edition (J.Polym.Sci.Polym.Lett.Ed.), Vol. 21, p. 373 (1983), 2-Methylene-1,3-dioxepan, Polymer Preprints, No. Dioxoranes, Journal of Polymer Science Polymer Letter Edition (J.Polym.Sci.Polym.Lett.Ed.), Vol. 34, p. 152 (1985), Vol. 20, p. 361 (1982). Year), Macropolymer. Chem., Vol. 183, p. 1913 (1982) and Macropolymer. Chem., Vol. 186, p. 1543 (1985) 2- Methylene-4-phenyl-1,3-dioxepan, Macromolecules, Vol. 15, p. 1711 (1982), 4,7-dimethyl-2-methylene-1,3-dioxepan, polymer. Preprints (Polym. Preprints), Vol. 34, p. 154 (1985), 5,6-benzo-2-methylene-1,3-geosepan.

Further, as the active energy ray-curable compound (B), those described in the following documents can also be mentioned. For example, Shinzo Yamashita et al., "Handbook of Crosslinking Agents", (1981, Taiseisha) and Kiyomi Kato, "UV / EB Curing Handbook (Raw Materials)", (1985, Polymer Publishing Association), Radtech Research Kai, Kiyoshi Akamatsu, "New Practical Technology for Photosensitive Resins", (1987, CMC), Tsuyoshi Endo, "Precision of Thermosetting Polymers", (1986, CMC), Takiyama Eiichiro, "Polyester Resin Handbook", (1988, Nikkan Kogyo Shimbun), Radtech Study Group, "Application and Market of UV / EB Curing Technology", (2002, CMC).

Further, as the active energy ray-curable compound (B), a highly hydrophobic polybutadiene (meth) acrylate-based oligomer having a (meth) acrylate group in the side chain of the polybutadiene oligomer and a silicone having a polysiloxane bond in the main chain are also used. (Meta) acrylate-based oligomers, aminoplast resin (meth) acrylate-based oligomers modified from aminoplast resins having many reactive groups in small molecules, novolak-type epoxy resins, bisphenol-type epoxy resins, aliphatic vinyl ethers, aromatics There are oligomers having a cationically polymerizable functional group in molecules such as group vinyl ethers.

As the active energy ray-curable compound (B), those called oligomers and prepolymers can be used in addition to the above-mentioned monomers. Specifically, "Ebeclyl230, 244, 245, 270, 280/15IB, 284, 285, 4830, 4835, 4858, 4883, 8402, 8803, 8800, 254, 264, 265, 294 / 35HD, manufactured by Daicel UCB, Inc. 1259, 1264, 4866, 9260, 8210, 1290.129K, 5129, 2000, 2001, 2002, 2100, KRM7222, KRM7735, 4842, 210, 215, 4827, 4849, 6700, 6700-20T, 204, 205, 6602, 220, 4450, 770, IRR567, 81, 84, 83, 80, 657, 800, 805, 808, 810, 812, 1657, 1810, IRR 302, 450, 670, 830, 835, 870, 1830, 1870, 2870, IRR267, 813, IRR483, 811, 436, 438, 456, 505, 524, 525, 554W, 584, 586, 745, 767, 1701, 1755, 740/40TP, 600, 601, 604, 605, 607, 608, 609, 600 / 25TO, 616, 645, 648, 860, 1606, 1608, 1629, 1940, 2598, 2959, 3200, 3201, 3404, 3411, 3412, 3415, 3500, 3502, 3600, 3603, 3604, 3605, 3608, 3700, 3700-20H, 3700-20T, 3700-25R, 3701, 3701-20T, 3703, 3702, RDX63182, 6040, IRR419 ", Sartmer" CN104, CN120, CN124, CN136, CN151, CN2270, CN2271E , CN435, CN454, CN970, CN971, CN972, CN9782, CN981, CN9893, CN991 ", MIWON" MIRAMERPU240, PU340, SC2152, MU9500, PU610, PS240, SIU2400, HR3200, HR3700, ", BASF" La , LR8713, LR8765, LR8986, PE56F, PE44F, LR8800, PE46T, LR8907, PO43F, PO77F, PE55F, LR8967, LR8881, LR8982, LR8992, LR9004, LR8956, LR8985, LR8987, UP35D. UA19T, LR9005, PO83F, PO33F, PO84F, PO9s4F, LR8863, LR8869, LR8889, LR8997, LR8996, LR9013, LR9019, PO9026V, PE9027V, Cognis Co., Ltd. 5249, 5430, 5432, 5662, 5806, 5930, 6008, 6010, 6019, 6184, 6210, 6217, 6230, 6891, 6892, 6893-20R, 6363, 6571, 3660, "Art Resin UN-" manufactured by Negami Kogyo Co., Ltd. 9000HP, 9000PEP, 9200A, 7600, 5200, 1003, 1255, 3320HA, 3320HB, 3320HC, 3320HS, 901T, 1200TPK, 6060PTM, 6060P, 333, 350, 352, 353, 2600, 2700, 5500, 5590, 5507, 6200, 6202, 6303, 6304, 6305, 7700, 904, 906S, 905, 952, Art Cure RA-3602MI, 3704MB, 3953MP, 4010, 331MB, 341, OAP-5000, 2511, AHC-9202MI80, MAP-4000, 2801 " , Nippon Kayaku Chemical Co., Ltd. "Shikou UV-6630B, 7000B, 7510B, 7461TE, 3000B, 3200B, 3210EA, 3310B, 3500BA, 3520TL, 3700B, 6100B, 6640B, 1400B, 1700B, 6300B, 7550B, 7605B, 7610B, 7620EA, 7630B, 7640B, 2000B, 2010B, 2250EA, 2750B ", Nippon Kayaku Co., Ltd." Kayarad R-280, R-146, R131, R-205, EX2320, R190, R130, R-300, C-0011, TCR- 1234, ZFR-1122, UX-2201, UX-2301, UX3204, UX-3301, UX-4101, UX-6101, UX-7101, MAX-5101, MAX-5100, MAX-3510, UX-4101 "etc. Can be mentioned.

Further, the active energy ray-curable compound (B) is an epoxy-based compound having at least one epoxy group, a silicon-based compound having at least one alkoxysilyl group, a silanol group, or the like, and an oxetane-based compound containing an oxetane ring. , Cyclic lactone compound, cyclic acetal compound, cyclic thioether compound, spirothoester compound, vinyl compound and the like can also be used.

The epoxy-based compound (epoxy-based resin) is not particularly limited, and for example, diglycidyl ether, ethylene glycol diglycidyl ether, glycerin diglycidyl ether, propylene glycol diglycidyl ether, butanediol diglycidyl ether, diethylene glycol diglycidyl ether, glycerol. Polyglycidyl ether, diglycerol polyglycidyl ether, sorbitol polyglycidyl ether, allyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, alkylphenol glycidyl ether, polyethylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, neopentyl glycol diglycidyl Ether, 1,6-hexanediol diglycidyl ether, glycerin polyglycidyl ether, diglycerin polyglycidyl ether, trimethylolpropane polyglycidyl ether, cresyl glycidyl ether, aliphatic diglycidyl ether, polyfunctional glycidyl ether, tertiary fatty acid mono Examples thereof include glycidyl ether, spiroglycol diglycidyl ether, and glycidyl propoxytrimethoxysilane. These epoxy compounds may be halogenated or hydrogenated, and these epoxy compounds also include derivatives. Then, these epoxy compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

The silicon-based compound (silicon-based resin) is not particularly limited, and for example, an alkoxysilane compound, a silane coupling agent, or the like can be used. Examples of the alkoxysilane compound include trimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, tetramethoxysilane, methyldimethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, tetraethoxysilane, diphenyldimethoxysilane, and phenyl. Examples thereof include trimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, hexyltrimethoxysilane, tetrapropoxysilane, and tetrabutoxysilane. These alkoxysilane compounds may be used alone or in combination of two or more.

The silane coupling agent is not particularly limited, and examples thereof include vinylsilane, acrylicsilane, epoxysilane, and aminosilane. Examples of vinylsilane include vinyltrichlorsilane, vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane and the like. Examples of the acrylic silane include γ-methacryloxypropyltrimethoxysilane and γ-methacryloxypropylmethyldimethoxysilane. Examples of the epoxy silane include β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane and the like. Examples of aminosilanes include N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, and N-phenyl-. Examples thereof include γ-aminopropyltrimethoxysilane. Examples of other silane coupling agents include γ-mercaptopropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysisilane and the like. These silane coupling agents may be used alone or in combination of two or more.

The oxetane-based compound (oxetane-based resin) is not particularly limited, but a monomeric oxetane-based compound, a dimer oxetane-based compound, or the like can be used. Examples of oxetane-based compounds that can be used include 4,4'-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl and bis 1,4-benzenedicarboxylate [(3-ethyl-3-oxetanyl)). Methyl] ester, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene and other xylylene oxetane, 3-ethyl-3-(((3-ethyloxetane-3-yl) methoxy) methyl) ) Oxetane (or 3-(((3-ethyloxetane-3-yl) methoxy) methyl) -3-ethyloxetane), 3-ethylhexyloxetane, 3-ethyl-3-hydroxyoxetane, 3-ethyl- Examples thereof include 3-hydroxymethyloxetane and oxetaneized phenol novolak. These oxetane compounds may be used alone or in combination of two or more.

Other compounds are not particularly limited, but are oxolan compounds such as tetrahydrofuran and 2,3-dimethyltetraoxide, cyclic acetal compounds such as trioxane, 1,3-dioxolane and 1,3,6-trioxanecyclooctane, and β-pro. Cyclic lactone compounds such as piolactone and ε-caprolactone, thiirane compounds such as ethylene sulfide and thioepichlorohydrin, thietan compounds such as 1,3-propine sulfide and 3,3-dimethylthietan, and cyclic thioether compounds such as tetrahydrothiophene derivatives. , Ethylene glycol divinyl ether, alkyl vinyl ether, 2-chloroethyl vinyl ether, 2-hydroxyethyl vinyl ether, triethylene glycol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, hydroxybutyl vinyl ether, vinyl ether compounds such as propylene glycol propenyl ether. , Spiro-orthoester compounds obtained by the reaction of epoxy compounds and lactones, ethylenically unsaturated compounds such as styrene, vinylcyclohexene, isobutylene and polybutadiene, and the above derivatives and the like, and one of them may be used alone. You may use a combination of seeds or more.

As the active energy ray-curable compound (B), only one kind may be used, or two or more kinds may be mixed at an arbitrary ratio in order to improve the desired properties.

The active energy ray-curable compound (B) is 1 in 100 parts by weight of the total solid content of the active energy ray-curable resin composition from the viewpoint of hard coatability and processability of the active energy ray-curable resin composition. It is preferably used in an amount of ~ 99 parts by weight, more preferably 20 to 80 parts by weight.

Among the above-mentioned compounds that can be used as the active energy ray-curable compound (B), polyfunctional (meth) acrylates and urethane (meth) acrylates are preferable from the viewpoints of hard coatability, processability, cost and the like.

The ratio of the resin (A) to the active energy ray-curable compound (B) is preferably 1: 6 to 6: 1, more preferably 1: 4 to 5: 1, and further. Preferably, the weight ratio is 1: 3 to 3: 1. Within the above range, extensibility and chemical resistance are excellent.

The ratio of the solid content of the active energy ray-curable resin composition is preferably 80% by weight or less. If the solid content is more than 80% by weight, the fluidity of the active energy ray-curable resin composition may be lowered, which may cause deterioration of coating suitability, repelling during coating, and yuzu skin of the cured film. be.

<Inorganic filler (C)>
As the inorganic filler (C), it is preferable to add the inorganic filler from the viewpoint of imparting scratch resistance. Although not particularly limited, for example, silica (coloidal silica, fumed silica, precipitating silica, etc.), alumina, talc, zirconia, titania, zinc oxide, magnesium carbonate, calcium carbonate, natural mica, synthetic mica, aluminum hydroxide, precipitating property. Examples thereof include barium sulfate, precipitating barium carbonate, barium titanate, zirconium oxide, titanium oxide, APO, IPO, TPO, barium sulfate, smectite and the like. Alumina, silica, titanium oxide, zirconium oxide, APO, IPO, TPO, zinc oxide and magnesium fluoride are preferable, and alumina, silica, titanium oxide and zirconium oxide are more preferable.

From the viewpoint of crosslinkability, the inorganic filler (C) preferably has a reactive functional group on its surface, and specific examples of the reactive functional group include a vinyl group, a (meth) acryloyl group, and a reactive functional group. Examples thereof include an ethylenically unsaturated bond such as an allyl group, an epoxy group and a silanol group, but the present invention is not limited thereto.

Examples of the shape of the inorganic filler (C) include a sphere, an ellipsoid, a polyhedron, and a scaly shape, and it is preferable that these shapes are uniform and sized. The average particle size is preferably 0.005 to 0.5 μm, more preferably 0.01 to 0.1 μm.

<Organic solvent (D)>
The organic solvent (D) is not particularly limited, but conventionally known organic solvents can be used, and specifically, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol, and pen. Tanol, 3-methyl-1,3-butanediol, 1,3-butanediol, 1,3-butylene glycol, octanediol, 2,4-diethylpentanediol, butylethylpropanediol, 2-methyl-1,3 -Propanediol, 4-hydroxy-4-methyl-2-pentanone, 2-ethyl-1-hexanol, 3,5,5-trimethyl-1-hexanol, isodecanol, isotridecanol, 3-methoxy-3-methyl-1 -Butanol, 2-methoxybutanol, 3-methoxybutanol, cyclohexanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, benzyl alcohol, methylcyclohexanol, ethylene glycol, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, Tetraethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, diethylene glycol mono-2-ethylhexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, Propropylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monotert-butyl ether, ethylene glycol monopropyl ether, ethylene glycol monomethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monomethyl ether, dipropylene glycol mono Ethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monobutyl ether tripropylene glycol monomethyl ether, propylene glycol monophenyl ether, 1,3-butylene glycol, propylene glycol n- Propyl ether, Alcohol-based solvents such as propylene glycol n-butyl ether, diethylene glycol monoethyl ether, dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, tripropylene glycol methyl ether, tripropylene glycol n-butyl ether, acetone, methyl ethyl ketone, etc. Ketone solvents such as methylisobutylketone, diisobutylketone, cyclohexanone, 2-heptanone, 4-heptanone, 3,5,5-trimethyl-2-cyclohexene-1-one, 3,3,5-trimethylcyclohexanone, methyl acetate, Ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, tert-butyl acetate, amyl acetate, isoamyl acetate, ethyl 3-ethoxypropionate, ethyl lactate ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether Acetate, Dipropylene glycol methyl ether acetate, 3-methoxy-3-methylbutyl acetate, 3-methoxybutyl acetate, Propylene glycol monomethyl acetate, Propylene glycol dimethyl acetate, Ethylene glycol monoethyl ether acetate, Ethylene glycol monomethyl ether acetate, Diethylene glycol mono Ethyl Ether Acetate, Cyclohexanol Acetate, Propylene Glycol Diacetate, Propylene Glycol Monomethyl Ether Acetate, Propylene Glycol Monoethyl Ether Acetate, Propylene Glycol Monobutyl Ether Acetate, Propylene Glycol Monopropyl Ether Acetate, Propylene Glycol Diacetate, Dipropylene Glycol Methyl Air Ester-based solvents such as telacetate, 1,3-butylene glycol diacetate, 1,4-butanediol diacetate, 1,3-butylene glycol diacetate, 1,6-hyoxanediol diacetate, diethyl ether, cyclopentyl Methyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol dibuty Ethereal solvents such as ruether, tetraethylene glycol dimethyl ether, polyethylene glycol dimethyl ether, benzene, toluene, ethylbenzene, o-xylene, m-xylene, p-xylene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, n-butylbenzene. , Se-butylbenzene, tert-butylbenzene and other aromatic solvents, cycloheptane, cyclohexane and other alicyclic solvents, pentane, hexane, octane, isohexane, isooctane, isononane and other aliphatic solvents, dichloromethane, chloroform. , Chlorine-based solvents such as carbon tetrachloride, chlorobenzene, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, m-dichlorobenzene, 1,2,3-trichloropropane, N, N-dimethylformamide, N, Amido-based solvents such as N-dimethylacetamide and dimethylacetamide, acetonitrile, dimethylsulfoxide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, γ-butyrolactone, isophorone, triacetin, propylene glycol monomethyl ether propionate. , 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate and the like, but are not limited thereto. One of these solvents may be used alone, or two or more of them may be mixed and used.

<Active energy ray curable resin composition>
When the radically polymerizable crosslinking component is crosslinked by ultraviolet rays or the like, a photopolymerization initiator can be used, and a polymerization accelerator can also be used in combination. When cross-linking with an electron beam, these may not be blended.

The photopolymerization initiator is not particularly limited, and specific examples thereof include the following.
Diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzylmethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl Phenyl Ketone, 2-Methyl-1- [4- (Methylthio) Phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane, oligo {2- Hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone}, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2 -Acetphenones such as methylpropane-1-one;
Benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether;
Phosphines such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide;
Other examples include, but are not limited to, phenylglycoxymethyl ester. More specifically, Irgacure 651, Irgacure 184, Darocure 1173, Irgacure 500, Irgacure 1000, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure 1700, Irgacure 149, Irgacure. Cure 1800, Irgacure 1850, Irgacure 819, Irgacure 784, Irgacure 261, Irgacure OXE-01 (CGI124), CGI242 (BASF), Adecaoptomer N1414, Adecaoptomer N1717 (ADEKA), Esacure1001M Lamberti), JP-A-59-1281, JP-A-61-9621, and Triazine Derivatives described in JP-A-60-60104, JP-A-59-1504 and JP-A-61-243807. The organic peroxides described in Japanese Patent Publication No. 43-23684, Japanese Patent Publication No. 44-6413, Japanese Patent Publication No. 47-1604, and Diazonium Compound Publication No. USP 3567453, USP No. 2848328, Organic azide compounds described in USP No. 2852379 and USP No. 2940853, Japanese Patent Publication No. 36-22062, Japanese Patent Publication No. 37-13109, Japanese Patent Publication No. 38-18015 and Japanese Patent Publication No. 45-9610. Ortho-quinone diazides described, JP-A-55-39162, JP-A-59-140203, and "MACROMOLE CULES", Vol. 10, p. 1307 (1977). Various onium compounds including, azo compounds described in JP-A-59-142205, JP-A No. 1-54440, European Patent No. 109851, European Patent No. 126712, "Journal of Imaging". "Science (J.IMAG.SCI.)", Vol. 30, p. 174 (1986), Metal Allen Complex, Titanosens, Japanese Patent Application Laid-Open No. 61-151197, "Coordination Chemistry Review (COORDINATION)" CHEMISTRY REVIEW) ”, Vol. 84, pp. 85-277 (1988), and a transition metal complex containing a transition metal such as ruthenium described in JP-A-2-182701, JP-A-3-2. Aluminato complexes described in JP-A-09477, borate compounds described in JP-A No. 2-157760, JP-A-55-127550 and JP-A-60-202437 described in JP-A-60-202437, 2,4,5-triaryls. Imidazole dimer, carbon tetrabromide, organic halogen compounds described in JP-A-59-107344, sulfonium complexes or oxosulfonium complexes described in JP-A-5-255347, JP-A-54-99185, Japanese Patent Laid-Open No. Kaisho 63-264560 and the aminoketone compounds described in JP-A-10-29977, JP-A-2001-264530, JP-A-2001-261661, JP-A-2000-80068, JP-A-2001-233842, JP-A-2004-534977, JP-A-2006-342166, JP-A-2008-09470, JP-A-2009-40762, JP-A-2010-15025, JP-A-2010-189279, JP-A-2010-189280, JP-A-2010-526846 , JP-A-2010-527338, JP-A-2010-527339, USP3558309 (1971), USP4202697 (1980), and oxime ester compounds described in JP-A-61-24558.

Further, as the photopolymerization initiator, a hydrogen abstraction type radical initiator can be used, and specific examples thereof include aromatic ketones such as acetophenone, benzophenone, benzyl, Michler ketone, thioxanthone, and anthraquinone. , Not limited to these. It is common in the art to use these compounds in combination with tertiary amines, specifically trimethylamine, triethylamine, tripropylamine, tributylamine, N-methyldiethanolamine, p-dimethylaminophenylalkyl. Esters and the like are mentioned, but not limited to these.

It is also possible to use a photobase generator, a photoacid generator, or the like as the photopolymerization initiator. One of these may be used alone, or two or more thereof may be used at an arbitrary ratio.

The photobase generator is not particularly limited, and for example, various compounds that produce a primary amine, a secondary amine, or a tertiary amine, for example, a cobalt amine complex, o-acyloximes, a carbamate derivative, and the like. Formamide derivatives, sulfonamides (eg, N-cyclohexyl-4-methylphenylsulfoneamide, etc.), quaternary ammonium salts, tosylamines, carbamate (eg, 2-nitrobenzylcarbamate, 2,5-dinitrobenzylcyclohexylcarbamate, etc.) Examples thereof include 1,1-dimethyl-2-phenylethyl-N-isopropylcarbamate), amineimide compounds (see JP-A-2003-35949), compounds having an amidin structure, α-aminoacetophenone and the like. The photobase generator can be used alone or in combination of two or more.

The photoacid generator is not particularly limited, but for example, diazonium salt, iodonium salt, sulfonium salt, phosphonium salt, selenium salt, metallocene complex, oxathiazole derivative, s-triazine derivative, imide compound, oxime sulfonate, diazonaphthoquinone, sulfonic acid. Ester [1-Phenyl-1- (4-Methylphenyl) sulfonyloxy-1-benzoylmethane, 1,2,3-trisulfonyloxymethylbenzene, 1,3-dinitro-2- (4-phenylsulfonyloxymethyl) Benzene, 1-Phenyl-1- (4-Methylphenyl) sulfonyloxymethyl-1-hydroxy-1-benzoylmethane, disulfone derivatives (diphenyldisulfone, etc.), benzointosylate, etc.] and Lewis acid salt (triphenylsulfonium hexafluoro) antimony _{^{(Ph) 3S + SbF 6 -}} , triphenylsulfonium hexafluorophosphate _{^{(Ph) 3 S + PF 6}} -, triphenylsulfonium methanesulfonyl _{^{(Ph) 3 S + CH 3}} SO 3 -, such as diphenyliodonium hexafluorophosphate It can be used. Ph represents a phenyl group.

Among these, acetophenones, phosphine oxides and the like can be preferably used as the photopolymerization initiator.

The photopolymerization initiator can be used alone or in combination of two or more, and can be arbitrarily mixed and used depending on the characteristics required for the reaction-cured product and the resin or compound contained in the active energy ray-curable composition. Is. When these photopolymerization initiators are used, the amount used is preferably 0.1 to 50 parts by weight, more preferably 0.5 to 25 parts by weight, based on 100 parts by weight of the total solid content of the active energy ray-curable resin composition. Is more preferable.

When obtaining a cured film using the active energy ray-curable resin composition, it is not necessary to include a photopolymerization initiator when irradiating with an electron beam.

Further, the active energy ray-curable resin composition of the present invention may contain a sensitizer. Examples of the sensitizer include unsaturated ketones represented by chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives represented by benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, and anthraquinone. Polymethine dyes such as derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonoal derivatives, aclysine derivatives, azine derivatives, thiadine derivatives, oxadin derivatives, indolin derivatives. , Azulene derivative, Azurenium derivative, Squalylium derivative, Porphyrin derivative, Tetraphenylporphyrin derivative, Triarylmethane derivative, Tetrabenzoporphyrin derivative, Tetrapyrazinoporphyrazine derivative, Phthalocyanin derivative, Tetraazaporphyrazine derivative, Tetraquinoxalyloporphyrazine Derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrilium derivatives, tetraphyllin derivatives, anurene derivatives, spiropyrane derivatives, spiroxazine derivatives, thiospiropyrane derivatives, metal allene complexes, organic ruthenium complexes, Mihiler ketone derivatives, biimidazole derivatives, etc. However, but not limited to these.

Specific examples of sensitizers include Nobu Okawara et al., "Dye Handbook" (1986, Kodansha), Nobu Okawara et al., "Chemistry of Functional Dyes" (1981, CMC), Tadashi Ikemori. Examples include, but are not limited to, the sensitizers described in "Special Functional Materials" (1986, CMC) edited by Saburo et al. In addition, a sensitizer that absorbs light from the ultraviolet to the near infrared region can also be contained. As the sensitizer, one kind may be used alone, or two or more kinds of sensitizers may be contained in an arbitrary ratio.

The sensitizer is preferably used in an amount of 0.1 to 150 parts by weight, more preferably 1 to 100 parts by weight, based on 100 parts by weight of the photopolymerization initiator.

In addition to the above-mentioned essential components of the active energy ray-curable resin composition of the present invention, the coatability at the time of manufacturing the decorative sheet and the characteristics required as the active energy ray-curable resin composition for the decorative sheet are exhibited. A resin, a solvent, an organic filler, a thiol-based compound, or the like may be added for the purpose of imparting.

The active energy ray-curable resin composition of the present invention further depending on the purpose, an oxygen removing agent such as a dye, an organic and inorganic pigment, a pigment dispersant, a phosphine, a phosphonate, and a phosphite, a reducing agent, an antifoaming agent, and a fading prevention agent. Agents, anti-halation agents, fluorescent whitening agents, surfactants, colorants, bulking agents, plasticizers, flame retardants, antioxidants, pigment precursors, UV absorbers, foaming agents, antifungal agents, antistatic agents, Dispersants such as magnetic materials and resin-type dispersants, storage stabilizers such as silane coupling agents and quaternary ammonium chlorides, plasticizers, surface tension regulators, slipping agents, anti-blocking agents, light stabilizers, leveling agents , Antifoaming agent, infrared absorber, surfactant, thixotropic agent, antibacterial agent, fine particles such as silica, other additives imparting various properties, diluting solvent and the like may be mixed and used. The types are not particularly limited.

<Decorative sheet>
The decorative sheet of the present invention is not particularly limited as long as the cured film is formed by using the active energy ray-curable resin composition of the present invention. The layer is formed by freely combining with an adhesive layer, a release layer, an antistatic layer, and the like. For example, the decorative sheet of the present invention is not limited, but a decorative sheet for laminating, a decorative sheet for transfer, and the like are preferable.

The decorative sheet for lamination has a layer structure in which a cured film using the active energy ray-curable resin composition of the present invention is provided on one side of a base material, and a pattern layer and an adhesive layer are laminated on the other side. It is a decorative sheet and is decorated by attaching it to the surface of the object to be decorated (plastic housing).

The decorative sheet for transfer is a decorative sheet in which a release layer is formed on one side of a base material and a transfer layer is laminated on the release layer. Here, the transfer layer is a layer in which a cured film using the active energy ray-curable resin composition of the present invention is laminated in this order, a pattern layer, and an adhesive layer, but if necessary, an anchor layer and an antistatic layer are used. A layer, an ultraviolet absorbing layer, a low reflecting layer, a near infrared blocking layer, an electromagnetic wave absorbing layer and the like can also be combined, but the layer structure in the decorative sheet of the present invention is not limited to these.

The anchor layer is, for example, a layer provided between a cured film and an adhesive layer using the active energy ray-curable resin composition of the present invention, or between pattern layers in order to enhance the adhesion between the two different layers. The anchor layer in the present invention is not limited to these, and can be provided between any layers as needed.

The anchor layer includes a two-component curable urethane resin, a heat-curable urethane resin, a melamine resin, a cellulose ester resin, a chlorine-containing rubber resin, a chlorine-containing vinyl resin, an acrylic resin, an epoxy resin, and a vinyl-based co-weight. Gravure coat method, gravure offset method, kiss coat method, rod coat method, reverse gravure coat method, roll coat method, comma coat method, top coat method, die coat method, knife coat method, lip coat method, using coalesced resin, etc. Laminating can be performed using known coating methods and printing methods such as spray coating method, spin coating method, bar coating method, slit coating method, gravure printing, offset printing, screen printing, transfer printing, sublimation transfer printing, and inkjet printing. can.

The above-mentioned pattern layer is a layer necessary for obtaining a desired design on the decorative sheet, and there are no particular restrictions on the pattern. For example, wood grain, stone grain, cloth grain, sand grain, geometric pattern, characters, etc. Designs consisting of photographs, illustrations, etc. can be mentioned, and the combination of the patterns is also free. In addition to being free to recoat, it is also possible to perform metal vapor deposition on a part or the entire surface.

Examples of the method required to obtain a pattern include a method of forming an ink composed of an appropriate colorant such as a pigment or dye and a binder resin by using a known printing method. Here, examples of the pineapple resin include, but are not limited to, polyvinyl-based resin, polyester-based resin, polyacrylic resin, polyamide-based resin, polyvinyl acetal-based resin, cellulose-based resin, and alkyd resin. As known printing methods, a gravure coating method, a gravure offset method, a kiss coating method, a rod coating method, a reverse gravure coating method, a roll coating method, a comma coating method, a top coating method, a die coating method, a knife coating method, and a lip coating method are used. Methods, spray coating methods, spin coating methods, bar coating methods, slit coating methods, gravure printing, offset printing, screen printing, transfer printing, sublimation transfer printing, inkjet printing, etc., but are not limited thereto. ..

The above-mentioned adhesive layer is a layer necessary for adhering the transfer layer when it is transferred to the resin molded body. The adhesive layer may be the entire surface or a part to be transferred.

As the adhesive layer, any resin having adhesiveness can be used without particular limitation, but preferably acrylic resin, polystyrene-based, polyamide-based resin, inden resin, chlorinated polyolefin resin, and chlorinated ethylene-vinyl acetate. Examples thereof include copolymer resins, and it is also possible to mix and use one or more of them as needed. Further, it is more preferable to appropriately select from the viewpoint of affinity with the resin molded body.

The release layer is a layer necessary for separating the transfer layer from the base material, and is a melamine resin-based mold release agent, a silicone resin-based mold release agent, a fluororesin-based mold release agent, a cellulose resin-based mold release agent, and urea. Examples thereof include, but are not limited to, a resin-based mold release agent, a polyolefin resin-based mold release agent, a paraffin resin-based mold release agent, and an acrylic resin-based mold release agent. The above-mentioned mold release agent can be used by arbitrarily mixing one or more kinds as necessary.

The base material that can be used for the decorative sheet of the present invention is not particularly limited, but is polycarbonate, polymethylmethacrylate, polyethylmethacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetylcellulose resin, and ABS resin. , AS resin, norbornene-based resin, vinyl-based resin and other plastic materials are preferably mentioned.

Examples of the base material that can be used for the decorative sheet include, but are not limited to, a film or a sheet formed by a casting method or a non-stretching biaxial stretching method from the plastic material. Further, from the viewpoint of imparting adhesion, the surface of the base material may be coated with an undercoat paint such as a corona discharge treatment or a primer.

The thickness of the base material is not particularly limited, and it is desirable to select the optimum thickness depending on the molding method.

As a method for producing a decorative sheet, the active energy ray-curable resin composition of the present invention is formed on a substrate so as to form a uniform and predetermined thick film, and then dried as necessary. Further, it is formed by performing photocrosslinking by irradiation with active energy rays.

As a film forming method, a known printing or coating method can be used, for example, a gravure coating method, a gravure offset method, a kiss coating method, a rod coating method, a reverse gravure coating method, a roll coating method, a comma coating method, and the like. Top coat method, die coat method, knife coat method, lip coat method, spray coat method, spin coat method, bar coat method, slit coat method, gravure printing, offset printing, screen printing, transfer printing, sublimation transfer printing, inkjet printing, etc. However, it is not limited to these.

As described in the description of the solvent that can be used for the active energy ray-curable resin composition of the present invention, the solvent may be used from the viewpoint of coatability. However, cross-linking by irradiation with active energy rays while a large amount of solvent is contained in the coating film may adversely affect the control of cross-linking, so it is desirable to remove the coating film by drying to some extent. As a method of drying, it is possible to carry out vacuum drying by vacuum drying using a vacuum dryer or the like, drying by baking using a convection oven (hot air dryer), IR oven, hot plate, etc., or a combination thereof. be. It is preferable to select the bake from the viewpoint of equipment cost and productivity, but it is more preferable to pay attention to the following conditions.

The baking conditions (temperature, time) can be appropriately selected according to the boiling point and film thickness used and the drying performance of the oven, but the active energy ray-curable resin composition of the present invention has a temperature of 150 ° C. or higher. Since the thermal cross-linking reaction of the cross-linking group can proceed in the high temperature region of the above, 150 ° C. or lower is preferable. Further, baking for a long time may also proceed with the thermal cross-linking reaction, so 20 minutes or less is preferable. If the thermal cross-linking reaction proceeds at the time of pre-baking, it adversely affects photocross-linking due to irradiation with active energy, and as a result of increasing the degree of cross-linking more than necessary, extensibility may be impaired, which is not preferable.

The film thickness of the active energy ray-curable resin composition of the present invention is not particularly limited, but is preferably 1 μm to 100 μm, and preferably 3 μm to 50 μm from the viewpoint of moldability and hard coatability.

The active energy rays required for photocrosslinking the composition of the present invention are heat, ultraviolet rays, visible rays, near infrared rays, electron beams, and the like. As the light source for imparting the active energy ray, a light source having a main wavelength of emission in the wavelength region of 100 nm to 450 nm is preferable. Examples of light sources having a main emission wavelength in the wavelength range of 100 nm to 450 nm include ultra-high pressure mercury lamps, high pressure mercury lamps, medium pressure mercury lamps, mercury xenon lamps, metal halide lamps, high power metal halide lamps, xenon lamps, and pulsed light emission. Xenon lamp, heavy hydrogen lamp, fluorescent lamp, ND-YAG triple wave laser, HE-CD laser, nitrogen laser, XE-Cl excima laser, XE-F excima laser, semiconductor-pumped solid-state laser, emission wavelengths at 365 nm, 375 nm, and 385 nm. Examples thereof include various light sources such as an LED lamp light source having the above. In this specification, the definitions of ultraviolet rays, visible light, near infrared rays, etc. are based on "Iwanami Physics and Chemistry Dictionary 4th Edition" (1987, Iwanami) edited by Ryogo Kubo et al.

As mentioned above, the cured film is laminated with other necessary layers and used as a decorative sheet. By using the active energy ray-curable resin composition of the present invention by the above-mentioned mechanism of action, it has moldability corresponding to various moldings. Further, in the decorative sheet of the present invention, the cured film is further thermally crosslinked by the heat at the time of molding, so that a better hard coat property can be obtained. Thermal cross-linking can proceed sufficiently with the heat applied during molding, but when a baking step may be added as needed, the temperature during the baking step is preferably 80 ° C. or higher, more preferably. It is preferably 100 ° C. or higher.

As a molding method, it is molded by various methods such as vacuum forming, compressed air forming, membrane press molding, in-mold molding, insert molding, insert molding, and overlay vacuum forming. In either case, the decorative sheet is stretched or bent according to the shape of the object to be decorated (plastic housing) or the shape of the mold.

Hereinafter, the present invention will be described in more detail by way of examples, but the following examples do not limit the scope of rights of the present invention in any way. In addition, each evaluation in an Example followed the following method. In the examples, "parts" means "parts by weight" and "%" means "% by weight".

<Weight average molecular weight>
The weight average molecular weight was measured by using GPC (gel permeation chromatography) "GPC-8020" manufactured by Tosoh Corporation, and the columns used were two SOIDX KF-806L, one KF-804L, and one KF-802 solvent. Used tetrahydrofuran. The weight average molecular weight was converted to standard polystyrene.

The structure of the structural unit (a) having an aliphatic cyclic structure in the main chain in the monomer and the polymer (A) used in the examples is shown below.

The monomer (1) was obtained by using the method described in Japanese Patent Application Laid-Open No. 5977063.
The monomer (2) was prepared by reacting with methyl α-allyloxymethylacrylate and 2-methyl-1-butanol as raw materials according to the method described in Japanese Patent Application Laid-Open No. 5591543.
The monomer (3) was prepared by reacting with methyl α-allyloxymethylacrylate as a raw material according to the method described in Japanese Patent Publication No. 5591543.
The monomer (4) was obtained by using the method described in Japanese Patent Application Laid-Open No. 5977063.

The monomers constituting the structural unit (b) having a hydroxyl group in the polymer (A) are shown below.
2-Hydroxyethyl methacrylate (HEMA): "HEMA" manufactured by Nippon Shokubai Co., Ltd.
Glycerin Monomethacrylate (GLM): NOF Corporation "GLM"

The following commercially available products were used as other monomers.
Methyl Methacrylate (MMA): "Acryester M" manufactured by Mitsubishi Chemical Corporation
Butyl methacrylate (BMA): "Acryester B" manufactured by Mitsubishi Chemical Corporation
Acryloyl morpholine (ACMO): "ACMO" manufactured by KJ Chemicals

The following commercially available products were used as other solvents and initiators.
Methyl ethyl ketone: "Methyl ethyl ketone" manufactured by Japan Alcohol Trading Co., Ltd.
Methanol: "Methanol" manufactured by Japan Alcohol Trading Co., Ltd.
2,2'-Azobis (2,4-dimethylvaleronitrile): "V-65" manufactured by Wako Pure Chemical Industries, Ltd.

<Manufacturing method of resin (A)>
(Production Example 1; Preparation of Resin (A-1))
90 parts by weight of methyl ethyl ketone was charged as a solvent into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a gas introduction tube, and the temperature was raised to 70 ° C. under a nitrogen atmosphere. Then, 50 parts by weight of the monomer (1), 26 parts by weight of HEMA, 24 parts by weight of MMA, 0.3 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) as an initiator, and 41 parts by weight of methyl ethyl ketone as a solvent. The monomer solution in which the parts were mixed in advance was added dropwise over 2 hours. After further reacting at 70 ° C. for 1 hour, 0.1 part by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) was added as a post-addition initiator and reacted for 1 hour. After that, the mixture was cooled to room temperature. Methyl ethyl ketone was added as a solvent to obtain a resin (A-1) having a solid content of 50%.

(Production Examples 2-37; Preparation of Resins (A-2-37))
Resins (A-2) to (A-35) having a solid content of 50% were obtained in the same manner as in Production Example 1 except that the compositions were changed to those shown in Tables 2 to 4. The blending amounts in Tables 2 to 4 indicate parts by weight. The weight average molecular weight (Mw), Tg, and hydroxyl value of the obtained resin are as shown in the table.

<Preparation of active energy ray-curable resin composition>
(Example 1)
50 parts by weight of resin (A-1) in solid content, 50 parts by weight of trifunctional acrylate (KAYARAD PET-30 manufactured by Nippon Kayaku Co., Ltd.) as active energy ray-curable compound (B), photopolymerization initiator 2.5 parts by weight of ESACUREONE manufactured by Lamberti, 160 parts by weight of methyl ethyl ketone as an organic solvent (D), 160 parts by weight of propylene glycol monomethyl ether acetate, and alumina (AEROXIDE AluC manufactured by Aerosil Japan) as an inorganic filler (C). 2.7 parts by weight was added, and the mixture was stirred using a disper to obtain an active energy ray-curable resin composition.

(Examples 2 to 44, Comparative Examples 1 to 13)
According to the method for preparing the active energy ray-curable resin composition of Example 1 described above, the resin (A), the active energy ray-curable compound (B), the inorganic filler (C), and the like in the blending ratios shown in Tables 5 to 7. Was blended to obtain an active energy ray-curable resin composition.

The abbreviations in Tables 5 to 7 are as follows.
PET-30: "KAYARAD PET-30" (trifunctional acrylate) manufactured by Nippon Kayaku Co., Ltd.
DPGDA: "DPGDA" (bifunctional acrylate) manufactured by Dycel Ornex
DPHA: "A-DPH" (six-functional acrylate) manufactured by Shin-Nakamura Chemical Industry Co., Ltd.
DPCA-30: "KAYARAD DPCA-30" (six-functional acrylate) manufactured by Nippon Kayaku Co., Ltd.
UV-7650B: "Shikou UV-7650B" (urethane acrylate oligomer) manufactured by Nippon Synthetic Chemistry Co., Ltd.
UV-7550B: "Shikou UV-7550B" (urethane acrylate oligomer) manufactured by Nippon Synthetic Chemistry Co., Ltd.
UA-306I: "UA-306I" manufactured by Kyoeisha Chemical Co., Ltd. (urethane acrylate oligomer)
EBECRYL3500: "EBECRYL3500" (epoxy acrylate) manufactured by Dycel Ornex.
V-5500: "Unidic V-5500" (epoxy acrylate) manufactured by DIC Corporation.
8KX-012C: "Acryt 8KX-012C" (acrylic acrylate) manufactured by Taisei Fine Chemical Co., Ltd.
EBECRYL1830: "EBECRYL1830" (ester acrylate) manufactured by Dycel Ornex.
ESACURE ONE: "ESACUREONE" manufactured by Lamberti (photopolymerization initiator)
Irg184: "Irg184" manufactured by BASF (formerly Ciba Japan) (photopolymerization initiator)
Irg369: "Irg369" manufactured by BASF (formerly Ciba Japan) (photopolymerization initiator)
TPO: "TPO" (photopolymerization initiator) manufactured by BASF (formerly Ciba Japan)
MEK: Methyl Ethyl Ketone PGMAC: Propylene Glycol Monomethyl Ether Acetate Alu C: "AEROXIDE AluC" manufactured by Aerosil Japan (alumina)
AEROSIL50: "AEROSIL50" (silica) manufactured by Aerosil Japan Co., Ltd.
PCS-60: "PCS-60" manufactured by Nippon Denko Co., Ltd. (zirconia oxide)
MT-05: "MT-05" manufactured by TAYCA (titanium oxide)

The compositions obtained in Examples 1 to 44 and Comparative Examples 1 to 13 were applied to a PET substrate (thickness 100 μm: “Cosmo Shine A4100” manufactured by Toyobo Co., Ltd.) using a bar coater, and then applied. A coated film having a film thickness of 5 μm was obtained by drying at 80 ° C. for 1 minute using a hot air dryer. The coating film was cured under the following irradiation conditions to obtain a cured film 1. Subsequently, the film was heated at 160 ° C. for 10 minutes using a hot air dryer to obtain a cured film 2 assuming a coating film state after heat molding.
(When irradiating with ultraviolet rays)
UV irradiation: a high-pressure mercury lamp 120W ^/ cm ² -400mJ ^/ cm 2
(When irradiating an electron beam)
Electron beam irradiation: 125kV-30kGy

The following items were evaluated. The results are as shown in Tables 8-10.

(Scratch resistance test)
# 0000 steel wool was used for the cured film 1 and the cured film 2, a ^{load of 750 g / cm 2} was applied, and after 10 reciprocating scratches, the presence or absence of scratches was visually determined.
(criterion)
⊚: No scratches 〇: 1.2 scratches △: 3 or more scratches ×: Many scratches Practical level is 〇 and ◎.

The compositions obtained in Examples 1 to 44 and Comparative Examples 1 to 13 are applied to a polycarbonate substrate (thickness 1 mm: "Iupilon Sheet NF-2000" manufactured by Mitsubishi Gas Chemical Company, Inc.) using a bar coater. After the work, it was dried at 80 ° C. for 1 minute using a hot air dryer to obtain a coated film having a film thickness of 5 μm. The coating film was cured by irradiating it with ultraviolet rays (integrated light amount 400 mJ / cm ² ) at a conveyor speed of 10 m / min using a belt conveyor type ultraviolet irradiation device (high pressure mercury lamp 120 W / cm ² ) to obtain a cured film 3. .. Subsequently, the film was heated at 160 ° C. for 10 minutes using a hot air dryer to obtain a cured film 4 assuming the state of the coating film after heat molding.

(Extensibility test)
An extensibility test piece was obtained by cutting the cured film 3 and the cured film 4 together with the base material into a dumbbell shape conforming to JIS K6251-1 standard. The distance between the chucks is 4 cm and the width is 1 cm. An "EZ-SX" manufactured by Shimadzu Corporation was used as a testing machine, and a tensile test was conducted using this dumbbell piece.

Stretching conditions: Performed at a pulling speed of 100 mm / min at room temperature.

Elongation determination: Based on the distance between chucks of 4 cm, the presence or absence of scratches and whitening of the coating film were confirmed when the coating film was pulled to 4.0 cm, which corresponds to 100% of the original length.
(criterion)
⊚: No scratches 〇: 1 scratch is made Δ: 2 to 10 scratches are made ×: Many scratches are made The practical level is 〇 and ◎.

(Chemical resistance test)
After cutting the cured films 3 and 4 together with the base material into 4 cm squares, place 30 mg of sunscreen cream (Neutrogena's "UltraSheer, SPF # 55") on the center of the test piece, and then 3 cm square. A PET film (thickness 50 μm) cut into squares was put on it. The cream was spread in a uniform circle (1.8 cm in diameter) by applying a uniform load from the upper part of the PET film.

Under the following conditions, stand in a hot air dryer (80 ° C., 20 hours), allow to cool to room temperature, rinse the cream with tap water, and visually observe the appearance of the surface of the test piece to resist chemicals. Was judged.

Condition 1: The PET film is peeled off and the test piece and cream are released.
Condition 2: The PET film is not peeled off, the test piece is sandwiched between 10 cm square glass substrates (thickness 5 mm), and a load of 500 g is applied from the upper part of the glass substrate (sealed state).

(criterion)
◎: No change in appearance 〇: Slight dripping marks △: Slightly cloudy ×: Whitening occurs (no transparency)
Practical levels are 〇 and ◎.

<Vacuum formability test>
The compositions obtained in Examples 1 to 44 and Comparative Examples 1 to 13 are coated on a polycarbonate substrate (thickness 1 mm: "Iupilon Sheet NF-2000" manufactured by Mitsubishi Gas Chemical Company, Inc.) using a bar coater. Then, the coating film was dried at 80 ° C. for 1 minute using a hot air dryer to obtain a coating film having a film thickness of 5 μm. The coating film was coated with a belt conveyor type ultraviolet irradiation device (high pressure mercury lamp 120 W / cm ² ). Then, the decorative sheet was obtained by irradiating with ultraviolet rays (integrated light amount 400 mJ / cm ^{2) at a conveyor speed of 10 m / min.}
Next, the decorative sheet is set in a vacuum forming machine (“300X” manufactured by Seikou Sangyo Co., Ltd.), and using a rectangular parallelepiped (length: 65 mm, width 65 mm, height 30 mm) mold, heat vacuum forming (heater). A temperature of 300 ° C. and an estimated substrate surface temperature of 200 ° C.) were carried out. By observing the appearance, it was confirmed whether or not there were cracks or cracks in the accompanying decorative sheet during molding.

(criterion)
◎: Transparent without cracks or cracks 〇: Cracks or cracks cannot be confirmed, but there is some change in appearance such as cloudiness △: Partial cracks or cracks are confirmed ×: Overall cracks or cracks are confirmed Practical level Are 〇 and ◎.

<Stability test over time>
In order to evaluate the dispersion stability of the active energy ray-curable resin composition of the present invention, each of the active energy ray-curable resin compositions of Examples and Comparative Examples was left in a constant temperature room at 50 ° C. for 30 days. The degree of precipitation of the inorganic filler (C) before and after standing was observed and evaluated according to the following criteria.
Evaluation criteria ◎: No change before and after leaving ○: Precipitation does not occur after leaving, but a difference in concentration of inorganic filler is confirmed between the upper layer and the lower layer △: Precipitation occurs after leaving, but by stirring with a dispersion , Inorganic filler is redispersed.
X: Precipitation occurs after standing, but it does not redisperse even if it is stirred using a disper.
Practical levels are 〇 and ◎.

<Base material adhesion test>
The adhesiveness of the cured film 3 and the cured film 4 immediately after production was evaluated according to the test method described in JIS K 5600-5-6. Specifically, 100 grid-shaped cuts were made using a cutter guide with a gap spacing of 1 mm. Next, a 30 mm wide cellophane adhesive tape was attached to the cut surface on the square, and a 5.0 kg / cm2 roller was reciprocated 30 times to completely attach it, and then it was rapidly peeled off at a peeling angle of 90 degrees. The peeled surface was observed and ranked according to the peeled area (peeled grain ratio) according to the following evaluation criteria, and the adhesion was evaluated.
⊚: The remaining number of grids is 100 and there is no change in the cured film before and after peeling of the cellophane adhesive tape. There is a grid with a chip, etc. △: The number of remaining grids is 100, but there is a grid with a chip at the end after the cellophane adhesive tape is peeled off, and there is a change in the cured film before and after the test. ..
X: The remaining number of grids is 99 or less, and the practical levels are 〇 and ◎.

Claims (6)

An active energy ray-curable composition containing a resin (A), an active energy ray-curable compound (B), an inorganic filler (C) and an organic solvent (D), wherein the resin (A) has the following general formula ( It is an acrylic copolymer containing a structural unit (a) 25 to 99% by weight having an aliphatic cyclic structure in the main chain represented by 1) and a structural unit (b) 1 to 75% by weight having a hydroxyl group. An active energy ray-curable resin composition characterized by the above.
General formula (1)

(In the general formula (1), R ₁ is a hydrogen atom or an organic residue having 1 to 30 carbon atoms, R ₂ is a direct bond, a methylene group or an ethylene group, and R ₃ is a direct bond, a methylene group or an ethylene group. R ₄ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, a carboxyl group, an ester group or a cyano group, R ₅ is a direct bond, a methylene group or an ethylene group, and X and Y are independent of each other.
Methylene group, imino group, carbonyl group, oxygen atom or sulfur atom, Z may be directly bonded and may have an alkyl group having 1 to 4 carbon atoms. Good methylene, imino, carbonyl, oxygen or sulfur groups, at least one of X, Y and Z is a non-adjacent oxygen, sulfur or imino group) The active energy ray-curable resin composition according to claim 1, wherein the structural unit (a) having an aliphatic cyclic structure in the main chain is represented by the following general formula (2).
General formula (2)

(In the general formula (2), R ₆ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and R ₇ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a carboxyl group. , Esther group or cyano group, R ₈ represents a direct bond or a methylene group, and R ₉ represents a direct bond or a methylene group.) The active energy ray-curable composition according to claim 1 or 2 , wherein the resin (A) has a weight average molecular weight of 500 or more and less than 100,000. The active energy ray curable according to any one of claims 1 to 3 , wherein the inorganic filler (C) is at least one selected from the group consisting of alumina, silica, titanium oxide, and zirconium oxide. Resin composition. A decorative sheet having a cured film formed from the active energy ray-curable resin composition according to any one of claims 1 to 4 on a substrate. A molded product formed from the decorative sheet according to claim 5.