JP2019112484A - Active energy ray-curable resin composition, decorative sheet, and molded product - Google Patents

Abstract

To provide an active energy ray-curable resin composition excellent in scratch resistance, extensibility, chemical resistance, moldability, temporal stability, and adhesion to a substrate.SOLUTION: The active energy ray-curable resin composition contains 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 25-99 wt.% of a structural unit (a) having an aliphatic structure in the main chain and 1-75 wt.% of a structural unit (b) having a hydroxyl group.SELECTED DRAWING: None

Description

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

  In the past, on the surface of plastic casings used in various fields such as mobile phones such as smartphones, electronic devices such as laptop computers including mobile PCs, interior and exterior parts for automobiles, construction materials, etc. The high designability (design, texture, high-class feeling such as appearance) etc. is given (decored) by processing of. In addition, a protective layer (hard coat layer) is often provided for the purpose of protecting such a decorative body or soft plastic itself.

  In recent years, in manufacturing for decorating such plastic, in order to cope with environmental load reduction, productivity and cost, and complicated product shape, bonding of films and sheets from a method directly to the conventional case Replacement with transfer decoration technology is in progress. That is, a decorative sheet in which a design layer for achieving the above-described design, a hard coat layer for protection, and the like are laminated is bonded to a base material such as plastic. Conventional decorative sheets may be constructed by laminating a single layer or multiple layers on a sheet substrate, but are constructed such that the outermost layer after final forming processing is a protective layer (hard coat layer) It is done.

A decorative sheet provided with a protective layer on such a film or sheet-like substrate can be produced by various methods such as vacuum molding, pressure molding, membrane press molding, in-mold molding, insert molding, insert molding, overlay vacuum molding, etc. It is molded and processed. In any case, the decorative sheet is stretched or bent in accordance with the shape of the body to be decorated (plastic casing) or the shape of the mold.

  In the molding process, heat of tens to hundreds of degrees is generally applied to the sheet. As a main reason, the purpose is to join the decorative sheet and the object to be decorated (plastic casing) required in the process by heat or to improve the stretchability of the decorative sheet by heating. However, when the hard coat layer does not have sufficient flexibility and extensibility, moldability is poor, whitening, flaws, cracks, peeling and the like occur, which is not desirable because the designability is greatly impaired. (Patent Document 1)

  As a method generally used by the method of forming a hard-coat layer in a film or a sheet-like base material, for example, the invention of patent document 2 forms a photosensitive coating composition into a film on a film, The hard coat layer is formed by photocuring (crosslinking) by irradiation. By using a polyfunctional photocrosslinkable monomer in the composition, the hard coat property is obtained by improving the degree of crosslinking after light irradiation. However, a highly crosslinked membrane is hard and brittle and therefore has poor flexibility and extensibility. Therefore, in the technique for obtaining the conventional hard coat layer, it is extremely difficult to cope with processing such as bending and stretching performed in accordance with various product shapes in the forming step of the decorative sheet.

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

  In addition, technical problems are avoided by devising the entire manufacturing process including the decorative sheet and the molding process using the same. For example, Patent Document 3 proposes a method of securing the extensibility necessary for molding by semi-curing the photosensitive composition with active energy rays and obtaining a hard coat layer by further irradiating active energy rays after molding. Although it is difficult to control the light irradiation conditions to obtain a semi-cured state, the difference between the UV irradiator and the lamp greatly affects, and the processor is charged with an active energy ray irradiation device necessary for post-crosslinking. And other disadvantages. In addition, it is proposed in Patent Document 4 to increase the hard coat property by carrying out thermal crosslinking as post-processing after molding by using a thermally crosslinkable composition in combination with the photosensitive composition. In order to obtain a sufficient hard coat property, a long time of thermal crosslinking time is required, and a demerit such as making a heating equipment necessary for the thermal crosslinking be burdened on a processor is large.

  In addition, 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. The thermoplastic resin acts as an inactive component, thereby expressing extensibility by suppressing the degree of crosslinking. As a result, although it shows a certain degree of moldability, it is insufficient for the level required in recent years. In addition, due to the adverse effect of the non-curing component, in particular, the hard coat properties such as curability and chemical resistance are insufficient.

  In any case, the control of the degree of crosslinking of the crosslinked film to cope with the molding process is the key, but the technical difficulty of the control of crosslinking is high, and the disadvantage is large in that the process becomes complicated. Therefore, in the prior art, as a result of forming a soft crosslinked film to obtain moldability, hard coatability is lost. Thus, a decorated molded product can be obtained from the crosslinked film formation by a simple process of molding process only. It is difficult. Therefore, it is the present situation that it copes with a complicated method.

  Therefore, there is a need for a crosslinkable composition that has both the hard coatability and the moldability necessary for the decorative sheet and that enables to obtain a molded product in a simpler process.

  Furthermore, the use of plastic products in various applications is increasing, and the extensibility, scratch resistance, adhesion to substrates and chemical resistance of the products are universally required. Patent Document 6 proposes an active energy ray-curable resin composition in which a resin having a ring structure in its main chain is used as a main polymer. However, the active energy ray-curable resin composition described in the present patent can not obtain the level of extensibility, chemical resistance, scratch resistance and substrate adhesion required in recent years. In addition, even if an inorganic filler is added for the purpose of imparting scratch resistance, there is a problem that the stability of the active energy ray-curable resin composition over time is poor, and the inorganic filler precipitates over time. Furthermore, because of its aqueous nature, handling is difficult in hard coat applications where the solvent system is the main component.

Patent No. 5704929 Patent No. 5524455 JP, 2015-54886, A Patent No. 5389904 Unexamined-Japanese-Patent No. 2007-290392 JP, 2016-180081, A

  The present invention has been made in view of the above-mentioned present situation, and provides an active energy ray-curable resin composition having excellent long-term stability. In addition, a novel composition is obtained to obtain a protective layer having high levels of hard coatability, extensibility, moldability and substrate adhesion required for an excellent decorative sheet capable of coping with various molding processes. Do. Furthermore, the composition for obtaining the decoration sheet which does not require processes, such as photocuring, after molding processing is provided.

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

The present invention is an active energy ray curable composition comprising 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 comprising 25 to 99% by weight of a structural unit (a) having an aliphatic cyclic structure in the main chain and 1 to 75% by weight of a structural unit (b) having a hydroxyl group The present invention relates to an active energy ray-curable resin composition that is characterized.

The active energy ray curable resin according to claim 1, wherein the structural unit (a) having an aliphatic cyclic structure in its main chain is a structure represented by the following general formula (1): It relates to a 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, 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 each independently a carbon number A methylene group optionally having 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, or a methylene group optionally having an alkyl group having 1 to 4 carbon atoms , An imino group, a carbonyl group, an oxygen atom or a sulfur atom, and at least one of X, Y and Z is an oxygen atom, a sulfur atom or an imino group not adjacent to each other)

The present invention relates to the above-mentioned active energy ray curable resin composition characterized in that a structural unit (a) having an aliphatic cyclic structure in its 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, or a substituted or unsubstituted aryl group, R ₇ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a carboxyl group , Ester 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 weight average molecular weight of the resin (A) is 500 or more and less than 100,000.

The present invention relates to the active energy ray curable resin composition characterized in that 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 article formed from the decorative sheet.

According to the present invention, it is possible to provide an active energy ray-curable resin composition having excellent long-term stability. In addition, a novel composition is obtained to obtain a protective layer having high levels of hard coatability, extensibility, moldability and substrate adhesion required for an excellent decorative sheet capable of coping with various molding processes. You can do it. Furthermore, the composition for obtaining the decoration sheet which does not require processes, such as photocuring, after shaping | molding process can be provided.

In the present application, in particular, when it is described as “(meth) acryloyl”, “(meth) acrylic”, “(meth) acrylic acid”, “(meth) acrylate” and “(meth) acryloyloxy”, in particular Unless otherwise stated, respectively, "acryloyl and / or methacryloyl", "acrylic and / or methacrylic", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", and "acryloyloxy and / or methacryloyloxy" It represents ".

  Further, in the present specification, the curability (hard coatability) includes scratch resistance, chemical resistance and the like. Moreover, moldability means that the problem which impairs design property, such as whitening, a flaw, a crack, peeling, largely does not generate | occur | produce by molding process. The weather resistance means that even if exposed to light, heat, water, air pollutants and the like for a long time, the state of the coating does not change.

Each component of the invention will be described. 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), and 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 comprises 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. Preferably it is an acrylic polymer. In the present specification, the main chain means a carbon chain forming 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) from the viewpoint of availability, production cost and performance Preferably, it is a structure represented by the following general formula (2). 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.

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, 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 each independently a carbon number A methylene group optionally having 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, or a methylene group optionally having an alkyl group having 1 to 4 carbon atoms , An imino group, a carbonyl group, an oxygen atom or a sulfur atom, and at least one of X, Y and Z is an oxygen atom, a sulfur atom or an imino group not adjacent to each other)

As a C1-C30 organic group in R ₁ of General formula (1), a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, an unsaturated hydrocarbon group, and a C2-C30 cyclic ether Although a group etc. can be mentioned, it is not limited to these. Some or all of the hydrogen atoms of these organic groups are at least one selected from the group consisting of an alkoxy group having 1 to 30 carbon atoms, a hydroxyl group, a halogen atom, or a cyclic ether group substituted with a halogen atom. It may be substituted by a group.

The substituted or unsubstituted alkyl group is a linear, branched, monocyclic, or fused polycyclic alkyl group having 1 to 30 carbon atoms, or 2 to 30 carbon atoms, and in some cases, one or more -O- And a linear, branched, monocyclic or fused polycyclic alkyl group interrupted by Specific examples of the linear or branched alkyl group having 1 to 30 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an amyl group, a hexyl group, a heptyl group, an octyl group and a nonyl group. , Decyl, dodecyl, octadecyl, capryl, undecyl, lauryl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, stearyl, nonadecyl, eicosyl, ceryl, mesyl, 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- group Octyl group, neopentyl group, 2-ethylhexyl group, cyclopropyl group, 4-butylcyclohexyl, cyclopentyl, cyclohexyl, adamantyl, 4-methylcyclohexyl, 4-tert-butylcyclohexyl, tricyclodecanyl, isobornyl, dicyclopentadienyl, norbornyl, boronyl, 4- Although a decylcyclohexyl group etc. can be mentioned, it is not limited to these. Further, specific examples of the linear or branched alkyl group having 2 to 30 carbon atoms and optionally interrupted by one or more of -O- include -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, the present invention is not limited thereto.

Some or all of the hydrogen atoms of the organic group having 1 to 30 carbon atoms may be substituted with at least one type of substituent selected from the group consisting of a hydroxyl group and a halogen atom. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example. Specific examples thereof include fluoroethyl group, difluoroethyl group, chloroethyl group, dichloroethyl group, bromoethyl group and dibromoethyl group, but are not particularly limited.

As the unsaturated hydrocarbon group, specifically, a C2-C30 chain unsaturated hydrocarbon group such as vinyl group, allyl group, methallyl group, crotyl group, propargyl group and the like, and a part of its hydrogen atom is carbon number Examples thereof include, but are not limited to, 1 to 30 alkoxy groups, and a chain unsaturated hydrocarbon group substituted with a hydroxyl group or a halogen atom.

The substituted or unsubstituted aryl group in R ₁ of the general formula (1) includes a monocyclic or fused polycyclic aryl group having 6 to 24 carbon atoms, and specific examples thereof include a phenyl group, a methylphenyl group, and dimethyl Phenyl group, trimethylphenyl group, 4-tert-butylphenyl group, benzyl group, diphenylmethyl group, diphenylethyl group, triphenylmethyl group, cinnamyl group anthranyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group 9-anthryl group, 2-phenanthryl group, 3-phenanthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azulenyl group, 1-acenaphthyl group, 2-fluorenyl group 9-fluorenyl group, 3-perylenyl group, o-tolyl group, m-tolyl group, p-tolyl group Group, 2,3-xylyl 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-carboxyphenyl group, o-mercaptophenyl group, p-cyanophenyl group, m-nitrophenyl group, m-azidophenyl group etc. can be mentioned. However, it is not limited to these.

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

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

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

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

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. Here, 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, more preferably a hydrogen atom or 1 carbon atom, from the viewpoint of obtaining raw materials and physical properties of copolymerization. It is a -4 alkyl group.

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

X and Y each independently represent a methylene group optionally having an alkyl group having 1 to 4 carbon atoms, an imino group, a carbonyl group, an oxygen atom or a sulfur atom. From the viewpoint of physical properties and the like, X and Y each independently are preferably a methylene group optionally having an alkyl group of 1 to 4 carbon atoms, a carbonyl group or an oxygen atom, and more preferably 1 to 4 carbon atoms It is a methylene group optionally having an alkyl group of 4, a carbonyl group or an oxygen atom, and still more preferably a methylene group.

Z is a direct bond, a methylene group which may have an alkyl group having 1 to 4 carbon atoms, an imino group, a carbonyl group, an oxygen atom or a sulfur atom. 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, a sulfur atom or an imino group, and the oxygen atom, the sulfur atom or the imino group is not adjacent to each other. Here, an oxygen atom is preferable from the viewpoints of raw material availability and physical properties of copolymerization.

General formula (2)

(In the general formula (2), R ₆ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, R ₇ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a carboxyl group , Ester 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 for R ₆ in the general formula (2) is a linear, branched, monocyclic or fused polycyclic alkyl group having 1 to 18 carbon atoms, or 2 to 18 carbon atoms Examples include linear, branched, monocyclic or fused polycyclic alkyl groups which are optionally interrupted by one or more -O-. Specific examples of the linear or branched alkyl group 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, decyl group , Dodecyl, octadecyl, isopropyl, isobutyl, isopentyl, sec-butyl, tert-butyl, sec-pentyl, tert-pentyl, tert-octyl, neopentyl, cyclopropyl, cyclobutyl Examples thereof include, but are not limited to, cyclopentyl, cyclohexyl, adamantyl, norbornyl, boronyl, 4-decylcyclohexyl and the like. Further, specific examples of the linear or branched alkyl group having 2 to 18 carbon atoms and optionally interrupted by one or more of -O- include -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 To 8),-(CH ₂ -CH ₂ -CH ₂ -O) l -CH ₃ (where l is 1 to 5), -CH ₂ -CH (CH ₃ ) -O-CH _{2- CH 3 -, - CH 2 -CH-} (OCH 3) but ₂ and the like, but is not limited thereto.

The substituted or unsubstituted aryl group in R ₆ of the general formula (2) includes a monocyclic or fused polycyclic aryl group having 6 to 24 carbon atoms, and specific examples thereof include a phenyl group, a 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 9-anthryl group, 2-phenanthryl group, 3-phenanthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azulenyl group, 1-acenaphthyl group, 2-fluorenyl group, 9-fluorenyl group, 3-perylenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,3-xylyl 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-carboxyphenyl group, o-mercaptophenyl group, p-cyanophenyl group, m-nitrophenyl group, m-azidophenyl group etc. can be mentioned, but It is not limited.

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

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

R ₈ in the general formula (2) may be a direct bond or a methylene group. Here, it is preferable that R ₈ be a direct bond from the viewpoint of obtaining raw materials and physical properties of copolymerization.

R ₉ in the general formula (2) represents a direct bond or a methylene group. Here, a methylene group is preferable as 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 it is obtained by acrylic polymerization of the diene structure-containing monomer (c) It is possible that the polymerization proceeds according to the mechanism described in JP2013-216736.

In the case of introducing the structural unit (a) having an aliphatic cyclic structure in the main chain of the resin (A) by causing the polymerization to proceed according to the mechanism described in JP2013-216736, R ₄ in the general formula (1) When is a hydrogen atom, R ₃ is preferably 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, R ₃ is preferably a methylene group and R ₅ is a direct bond.

R ₇ in General Formula (2) when the polymerization is carried out according to the mechanism described in JP 2013-216736 as a method for introducing the structural unit (a) having an aliphatic cyclic structure in the main chain of the resin (A) When is a hydrogen atom, R ₈ is preferably a direct bond and R ₉ is a methylene group. On the other hand, when R ₇ is an alkyl group having 1 to 4 carbon atoms, a carboxyl group, an ester group and a cyano group, it is preferable that R _{8 be} a methylene group and R _{9 be} 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), more preferably from the viewpoint of availability, production cost and performance. It is a structure as described in General formula (4).

General formula (3)


(R ₁ , R ₄ , X, Y and Z in the general formula (3) are the same as above.)

General formula (4)


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

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

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-hydroxypropyl phthalate or caprolactone adducts of these monomers Acrylates having a hydroxyl group such as 1 to 5). Polyalkylene glycol having a polyoxyalkylene chain whose molecular terminal is a hydroxyl group such as polyethylene glycol acrylate, polypropylene glycol acrylate, polyethylene glycol acrylate, polypropylene glycol acrylate and the like and polyalkylene glycol having a polyoxyalkylene chain which is acrylic acid and hydroxyl group Oxalic acid monohydroxyethyl acrylate, tetrahydrophthalic acid monohydroxyethyl acrylate, tetrahydrophthalic acid monohydroxypropyl acrylate, 5-methyl-1,2-cyclohexanedicarboxylic acid monohydroxyethyl acrylate, phthalic acid monohydroxyethyl acrylate, phthalic acid monohydroxy Propyl acrylate, monohydroxyethyl acrylate maleate DOO, maleic acid-hydroxypropyl acrylate, tetrahydrophthalic acid mono-hydroxybutyl acrylate and the like.

Examples of hydroxy methacrylates 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, Methacrylates having a hydroxyl group such as 2-hydroxy-3-allyloxypropyl methacrylate, 2-methacryloyloxyethyl-2-hydroxypropyl phthalate or caprolactone adducts of these monomers (additional mole number is 1 to 5). Esterified polyalkylene glycol having a hydroxyl group at the molecular end such as polyethylene glycol methacrylate, polypropylene glycol methacrylate, polyethylene glycol methacrylate, polypropylene glycol methacrylate, etc. and methacrylic acid, monohydroxyethyl methacrylate oxalate, tetrahydrofuran Monohydroxyethyl methacrylate phthalate, Monohydroxypropyl methacrylate tetrahydrophthalate, Monohydroxyethyl methacrylate 5-methyl-1,2-cyclohexanedicarboxylate, Monohydroxyethyl methacrylate phthalate, Monohydroxypropyl methacrylate phthalate, Monohydroxyethyl maleate Methacrylate, hydroxy maleate B pills methacrylate, tetrahydrophthalic acid mono-hydroxybutyl methacrylate

Examples of hydroxy (meth) acrylates having a bifunctional or higher functional hydroxyl group:
Glycerin mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, pentaerythritol mono (meth) acrylate, diglycerin mono (meth) acrylate, ditrimethylolpropane 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) acrylate of pentaerythritol alkylene oxide adduct Acrylate, mono (meth) acrylate of ditrimethylolpropane alkylene oxide adduct, diglycerin alkylene oxide adduct Mono (meth) acrylate Roh (meth) acrylate and dipentaerythritol alkylene oxide adducts.

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

  As the resin (A), other monomers can be used according to the necessary physical properties. The other monomers may be used alone or in any ratio of two or more.

  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) ) Acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate Linear or branched alkyl (meth) acrylates such as fine adamantyl (meth) acrylate;

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

  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, (meth) acrylic acid 2-hydroxy-3-allyloxypropyl, 2- (meth) acryloyloxyethyl -2-hydroxypropyl phthalate, glycerin mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, 4-hydroxy vinyl benzene, polypropylene glycol mono (meth) acrylate, and Rorakuton adducts (addition molar number of 1 to 5) having a hydroxyl group such as (meth) acrylates;

  (2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H-hexafluoroisopropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (Meth) acrylate, 1H, 1H, 2H, 2H-heptadecafluorodecyl (meth) acrylate, 2,6-dibromo-4-butylphenyl (meth) acrylate, 2,4,6-tribromophenoxyethyl (meth) Fluoroalkyl (meth) acrylates such as acrylate, 2,4,6-tribromophenol 3EO addition (meth) acrylate, and perfluorooctylethyl (meth) acrylate;

Tetrahydrofurfuryl (meth) acrylate, dioxolane (meth) acrylate, acryloyl furfuryl (meth) acrylate, 2-isocyanatoethyl (meth) acrylate modified furfuryl alcohol, 2-isocyanatoethyl (meth) acrylate modified furfurylamine, 2 -(Meth) acrylates having a heterocyclic ring such as bromofuran EO addition (meth) acrylate and 3-methyl-3-oxetanyl (meth) acrylate;

  Benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, paracumyl phenoxyethyl (meth) acrylate, paracumyl phenoxy polyethylene glycol (meth) acrylate, and nonyl phenoxy polyethylene glycol (meth) acrylate (Meth) acrylates having an aromatic ring of

  2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, n-butoxydiethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, 1,3-butylene glycol methyl ether (meth) acrylate, methoxy tri Ethylene glycol (meth) acrylate, methoxypolyethylene glycol mono (meth) acrylate, methoxypolyethylene glycol # 400 (meth) acrylate, methoxy polyethylene glycol # 100 (meth) acrylate, methoxy polyethylene glycol # 1000 (meth) acrylate, methoxy polyethylene glycol # 4000 (meth) acrylate, methoxypolyethylene glycol # 200 (meth) acrylate, methoxy dipropyl Glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, ethyl carbitol (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, tetrahydro Furfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, cresyl polyethylene glycol (meth) acrylate, (meth) acrylic acid-2- (vinyloxyethoxy) ) Ethyl, p-nonyl phenoxyethyl (meth) acrylate, p-nonyl phenoxy polyethylene glycol Meta) acrylate, glycidyl (meth) acrylate, β-carboxyethyl (meth) acrylate, succinic acid mono (meth) acryloyloxyethyl ester, ω-carboxypolycaprolactone mono (meth) acrylate, 2- (meth) acryloyloxyethyl hydrogen Phthalate, 2- (meth) acryloyloxypropyl hydrogen phthalate, 2- (meth) acryloyloxypropyl hexahydrohydrogen phthalate, 2- (meth) acryloyloxypropyl tetrahydrohydrogen phthalate, octoxy polyethylene glycol polypropylene glycol mono (meth) acrylate, Lauroxy polyethylene glycol mono (meth) acrylate, stearoxy polyethylene glycol mono (meth) acrylate Phenoxy polyethylene glycol mono (meth) acrylate, phenoxy polyethylene glycol polypropylene glycol mono (meth) acrylate, polyethylene glycol mono methyl ether (meth) acrylate, nonyl phenoxy polyethylene glycol mono (meth) acrylate, nonyl phenoxy polypropylene glycol mono (meth) acrylate, nonyl (Meth) acrylates having an ether group such as phenoxy polyethylene 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- (methacryloyloxymethyl) Oxetanyl groups such as (acryloyloxymethyl) 3-butyl oxetane, 3- (methacryloyloxymethyl) 3-butyl oxetane, 3- (acryloyloxymethyl) 3-hexyl oxetane, and 3- (methacryloyl oxymethyl) 3-hexyl oxetane (Meth) acrylates having

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

(Meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N , N-dimethylaminopropyl acrylamide, morpholinoethyl (meth) acrylate, N-methylol (meth) acrylamide, diacetone (meth) acrylamide, N, N- dimethyl (meth) acrylamide, N, N- diethyl (meth) acrylamide, N -(Meth) acrylamides such as isopropyl (meth) acrylamide, diacetone (meth) acrylamide, and (meth) acryloyl morpholine;

  Nitriles such as (meth) 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;

  Trade name "Syllaplane FM-0711" (manufactured by JNC Co., Ltd.), trade name "Syraplane FM 0721" (manufactured by JNC Co., Ltd.) Trade name "Syraplane FM 0725" (JNC Co., Ltd.) Product name, “X-22-174DX” (Shin-Etsu Silicone Co., Ltd.) “X-22-2426” (Shin-Etsu Silicone Co., Ltd.), trade name “X-22-174 ASX” (Shin-Etsu Silicone Co.) Polysiloxane (meth) acrylates;

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

As an isocyanate group, a block isocyanate group is also included and can be used. With a blocked isocyanate group, under ordinary conditions, while the reactivity of the isocyanate group is suppressed by protecting the isocyanate group with another functional group, it can be deprotected by heating to regenerate an active isocyanate group. Indicates an isocyanate block.

As a commercial item of (meth) acrylates having such a blocked isocyanate group, for example, 2-[(3,5-dimethylpyrazolyl) carboxyamino] ethyl methacrylate (Karenz MOI-BP, manufactured by Showa Denko); methacrylic acid 2- (0- [1'-methylpropylideneamino] carboxyamino) ethyl (Karenz MOI-BM, manufactured by Showa Denko K. K.) and the like.

  Other polymerizable monomers include vinyl acetate, vinyl monochloroacetate, vinyl benzoate, vinyl pivalate, vinyl butyrate, vinyl laurate, vinyl 2-ethylhexanoate, N-vinylcarbazole, N-vinyl pyrrolidone and the like These include, but are not limited to.

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

  When the other polymerizable monomer is contained, its content is preferably 1 to 50% by weight, and 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, and more preferably 40 to 99%, in 100% by weight of the resin (A) More preferably, it is 40 to 80% by weight.

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

  The resin (A) is preferably synthesized using acrylic polymerization from the viewpoint of introduction of the polymerization units of the general formulas (1) and (2) and control of the amount. Moreover, you may have the polymer unit based on another monomer as needed, such as a physical property.

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

In the living radical polymerization method, side reactions which occur in general radical polymerization are suppressed, and furthermore, since the growth of polymerization occurs uniformly, it is possible to easily synthesize a block polymer and a resin with a uniform molecular weight.

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 is applicable to a wide range of monomers, and a polymerization temperature applicable to existing equipment. It is preferable in that it can be adopted. The atom transfer radical polymerization method can be performed by the method described in the following references 1 to 8 and the like.

(Reference 1) Fukuda et al., Prog. Polym. Sci. 2004, 29, 329
(Reference 2) Matyjaszewski et al., Chem. Rev. 2001, 101,
2921
(Reference 3) Matyjaszewski et al. Am. Chem. Soc. 1995, 117, 5614
(Reference 4) Macromolecules 1995, 28, 791, Science, 1996, 272, 866
(Reference 5) WO 96/030421
(Reference 6) WO 97/018247
(Reference 7) JP-A-9-208616 (Reference 8) JP-A-8-41117

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

The reaction time is preferably adjusted according to the type of the polymerization initiator and the monomer to be used, but it is preferably 2 to 30 hours, more preferably 3 to 15 hours.

  The polymerization environment is preferably performed under an inert gas atmosphere for the purpose of preventing color reduction, deactivation of the polymerization initiator, etc. Nitrogen gas is preferable in terms of availability and cost. It is not limited to

  As the polymerization initiator, an azo compound and an organic peroxide can be used. Examples of the azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane 1-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 ′ Examples include, but are not limited to, -azobis (1-cyclohexanecarboxylate) and 2,2'-azobis [2- (2-imidazolin-2-yl) propane] and the like.

Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxy dicarbonate, di-n-propyl peroxy dicarbonate, di (2-ethoxyethyl) peroxy Dicarbonate, t-butylperoxy 2-ethylhexamate, t-butylperoxyneodecanoate, t-butylperoxy-2-ethylhexanoate, dilauroxyperoxide, peroxyneodecanoate, Examples include, but are not limited to, t-butyl peroxy bivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, and diacetyl peroxide.

  These polymerization initiators can be used alone or in combination of two or more kinds, and the amount used thereof is 0.001 to 20 parts by weight to the total amount of monomers (total 100 parts by weight) used in polymerization. It is possible to adjust arbitrarily in the range of parts.

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

The chain transfer agent is not particularly limited as long as it is a compound capable of controlling molecular weight, and known chain transfer agents can be used. For example,
Octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, mercaptoethanol, 1-thioglycerol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 2 -Ethylhexyl 3-mercapto propionate, n-octyl 3-mercapto propionate, methoxybutyl 3-mercapto propionate, stearyl 3-mercapto propionate, trimethylolpropane tris (3-mercapto propio) Salts), tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate, pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-) Mercaptans such as mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), thiomalic acid, thioglycolic acid octyl, octyl 3-mercaptopropionate, 2-mercaptoethanesulfonic acid, butyl thioglycollate ;
Disulfides such as dimethyl xanthogen disulfide, diethyl xanthogen disulfide, diisopropyl xanthigene disulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, carbon tetrachloride, methylene chloride, bromoform, bromotrichloroethane, carbon tetrabromide, bromide Halogenated hydrocarbons such as ethylene;
Secondary alcohols such as isopropanol and glycerin;
Phosphorous acid, hypophosphorous acid, and their salts (sodium hypophosphite, potassium hypophosphite, etc.), sulfite, hydrogen sulfite, dithionite, metabisulfite, and salts thereof (sodium bisulfite) Lower oxides and their salts such as potassium bisulfite, sodium dithionite, potassium dithionite, sodium metabisulfite, potassium metabisulfite, etc .; and allyl alcohol, 2-ethylhexyl thioglycolate, α -Methylstyrene dimer, terpinorene, α-terpinene, γ-terpinene, dipentene, anisole and the like can be mentioned, but it is not limited thereto. These may be used alone or in combination of two or more.

  In the polymerization, an organic solvent can be used as a 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, diethoxy diethylene glycol, Although 3-methoxy-1-butanol etc. are used, it is not limited in particular in these. These polymerization solvents may be used as a mixture of two or more, but it is preferably a solvent used in an end use.

  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 preferable. In the present specification, the weight average molecular weight indicates a polystyrene equivalent molecular weight measured by gel permeation chromatography.

The resin (A) is 1 to 99 parts by weight in total 100 parts by weight of the solid content of the active energy ray-curable resin composition from the viewpoint of the hard coatability and processability of the active energy ray-curable resin composition The amount is preferably used, 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 more and 120 ° C. or less.

  From the viewpoint of moldability, chemical resistance, etc., the hydroxyl value of the resin (A) of the present invention is preferably 1 to 350 mg KOH / g, more preferably 1 to 330 mg KOH / g, still more preferably 100 to It is 330 mg KOH / 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 to improve the curability upon reaction. The compound having a polymerizable group in the present invention means a compound (but not including the resin (A)) having at least one or more polymerizable skeleton in the molecule. In addition, they all have chemical forms of monomers, oligomers or polymers which are liquid to solid at ordinary temperature and pressure.

As the active energy ray curable compound (B), preferably, a polymerizable oligomer, a polymerizable monomer and the like can be mentioned. The polymerizable oligomer can impart resistance, flexibility, and curability to the surface protective layer, and one having a number average molecular weight (measured by gel permeation chromatography (GPC); hereinafter the same) of 100 or more is 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 and salts thereof, esters, acid amides, acid anhydrides, and the like. (Meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, acrylic (meth) acrylate, ester (meth) acrylate, ester (meth) acrylate acrylonitrile, ether (meth) acrylate, styrene derivative, Although various unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, unsaturated polyurethanes, etc. are mentioned, they are not limited to these. Below, the specific example of the radically polymerizable compound in this invention is given.

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, dicyclopentenyl oxyethyl 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-hydroxypropyl phthalate.

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 addition acrylate.

Examples of monofunctional ether-containing acrylates:
2-methoxyethyl acrylate, 1,3-butylene glycol methyl ether acrylate, butoxyethyl acrylate, methoxy triethylene glycol acrylate, methoxy polyethylene glycol # 400 acrylate, methoxy dipropylene glycol acrylate, methoxy tripropylene glycol acrylate, methoxy polypropylene glycol acrylate, Ethoxydiethylene glycol acrylate, ethyl carbitol acrylate, 2-ethylhexyl carbitol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, phenoxy diethylene glycol acrylate, phenoxy polyethylene glycol acrylate, cresyl polyethylene glycol acrylate, Acrylic acid 2- (vinyloxy) ethyl, p- nonyl phenoxyethyl acrylate, p- nonylphenoxy polyethylene glycol acrylate, glycidyl acrylate.

Examples of monofunctional carboxyl-containing acrylates:
β-Carboxyethyl acrylate, succinic acid monoacryloyloxyethyl ester, ω-carboxypolycaprolactone monoacrylate, 2-acryloyloxyethyl hydrogen phthalate, 2-acryloyloxypropyl hydrogen phthalate, 2-acryloyloxypropyl hexahydrohydrogen phthalate, 2- Acryloyloxypropyl tetrahydrohydrogen phthalate.

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-acryloylyl Oxyethyl acid phosphate, 2-hydroxy-1-acryloxy-3-methacryloxypropane.

Examples of difunctional 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, ne Pentyl glycol PO modified diacrylate, hydroxypivalic acid neopentyl glycol ester diacrylate, caprolactone adduct of hydroxypivalic acid neopentyl glycol ester 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 hydrogenated bisphenol A diacrylate EO Hydrogenated Bisphenol A Diacrylate, PO Modified Hydrogenated Bisphenol A Diacrylate, Bisphenol F Diacrylate, EO Modified Bisphenol F Diacrylate, PO Modified Bisphenol F Diacrylate, EO Modified Tetrabromo Bisphenol A Diacrylate, Tricyclodecane Dimethylol 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 2 molecules of ethoxylated isocyanuric acid diacrylate are linked by hexamethylene diisocyanate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate monopropionate, dipentaerythritol hexaacrylate, dipentaerythritol ε-caprolactone Modified hexaacrylate, dipentaerythritol EO modified hexaacrylate, tetramethylolmethane tetraacrylate, oligoester tetraacrylate, 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, dicyclopentenyl oxyethyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, lauryl methacrylate, stearyl methacrylate Rate.

Examples of monofunctional hydroxy methacrylates:
2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxy-3-chloropropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-allyloxypropyl methacrylate, 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 addition methacrylate.

Examples of monofunctional ether-containing methacrylates:
2-methoxyethyl methacrylate, 1,3-butylene glycol methyl ether methacrylate, butoxyethyl methacrylate, methoxytriethylene glycol methacrylate, methoxy polyethylene glycol # 400 methacrylate, methoxy dipropylene glycol methacrylate, methoxy tripropylene glycol methacrylate, methoxy polypropylene glycol methacrylate, Methacrylic acid-2- (vinyloxyethoxy) ethyl, ethoxydiethylene glycol methacrylate, 2-ethylhexyl carbitol methacrylate, tetrahydrofurfuryl methacrylate, phenoxyethyl methacrylate, phenoxydiethylene glycol methacrylate, phenoxy polyethylene glycol methacrylate, Polyethylene glycol methacrylate, p- nonyl phenoxyethyl methacrylate, p- nonylphenoxy polyethylene glycol methacrylate, glycidyl methacrylate.

Examples of monofunctional carboxyl methacrylates:
β-Carboxyethyl methacrylate, succinic acid monomethacryloyloxyethyl ester, ω-carboxypolycaprolactone monomethacrylate, 2-methacryloyloxyethyl hydrogen phthalate, 2-methacryloyloxypropyl hydrogen phthalate, 2-methacryloyloxypropyl hexahydrohydrogen phthalate, 2- Methacryloyloxypropyl tetrahydrohydrogen phthalate.

Examples of other monofunctional methacrylates:
Dimethylaminomethyl methacrylate, 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 and the like.

Examples of difunctional 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, neopenty Glycol dimethacrylate, neopentyl glycol PO modified dimethacrylate, hydroxypivalic acid neopentyl glycol ester dimethacrylate, hydroxypivalic acid neopentyl glycol ester caprolactone adduct dimethacrylate, 1,6-hexanediol bis (2-hydroxy-3- Methacryloyloxypropyl) ether, 1,9-nonanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol dimethacrylate monostearate, pentaerythritol dimethacrylate monobenzoate, 2,2-bis (4-methacryloxypolyethoxyphenyl) 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, tricyclodecane dimethylol dimethacrylate, isocyanuric acid EO modified dimethacrylate, 2-hydroxy-1,3-dimethacryloxypropane, tricyclodecane dimethanol diacrylate.

Examples of trifunctional methacrylates:
Glycerin PO modified trimethacrylate, trimethylolethane trimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane EO modified trimethacrylate, trimethylolpropane PO modified trimethacrylate, isocyanuric acid EO modified trimethacrylate, isocyanuric acid EO modified ε-caprolactone modified tri Methacrylate, 1,3,5-trimethacryloyl hexahydro-s-triazine, pentaerythritol trimethacrylate, dipentaerythritol trimethacrylate tripropionate.

Examples of tetrafunctional or higher methacrylates:
Pentaerythritol tetramethacrylate, dipentaerythritol pentamethacrylate monopropionate, dipentaerythritol hexamethacrylate, dipentaerythritol ε-caprolactone modified hexamethacrylate, dipentaerythritol EO modified hexamethacrylate, tetramethylolmethane tetramethacrylate, oligoester tetramethacrylate, Tris (methacryloyloxy) phosphates and their ε-lactone modified compounds.

Examples of arylates:
Allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, isocyanurate triarylate.

Examples of acid amides:
Acrylamide, N-methylol acrylamide, diacetone acrylamide, N, N-dimethyl acrylamide, N, N-diethyl acrylamide, N-isopropyl acrylamide, acryloyl morpholine, methacrylamide, N-methylol methacrylamide, diacetone methacrylamide, N, N -Dimethyl methacrylamide, N, N-diethyl methacrylamide, N-isopropyl methacrylamide, methacryloyl morpholine.

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

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

  The above-described radically polymerizable compound can be easily obtained as a commercial product of a manufacturer shown below. For example, “light acrylate”, “light ester”, “epoxy ester”, “urethane acrylate” and “high functional oligomer” series manufactured by Kyoeisha Yuka Chemical Co., Ltd., “high functional oligomer” series, “Shin-Nakamura Chemical Co.” NK Ester "and" NK Oligo "series," Funkryl "series manufactured by Hitachi Chemical Co., Ltd.," Aronix M "series manufactured by Toagosei Chemical Co., Ltd., Daihachi Chemical Industry Co., Ltd. "Functional monomer" series, "Special acrylic monomer" series manufactured by Osaka Organic Chemical Industry Co., Ltd., "Acryester" and "Dia beam 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, Nippon Synthetic Chemical Industry Co., Ltd. Made in "Nichigo-UV Shiko urethane acrylate oligomer" series, Shin-Etsu vinyl acetate Co., Ltd. "carboxylic vinyl ester monomers" series include Co. Kohjin Co. "functional monomer" series, and the like.

Moreover, the cyclic compound shown below is also mentioned as a radically polymerizable compound.
Examples of three-membered ring compounds:
Journal of Polymer Science Polymer Chemistry Edition (J. Polym. Sci. Polym. Chem. Ed.), Vol. 17, p. 3169 (1979) described in Vinylcyclopropanes, Macromolecular Chemie. 1-phenyl-2-vinylcyclopropanes described in Rapid Communication (Makromol. Chem. Rapid Commun.), P. 63, (1984), Journal of Polymer Science Polymer Chemistry Edition ( 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. 2-phenyl-3-vinyl oxiranes described in Volume 21, pp. 4331 (1983), Proceedings of the 50th Annual Meeting of the Chemical Society of Japan, p. 1564 (1985) Mounting No 2,3-vinyl oxirane.

Examples of cyclic ketene acetals:
Journal of Polymer Science Polymer Chemistry Edition (J. Polym. Sci. Polym. Chem. Ed.), Volume 20, page 3021 (1982) and Journal of Polymer Science Polymer Letter 2-Methylene-1,3-dioxepane as described in Edition (J. Polym. Sci. Polym. Lett. Ed.), Vol. 21, p. 373 (1983), Polymer Preprints, Polym. 34, p. 152 (1985), Journal of Polymer Science, Polymer Letter Edition (J. Polym. Sci. Polym. Lett. Ed.), Vol. 20, p. 361 (1982). 2), Macromolecular Chemie (Makromol. Chem.), Vol. 183, p. 1913 (1982) and Macromolecular Chemie (Makromol. Chem.), Vol. 186, p. 1543 (1985). 4,7-Dimethyl-2-methylene-1,3-dioxepane, polymers described in Methylene-4-phenyl-1,3-dioxepane, Macromolecules, Volume 15, page 1711 (1982) 5,6-benzo-2-methylene-1,3-diocepan as described in Premprints (Polym. Preprints), Vol. 34, p. 154 (1985).

  Furthermore, as the active energy ray-curable compound (B), those described in the documents shown below can also be mentioned. For example, Y. Yamashita et al., "Crosslinker Handbook", (1981, Taisei Co., Ltd.) and Kiyohiro Kato, "UV / EB Curing Handbook (raw materials)", (1985, Polymer Publications), Radtech Research Ed., Akamatsu Kiyoshi, "The actual technology of new photosensitive resin", (1987, CMC), Endo Takeshi, "The refinement of thermosetting polymer", (1986, CMC), Takiyama Koichiro, "Polyester resin handbook", (1988, Nikkan Kogyo Shimbun Co., Ltd.), edited by RadTech Research Institute, "Application and market of UV / EB curing technology", (2002, CMC).

Furthermore, as the active energy ray-curable compound (B), a highly hydrophobic polybutadiene (meth) acrylate oligomer having a (meth) acrylate group in the side chain of a polybutadiene oligomer, and a silicone having a polysiloxane bond in the main chain (Meth) acrylate oligomers, aminoplast resin (meth) acrylate oligomers modified with aminoplast resin having many reactive groups in small molecules, or novolak epoxy resin, bisphenol epoxy resin, aliphatic vinyl ether, aromatic And oligomers having a cationically polymerizable functional group in the molecule such as vinyl ether.

  As the active energy ray-curable compound (B), in addition to the above-mentioned monomers, those called oligomers and prepolymers can be used. Specifically, “Ebecryl 230, 244, 245, 270, 280/15 IB, 284, 285, 4830, 4858, 4858, 4883, 8402, 8803, 8800, 254, 264, 265, 294/35 HD manufactured by Daicel UCB. 1259, 1264, 4866, 9260, 8210, 1290.1290 K, 5129, 2000, 2001, 2002, 2100, KRM 7222, KRM 7735, 4842, 210, 215, 4827, 4849, 6700, 6700-20 T, 204, 205, 6602, 220, 4450, 770, IRR 567, 81, 84, 83, 80, 657, 800, 805, 808, 810, 812, 1657, 1810, IRR 302, 450, 670, 830, 835, 870, 1 30, 1870, 2870, IRR 267, 813, IRR 483, 813, 436, 446, 505, 524, 554 W, 584, 586, 745, 767, 1701, 1755, 740/40 TP, 600, 601, 604, 605, 607, 608, 609, 600/25 TO, 616, 645, 648, 860, 1606, 1608, 1629, 1940, 2958, 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 ", manufactured by Sartmar CN104, CN120, CN124, CN136, CN151, CN2270, CN2271E, CN435, CN454, CN970, CN970, CN971, CN972, CN9782, CN981, CN9893, CN991 manufactured by MIWON "MIRAMER PU240, PU340, SC2152, MU9500, PU610, PS240, SIU2400" , HR3200, HR3700 ", BASF Corporation" Laromer EA81, LR8713, LR8765, LR8986, PE56F, PE44F, LR4800, PE46T, LR4907, PO43F, PO77F, PE55F, LR8961, LR8982, LR8992, LR9004, LR8954, LR8954, LR8956, LR8987, UP35D, U 19T, LR9005, PO83F, PO33F, PO84F, PO9s4F, LR8863, LR8869, LR8899, LR8996, LR8913, LR9013, LR9019, PO9026V, PE9027V "manufactured by Cognis" Photomers 3005, 3015, 3016, 3072, 398, 3215, 5010, 5010 5429, 5430, 5432, 5662, 5806, 5930, 60010, 6019, 6184, 6210, 6217, 6289, 6892, 6893-20R, 6363, 6572, 3660 "," Art Resin UN- 9000 HP, 9000 PEP, 9200 A, 7600, 5200, 1003, 1255, 3320 HA, 3320 HB, 3320 HC, 3320 H , 901 T, 1200 TPK, 6060 P, 6060 P, 333, 350, 352, 353, 2600, 2700, 5500, 5590, 5507, 6200, 6302, 6303, 6305, 7700, 904, 906 S, 905, 952, RA, Art Cure RA -3602 MI, 3704 MB, 3953 MP, 4010, 331 MB, 341, OAP-5000, 2511, AHC-9202 MI80, MAP-4000, 2801 "manufactured by Japan Synthetic Chemical Co., Ltd." Purple light UV-6630 B, 7000 B, 7510 B, 7461 TE, 3000 B, 3200 B " , 3210 EA, 3310 B, 3500 BA, 3520 TL, 3700 B, 6100 B, 6640 B, 1400 B, 1700 B, 6300 B, 7550 B, 7605 B, 76. 0B, 7620EA, 7630B, 7640B, 2000B, 2010B, 2250EA, 2750B "manufactured by Nippon Kayaku Co., Ltd." Kayarad R-280, R-146, R131, R-205, EX2320, R190, R130, R-300, C- 0011, TCR-1234, ZFR-1222, UX-2, 201, UX-2, 301, UX-3301, UX-4101, UX-6101, UX-7101, MAX-5101, MAX-5100, MAX-3510, UX- 4101 "and the like.

  Furthermore, the active energy ray curable compound (B) is an epoxy compound having at least one or more epoxy group, a silicon compound having at least one or more alkoxysilyl group or silanol group, or an oxetane compound containing an oxetane ring. It is also possible to use cyclic lactone compounds, cyclic acetal compounds, cyclic thioether compounds, spiroorthoester compounds, vinyl compounds and the like.

Although it does not specifically limit as an epoxy type compound (epoxy resin), For example, diglycidyl ether, ethylene glycol diglycidyl ether, glycerol 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-hexanedio Diglycidyl ether, glycerin polyglycidyl ether, diglycerin polyglycidyl ether, trimethylolpropane polyglycidyl ether, cresyl glycidyl ether, aliphatic diglycidyl ether, polyfunctional glycidyl ether, tertiary fatty acid monoglycidyl ether, spiroglycol diglycidyl ether And glycidyl propoxy trimethoxysilane. These epoxy compounds may be halogenated or may be hydrogenated, and these epoxy compounds also include derivatives. And these epoxy compounds may be used individually by 1 type, and may be used combining 2 or more types.

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

  The silane coupling agent is not particularly limited, and examples thereof include vinylsilane, acrylsilane, epoxysilane, aminosilane and the like. As vinylsilane, vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane and the like can be mentioned. Examples of acrylic silanes include γ-methacryloxypropyltrimethoxysilane and γ-methacryloxypropylmethyldimethoxysilane. Examples of epoxysilanes include β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropylmethyldiethoxysilane. As the aminosilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl- γ-aminopropyltrimethoxysilane and the like can be mentioned. Examples of other silane coupling agents include γ-mercaptopropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, and γ-chloropropylmethyldiethoxysilane. One of these silane coupling agents may be used alone, or two or more thereof may be used in combination.

  Although it does not specifically limit as an oxetane type compound (oxetane type resin), The oxetane type compound of a monomer, the oxetane type compound of a dimer, etc. can be used. Examples of usable oxetane compounds include 4,4'-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl, and 1,4-benzenedicarboxylic acid bis [(3-ethyl-3-oxetanyl)] Methyl] ester, xylylene dioxetane such as 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, 3-ethyl-3-(((3-ethyloxetan-3-yl) methoxy) methyl ) Oxetane (or 3-(((3-ethyloxetan-3-yl) methoxy) methyl) -3-ethyloxetane), 3-ethylhexyl oxetane, 3-ethyl-3-hydroxyoxetane, 3-ethyl-) 3-hydroxymethyl oxetane, or oxetanated phenol novolac, etc. may be mentioned. One of these oxetane compounds may be used alone, or two or more thereof may be used in combination.

Other compounds are not particularly limited, but are oxolane compounds such as tetrahydrofuran and 2,3-dimethyltetrahydrofuran, trioxane, cyclic acetal compounds such as 1,3-dioxolane and 1,3,6-trioxane cyclooctane, and β-pro Cyclic lactone compounds such as pyolactone and ε-caprolactone, thiirane compounds such as ethylene sulfide and thioepichlorohydrin, thietane compounds such as 1,3-propyne sulfide and 3,3-dimethylthietane, 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-cyclohexane Vinyl ether compounds such as methanol divinyl ether, hydroxybutyl vinyl ether, propenyl ether of propylene glycol, spiro ortho ester 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 type may be used alone, or two or more types may be used in combination.

  The active energy ray-curable compound (B) may be used alone or in combination of two or more at an arbitrary ratio in order to improve the desired properties.

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

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

The weight 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 Preferably, the weight ratio is 1: 3 to 3: 1. It is excellent in extensibility and chemical-resistance as it is in the said range.

The proportion of the solid content of the active energy ray curable resin composition is preferably 80% by weight or less. When the solid content is more than 80% by weight, the flowability of the active energy ray-curable resin composition is lowered to cause deterioration in coating suitability, cause of repelling at the time of coating, or cause of wrinkles of the cured film is there.

<Inorganic filler (C)>
It is preferable to add an inorganic filler to the inorganic filler (C) from the viewpoint of imparting scratch resistance. Although not particularly limited, for example, silica (colloidal silica, fumed silica, precipitated silica, etc.), alumina, talc, zirconia, titania, zinc oxide, magnesium carbonate, calcium carbonate, natural mica, synthetic mica, aluminum hydroxide, sedimentation Barium sulfate, precipitated barium carbonate, barium titanate, zirconium oxide, titanium oxide, APO, IPO, TPO, barium sulfate, smectite and the like can be mentioned. Preferably, 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.

  It is more preferable that the inorganic filler (C) has a reactive functional group on the surface from the viewpoint of crosslinkability and the like, and specific examples of the reactive functional group include a vinyl group, a (meth) acryloyl group, and Examples thereof include, but are not limited to, an ethylenically unsaturated bond such as an allyl group, an epoxy group, and a silanol group.

  The shape of the inorganic filler (C) may, for example, be a sphere, an ellipsoid, a polyhedron or a scale shape, and it is preferable that the shape is uniform and the particle size is adjusted. The average particle diameter is preferably 0.005 to 0.5 μm, and more preferably 0.01 to 0.1 μm.

<Organic solvent (D)>
The organic solvent (D) is not particularly limited, and conventionally known organic solvents can be used. Specifically, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol, 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-methoxy Butanol, cyclohexanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, benzyl alcohol, methyl cyclohexanol, 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-ethyl hexyl ether, diethylene glycol mono-2-ethyl hexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monopropyl ether Ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol mono tert-butyl ether, ethylene glycol monopropyl ether, ethylene glycol monomethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monomethyl ether, dipropylene glycol monoethyl 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 solvents such as ropylene 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, Ketone solvents such as methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, 2-heptanone, 4-heptanone, 3,5,5-trimethyl-2-cyclohexen-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 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 monoethyl 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 ether acetate, 1,3-butylene glycol diacetate, 1,4-butanediol diacetate, 1, Ester solvents such as 3-butylene glycol diacetate, 1, 6-hyoxane diol 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 dibutyl Ether solvents such as ether, 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 Aromatic solvents such as sec-butylbenzene and tert-butylbenzene, Aliphatic solvents such as cycloheptane and cyclohexane, Aliphatic solvents such as pentane, hexane, octane, isohexane, isooctane and isononane, dichloromethane, chloroform Chlorinated solvents such as carbon tetrachloride, chlorobenzene, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, m-dichlorobenzene, 1,2,3-trichloropropane, N, N -Amide solvents such as dimethylformamide, N, N-dimethylacetamide, dimethylacetamide, acetonitrile, dimethylsulfoxide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, γ-butyrolactone, isophorone, triacetin, propylene Examples include 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 thereof may be mixed and used.

<Active energy ray curable resin composition>
When the radically polymerizable crosslinking component is crosslinked by ultraviolet light or the like, a photopolymerization initiator can be used, and it is also possible to use a polymerization accelerator in combination. When making it bridge | crosslink by an electron beam, it is not necessary to mix | blend these.

The photopolymerization initiator is not particularly limited, but the following may be mentioned as specific examples.
Diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl methyl 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 -Acetophenones such as methylpropan-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, phenylglyoxylic methyl esters. 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 (CGI 124), CGI 242 (BASF Corporation), Adeka Optomer N 1414, Adeka Optomer N 1717 (ADEKA Corporation), Esacure 1001 M ( Lamberti), JP-B-59-1281, JP-B-61-9621 and triazines described in JP-A-60-60104. Conductors, organic peroxides described in JP-A-59-1504 and JP-A-61-243807, JP-B-43-23684, JP-B-44-6413, JP-B-47-1604 and US Pat. No. 3,567,453, diazonium compound, US Pat. No. 2,848,328, US Pat. No. 2,852,379 and US Pat. No. 2,940,853 described in JP-B-36-22062, JP-B-37- Ortho-quinonediazides described in JP-A- 13109, JP-B-38-18015 and JP-B-45-9610, JP-B-55-39162, JP-A-59-140203 and "Macromoleculs (MACROM OL ECULES) 10, page 1307 (1977)). Various onium compounds including a donium compound, an azo compound described in JP-A-59-142205, JP-A-1-54440, EP109851, EP-126712, Journal No. 30, pp. 174 (1986), titanocenes described in JP-A-61-151197, “coordination chemistry”, J. IMAG. SCI. Transition metal complexes containing transition metals such as ruthenium described in "COORDINATION CHEMISTRY REVIEW", vol. 84, p. 85-277 (1988) and JP-A-2-182701, JP-A-3-209477. Patent Document 1: Aluminate complex described in Japanese Patent Application Laid-Open No. 2-157760; 2, 4, 5-triarylimidazole dimers described in JP-A-60-202437, carbon tetrabromide, organic halogen compounds described in JP-A-59-107344, JP-A-5. Sulfonium complexes or oxosulfonium complexes described in JP-A-255347; amino ketone compounds described in JP-A-54-99185, JP-A-63-264560 and JP-A-10-29977; JP-A-2001-264530; JP 2001-216176 A, JP-A 2000-80068 A, JP-A 2001-233842 A, JP-A-2004-534797, JP-A-2006-342166, JP-A 2008-094770, JP-A 2009-40762, and JP-A-2009-40762. Open 2010-15025, JP-A-2010-1 9279, JP-A-2010-189280, JP-A-2010-526846, JP-A-2010-527338, JP-A-2010-527339, USP 3558309 (1971), USP 4202697 (1980) and JP-A-61- The oxime ester compound etc. of 24558 gazette are mentioned.

  In addition, it is possible to use a hydrogen abstraction type radical initiator as the photopolymerization initiator, and specific examples thereof include aromatic ketones such as acetophenone, benzophenone, benzyl, Michler's ketone, thioxanthone, or anthraquinone and the like. Not limited to these. These compounds are generally used in the art in combination with tertiary amines, and specifically, trimethylamine, triethylamine, tripropylamine, tributylamine, N-methyldiethanolamine, p-dimethylaminophenylalkyl Esters and the like may be mentioned, but not limited thereto.

  Moreover, it is also possible to use a photobase generator, a photoacid generator, etc. as a photoinitiator. One of these may be used alone, or two or more may be used in an arbitrary ratio.

The photobase generator is not particularly limited, but, for example, various compounds that form a primary amine, a secondary amine or a tertiary amine, such as cobalt amine complex, o-acyloximes, carbamic acid derivatives, Formamide derivatives, sulfonamides (eg, N-cyclohexyl-4-methylphenylsulfonamide etc.), quaternary ammonium salts, tosylamines, carbamates (eg, 2-nitrobenzyl carbamate, 2,5-dinitrobenzyl cyclohexyl carbamate, Examples include 1,1-dimethyl-2-phenylethyl-N-isopropyl carbamate and the like, amine imide compounds (see JP-A-2003-35949), compounds having an amidine structure, α-aminoacetophenone and the like. The photobase generators 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 (such as diphenyldisulfone), benzoin tosylate, etc.] and Lewis acid salts (triphenylsulfone) Arm hexafluoroantimonate _{^{(Ph) 3S + SbF 6 -}} , triphenylsulfonium hexafluorophosphate _{^{(Ph) 3 S + PF 6}} -, triphenylsulfonium methanesulfonyl _{^{(Ph) 3 S + CH 3}} SO 3 -, diphenyliodonium hexafluoro Phosphate etc. can be used and Ph shows 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 singly 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 and compound contained in the active energy ray curable composition. It is. The use amount of these photopolymerization initiators is preferably 0.1 to 50 parts by weight, and more preferably 0.5 to 25 parts by weight in 100 parts by weight of the solid content of the active energy ray curable resin composition. Is more preferred.

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

  Furthermore, the active energy ray curable resin composition of the present invention can contain a sensitizer. As a sensitizer, for example, unsaturated ketones represented by chalcone derivatives and dibenzalacetone etc., 1,2-diketone derivatives represented by benzyl and camphorquinone etc., benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone Derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine dyes such as oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives , Azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives Body, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrylium derivative, tetraphilin derivative, anurene derivative, spiropyran derivative, Examples thereof include, but are not limited to, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, Michler's ketone derivatives, biimidazole derivatives and the like.

  Further, specific examples of the sensitizer include Shin Ogawara et al., "Dye Handbook" (1986, Kodansha), Shin Ohkawara et al., "Chemicals of functional dyes" (1981, CMC), Tada Ikemori Sensitizers described in Sanro et al., "Specially functional materials" (1988, CMC) can be mentioned, but the invention is not limited thereto. In addition, a sensitizer that absorbs light in the ultraviolet to near-infrared region can also be contained. The sensitizer may be used alone, or may contain two or more sensitizers in any ratio.

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

  In addition to the essential components of the active energy ray curable resin composition of the present invention described above, the coating properties at the time of producing the decorative sheet, and the characteristics required as the active energy ray curable resin composition for the decorative sheet A resin, a solvent, an organic filler, a thiol compound or the like may be added for the purpose of imparting.

  The active energy ray-curable resin composition of the present invention further comprises, depending on the purpose, dyes, organic and inorganic pigments, pigment dispersants, oxygen removing agents such as phosphines, phosphonates and phosphites, reducing agents, antifoggants, antifade agents Agents, antihalation agents, optical brighteners, surfactants, colorants, extenders, plasticizers, flame retardants, antioxidants, dye precursors, UV absorbers, antifoams, antifungal agents, antistatic agents, Magnetic substance, dispersing agent such as resin type dispersing agent, silane coupling agent, storage stabilizer such as quaternary ammonium chloride, plasticizer, surface tension adjusting agent, slipping agent, antiblocking agent, light stabilizer, leveling agent It may be used by mixing it with an antifoamer, an infrared absorber, a surfactant, a thixotropic agent, an antibacterial agent, fine particles such as silica, and other additives imparting various characteristics, a dilution solvent, and the like. There is no particular limitation on those types.

<Decoration sheet>
The decorative sheet of the present invention is not particularly limited as long as the cured film is formed using the active energy ray-curable resin composition of the present invention, and if necessary, an anchor layer, a picture layer, and the like on the substrate A layer is formed by freely combining with an adhesive layer, a release layer, an antistatic layer and the like. For example, although the decoration sheet of the present invention is not limited, a decoration sheet for lamination, a decoration sheet for transfer, etc. are mentioned preferably.

  The decorative sheet for laminate 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 on a substrate, and a picture layer and an adhesive layer are laminated on the other side. It is a decorating sheet and is decorated by sticking on the surface of a body to be decorated (plastic casing).

  The decorative sheet for transfer is a decorative sheet in which a release layer is formed on one side on a base material, and a transfer layer is laminated on the release layer. Here, the transfer layer is a layer formed by laminating the cured film using the active energy ray-curable resin composition of the present invention, the design layer, and the adhesive layer in this order, and further, if necessary, an anchor layer and antistatic It is possible to combine a layer, an ultraviolet absorbing layer, a low reflection layer, a near infrared blocking layer, an electromagnetic wave absorbing layer and the like, but the layer configuration in the decorative sheet of the present invention is not limited thereto.

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

  As the anchor layer, two-component cured urethane resin, thermosetting urethane resin, melamine based resin, cellulose ester based resin, chlorine containing rubber based resin, chlorine containing vinyl based resin, acrylic based resin, epoxy based resin, vinyl based copolymer Combined resin etc., gravure coating method, gravure offset method, kiss coating method, rod coating method, reverse gravure coating method, roll coating method, comma coating method, top coating method, die coating method, knife coating method, lip coating method, Laminating using known coating 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, ink jet printing, etc. it can.

  The above-mentioned pattern layer is a layer necessary for obtaining the desired design of the decorative sheet, and the pattern is not particularly limited. For example, grain, grain, grain, grain, geometric pattern, characters, The pattern which consists of a photograph, an illustration, etc. is mentioned, It is free also about the combination of the pattern. Moreover, it is also possible to perform metal vapor deposition on a part or whole surface other than being overpainted freely.

  As a method required to obtain a pattern, there may be mentioned a method of forming an ink comprising a suitable pigment, a colorant such as a dye, and a binder resin using a known printing method. Here, examples of the pinder resin include polyvinyl resins, polyester resins, polyacrylic resins, polyamide resins, polyvinyl acetal resins, cellulose resins, alkyd resins and the like, but are not limited thereto. Further, as a known printing method, 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, a lip coating Methods such as spray coating, spin coating, bar coating, slit coating, gravure printing, offset printing, screen printing, transfer printing, sublimation transfer printing, ink jet printing, etc., but are not limited thereto. .

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

  Any adhesive resin can be used without particular limitation as the adhesive layer, but acrylic resins, polystyrene resins, polyamide resins, indene resins, chlorinated polyolefin resins, chlorinated ethylene-vinyl acetate are preferable. A copolymer resin etc. are mentioned and it is also possible to use it in mixture of 1 or more types as needed. Moreover, it is more preferable to select suitably from a viewpoint of affinity with a resin molding.

  The release layer is a layer necessary to separate the transfer layer from the substrate, and is a melamine resin-based release agent, a silicone resin-based release agent, a fluorocarbon resin-based release agent, a cellulose resin-based release agent, urea Examples include resin-based mold release agents, polyolefin resin-based mold release agents, paraffin resin-based mold release agents, and acrylic resin-based mold release agents, but are not limited thereto. The above-mentioned mold release agent can be used by mixing arbitrarily 1 or more types as needed.

  The base material usable for the decorative sheet of the present invention is not particularly limited, and polycarbonate, polymethyl methacrylate, polyethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin Preferred are plastic materials such as AS resin, norbornene resin, vinyl resin and the like.

  The base material usable for the decorative sheet is more preferably a cast or non-stretching film from the plastic material, or a film or sheet shape by a biaxial stretching method, but is not limited to the production method. From the viewpoint of adhesion, the substrate surface may be coated with an undercoat paint such as corona discharge treatment or a primer.

  The thickness of the substrate is not particularly limited, and it is desirable to select the optimum thickness according to the molding method.

  As a method for producing a decorative sheet, after the active energy ray-curable resin composition of the present invention is deposited on a substrate so as to have a uniform and predetermined thick film, it is dried if necessary, Furthermore, it forms by performing photocrosslinking by irradiation of an active energy ray.

  As a film forming method, it is possible to use a known printing or coating method, 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, 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, the present invention is not limited thereto.

  As described in the description of the solvent which can be used for the active energy ray curable resin composition of the present invention, a solvent may be used from the viewpoint of coatability. However, since crosslinking by active energy radiation in the state where a large amount of solvent is contained in the coating may adversely affect the control of crosslinking, it is desirable to remove the coating to some extent by drying. The drying can be carried out by vacuum drying under reduced pressure using a vacuum dryer or the like, drying by baking using a convection oven (hot air dryer), an IR oven, a hot plate or the like, or a combination thereof. is there. It is preferable to select baking from the viewpoint of equipment cost and productivity, but it is more preferable to be carried out paying attention to the following conditions.

  The baking conditions (temperature and time) can be appropriately selected according to the boiling point and film thickness to be 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 The thermal crosslinking reaction of the crosslinkable group can proceed in the high temperature region of the above, so 150 ° C. or less is preferable. Further, the baking for a long time is also preferably 20 minutes or less because the thermal crosslinking reaction may proceed. If the thermal crosslinking reaction proceeds at the pre-baking time, it has an adverse effect on photocrosslinking due to active energy irradiation, and as a result the degree of crosslinking rises more than necessary, there is a possibility of impairing the extensibility, which is not preferable.

  The 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 more preferably 3 μm to 50 μm from the viewpoint of moldability and hard coatability.

  The active energy ray necessary for photocrosslinking the composition of the present invention is heat, ultraviolet ray, visible ray, near infrared ray, electron beam or the like. As a light source for application of active energy rays, a light source having a main wavelength of light emission in a wavelength range of 100 nm to 450 nm is preferable. Examples of light sources having a dominant wavelength of light emission 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, pulsed light emission Xenon lamp, deuterium lamp, fluorescent lamp, ND-YAG third harmonic laser, HE-CD laser, nitrogen laser, XE-Cl excimer laser, XE-F excimer laser, semiconductor pumped solid state laser, issue wavelength at 365 nm, 375 nm, 385 nm And various light sources such as LED lamp light sources. In the present specification, the definitions of ultraviolet light, visible light, near infrared light, etc. are as defined in Kubo Sogo et al., “Iwanami Rishi Dictionary 4th Edition” (1987, Iwanami).

  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 according to the above-mentioned action mechanism, it has moldability that can cope with various moldings. Furthermore, the decorative sheet of the present invention can obtain better hard coat properties by heat crosslinking of the cured film by heat at the time of molding. Thermal crosslinking can be sufficiently progressed by the heat applied during molding, but if a baking step is optionally added, a baking step may be added, the temperature at the baking step is preferably 80 ° C. or higher, and more preferably Preferably it is 100 degreeC or more.

As a molding method, it is molded by various methods such as vacuum molding, pressure molding, membrane press molding, in-mold molding, insert molding, insert molding, overlay vacuum molding and the like. In any case, the decorative sheet is stretched or bent in accordance with the shape of the body to be decorated (plastic casing) 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 in any way limit the scope of the present invention. In addition, each evaluation in the 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 using GPC (gel permeation chromatography) “GPC-8020” manufactured by Tosoh Corporation, using two columns of SHODEX KF-806L, one column of KF-804L, and one column of KF-802. Used tetrahydrofuran. The weight average molecular weight was calculated in terms of standard polystyrene.

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

The monomer (1) was obtained using the method described in Patent Publication No. 5977063.
Monomer (2) was prepared by reacting methyl α-allyloxymethyl acrylate and 2-methyl-1-butanol as raw materials according to the method described in Patent Publication 5591543.
Monomer (3) was prepared by reacting methyl α-allyloxymethyl acrylate and 1,3-pentanediol as raw materials according to the method described in Patent Publication 5591543.
The monomer (4) was obtained using the method described in Patent Publication No. 5977063.

About the monomer which comprises the structural unit (b) which has a hydroxyl group in a polymer (A), it shows below.
2-hydroxyethyl methacrylate (HEMA): "HEMA" manufactured by Nippon Shokubai Co., Ltd.
Glycerin monomethacrylate (GLM): "GLM" manufactured by NOF Corporation

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

<Method of producing resin (A)>
Preparation Example 1 Preparation of Resin (A-1)
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a gas introduction pipe, 90 parts by weight of methyl ethyl ketone as a solvent was charged, and the temperature was raised to 70 ° C. under a nitrogen atmosphere. Then, 50 parts by weight of 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 liquid which mixed the part previously was dripped over 2 hours. Further, after reacting for 1 hour at 70 ° C., adding 0.1 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) as a post-addition initiator and reacting for 1 hour, the addition rate of the monomer 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%.

(Preparation Examples 2 to 37; Preparation of Resin (A-2 to 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 described in Tables 2 to 4. The compounding 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 solid content of resin (A-1), 50 parts by weight of solid content 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 made by Lambarty, 160 parts by weight of methyl ethyl ketone as organic solvent (D), 160 parts by weight of propylene glycol monomethyl ether acetate, alumina as inorganic filler (C) (AEROXIDE AluC by Nippon Aerosil Co., Ltd.) An active energy ray-curable resin composition was obtained by adding 2.7 parts by weight and stirring using a disper.

(Examples 2 to 44, Comparative Examples 1 to 13)
Resin (A), active energy ray curable compound (B), inorganic filler (C) according to the preparation method of the active energy ray curable resin composition of Example 1 described above in the compounding ratio described in Tables 5 to 7 An active energy ray curable resin composition was obtained by blending

In addition, the abbreviation in Tables 5-7 is as follows.
PET-30: "KAYARAD PET-30" manufactured by Nippon Kayaku Co., Ltd. (trifunctional acrylate)
DPGDA: "DPGDA" (bifunctional acrylate) manufactured by Daicel Ornex
DPHA: "A-DPH" (6-functional acrylate) manufactured by Shin-Nakamura Chemical Co., Ltd.
DPCA-30: "KAYARAD DPCA-30" (6-functional acrylate) manufactured by Nippon Kayaku Co., Ltd.
UV-7650B: "purple light UV-7650B" (urethane acrylate oligomer) manufactured by Japan Synthetic Chemical Industries, Ltd.
UV-7550B: "purple light UV-7550B" (urethane acrylate oligomer) manufactured by Nippon Synthetic Chemical Co., Ltd.
UA-306I: "UA-306I" (urethane acrylate oligomer) manufactured by Kyoeisha Chemical Co., Ltd.
EBECRYL3500: "EBECRYL3500" (epoxy acrylate) manufactured by Daicel Ornex
V-5500: "UNIDIC V-5500" (epoxy acrylate) manufactured by DIC Corporation
8KX-012C: "Akrit 8KX-012C" (acrylic acrylate) manufactured by Taisei Fine Chemical Co., Ltd.
EBECRYL 1830: "EBECRYL 1830" (ester acrylate) manufactured by Daicel Ornex
ESACURE ONE: Lambarty "ESACUREONE" (photopolymerization initiator)
Irg184: "Irg184" (photopolymerization initiator) manufactured by BASF (old Ciba Japan)
Irg369: "Irg 369" (photopolymerization initiator) manufactured by BASF (old Ciba Japan)
TPO: "TPO" (photopolymerization initiator) manufactured by BASF (old Ciba Japan)
MEK: methyl ethyl ketone PGMAC: propylene glycol monomethyl ether acetate Alu C: Nippon Aerosil Co. "AEROXIDE AluC" (alumina)
AEROSIL 50: Nippon Aerosil "AEROSIL 50" (silica)
PCS-60: "PCS-60" manufactured by Nippon Denko Corporation (zirconia oxide)
MT-05: "MT-05" (Titanium oxide) manufactured by Tayca Corporation

The compositions obtained in Examples 1 to 44 and Comparative Examples 1 to 13 are coated on a PET substrate (thickness 100 μm: “Cosmo Shine A4100” manufactured by Toyobo Co., Ltd.) using a bar coater, The coated film having a film thickness of 5 μm was obtained by drying at 80 ° C. for 1 minute using a hot air drier. The coated film was cured under the following irradiation conditions to obtain a cured film 1. Then, the cured film 2 which assumed the coating-film state after heat shaping was obtained by performing heating for 10 minutes at 160 degreeC using a hot air dryer.
(In the case of ultraviolet radiation)
UV irradiation: a high-pressure mercury lamp 120W ^/ cm ² -400mJ ^/ cm 2
(When irradiating electron beam)
Electron beam irradiation: 125kV-30kGy

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

(Abrasion resistance test)
A # 750 steel wool was used for the cured film 1 and the cured film 2 and a load of 750 g / cm ² was applied for 10 cycles of abrasion, and then the presence or absence of a scratch was visually determined.
(Judgment criteria)
:: no scratch: 1: 1 · 2 scratches △: 3 or more scratches ×: multiple scratches 実 用 and 実 用 are practical levels.

The compositions obtained in Examples 1 to 44 and Comparative Examples 1 to 13 were coated on a polycarbonate substrate (thickness 1 mm: "Iupilon sheet NF-2000" manufactured by Mitsubishi Gas Chemical Co., Ltd.) using a bar coater. After processing, a coated film having a thickness of 5 μm was obtained by drying for 1 minute at 80 ° C. using a hot air drier. The coated film was cured by ultraviolet irradiation (integrated light quantity: 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, heating was performed at 160 ° C. for 10 minutes using a hot air drier to obtain a cured film 4 in which the coated film state after heat molding was assumed.

(Extensibility test)
An extensible 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 the JIS K6251-1 standard. The distance between the chucks is 4 cm and the width is 1 cm. A tensile test was conducted using "DZ-SX" manufactured by Shimadzu Corporation as a testing machine, and using the dumbbell piece.

  Stretching conditions: It was carried out at room temperature at a pulling speed of 100 mm / min.

Elongation Judgment: Based on 4 cm of the distance between chucks, the presence or absence of scratches and whitening of the coating film were confirmed when each was pulled to 4.0 cm corresponding to 100% of the original length.
(Judgment criteria)
:: no scratch: 1: 1 scratch is included △: 2 to 10 scratches are included ×: practical level is multiple scratches is 入 る and ◎.

(Chemical resistance test)
After cutting the cured films 3 and 4 together with the base material into 4 cm square, 30 mg of sunscreen cream ("UltraSheer, SPF # 55" manufactured by Neutrogena) is placed on the central part of the test piece, and then 3 cm 4 square A square-cut PET film (thickness 50 μm) was placed on top of it. The cream was stretched in a uniform circular shape (diameter 1.8 cm) by applying a load uniformly from the top of the PET film.

  Leave in a hot air drier (80 ° C, 20 hours) under the following conditions, allow to cool to room temperature, wash away the cream with tap water, and visually observe the appearance of the surface of the test specimen, to make it drug resistant Was judged.

Condition 1: The PET film was peeled off, and the test piece and the cream were released.
Condition 2: Without peeling off the PET film, the test piece is sandwiched by a 10 cm square glass substrate (thickness 5 mm), and a load of 500 g is applied from the top of the glass substrate (sealed state).

(Judgment criteria)
:: no change in appearance :: slight dripping marks :: slightly cloudy ×: whitening occurs (no transparency)
The 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, Ltd.) using a bar coater. The coated film was then dried for 1 minute at 80 ° C. using a hot air drier to obtain a coated film having a thickness of 5 μm using a belt conveyor type ultraviolet irradiation device (high-pressure mercury lamp 120 W / cm ² ). The coated sheet was irradiated with ultraviolet light (integrated light quantity: 400 mJ / cm ² ) at a conveyor speed of 10 m / min to obtain a decorated sheet.
Subsequently, the decorative sheet is subjected to setting in a vacuum forming machine ("300X" manufactured by Seimitsu Sangyo Co., Ltd.), and heated vacuum forming (heater) using a rectangular solid (65 mm long, 65 mm wide, 30 mm high) mold. A temperature of 300 ° C. and an estimated substrate surface temperature of 200 ° C.) were carried out. The appearance was observed, and it was confirmed whether or not there was a crack or a crack of the decorative sheet accompanying molding.

(Judgment criteria)
:: no cracks or cracks, transparent :: no cracks or cracks, but some changes in appearance such as cloudiness △: partial cracks or cracks confirmed ×: overall cracks or cracks checked Practical level Are 〇 and ◎.

<Temporal stability test>
In order to evaluate the dispersion stability of the active energy ray curable resin composition of the present invention, each active energy ray curable resin composition of Examples and Comparative Examples was left to stand in a temperature-controlled room at 50 ° C. for 30 days. The precipitation condition 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 ○: No precipitation occurs after standing, but a difference in concentration of the inorganic filler is confirmed in the upper layer and the lower layer Δ: Precipitation occurs after being left, but it is stirred using a disper , Inorganic fillers redisperse.
X: Precipitation occurs after standing, but it does not redisperse even if it is stirred using a disper.
The practical levels are 〇 and ◎.

<Base material adhesion test>
The adhesion of the cured film 3 and the cured film 4 immediately after preparation was evaluated according to the test method described in JIS K 5600-5-6. Specifically, 100 square cuts were made using a cutter guide with a gap of 1 mm. Next, a cellophane adhesive tape of 30 mm width is attached to the cut surface on the square, and after 30 cycles of a 5.0 kg / cm 2 roller is completely attached, the film is rapidly peeled off at a peeling angle of 90 degrees. The peeled surface was observed, and ranked according to the peeled area (the ratio of peeled squares) according to the following evaluation criteria to evaluate the adhesion.
碁: The number of remaining grid squares is 100 and the cured film does not change before and after peeling of the cellophane adhesive tape ○: The number of remaining grid squares is 100, but the cured film at the intersection of cuts after peeling of the cellophane adhesive tape碁: There are 100 remaining grids, but there is a grid with chips at the end after peeling off the cellophane adhesive tape, and the cured film changes before and after the test .
×: Remaining number of the grid of 99 or less The practical level is 〇 and ◎.

Claims (7)

An active energy ray curable composition comprising 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 comprising 25 to 99% by weight of a structural unit (a) having an aliphatic cyclic structure in the main chain and 1 to 75% by weight of a structural unit (b) having a hydroxyl group An active energy ray curable resin composition characterized by the above. 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 a structure represented by the following general formula (1).
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, 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 each independently a carbon number A methylene group optionally having 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, or a methylene group optionally having an alkyl group having 1 to 4 carbon atoms , An imino group, a carbonyl group, an oxygen atom or a sulfur atom, and at least one of X, Y and Z is an oxygen atom, a sulfur atom or an imino group not adjacent to each other) The active energy ray curable resin composition according to claim 1, wherein the structural unit (a) having an aliphatic cyclic structure in its 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, or a substituted or unsubstituted aryl group, R ₇ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a carboxyl group , Ester 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 weight average molecular weight of resin (A) is 500 or more and less than 100,000, The active energy ray curable composition in any one of Claims 1-3 characterized by the above-mentioned.   The active energy ray-curable resin composition according to any one of claims 1 to 4, wherein the inorganic filler (C) is at least one selected from the group consisting of alumina, silica, titanium oxide, and zirconium oxide. object.   The decorative sheet which has a cured film formed from the active energy ray curable resin composition in any one of Claims 1-5 on a base material. A molded article formed from the decorative sheet according to claim 6.