Active energy ray curable resin composition, cured product and article

Abstract

To provide: an active energy ray-curable resin composition which can form a curd product excellent in heat resistance, extensibility and elasticity; a cured product of the active energy ray-curable resin composition; and an article having a cured coating comprising the cured product.SOLUTION: An active energy ray-curable resin composition comprises an imidazole compound (A) represented by the general formula (1) in the figure, and a photoinitiator (B). The invention also employs a cured product of the active energy ray-curable resin composition, and an article.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to an active energy ray-curable resin composition capable of forming a cured product having excellent heat resistance, elongation and elasticity, and to a cured product and article of the active energy ray-curable resin composition. [Background technology]

[0002] In recent years, curable compositions such as active energy ray curable compositions that can be cured by active energy rays such as ultraviolet rays and heat curable compositions that can be cured by heat have been widely used in the fields of inks, paints, coating agents, adhesives, optical members, etc. In particular, for the above-mentioned coating agent applications, it is generally required that the coating agent can impart design to the surfaces of various substrates, has excellent curability, and can form a coating film that can prevent deterioration of the substrate surface. Furthermore, in recent years, the industrial world has been demanding a material that can form a cured coating film that has not only curability but also performance such as heat resistance at a level that can protect the coated object even under various temperature environments.

[0003] Known techniques for improving the heat resistance of cured coating films include curable compositions containing di(meth)acrylate represented by the following general formula (1) (see, for example, Patent Document 1).

[0004] [ka] [In formula (1), R1 represents a hydrogen atom or a methyl group.]

[0005] However, the heat resistance of the curable composition in the cured coating film is insufficient, and the elongation and elasticity do not satisfy the increasingly high performance requirements of today.

[0006] Therefore, there has been a demand for materials having excellent heat resistance, elongation and elasticity. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] JP 2005-314320 A Summary of the Invention [Problem to be solved by the invention]

[0008] The problem to be solved by the present invention is to provide an active energy ray-curable resin composition capable of forming a cured product having excellent heat resistance, elongation and elasticity, and a cured product and article of the active energy ray-curable resin composition. [Means for solving the problem]

[0009] As a result of intensive research to solve the above problems, the present inventors have found that the above problems can be solved by using an active energy ray-curable resin composition containing an acid group-containing (meth)acrylate resin and a specific imidazole compound, and have completed the present invention.

[0010] That is, the present invention relates to an active energy ray-curable resin composition characterized by containing an imidazole compound (A) represented by the following general formula (1) and a photopolymerization initiator (B), and to a cured product and article of the active energy ray-curable resin composition.

[0011] [ka] [In formula (1), Ar 1 represents an aromatic hydrocarbon group having 6 to 20 carbon atoms. Ar 2 represents an aromatic hydrocarbon group having 6 to 20 carbon atoms. Ar 3 represents a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms. L 1 represents -O-, -COO- or -OCO-. L 2 represents a single bond or -O-. R1 represents a polyoxyalkylene group or a divalent hydrocarbon group having 1 to 50 carbon atoms which may have a substituent, and -CH2- contained in the hydrocarbon group may be replaced by -O- and / or -CO-. R a1 represents a reactive group. Effect of the Invention

[0012] The active energy ray-curable resin composition of the present invention can form a cured product having excellent heat resistance, elongation and elasticity, and can therefore be suitably used as a coating agent or adhesive. In the present invention, "excellent elasticity" refers to high elasticity. [Brief description of the drawings]

[0013] [Figure 1] FIG. 1 shows the 1H-NMR spectrum of the imidazole compound (1). [Diagram 2] FIG. 2 shows the 13C-NMR spectrum of the imidazole compound (1). [Diagram 3] FIG. 3 shows the MALDI-MS spectrum of the imidazole compound (1). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] The active energy ray-curable resin composition of the present invention is characterized by containing an imidazole compound (A) represented by general formula (1) and a photopolymerization initiator (B).

[0015] In the present invention, "(meth)acrylate" means acrylate and / or methacrylate. "(meth)acryloyl" means acryloyl and / or methacryloyl. "(meth)acrylic" means acrylic and / or methacrylic.

[0016] As the imidazole compound (A), a compound represented by the following general formula (1) is used.

[0017] [ka]

[0018] [In formula (1), Ar 1 represents an aromatic hydrocarbon group having 6 to 20 carbon atoms. Ar 2 represents an aromatic hydrocarbon group having 6 to 20 carbon atoms. Ar 3 represents a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms. L 1 represents -O-, -COO- or -OCO-. L 2 represents a single bond or -O-. R 1 represents a polyoxyalkylene group or a divalent hydrocarbon group having 1 to 50 carbon atoms which may have a substituent, and -CH2- contained in the hydrocarbon group may be replaced by -O- and / or -CO-. R a1 represents a reactive group.

[0019] Ar in formula (1) 1 , Ar 2 Examples of the aromatic hydrocarbon group represented by the formula (I) include a phenyl group, a naphthyl group, an anthracenyl group, etc. These aromatic hydrocarbon groups may have a substituent, and examples of the substituent include an alkyl group having 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms), such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, etc.; an aromatic hydrocarbon group having 6 to 10 carbon atoms, such as a phenyl group, a naphthyl group; a halogen atom, such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.; and a hydroxy group.

[0020] Ar in formula (1) 1 , Ar 2 The aromatic hydrocarbon group represented by the following formula (I) has 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms (including the carbon atoms of the substituent if the group has a substituent).

[0021] Ar in formula (1) 3 Examples of the aromatic hydrocarbon group represented by the formula (I) include a phenylene group, a naphthylene group, and an anthracenediyl group. These aromatic hydrocarbon groups may have a substituent, and the substituent may be any of the above-mentioned Ar 1 , Ar 2 The substituents which may be possessed by the group include the same as those exemplified above.

[0022] Ar in formula (1) 3 The aromatic hydrocarbon group represented by the following formula (I) has 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms (including the carbon atoms of the substituent if the group has a substituent).

[0023] L in formula (1) 1 is any one of -O-, -COO-, and -OCO-, and is preferably -O- or -COO-. In addition, -O-, -COO-, and -OCO- are the bonds on the left side of Ar 3 is assumed to be bound to

[0024] L in formula (1) 2 is either a single bond or -O-.

[0025] R in formula (1) 1 Examples of the polyoxyalkylene group represented by the formula (1) include groups having a repeating unit consisting of a combination of an alkylene group having 2 to 5 carbon atoms, such as a polyoxyethylene group, a polyoxypropylene group, or a polyoxybutylene group, and -O-. The number of repeating units is preferably in the range of 2 to 50, more preferably in the range of 2 to 20, and particularly preferably in the range of 2 to 10.

[0026] R in formula (1) 1Examples of the divalent hydrocarbon group represented by the formula (I) include divalent aliphatic hydrocarbon groups having 1 to 50 carbon atoms, divalent alicyclic hydrocarbon groups having 3 to 20 carbon atoms, divalent aromatic hydrocarbon groups having 6 to 20 carbon atoms, and groups having 4 to 50 carbon atoms which are a combination of two or more of the above divalent aliphatic hydrocarbon groups, divalent alicyclic hydrocarbon groups, and divalent aromatic hydrocarbon groups.

[0027] Examples of the aliphatic hydrocarbon group include saturated or unsaturated aliphatic hydrocarbon groups, and preferred are alkanediyl groups such as methylene, ethylene, propanediyl, butanediyl, pentanediyl, hexanediyl, heptanediyl, octanediyl, nonanediyl, decanediyl, undecanediyl, dodecanediyl, tridecanediyl, tetradecanediyl, pentadecanediyl, hexadecanediyl, heptadecanediyl, octadecanediyl, nonadecanediyl, and eicosanediyl. The aliphatic hydrocarbon group may be linear or branched.

[0028] R in formula (1) 1 may be a group in which one or more -CH2- contained in the aliphatic hydrocarbon group are replaced with -O- and / or -CO-. In addition, two or more -CH2- may be replaced with -O- and / or -CO- to form an ester bond (-OCO-, -COO-) or a carbonate bond (-OCOO-). The number of -CH2- replaced with -O- and / or -CO- in the aliphatic hydrocarbon group may be, for example, 1 or more, 2 or more, or 10 or less, 5 or less. However, it is preferable that adjacent -CH2- are not simultaneously replaced with -O-.

[0029] The aliphatic hydrocarbon group may include, as a substituent, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; a hydroxy group; 2 -L 3 -R a2 A group represented by the following formula may be bonded.

[0030] The aliphatic hydrocarbon group preferably has 1 to 50 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms.

[0031] Examples of the alicyclic hydrocarbon group include saturated or unsaturated alicyclic hydrocarbon groups. Preferred are monocyclic alicyclic hydrocarbon groups such as a cyclopropanediyl group, a cyclobutanediyl group, a cyclopentanediyl group, a cyclohexanediyl group, a cyclooctanediyl group, a cyclononanediyl group, and a cyclodecanediyl group; and polycyclic alicyclic hydrocarbon groups such as a bicyclo[1.1.0]butanediyl group, a tricyclo[2.2.1.0]heptanediyl group, a bicyclo[3.2.1]octanediyl group, a bicyclo[2.2.2.]octanediyl group, an adamantanediyl group, a bicyclo[4.3.2]undecanediyl group, and a tricyclo[5.3.1.1]dodecanediyl group.

[0032] The alicyclic hydrocarbon group may, as a substituent, be an alkyl group having 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms), such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, or a decyl group; an aromatic hydrocarbon group having 6 to 10 carbon atoms, such as a phenyl group or a naphthyl group; a halogen atom, such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; a hydroxy group; 2 -R a A group represented by the following formula may be bonded.

[0033] The alicyclic hydrocarbon group may include, as a substituent, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; a hydroxy group; 2 -L 3 -R a2 A group represented by the following formula may be bonded.

[0034] The alicyclic hydrocarbon group preferably has 3-50 carbon atoms (including the carbon atoms of the substituent if the group has a substituent), more preferably 5-20 carbon atoms, and particularly preferably 3-10 carbon atoms.

[0035] The aromatic hydrocarbon group may be monocyclic or polycyclic, and examples thereof include a phenylene group, a naphthylene group, an anthracenediyl group, and a fluorenediyl group.

[0036] The aromatic hydrocarbon group may, as a substituent, be an alkyl group having 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms), such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, or a decyl group; an aromatic hydrocarbon group having 6 to 10 carbon atoms, such as a phenyl group or a naphthyl group; a halogen atom, such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; a hydroxyl group; -R 2 -R a A group represented by the following formula may be bonded.

[0037] The aromatic hydrocarbon group may include, as a substituent, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; a hydroxy group; 2 -L 3 -R a A group represented by the following formula may be bonded.

[0038] The aromatic hydrocarbon group preferably has 6-50 carbon atoms (including the carbon atoms of the substituent if the group has a substituent), more preferably 6-20 carbon atoms, and particularly preferably 6-10 carbon atoms.

[0039] As the group combining two or more of the divalent aliphatic hydrocarbon group, the divalent alicyclic hydrocarbon group, and the divalent aromatic hydrocarbon group, a divalent group combining an aliphatic hydrocarbon group and an alicyclic hydrocarbon group, or a divalent group combining an aliphatic hydrocarbon group and an aromatic hydrocarbon group is preferred.

[0040] The group formed by combining two or more of the aliphatic hydrocarbon group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group preferably has 4-50 carbon atoms, more preferably 4-20 carbon atoms, and particularly preferably 4-10 carbon atoms.

[0041] R 1 The hydrocarbon group represented by the formula (I) may have as a substituent -R2 -L 3 -R a2 In the group represented by the formula 2 represents a polyoxyalkylene group or a divalent hydrocarbon group having 1 to 50 carbon atoms, in which -CH2- contained in the hydrocarbon group may be replaced by -O- and / or -CO-, and a hydrogen atom contained in the hydrocarbon group may be replaced by a hydroxy group. 3 R represents a single bond or -O-. a2 represents a reactive group.

[0042] R 2 Examples of the polyoxyalkylene group represented by the formula: 1 Examples of the polyoxyalkylene group represented by the following formula include the same groups as those exemplified above.

[0043] R 2 As the hydrocarbon group represented by the formula (including a group in which -CH- in the hydrocarbon group is replaced by -O- and / or -CO-), R 1 Examples of the hydrocarbon group represented by the formula (I) include the same groups as those exemplified above.

[0044] R 2 Examples of the substituent that the hydrocarbon group represented by the following formula may have include a hydroxy group.

[0045] L 3 represents a single bond or -O-.

[0046] R a1 , R a2 Examples of the reactive group represented by the formula (I) include groups capable of forming a polymer main chain by polycondensation reaction, and specific examples thereof include groups containing an ethylenic double bond such as a vinyl group, a (meth)acryloyl group, or a (meth)allyl group; and groups containing a cyclic ether such as an oxetanyl group. The group containing a cyclic ether may have an aliphatic hydrocarbon group having 1 to 5 carbon atoms as a substituent, such as a methyl group, an ethyl group, or a propyl group. Among these, R a1 , R a2The reactive group represented by the formula (I) is preferably a vinyl group, a (meth)acryloyl group, or an oxetanyl group which may have a substituent.

[0047] Examples of the imidazole compound (A) represented by the general formula (1) include compounds represented by the following formulas (1-1) to (1-68): In the formula, n represents an integer of 2 to 10.

[0048] [ka]

[0049] [ka]

[0050] [ka]

[0051] [ka]

[0052] [ka]

[0053] The method for producing the imidazole compound (A) can be, for example, the method represented by the following scheme. Route 1: Compound (a-1) is reacted with compound (b) to obtain compound (c) (step 1), and compound (d) is reacted with compound (e) to produce compound (c) (step 2); Route 2: It can also be produced by reacting compound (a-2) with compound (d) and compound (e) (step 3), and then reacting compound (g-1) or compound (g-2) (step 4), Route 3: Compound (a-1) can also be produced by reacting compound (h) with compound (a-1) to obtain compound (i) (step 5), hydrolyzing the ester bond of compound (i) to obtain compound (j) (step 6), reacting compound (d) with compound (e) to obtain compound (k) (step 7), and then further reacting with compound (l).

[0054] [ka]

[0055] [In the above scheme, Ar 1 , Ar 2 , Ar 3 , L 1 , L 2 , R 1 , R a1 is synonymous with the above. A 1 represents a heterocyclic group containing an oxygen atom. R 3 represents a polyoxyalkylene group or a hydrocarbon group having 1 to 47 carbon atoms, and -CH2- contained in the hydrocarbon group may be replaced by -O- and / or -CO-. R 4 represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms. X 1 , X 2 each independently represents a halogen atom.

[0056] A 1 The heterocyclic group containing an oxygen atom represented by the formula (I) may be a monocyclic or polycyclic group, and in the case of a polycyclic group, a plurality of monocyclic heterocyclic groups may be bonded to each other by a covalent bond, or a bridged ring may be formed. 1 Examples of the heterocyclic group containing an oxygen atom represented by the formula (I) include cyclic ether groups such as an oxiranyl group and an oxetanyl group; and epoxycycloalkyl groups such as an epoxycyclohexyl group and an epoxycyclopentyl group.

[0057] R 3 The oxyalkylene group represented by the formula:1 The number of repeating units of the oxyalkylene is preferably in the range of 2 to 49, more preferably in the range of 2 to 19, and particularly preferably in the range of 2 to 9.

[0058] R 3 The hydrocarbon group represented by R 1 Among the groups described above as the hydrocarbon group represented by the formula (R), a group having 1 to 47 carbon atoms can be mentioned. 3 The aliphatic hydrocarbon group represented by the formula (I) may contain, as a substituent, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; a hydroxy group; 2 -L 3 -R a2 A group represented by the following formula may be bonded to the ring. 3 The aliphatic hydrocarbon group represented by the following formula (I) preferably has 1 to 47 carbon atoms, more preferably 1 to 17 carbon atoms, and particularly preferably 1 to 7 carbon atoms.

[0059] R 3 The alicyclic hydrocarbon group represented by the formula (I) may contain, as a substituent, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; a hydroxy group; 2 -L 3 -R a2 A group represented by the following formula may be bonded to the ring. 3 The alicyclic hydrocarbon group represented by the following formula (I) preferably has 3 to 47 carbon atoms, more preferably 3 to 17 carbon atoms, and particularly preferably 3 to 7 carbon atoms.

[0060] R 3 The aromatic hydrocarbon group represented by the formula (I) may contain, as a substituent, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; a hydroxy group; 2 -L 3 -R a2 A group represented by the following formula may be bonded to the ring. 3 The aromatic hydrocarbon group represented by the following formula (I) preferably has 6 to 47 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 10 carbon atoms.

[0061] R 3The number of carbon atoms in the group consisting of two or more of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group represented by the formula (I) is preferably in the range of 4 to 47, more preferably in the range of 4 to 17, and particularly preferably in the range of 4 to 7.

[0062] R 4 Examples of the aliphatic hydrocarbon group represented by R include a methyl group, an ethyl group, a butyl group, and a pentyl group. 4 The aliphatic hydrocarbon group represented by the following formula (I) preferably has 1 to 5 carbon atoms, and more preferably has 1 to 3 carbon atoms.

[0063] X 1 , X 2 Examples of the halogen atom represented by the formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, a chlorine atom is preferred.

[0064] Each step will be described below.

[0065] Regarding steps 1 and 5 In steps 1 and 5, compound (a-2) is reacted with compound (b) or compound (h) to obtain compound (c) or compound (i).

[0066] During the reaction, a tertiary organic phosphorus compound such as triphenylphosphine and an azodicarboxylate such as diethyl azodicarboxylate or diisopropyl azodicarboxylate are allowed to coexist as catalysts.

[0067] As the reaction solvent, an ether solvent such as tetrahydrofuran can be used.

[0068] Regarding steps 2, 3, and 7 In steps 2, 3, and 7, compound (a-2), compound (c), or compound (j) is reacted with compound (d) and compound (e) to form an imidazole ring, thereby obtaining compound (f), imidazole compound (A) represented by general formula (1), or compound (k), respectively.

[0069] The reaction is carried out in the presence of a catalyst such as 1,4-diazabicyclo[2.2.2]octane.

[0070] As the reaction solvent, in steps 2 and 7, an alcohol solvent such as methanol, ethanol, isopropyl alcohol, or butanol can be used, and in step 3, glacial acetic acid or the like can be used.

[0071] About step 4 In step 4, compound (f) is reacted with compound (g-1) or compound (g-2) to react the carboxy group of compound (f) with the hydroxyl group of compound (g-1), or the carboxy group of compound (f) with the cyclic ether of compound (g-2), thereby obtaining imidazole compound (A) represented by general formula (1).

[0072] During the reaction, a catalyst is allowed to coexist. When reacting with compound (g-1), a tertiary organic phosphorus compound such as triphenylphosphine and an azodicarboxylate such as diethyl azodicarboxylate or diisopropyl azodicarboxylate are used as catalysts. As the reaction solvent, an amide solvent such as dimethylformamide or dimethylacetamide can be used.

[0073] In addition, when reacting with compound (g-2), a catalyst such as tetrabutylammonium chloride can be used. As the reaction solvent, an amide solvent such as dimethylformamide can be used.

[0074] About step 6 In step 6, the ester bond of compound (i) is hydrolyzed to give compound (j) represented by general formula (1).

[0075] The reaction may be carried out in the presence of an alkali catalyst such as potassium hydroxide, etc. As the reaction solvent, an alcohol solvent such as ethanol, etc. may be used.

[0076] About step 8 In step 8, the compound (k) is reacted with the compound (l) to obtain the imidazole compound (A) represented by the general formula (1).

[0077] In the reaction, an amine catalyst such as triethanolamine can be used, and an ether solvent such as tetrahydrofuran can be used as the reaction solvent.

[0078] As the imidazole compound (A), a dimer can also be used.

[0079] The dimer includes, for example, a compound represented by the following formula (1-69).

[0080] [ka]

[0081] Examples of the photopolymerization initiator (B) include photoradical polymerization initiators such as 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2'-dimethoxy-1,2-diphenylethan-1-one, diphenyl(2,4,6-trimethoxybenzoyl)phosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone.

[0082] Commercially available products of the photopolymerization initiator (B) include, for example, "Omnirad 1173", "Omnirad 184", "Omnirad 127", "Omnirad 2959", "Omnirad 369", "Omnirad 379", "Omnirad 907", "Omnirad 4265", "Omnirad 1000", "Omnirad 651", "Omnirad TPO", "Omnirad 819", "Omnirad 2022", "Omnirad 2100", "Omnirad 754", "Omnirad 784", "Omnirad 500", and "Omnirad 81" (manufactured by IGM Resins); "KAYACURE DETX", "KAYACURE MBP", "KAYACURE DMBI", "KAYACURE EPA", and "KAYACURE OA" (manufactured by Nippon Kayaku Co., Ltd.); "Vicure 10", "Vicure Examples of the photopolymerization initiator (B) include "Stoffa Chemical Co., Ltd.," "Trigonal P1" (Akzo Nobel Co., Ltd.), "SANDORAY 1000" (SANDOZ Co., Ltd.), "DEAP" (Upjohn Chemical Co., Ltd.), "Quantacure PDO," "Quantacure ITX," "Quantacure EPD" (Ward Blenkinsop Co., Ltd.), and "Runtecure 1104" (Runtec Co., Ltd.). These photopolymerization initiators (B) can be used alone or in combination of two or more kinds.

[0083] The amount of the photopolymerization initiator (B) added is, for example, preferably in the range of 0.05 to 15 mass %, and more preferably in the range of 0.1 to 10 mass %, of the total of the components other than the solvent of the active energy ray-curable resin composition.

[0084] The method for producing the active energy ray curable resin composition of the present invention is not particularly limited, and may be produced by any method. For example, the imidazole compound (A) and each compounding component including the photopolymerization initiator may be mixed to produce the composition. The mixing method is not particularly limited, and a paint shaker, a disperser, a roll mill, a bead mill, a ball mill, an attritor, a sand mill, a bead mill, etc. may be used.

[0085] The active energy ray-curable resin composition of the present invention may contain other components in addition to the imidazole compound (A) and the photopolymerization initiator (B). Examples of the other components include various (meth)acrylate compounds (C).

[0086] Examples of the (meth)acrylate compound (C) include aliphatic mono(meth)acrylate compounds such as methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, butyl(meth)acrylate, pentyl(meth)acrylate, hexyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, and octyl(meth)acrylate; and alicyclic mono(meth)acrylates such as cyclohexyl(meth)acrylate, isobornyl(meth)acrylate, and adamantyl mono(meth)acrylate. Compounds; heterocyclic mono(meth)acrylate compounds such as glycidyl (meth)acrylate, tetrahydrofurfuryl acrylate, etc.; benzyl (meth)acrylate, phenyl (meth)acrylate, phenylbenzyl (meth)acrylate, phenoxy (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxyethoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenoxybenzyl (meth)acrylate, phenylphenoxyethyl (meth)acrylate, etc. Mono(meth)acrylate compounds such as the aromatic mono(meth)acrylate compounds of the above: (poly)oxyalkylene-modified mono(meth)acrylate compounds in which a polyoxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the above-mentioned various mono(meth)acrylate compounds; lactone-modified mono(meth)acrylate compounds in which a (poly)lactone structure has been introduced into the molecular structure of the above-mentioned various mono(meth)acrylate compounds; ethylene glycol di(meth)acrylate, Aliphatic di(meth)acrylate compounds such as propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate; alicyclic di(meth)acrylate compounds such as 1,4-cyclohexanedimethanol di(meth)acrylate, norbornane di(meth)acrylate, norbornane dimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate;Aromatic di(meth)acrylate compounds such as biphenol di(meth)acrylate and bisphenol di(meth)acrylate; polyoxyalkylene-modified di(meth)acrylate compounds in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the various di(meth)acrylate compounds; lactone-modified di(meth)acrylate compounds in which a (poly)lactone structure has been introduced into the molecular structure of the various di(meth)acrylate compounds; aliphatic tri(meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate and glycerin tri(meth)acrylate; (poly)oxyalkylene chains in which a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the aliphatic tri(meth)acrylate compounds Examples of the alkylene-modified tri(meth)acrylate compound include: a lactone-modified tri(meth)acrylate compound obtained by introducing a (poly)lactone structure into the molecular structure of the aliphatic tri(meth)acrylate compound; aliphatic poly(meth)acrylate compounds having 4 or more functional groups, such as pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; aliphatic poly(meth)acrylate compounds having 4 or more functional groups, such as (poly)oxyalkylene chains, such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains, obtained by introducing a (poly)oxyalkylene chain into the molecular structure of the aliphatic poly(meth)acrylate compound; and a lactone-modified poly(meth)acrylate compound having 4 or more functional groups, such as (poly)lactone structure into the molecular structure of the aliphatic poly(meth)acrylate compound.

[0087] As the (meth)acrylate compound (C), a resin having a polymerizable unsaturated group can also be used.

[0088] The resin having a polymerizable unsaturated group may be any resin having a polymerizable unsaturated group in the resin, and examples thereof include an epoxy resin having a polymerizable unsaturated group, a urethane resin having a polymerizable unsaturated group, an acrylic resin having a polymerizable unsaturated group, an amide-imide resin having a polymerizable unsaturated group, an acrylamide resin having a polymerizable unsaturated group, and an ester resin having a polymerizable unsaturated group.

[0089] Examples of the epoxy resin having a polymerizable unsaturated group include an epoxy (meth)acrylate resin obtained by reacting an epoxy resin with an unsaturated monobasic acid and, if necessary, with a polybasic acid anhydride; and a urethane group-containing epoxy (meth)acrylate resin obtained by reacting an epoxy resin, an unsaturated monobasic acid, a polyisocyanate compound, and a (meth)acrylate compound having a hydroxyl group and, if necessary, with a polybasic acid anhydride.

[0090] Examples of the epoxy resin include bisphenol type epoxy resin, phenylene ether type epoxy resin, naphthalene type epoxy resin, naphthylene ether type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, biphenyl aralkyl type epoxy resin, fluorene type epoxy resin, xanthene type epoxy resin, dihydroxybenzene type epoxy resin, trihydroxybenzene type epoxy resin, oxazolidone type epoxy resin, etc. These epoxy resins can be used alone or in combination of two or more.

[0091] Examples of the bisphenol type epoxy resin include bisphenol A type epoxy resin, bisphenol AP type epoxy resin, bisphenol B type epoxy resin, bisphenol BP type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin.

[0092] Examples of the hydrogenated bisphenol type epoxy resin include hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol B type epoxy resin, hydrogenated bisphenol E type epoxy resin, hydrogenated bisphenol F type epoxy resin, and hydrogenated bisphenol S type epoxy resin.

[0093] Examples of the biphenol type epoxy resin include 4,4'-biphenol type epoxy resin, 2,2'-biphenol type epoxy resin, tetramethyl-4,4'-biphenol type epoxy resin, and tetramethyl-2,2'-biphenol type epoxy resin.

[0094] Examples of the hydrogenated biphenol type epoxy resin include hydrogenated 4,4'-biphenol type epoxy resin, hydrogenated 2,2'-biphenol type epoxy resin, hydrogenated tetramethyl-4,4'-biphenol type epoxy resin, and hydrogenated tetramethyl-2,2'-biphenol type epoxy resin.

[0095] Examples of the unsaturated monobasic acid include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, α-cyanocinnamic acid, β-styrylacrylic acid, and β-furfurylacrylic acid. Esters, acid halides, and acid anhydrides of the unsaturated monobasic acids can also be used. Furthermore, compounds represented by the following structural formula (1) can also be used.

[0096] [ka] [In formula (1), X represents an alkylene chain having 1 to 10 carbon atoms, a polyoxyalkylene chain, a (poly)ester chain, an aromatic hydrocarbon chain, or a (poly)carbonate chain, and may have a halogen atom, an alkoxy group, or the like in the structure. Y represents a hydrogen atom or a methyl group.]

[0097] Examples of the polyoxyalkylene chain include a polyoxyethylene chain and a polyoxypropylene chain.

[0098] An example of the (poly)ester chain is a (poly)ester chain represented by the following structural formula (X-1).

[0099] [ka] [In formula (X-1), R 1 is an alkylene group having 1 to 10 carbon atoms, and n is an integer of 1 to 5.

[0100] Examples of the aromatic hydrocarbon chain include a phenylene chain, a naphthylene chain, a biphenylene chain, a phenylnaphthylene chain, a binaphthylene chain, etc. In addition, a hydrocarbon chain having an aromatic ring such as a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring as a partial structure can also be used.

[0101] Examples of the polybasic acid anhydride include aliphatic polybasic acid anhydrides, alicyclic polybasic acid anhydrides, and aromatic polybasic acid anhydrides.

[0102] Examples of the aliphatic polybasic acid anhydride include anhydrides of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, etc. In addition, the aliphatic polybasic acid anhydride may have an aliphatic hydrocarbon group of either a straight-chain type or a branched type, and may have an unsaturated bond in the structure.

[0103] In the present invention, the alicyclic polybasic acid anhydride is one in which an acid anhydride group is bonded to an alicyclic structure, and the presence or absence of aromatic rings in other structural parts is not important. Examples of the alicyclic polybasic acid anhydride include tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, and 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydrides.

[0104] Examples of the aromatic polybasic acid anhydride include anhydrides of phthalic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, biphenyl dicarboxylic acid, biphenyl tricarboxylic acid, biphenyl tetracarboxylic acid, and benzophenone tetracarboxylic acid.

[0105] These polybasic acid anhydrides can be used alone or in combination of two or more kinds.

[0106] Examples of the polyisocyanate compound include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; alicyclic diisocyanate compounds such as norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate; tolylene diisocyanate, cyclohexane diisocyanate, and cyclohexane diisocyanate; Examples of the polyisocyanate include aromatic diisocyanate compounds such as silylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diisocyanato-3,3'-dimethylbiphenyl, and o-tolidine diisocyanate; polymethylene polyphenyl polyisocyanate having a repeating structure represented by the following structural formula (2); and isocyanurate-modified, biuret-modified, and allophanate-modified products thereof. These polyisocyanate compounds can be used alone or in combination of two or more.

[0107] [ka] [In the formula, R 1 R are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. 2 are each independently either an alkyl group having 1 to 4 carbon atoms or a bonding point connecting the structural portion represented by structural formula (2) via a methylene group marked with an *. l is 0 or an integer of 1 to 3, and m is an integer of 1 to 15.]

[0108] Examples of the (meth)acrylate compound having a hydroxyl group include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, trimethylolpropane (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol (meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ditrimethylolpropane (meth)acrylate, ditrimethylolpropane di(meth)acrylate, and ditrimethylolpropane tri(meth)acrylate. In addition, (poly)oxyalkylene modified compounds obtained by introducing (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains into the molecular structure of the various hydroxyl group-containing (meth)acrylate compounds described above, and lactone modified compounds obtained by introducing (poly)lactone structures into the molecular structure of the various hydroxyl group-containing (meth)acrylate compounds described above can also be used. These hydroxyl group-containing (meth)acrylate compounds can be used alone or in combination of two or more kinds.

[0109] The method for producing the epoxy resin having a polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the epoxy resin having a polymerizable unsaturated group may be carried out in an organic solvent as necessary, and a basic catalyst may be used as necessary.

[0110] Examples of the organic solvent include ketone solvents such as methyl ethyl ketone, acetone, dimethylformamide, and methyl isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; aromatic solvents such as toluene, xylene, and solvent naphtha; alicyclic solvents such as cyclohexane and methylcyclohexane; alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, and propylene glycol monomethyl ether; glycol ether solvents such as alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, and dialkylene glycol monoalkyl ether acetate; methoxypropanol, cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate. These organic solvents can be used alone or in combination of two or more. The amount of the organic solvent used is preferably in the range of about 0.1 to 5 times the total mass of the reaction raw materials, since this improves the reaction efficiency.

[0111] Examples of the basic catalyst include N-methylmorpholine, pyridine, 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), 1,4-diazabicyclo[2.2.2]octane (DABCO), tri-n-butylamine or dimethylbenzylamine, butylamine, octylamine, monoethanolamine, diethanolamine, triethanolamine, imidazole, 1-methylimidazole, 2,4- Amine compounds such as dimethylimidazole, 1,4-diethylimidazole, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(N-phenyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropylmethyldimethoxysilane, and tetramethylammonium hydroxide; trioctylmethylammonium chloride, trioctylmethylammonium acetate, and the like. Examples of the basic catalyst include quaternary ammonium salts, phosphine compounds such as trimethylphosphine, tributylphosphine, and triphenylphosphine, phosphonium salts such as tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, trimethyl(2-hydroxypropyl)phosphonium chloride, triphenylphosphonium chloride, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, and benzylphosphonium chloride, organic tin compounds such as dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dioctyltin diacetate, dioctyltin dineodecanoate, dibutyltin diacetate, tin octylate, and 1,1,3,3-tetrabutyl-1,3-dodecanoyldistannoxane, organic metal compounds such as zinc octylate and bismuth octylate, inorganic tin compounds such as tin octanoate, and inorganic metal compounds. These basic catalysts can be used alone or in combination of two or more.

[0112] Examples of the urethane resin having a polymerizable unsaturated group include those obtained by reacting a polyisocyanate compound, a (meth)acrylate compound having a hydroxyl group, and, if necessary, a polyol compound and a polybasic acid anhydride.

[0113] As the polyisocyanate compound, the same compounds as those exemplified above as the polyisocyanate compounds can be used, and the polyisocyanate compounds can be used alone or in combination of two or more kinds.

[0114] As the (meth)acrylate compound having a hydroxyl group, the same compounds as those exemplified as the (meth)acrylate compound having a hydroxyl group described above can be used, and the (meth)acrylate compound having a hydroxyl group can be used alone or in combination of two or more kinds.

[0115] Examples of the polyol compounds include aliphatic polyol compounds such as ethylene glycol, propylene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol; aromatic polyol compounds such as biphenol and bisphenol; (poly)oxyalkylene modified compounds in which (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains are introduced into the molecular structure of the various polyol compounds; lactone modified compounds in which (poly)lactone structures are introduced into the molecular structure of the various polyol compounds, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, and 2,2-dimethylolvaleric acid. The polyol compounds can be used alone or in combination of two or more.

[0116] As the polybasic acid anhydride, the same ones as those exemplified above as the polybasic acid anhydrides can be used, and the polybasic acid anhydrides can be used alone or in combination of two or more kinds.

[0117] The method for producing the urethane resin having a polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the urethane resin having a polymerizable unsaturated group may be carried out in an organic solvent as necessary, and a basic catalyst may be used as necessary.

[0118] As the organic solvent, the same organic solvents as those exemplified above can be used, and the organic solvents can be used alone or in combination of two or more kinds.

[0119] As the basic catalyst, the same ones as those exemplified above as the basic catalyst can be used, and the basic catalysts can be used alone or in combination of two or more kinds.

[0120] Examples of the acrylic resin having a polymerizable unsaturated group include a reaction product obtained by polymerizing an acrylic resin intermediate obtained by polymerizing, as an essential component, a (meth)acrylate compound (α) having a reactive functional group such as a hydroxyl group, a carboxyl group, an isocyanate group, or a glycidyl group, and then reacting the resulting acrylic resin intermediate with a (meth)acrylate compound (β) having a reactive functional group capable of reacting with the functional group, thereby introducing a (meth)acryloyl group, and a reaction product obtained by reacting a polybasic acid anhydride with a hydroxyl group in the reaction product as necessary.

[0121] The acrylic resin intermediate may be a copolymer of the (meth)acrylate compound (α) and other polymerizable unsaturated group-containing compounds as necessary. Examples of the other polymerizable unsaturated group-containing compounds include (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; alicyclic structure-containing (meth)acrylates such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and dicyclopentanyl (meth)acrylate; aromatic ring-containing (meth)acrylates such as phenyl (meth)acrylate, benzyl (meth)acrylate, and phenoxyethyl acrylate; silyl group-containing (meth)acrylates such as 3-methacryloxypropyltrimethoxysilane; and styrene derivatives such as styrene, α-methylstyrene, and chlorostyrene. These compounds may be used alone or in combination of two or more.

[0122] The (meth)acrylate compound (β) is not particularly limited as long as it can react with the reactive functional group of the (meth)acrylate compound (α), but the following combinations are preferable from the viewpoint of reactivity. That is, when water (meth)acrylate is used as the (meth)acrylate compound (α), it is preferable to use an isocyanate group-containing (meth)acrylate as the (meth)acrylate compound (β). When a carboxyl group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferable to use a glycidyl group-containing (meth)acrylate as the (meth)acrylate compound (β). When an isocyanate group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferable to use water (meth)acrylate as the (meth)acrylate compound (β). When a glycidyl group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferable to use a carboxyl group-containing (meth)acrylate as the (meth)acrylate compound (β). The (meth)acrylate compound (β) can be used alone or in combination of two or more kinds.

[0123] The polybasic acid anhydride may be the same as those exemplified above as the polybasic acid anhydride, and the polybasic acid anhydride may be used alone or in combination of two or more kinds.

[0124] The method for producing the acrylic resin having a polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the acrylic resin having a polymerizable unsaturated group may be carried out in an organic solvent as necessary, and may also use a basic catalyst as necessary.

[0125] As the organic solvent, the same organic solvents as those exemplified above can be used, and the organic solvents can be used alone or in combination of two or more kinds.

[0126] As the basic catalyst, the same ones as those exemplified above as the basic catalyst can be used, and the basic catalysts can be used alone or in combination of two or more kinds.

[0127] The amide-imide resin having a polymerizable unsaturated group may be, for example, a product obtained by reacting an amide-imide resin having an acid group and / or an acid anhydride group with a (meth)acrylate compound having a hydroxyl group and / or an epoxy group-containing (meth)acrylate compound, and, if necessary, a compound having one or more reactive functional groups selected from the group consisting of a hydroxyl group, a carboxyl group, an isocyanate group, a glycidyl group, and an acid anhydride group. The compound having a reactive functional group may or may not have a (meth)acryloyl group.

[0128] The amide-imide resin may have either an acid group or an acid anhydride group, or may have both. From the viewpoint of reactivity and reaction control with a (meth)acrylate compound having a hydroxyl group or an epoxy compound containing a (meth)acryloyl group, it is preferable that the resin has an acid anhydride group, and it is more preferable that the resin has both an acid group and an acid anhydride group. The solid content acid value of the amide-imide resin is preferably in the range of 60 to 350 mgKOH / g under neutral conditions, i.e., conditions in which the acid anhydride group is not ring-opened. On the other hand, it is preferably in the range of 61 to 360 mgKOH / g under conditions in which the acid anhydride group is ring-opened, such as in the presence of water.

[0129] The amide-imide resin may be, for example, one obtained by reacting a polyisocyanate compound with a polybasic acid anhydride as raw materials.

[0130] As the polyisocyanate compound, the same compounds as those exemplified above as the polyisocyanate compounds can be used, and the polyisocyanate compounds can be used alone or in combination of two or more kinds.

[0131] As the polybasic acid anhydride, the same ones as those exemplified above as the polybasic acid anhydrides can be used, and the polybasic acid anhydrides can be used alone or in combination of two or more kinds.

[0132] Furthermore, the amide-imide resin may contain, as necessary, a polybasic acid as a reaction raw material in addition to the polyisocyanate compound and the polybasic acid anhydride.

[0133] The polybasic acid may be any compound having two or more carboxyl groups in one molecule. For example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2,3 -dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, biphenyl dicarboxylic acid, biphenyl tricarboxylic acid, biphenyl tetracarboxylic acid, benzophenone tetracarboxylic acid, etc. In addition, as the polybasic acid, for example, a copolymer of a conjugated diene vinyl monomer and acrylonitrile, which has a carboxyl group in the molecule, can also be used. These polybasic acids can be used alone or in combination of two or more kinds.

[0134] As the (meth)acrylate compound having a hydroxyl group, the same compounds as those exemplified as the (meth)acrylate compound having a hydroxyl group described above can be used, and the (meth)acrylate compound having a hydroxyl group can be used alone or in combination of two or more kinds.

[0135] As the epoxy group-containing (meth)acrylate compound, the same compounds as those exemplified as the epoxy group-containing (meth)acrylate compound described above can be used, and the epoxy group-containing (meth)acrylate compound can be used alone or in combination of two or more kinds.

[0136] The method for producing the amide-imide resin having a polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the amide-imide resin having a polymerizable unsaturated group may be carried out in an organic solvent as necessary, and may also use a basic catalyst as necessary.

[0137] As the organic solvent, the same organic solvents as those exemplified above can be used, and the organic solvents can be used alone or in combination of two or more kinds.

[0138] As the basic catalyst, the same ones as those exemplified above as the basic catalyst can be used, and the basic catalysts can be used alone or in combination of two or more kinds.

[0139] Examples of the acrylamide resin having a polymerizable unsaturated group include those obtained by reacting a phenolic water compound with an alkylene oxide or alkylene carbonate, an N-alkoxyalkyl (meth)acrylamide compound, and, if necessary, a polybasic acid anhydride and an unsaturated monobasic acid.

[0140] The phenolic hydroxyl compound refers to a compound having at least one phenolic hydroxyl group in the molecule. Examples of the compound having at least one phenolic hydroxyl group in the molecule include compounds represented by the following structural formulas (3-1) to (3-4).

[0141] [ka]

[0142] In the above structural formulas (3-1) to (3-4), R 1 is any one of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, and a halogen atom; R 2 are each independently a hydrogen atom or a methyl group. p is 0 or an integer of 1 or more, preferably 0 or an integer of 1 to 3, more preferably 0 or 1, and even more preferably 0. q is an integer of 1 or more, preferably 2 or 3. The position of the substituent on the aromatic ring in the above structural formula is arbitrary. For example, in the naphthalene ring of structural formula (3-2), the substituent may be on any ring, in structural formula (3-3), the substituent may be on any ring of the benzene ring present in one molecule, and in structural formula (3-4), the substituent may be on any ring of the benzene ring present in one molecule, and the numbers of the substituents in one molecule are p and q.

[0143] The compound having a phenolic hydroxyl group may be, for example, a reaction product obtained by using as essential reaction raw materials a compound having one phenolic hydroxyl group in the molecule and a compound represented by any one of the following structural formulas (x-1) to (x-5). Also, a novolac-type phenolic resin may be used by using as reaction raw materials one or more compounds having at least one phenolic hydroxyl group in the molecule.

[0144] [ka]

[0145] [In formula (x-1), h is 0 or 1. In formulas (x-2) to (x-5), R 3is any one of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, and a halogen atom, and i is 0 or an integer of 1 to 4. In formulas (x-2), (x-3), and (x-5), Z is any one of a vinyl group, a halomethyl group, a hydroxymethyl group, and an alkyloxymethyl group. In formula (x-5), Y is any one of an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, and a carbonyl group, and j is an integer of 1 to 4.]

[0146] These compounds having a phenolic hydroxyl group can be used alone or in combination of two or more kinds.

[0147] Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and pentylene oxide. Among these, ethylene oxide or propylene oxide is preferred because it can provide a curable resin composition capable of forming a cured product having excellent heat resistance, elongation, and elasticity. The alkylene oxides can be used alone or in combination of two or more kinds.

[0148] Examples of the alkylene carbonate include ethylene carbonate, propylene carbonate, butylene carbonate, and pentylene carbonate. Among these, ethylene carbonate or propylene carbonate is preferred because it can provide a curable resin composition capable of forming a cured product having excellent heat resistance, elongation, and elasticity. The alkylene carbonate can be used alone or in combination of two or more kinds.

[0149] Examples of the N-alkoxyalkyl(meth)acrylamide compound include N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, N-methoxyethyl(meth)acrylamide, N-ethoxyethyl(meth)acrylamide, N-butoxyethyl(meth)acrylamide, etc. The N-alkoxyalkyl(meth)acrylamide compound can be used alone or in combination of two or more kinds.

[0150] As the polybasic acid anhydride, the same ones as those exemplified above as the polybasic acid anhydrides can be used, and the polybasic acid anhydrides can be used alone or in combination of two or more kinds.

[0151] As the unsaturated monobasic acid, the same as those exemplified above as the unsaturated monobasic acid can be used, and the unsaturated monobasic acids can be used alone or in combination of two or more kinds.

[0152] The method for producing the acrylamide resin having a polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the acrylamide resin having a polymerizable unsaturated group may be carried out in an organic solvent as necessary, and a basic catalyst and an acid catalyst may be used as necessary.

[0153] As the organic solvent, the same organic solvents as those exemplified above can be used, and the organic solvents can be used alone or in combination of two or more kinds.

[0154] As the basic catalyst, the same ones as those exemplified above as the basic catalyst can be used, and the basic catalysts can be used alone or in combination of two or more kinds.

[0155] Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, etc., organic acids such as methanesulfonic acid, paratoluenesulfonic acid, oxalic acid, etc., Lewis acids such as boron trifluoride, anhydrous aluminum chloride, zinc chloride, etc. These acid catalysts can be used alone or in combination of two or more kinds.

[0156] Examples of the ester resin having a polymerizable unsaturated group include those obtained by reacting a compound having a phenolic hydroxyl group, an alkylene oxide or an alkylene carbonate, an unsaturated monobasic acid, and, if necessary, a polybasic acid anhydride.

[0157] As the compound having a phenolic hydroxyl group, the same compounds as those exemplified above as the compound having a phenolic hydroxyl group can be used, and the compound having a phenolic hydroxyl group can be used alone or in combination of two or more kinds.

[0158] The alkylene oxide may be the same as those exemplified above. Among these, ethylene oxide or propylene oxide is preferred because it can provide a curable resin composition capable of forming a cured product having excellent heat resistance, elongation and elasticity. The alkylene oxide may be used alone or in combination of two or more kinds.

[0159] The alkylene carbonate may be the same as those exemplified above. Among these, ethylene carbonate or propylene carbonate is preferred because it can provide a curable resin composition capable of forming a cured product having excellent heat resistance, elongation and elasticity. The alkylene carbonate may be used alone or in combination of two or more kinds.

[0160] As the unsaturated monobasic acid, the same as those exemplified above as the unsaturated monobasic acid can be used, and the unsaturated monobasic acids can be used alone or in combination of two or more kinds.

[0161] As the polybasic acid anhydride, the same ones as those exemplified above as the polybasic acid anhydrides can be used, and the polybasic acid anhydrides can be used alone or in combination of two or more kinds.

[0162] The method for producing the ester resin having a polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the ester resin having a polymerizable unsaturated group may be carried out in an organic solvent as necessary, and a basic catalyst and an acid catalyst may be used as necessary.

[0163] As the organic solvent, the same organic solvents as those exemplified above can be used, and the organic solvents can be used alone or in combination of two or more kinds.

[0164] As the basic catalyst, the same ones as those exemplified above as the basic catalyst can be used, and the basic catalysts can be used alone or in combination of two or more kinds.

[0165] As the acid catalyst, the same as those exemplified above as the acid catalyst can be used, and the acid catalyst can be used alone or in combination of two or more kinds.

[0166] The content of the (meth)acrylate compound (C) is preferably 90 mass% or less in the non-volatile content of the active energy ray curable resin composition of the present invention. The mass ratio [(A) / (C)] of the solid content of the imidazole compound (A) and the (meth)acrylate compound (C) is preferably in the range of 5 / 95 to 95 / 5, since an active energy ray curable resin composition capable of forming a cured product excellent in heat resistance, elongation and elasticity can be obtained.

[0167] In addition, the active energy ray-curable resin composition of the present invention may contain various additives, such as a curing agent, a curing accelerator, an ultraviolet absorber, a polymerization inhibitor, an antioxidant, an organic solvent, an inorganic filler or polymer fine particles, a pigment, an antifoaming agent, a viscosity adjuster, a leveling agent, a flame retardant, and a storage stabilizer, as necessary.

[0168] Examples of the curing agent include epoxy resins, polybasic acids, unsaturated monobasic acids, amine compounds, amide compounds, azo compounds, organic peroxides, polyol compounds, and epoxy resins.

[0169] Examples of the epoxy resin include bisphenol type epoxy resin, phenylene ether type epoxy resin, naphthalene type epoxy resin, naphthylene ether type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, biphenyl aralkyl type epoxy resin, fluorene type epoxy resin, xanthene type epoxy resin, dihydroxybenzene type epoxy resin, trihydroxybenzene type epoxy resin, oxazolidone type epoxy resin, etc. These epoxy resins can be used alone or in combination of two or more.

[0170] Examples of the bisphenol type epoxy resin include bisphenol A type epoxy resin, bisphenol AP type epoxy resin, bisphenol B type epoxy resin, bisphenol BP type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin.

[0171] Examples of the hydrogenated bisphenol type epoxy resin include hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol B type epoxy resin, hydrogenated bisphenol E type epoxy resin, hydrogenated bisphenol F type epoxy resin, and hydrogenated bisphenol S type epoxy resin.

[0172] Examples of the biphenol type epoxy resin include 4,4'-biphenol type epoxy resin, 2,2'-biphenol type epoxy resin, tetramethyl-4,4'-biphenol type epoxy resin, and tetramethyl-2,2'-biphenol type epoxy resin.

[0173] Examples of the hydrogenated biphenol type epoxy resin include hydrogenated 4,4'-biphenol type epoxy resin, hydrogenated 2,2'-biphenol type epoxy resin, hydrogenated tetramethyl-4,4'-biphenol type epoxy resin, and hydrogenated tetramethyl-2,2'-biphenol type epoxy resin.

[0174] Examples of the polybasic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, and bicyclo[2.2.1]heptacarboxylic acid. Examples of the polybasic acid include 2,3-dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, biphenyl dicarboxylic acid, biphenyl tricarboxylic acid, biphenyl tetracarboxylic acid, and benzophenone tetracarboxylic acid. In addition, examples of the polybasic acid include a copolymer of a conjugated diene vinyl monomer and acrylonitrile, which has a carboxyl group in the molecule. These polybasic acids can be used alone or in combination of two or more.

[0175] As the unsaturated monobasic acid, the same as those exemplified above as the unsaturated monobasic acid can be used, and the unsaturated monobasic acids can be used alone or in combination of two or more kinds.

[0176] Examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF3-amine complex, guanidine derivatives, etc. These amine compounds can be used alone or in combination of two or more kinds.

[0177] Examples of the amide-based compound include dicyandiamide, a polyamide resin synthesized from a dimer of linoleic acid and ethylenediamine, etc. These amide compounds can be used alone or in combination of two or more kinds.

[0178] Examples of the azo compound include azobisisobutyronitrile.

[0179] Examples of the organic peroxide include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxy esters, peroxydicarbonates, alkyl peroxycarbonates, etc. These organic peroxides can be used alone or in combination of two or more kinds.

[0180] Examples of the polyol compound include polyol monomers such as ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, glycerin, glycerin mono(meth)acrylate, trimethylolethane, trimethylolmethane mono(meth)acrylate, trimethylolpropane, trimethylolpropane mono(meth)acrylate, pentaerythritol mono(meth)acrylate, and pentaerythritol di(meth)acrylate; mixtures of the above polyol monomers with succinic acid, adipic acid, azelaic acid, sebacic acid, and the like. polyester polyols obtained by co-condensation of the polyol monomers with dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, and 1,4-cyclohexanedicarboxylic acid; lactone-type polyester polyols obtained by polycondensation of the polyol monomers with various lactones such as ε-caprolactone, δ-valerolactone, and 3-methyl-δ-valerolactone; and polyether polyols obtained by ring-opening polymerization of the polyol monomers with cyclic ether compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, and propyl glycidyl ether. These polyol compounds can be used alone or in combination of two or more.

[0181] As the epoxy resin, the same ones as those exemplified above as the epoxy resin can be used, and the epoxy resins can be used alone or in combination of two or more kinds.

[0182] The curing accelerator is one that accelerates the curing reaction, and examples thereof include phosphorus compounds, amine compounds, imidazole, organic acid metal salts, Lewis acids, and amine complex salts. These curing accelerators can be used alone or in combination of two or more. The amount of the curing accelerator added is preferably within a range of 0.01 to 10 mass % based on the solid content of the active energy ray-curable resin composition.

[0183] Examples of the ultraviolet absorbent include triazine derivatives such as 2-[4-{(2-hydroxy-3-dodecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-[4-{(2-hydroxy-3-tridecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2'-xanthenecarboxy-5'-methylphenyl)benzotriazole, 2-(2'-o-nitrobenzyloxy-5'-methylphenyl)benzotriazole, 2-xanthenecarboxy-4-dodecyloxybenzophenone, and 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone. These ultraviolet absorbents can be used alone or in combination of two or more.

[0184] Examples of the polymerization inhibitor include p-methoxyphenol, p-methoxycresol, 4-methoxy-1-naphthol, 4,4'-dialkoxy-2,2'-bi-1-naphthol, 3-(N-salicyloyl)amino-1,2,4-triazole, N'1,N'12-bis(2-hydroxybenzoyl)dodecane dihydrazide, styrenated phenol, N-isopropyl-N'-phenylbenzene-1,4-diamine, 6-ethoxy-2,2,4-trimethyl- Phenol compounds such as 1,2-dihydroquinoline, quinone compounds such as hydroquinone, methylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, 2,5-diphenylbenzoquinone, 2-hydroxy-1,4-naphthoquinone, anthraquinone, and diphenoquinone, melamine, p-phenylenediamine, 4-aminodiphenylamine, N.N'-diphenyl-p-phenylenediamine, Ni-propyl-N'-phenyl-p-phenylenediamine, N-(1.amine compounds such as 3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, diphenylamine, 4,4'-dicumyl-diphenylamine, 4,4'-dioctyl-diphenylamine, poly(2,2,4-trimethyl-1,2-dihydroquinoline), styrenated diphenylamine, reaction products of styrenated diphenylamine and 2,4,4-trimethylpentene, reaction products of diphenylamine and 2,4,4-trimethylpentene, phenothiazine, distearyl thiodipropionate, 2,2-bis({[3-(dodecyl) thioether compounds such as N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, p-nitrosophenol, nitrosobenzene, p-nitrosodiphenylamine, α-nitroso-β-naphthol, N,N-dimethyl p-nitrosoaniline, p-nitrosodiphenylamine, p-nitrosodimethylamine, p-nitroso ... -N,N-diethylamine, N-nitrosoethanolamine, N-nitrosodi-n-butylamine, N-nitroso-Nn-butyl-4-butanolamine, N-nitroso-diisopropanolamine, N-nitroso-N-ethyl-4-butanolamine, 5-nitroso-8-hydroxyquinoline, N-nitrosomorpholine, N-nitroso-N-phenylhydroxylamine ammonium salt, nitrosobenzene, N-nitroso-N-methyl-p-toluenesulfonamide, N-nitroso-N-ethylurethane, N-nitroso-Nn -Propyl urethane, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, sodium 1-nitroso-2-naphthol-3,6-sulfonate, sodium 2-nitroso-1-naphthol-4-sulfonate, 2-nitroso-5-methylaminophenol hydrochloride, 2-nitroso-5-methylaminophenol hydrochloride and other nitroso compounds, esters of phosphoric acid and octadecane-1-ol, triphenyl phosphite, 3,9-dioctadecan-1-yl-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]Undecane, trisnonylphenyl phosphite, phosphorous acid-(1-methylethylidene)-di-4,1-phenylenetetra-C12-15-alkyl ester, 2-ethylhexyl diphenyl phosphite, diphenyl isodecyl phosphite, triisodecyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite and other phosphite compounds, bis(dimethyldithiocarbamato-κ(2)S,S')zinc, diethyldithiocarbamate , zinc compounds such as zinc dibutyl dithiocarbamate, nickel compounds such as bis(N,N-dibutylcarbamodithioato-S,S')nickel, sulfur compounds such as 1,3-dihydro-2H-benzimidazole-2-thione, 4,6-bis(octylthiomethyl)-o-cresol, 2-methyl-4,6-bis[(octan-1-ylsulfanyl)methyl]phenol, dilauryl thiodipropionate, and distearyl 3,3'-thiodipropionate. These polymerization inhibitors can be used alone or in combination of two or more.

[0185] As the antioxidant, the same compounds as those exemplified as the polymerization inhibitor can be used, and the antioxidants can be used alone or in combination of two or more kinds.

[0186] In addition, examples of commercially available products of the polymerization inhibitor and the antioxidant include "Q-1300" and "Q-1301" manufactured by Wako Pure Chemical Industries, Ltd., and "Sumilizer BBM-S" and "Sumilizer GA-80" manufactured by Sumitomo Chemical Co., Ltd.

[0187] Examples of the organic solvent include ketone solvents such as methyl ethyl ketone, acetone, dimethylformamide, and methyl isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; aromatic solvents such as toluene, xylene, and solvent naphtha; alicyclic solvents such as cyclohexane and methylcyclohexane; alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, and propylene glycol monomethyl ether; glycol ether solvents such as alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, and dialkylene glycol monoalkyl ether acetate; methoxypropanol, cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate. These organic solvents can be used alone or in combination of two or more.

[0188] Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide.

[0189] As the pigment, known and commonly used inorganic pigments and organic pigments can be used.

[0190] Examples of the inorganic pigment include white pigments, antimony red, red iron oxide, cadmium red, cadmium yellow, cobalt blue, Prussian blue, ultramarine blue, carbon black, graphite, etc. These inorganic pigments can be used alone or in combination of two or more kinds.

[0191] Examples of the white pigment include titanium oxide, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, hollow resin particles, and zinc sulfide.

[0192] Examples of the organic pigment include quinacridone pigments, quinacridonequinone pigments, dioxazine pigments, phthalocyanine pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, flavanthrone pigments, perylene pigments, diketopyrrolopyrrole pigments, perinone pigments, quinophthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, azo pigments, etc. These organic pigments can be used alone or in combination of two or more kinds.

[0193] Examples of the flame retardant include inorganic phosphorus compounds such as red phosphorus, ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate, and phosphoric acid amides; phosphoric acid ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, organic nitrogen-containing phosphorus compounds, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxy, and the like. Examples of suitable flame retardants include organic phosphorus compounds such as cyclic organic phosphorus compounds such as 10-(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide and derivatives thereof reacted with compounds such as epoxy resins and phenolic resins; nitrogen-based flame retardants such as triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, and phenothiazine; silicone-based flame retardants such as silicone oils, silicone rubbers, and silicone resins; and inorganic flame retardants such as metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and low-melting glass. These flame retardants can be used alone or in combination of two or more. When these flame retardants are used, the amount is preferably in the range of 0.1 to 20 mass% in the total resin composition.

[0194] The cured product of the present invention can be obtained by irradiating the active energy ray curable resin composition with active energy rays. Examples of the active energy rays include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. When ultraviolet rays are used as the active energy rays, irradiation may be performed under an inert gas atmosphere such as nitrogen gas, or under an air atmosphere in order to efficiently carry out a curing reaction by ultraviolet rays.

[0195] As a source of ultraviolet light, ultraviolet lamps are generally used from the viewpoints of practicality and economy, and specific examples include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, sunlight, LEDs, etc.

[0196] The cumulative amount of the active energy rays is not particularly limited, but is preferably 0.1 to 50 kJ / m 2 is preferably 0.5 to 10 kJ / m 2 It is more preferable that the integrated light amount is within the above range, since the occurrence of uncured portions can be prevented or suppressed.

[0197] The irradiation of the active energy rays may be carried out in one step or in two or more steps.

[0198] The article of the present invention has a coating film made of the cured product. Examples of the article include plastic molded products such as mobile phones, home appliances, automobile interior and exterior materials, and office automation equipment, as well as semiconductor devices, display devices, and imaging devices. EXAMPLES

[0199] The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the examples given below.

[0200] (Synthesis Example 1: Synthesis of epoxy acrylate resin (1)) In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 346 parts by mass of bisphenol A type epoxy resin (DIC Corporation's "EPICLON 850CRP", epoxy equivalent 173 g / eq. Hereinafter, abbreviated as "bisphenol A type epoxy resin (1)") was charged, and 0.21 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.21 parts by mass of methoquinone as a thermal polymerization inhibitor were added, followed by adding 72 parts by mass of acrylic acid and 0.21 parts by mass of triphenylphosphine, and performing an esterification reaction at 100 ° C. for 10 hours while blowing in air. Next, after confirming that the acid value was 1 mgKOH / g or less, 0.21 parts by mass of oxalic acid was added, and the mixture was stirred at 70 ° C. for 3 hours to obtain an epoxy acrylate resin (1). The epoxy equivalent of this epoxy acrylate resin (1) was 450 g / eq.

[0201] (Synthesis Example 2: Production of epoxy acrylate resin (2)) In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 282 parts by mass of a naphthalene-type epoxy resin (DIC Corporation's "EPICLON 4032D", epoxy equivalent 141 g / eq. hereinafter abbreviated as "naphthalene-type epoxy resin (1)") was charged, and 0.18 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.18 parts by mass of methoquinone as a thermal polymerization inhibitor were added, followed by adding 72 parts by mass of acrylic acid and 0.18 parts by mass of triphenylphosphine, and carrying out an esterification reaction at 100°C for 10 hours while blowing in air. Next, after confirming that the acid value was 1 mgKOH / g or less, 0.18 parts by mass of oxalic acid was added, and the mixture was stirred at 70°C for 3 hours to obtain an epoxy acrylate resin (2). The epoxy equivalent of this epoxy acrylate resin (2) was 388 g / eq.

[0202] (Synthesis Example 3: Synthesis of epoxy acrylate resin (3)) A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 346 parts by mass of "bisphenol A type epoxy resin (1)", and 0.98 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.25 parts by mass of methoquinone as a thermal polymerization inhibitor were added thereto. Thereafter, 144 parts by mass of acrylic acid and 2.5 parts by mass of triphenylphosphine were added thereto, and an esterification reaction was carried out at 110°C for 8 hours while blowing in air, thereby obtaining an epoxy acrylate resin (3).

[0203] (Synthesis Example 4: Synthesis of Compound A)

[0204] [ka]

[0205] In a 100 mL four-neck flask equipped with a stirrer, a thermometer, and a reflux condenser, 14.17 parts by mass (98.26 mmol) of 4-hydroxybutyl acrylate (Osaka Organic Chemical Industry Co., Ltd. "4HBA"), 140 parts by mass of tetrahydrofuran (THF), 25.77 g (98.26 mmol) of triphenylphosphine (Ph3P), and 10.00 parts by mass (81.89 mmol) of 4-hydroxybenzaldehyde were added and stirred. A pale yellow transparent solution was obtained. Next, in an ice bath, 19.87 parts by mass (98.26 mmol) of diisopropyl azodicarboxylate (DIAD) diluted with 20 parts by mass of tetrahydrofuran was added dropwise over 30 minutes. The orange transparent reaction solution was stirred at room temperature for 10 hours. Hexane was added to the reaction solution, and by-products such as triphenylphosphine were precipitated and removed, followed by extraction with chloroform, washing with water and saturated saline, and drying with magnesium sulfate. The solvent was removed by distillation using an evaporator, and the resulting red viscous liquid was purified by column chromatography (developing solvent: n-hexane:ethyl acetate=80:20) to obtain the target compound A.

[0206] (Synthesis Example 5: Synthesis of imidazole compound (1))

[0207] [ka]

[0208] In a 100mL four-neck flask equipped with a stirrer, a thermometer, and a reflux condenser, 4.87 parts by mass (19.62 mmol) of compound A obtained in Synthesis Example 4, 15 parts by mass of methanol (MeOH), 0.00154 parts by mass (0.137 mmol) of 1,4-diazabicyclo[2.2.2]octane (DABCO), 4.948 parts by mass (23.54 mmol) of benzil, 3.629 parts by mass (47.08 mmol) of ammonium acetate (NH4OAc), 1500 ppm of methoquinone, and 500 ppm of BHT were added, and nitrogen gas was blown from above, air was bubbled through the liquid, and the mixture was stirred at 65°C for 24 hours. The mixture gradually became a reddish-brown solution, and after several hours, a yellow solid precipitated on the wall. After cooling to near room temperature, the mixture was extracted with ethyl acetate, washed with water and saturated saline, and then dried over magnesium sulfate. The solvent was removed by distillation using an evaporator, and the resulting red viscous liquid was purified by column chromatography (developing solvent: n-hexane:ethyl acetate=80:20) to obtain imidazole compound (1).

[0209] [Method of identifying structure] The structure of the product was identified under the following conditions: 1 H-NMR, 13 This was measured by C-NMR and MALDI-MS. 1 The H-NMR spectrum is shown in Figure 1. 13 The C-NMR spectrum is shown in FIG. 2, and the MALDI-MS spectrum is shown in FIG.

[0210] 1 H-NMR was measured using a JEOL RESONANCE “JNM-ECM400S” under the following conditions.

[0211] Magnetic field strength: 400MHz Number of times: 16 Solvent: Deuterated chloroform Sample concentration: 2mg / 0.5ml

[0212] 13 C-NMR was measured using a JEOL RESONANCE “JNM-ECM400S” under the following conditions.

[0213] Magnetic field strength: 100MHz Number of times: 1000 Solvent: Deuterated chloroform Sample concentration: 2mg / 0.5ml

[0214] MALDI-MS was performed using Shimadzu Corporation / KRATOS "AXIMA-QIT" under the following conditions. Device name:AXIMA-QIT Manufacturer: Shimadzu Corporation

[0215] Measurement range: m / z=50.00~2000.00 Rate of change: 25.6mA / min Final current value: 40mA Cathode voltage: -10kV Measurement mode m / z ~300: extraLow 300~750:Low 750~:Mid

[0216] (Synthesis Example 6: Synthesis of Compound B)

[0217] [ka]

[0218] Compound B represented by the above structural formula was obtained in the same manner as in Synthesis Example 4, except that hydroxyethyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., "HEA") was used instead of 4-hydroxybutyl acrylate.

[0219] (Synthesis Example 7: Synthesis of imidazole compound (2))

[0220] [ka]

[0221] The same procedure as in Synthesis Example 5 was carried out except that Compound B obtained in Synthesis Example 6 was used instead of Compound A, to obtain imidazole compound (2) represented by the above structural formula.

[0222] (Synthesis Example 8: Synthesis of Compound C)

[0223] [ka]

[0224] Compound C represented by the above structural formula was obtained in the same manner as in Synthesis Example 4, except that unsaturated fatty acid hydroxyalkyl ester-modified ε-caprolactone (Daicel Corporation, "Placcel FA2D") was used instead of 4-hydroxybutyl acrylate.

[0225] (Synthesis Example 9: Synthesis of imidazole compound (3))

[0226] [ka]

[0227] The same procedure as in Synthesis Example 5 was carried out except that Compound C obtained in Synthesis Example 8 was used instead of Compound A, to obtain imidazole compound (3) represented by the above structural formula.

[0228] (Synthesis Example 10: Synthesis of Compound D)

[0229] [ka]

[0230] In a 500 mL four-neck flask equipped with a stirrer, a thermometer, and a reflux condenser, 17.85 parts by mass (118.91 mmol) of terephthalaldehyde acid, 285 parts by mass of glacial acetic acid, 0.0934 parts by mass (0.832 mmol) of 1,4-diazabicyclo[2.2.2]octane (DABCO), 25.00 parts by mass (118.91 mmol) of benzil, and 27.50 parts by mass (356.75 mmol) of ammonium acetate were placed and stirred at 105° C. for 6 hours. After cooling to around room temperature, the mixture was added to ice water, and the resulting solid was filtered and washed with chloroform to obtain the target compound D.

[0231] (Synthesis Example 11: Synthesis of imidazole compound (4))

[0232] [ka]

[0233] In a 100mL four-neck flask equipped with a stirrer, a thermometer and a reflux condenser, 5.00 parts by mass (14.689mmol) of compound D, 2.54 parts by mass (17.63mmol) of 4-hydroxybutyl acrylate (Osaka Organic Chemical Industry Co., Ltd. "4HBA"), 4.62 parts by mass (17.63mmol), and 15.66 parts by mass of DMF were added and stirred. A pale yellow transparent solution was obtained. Next, in an ice bath, 3.56 parts by mass (17.63mmol) of diisopropyl azodicarboxylate diluted with 3.56 parts by mass of DMF was added dropwise over 30 minutes. The orange transparent reaction solution was stirred at room temperature for 10 hours. The reaction solution was dried up, chloroform and hexane were added, and by-products such as triphenylphosphine were precipitated and removed, followed by extraction with chloroform, washing with water and saturated saline, and drying with magnesium sulfate. The solvent was removed by distillation using an evaporator, and the resulting red viscous liquid was purified by column chromatography (developing solvent: n-hexane:ethyl acetate=80:20) to obtain imidazole compound (4).

[0234] (Synthesis Example 12: Synthesis of imidazole compound (5))

[0235] [ka]

[0236] The same procedure as in Synthesis Example 11 was carried out except that a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate ("Aronix M-305" manufactured by Toagosei Co., Ltd., hydroxyl value 116 mgKOH / g) was used instead of 4-hydroxybutyl acrylate ("4HBA" manufactured by Osaka Organic Chemical Industry Co., Ltd.), to obtain the imidazole compound (5) represented by the above structural formula.

[0237] (Example 1: Preparation of curable resin composition (1)) The imidazole compound (1) obtained in Synthesis Example 4 was mixed with a photopolymerization initiator (IGM's "Omnirad 184D") to obtain an active energy ray curable resin composition, and then the epoxy acrylate resin (1) obtained in Synthesis Example 1, glycidyl methacrylate, EO-modified diacrylate of bisphenol A (Miwon's "Miramer M-240"), and 2-ethyl-4-methylimidazole were blended in the parts by mass shown in Table 1, and kneaded with a roll mill to obtain a curable resin composition (1). Note that the parts by mass of the resin having an acid group and a polymerizable unsaturated group in Table 1 are solid content values.

[0238] (Examples 2 to 10: Preparation of curable resin compositions (2) to (10)) Using the compositions and blendings shown in Table 1, curable resin compositions (2) to (10) were obtained in the same manner as in Example 1.

[0239] (Comparative Example 1: Preparation of Curable Resin Composition (R1)) The epoxy acrylate resin (1) obtained in Synthesis Example 1, an EO-modified diacrylate of bisphenol A (Miwon's Miramer M-240), a photopolymerization initiator (IGM's Omnirad 184D), and 2-ethyl-4-methylimidazole were mixed in the parts by mass shown in Table 1 and kneaded with a roll mill to obtain a curable resin composition (R1).

[0240] The following evaluations were carried out using the curable resin compositions (1) to (10), (R1) and (R2) obtained in the above Examples and Comparative Examples.

[0241] [Heat resistance evaluation method] The curable resin composition obtained in each of the Examples and Comparative Examples was applied to a copper foil (electrolytic copper foil "F2-WS" 18 μm, manufactured by Furukawa Sangyo Kaisha) using an applicator to a thickness of 50 μm, and dried at 80° C. for 30 minutes. Then, a metal halide lamp was used to apply the applied coating to the copper foil. 2 After irradiating with ultraviolet light of 1000 nm, the sample was heated at 160°C for 1 hour to obtain a cured coating film. The cured coating film was then peeled off from the copper foil to obtain a cured product. A 6 mm x 35 mm test piece was cut out from the cured product, and the temperature at which the change in elastic modulus was maximum was evaluated as the glass transition temperature using a viscoelasticity measuring device (DMA: Rheometrics Corp. solid viscoelasticity measuring device "RSAII", tensile method: frequency 1 Hz, heating rate 3°C / min). Note that a higher glass transition temperature indicates better heat resistance.

[0242] [Method of measuring elongation and elastic modulus] The elongation and elastic modulus were measured based on a tensile test. <Preparation of test piece 1> The active energy ray-curable resin compositions obtained in the Examples and Comparative Examples were applied onto a copper foil (electrolytic copper foil "F2-WS" 18 μm, manufactured by Furukawa Sangyo Co., Ltd.) using a 50 μm applicator, and then exposed to 10 kJ / m using a metal halide lamp. 2 After being irradiated with ultraviolet light, the cured product was heated for 1 hour at 160° C. The cured product was peeled off from the copper foil to obtain a test piece 1 (cured product).

[0243] <Tensile test> The test piece 1 was cut into a size of 10 mm x 80 mm, and a tensile test was performed on the test piece 1 under the following measurement conditions using a precision universal testing machine "Autograph AG-IS" manufactured by Shimadzu Corporation. The elongation (%) and elastic modulus (MPa) until the test piece broke were measured and evaluated according to the following criteria.

[0244] Measurement conditions: temperature 23℃, humidity 50%, distance between gauge lines 20mm, distance between supports 20mm, tensile speed 10mm / min

[0245] Table 1 shows the compositions and evaluation results of the curable resin compositions (1) to (10), and (R1) obtained in the above examples and comparative examples.

[0246] [Table 1]

[0247] Examples 1 to 10 shown in Table 1 are examples of curable resin compositions using the active energy ray-curable resin composition of the present invention. It was confirmed that the cured products of these curable resin compositions had excellent heat resistance, elongation and elasticity.

[0248] On the other hand, Comparative Example 1 is an example of a curable resin composition that does not contain an imidazole compound. It was confirmed that the cured products of these curable resin compositions were insufficient in terms of heat resistance, elongation and elasticity.

Claims

1. An active energy ray-curable resin composition comprising an imidazole compound (A) represented by the following general formula (1), a photopolymerization initiator (B), and a (meth)acrylate compound (C), The energy ray-curable resin composition, wherein the mass ratio of the solid content of the imidazole compound (A) to the solid content of the (meth)acrylate compound (C) [(A) / (C)] is in the range of 5 / 95 to 95 / 5. 【Chemistry 1】 [In formula (1), Ar1 represents an aromatic hydrocarbon group having 6 to 20 carbon atoms. Ar2 represents an aromatic hydrocarbon group having 6 to 20 carbon atoms. Ar3 represents a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms. L1 represents —O—, —COO— or —OCO—. L2 represents a single bond or --O--. R1 represents a polyoxyalkylene group or a divalent hydrocarbon group having 1 to 50 carbon atoms which may have a substituent, and -CH2- contained in the hydrocarbon group is -O- and / or -C It may be replaced by O-. Ra1 represents a reactive group.

2. The active energy ray-curable resin composition according to claim 1, wherein in the imidazole compound (A), Ra1 in formula (1) is a vinyl group, a (meth)acryloyl group, or an oxetanyl group which may have a substituent.

3. A cured product of the active energy ray-curable resin composition according to any one of claims 1 to 2.

4. An article having a coating film comprising the cured product according to claim 3.

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