Compound, polymer, polymerizable composition, adhesive, coating agent, cured product, and method for producing the cured product

Abstract

To provide a polymerizable composition having less shrinkage during curing.SOLUTION: There is provided a compound having a group represented by the following general formula (I). In the formula, R1 and R2 represent a hydrogen atom or a methyl group, R3, R4, R5, R6, R7 and R8 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, a group in which one or more methylene groups in the hydrocarbon group having 1 to 20 carbon atoms are substituted with a divalent group selected from the following <group A> and * represents a bond. <Group A>: a carbon-carbon double bond, -O-, -S-, -CO-, -CO-O- and -SO2-.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polymerizable compound, and a polymer and a polymerizable composition using the same. [Background technology]

[0002] Urethane acrylates, which have a urethane bond and an acryloyl group, are UV-curable and are therefore widely used in coating agents, adhesives, UV-curable paints, resists, and the like.

[0003] For example, Patent Document 1 describes an ethylenically unsaturated group-containing reactive urethane compound having a urethane bond, a thiourethane bond, or an imino group, and a curable composition containing the same, and describes that a cured product having excellent properties such as flexibility and adhesive strength can be obtained. Also, Patent Document 2 describes an active energy ray-curable resin composition for coating containing a urethane (meth)acrylate (A) having a cyclo or bicyclo ring structure and a nurate ring structure, and colloidal silica (B), and describes that a cured coating film having high hardness and low cure shrinkage can be formed. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2008 / 146685 [Patent Document 2] Japanese Patent Application Laid-Open No. 2010-083959 Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present invention is to provide a polymerizable composition that shrinks little when cured. [Means for solving the problem]

[0006] As a result of extensive investigations, the present inventors have found that by introducing a group having two ethylenically unsaturated bonds into a compound, the volume change when the compound is polymerized can be suppressed, and have thus completed the present invention.

[0007] The present invention is a compound having a group represented by the following general formula (I).

[0008] [ka] In the formula, R 1 and R 2 each independently represents a hydrogen atom or a methyl group, R 3 , R 4 , R 5 , R 6 , R 7 and R 8 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group having 1 to 20 carbon atoms are substituted with a divalent group selected from the following <Group A>, * represents a bond. <Group A>: Carbon-carbon double bond, -O-, -S-, -CO-, -CO-O-, -SO2- [Effects of the Invention]

[0009] The polymerizable composition using the compound of the present invention is useful as a coating agent or adhesive because it has little shrinkage upon curing. DETAILED DESCRIPTION OF THE INVENTION

[0010] The compound of the present invention is a compound having a group represented by the general formula (I) above.

[0011] The hydrocarbon group having 1 to 20 carbon atoms in the general formula (I) is a group consisting of carbon atoms and hydrogen atoms and having 1 to 20 carbon atoms. Examples of the hydrocarbon group having 1 to 20 carbon atoms include aliphatic hydrocarbon groups having 1 to 20 carbon atoms and aromatic hydrocarbon ring-containing groups having 6 to 20 carbon atoms.

[0012] Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and a cycloalkylalkyl group having 4 to 20 carbon atoms.

[0013] The alkyl group having 1 to 20 carbon atoms may be linear or branched. Examples of linear alkyl groups include methyl, ethyl, propyl, butyl, iso-amyl, tert-amyl, hexyl, heptyl, and octyl. Examples of branched alkyl groups include iso-propyl, sec-butyl, tert-butyl, iso-butyl, iso-pentyl, tert-pentyl, 2-hexyl, 3-hexyl, 2-heptyl, 3-heptyl, iso-heptyl, tert-heptyl, iso-octyl, tert-octyl, 2-ethylhexyl, nonyl, isononyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, hebrotadecyl, and octadecyl.

[0014] Examples of cycloalkyl groups having 3 to 20 carbon atoms include saturated monocyclic alkyl groups having 3 to 20 carbon atoms, saturated polycyclic alkyl groups having 3 to 20 carbon atoms, and groups having 4 to 20 carbon atoms in which one or more hydrogen atoms in the ring of these groups have been substituted with an alkyl group. Examples of the saturated monocyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. Examples of the saturated polycyclic alkyl groups include adamantyl, decahydronaphthyl, octahydropentalene, and bicyclo[1.1.1]pentanyl. Examples of alkyl groups substituting hydrogen atoms in the ring of saturated monocyclic or saturated polycyclic alkyl groups include the groups exemplified above as alkyl groups having 1 to 20 carbon atoms. Examples of groups in which one or more hydrogen atoms in the ring of a saturated polycyclic alkyl group have been substituted with an alkyl group include bornyl.

[0015] A cycloalkylalkyl group having 4 to 20 carbon atoms means a group having 4 to 20 carbon atoms in which a hydrogen atom of an alkyl group is substituted with a cycloalkyl group. The cycloalkyl group in the cycloalkylalkyl group may be monocyclic or polycyclic. Examples of cycloalkylalkyl groups having 4 to 20 carbon atoms and a monocyclic cycloalkyl group include cyclopropylmethyl, 2-cyclobutylethyl, 3-cyclopentylpropyl, 4-cyclohexylbutyl, cycloheptylmethyl, cyclooctylmethyl, 2-cyclononylethyl, and 2-cyclodecylethyl. Examples of cycloalkylalkyl groups having 4 to 20 carbon atoms and a polycyclic cycloalkyl group include 3-3-adamantylpropyl and decahydronaphthylpropyl.

[0016] The aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms is a hydrocarbon group that contains an aromatic hydrocarbon ring but does not contain a heterocycle, and may have an aliphatic hydrocarbon group. Examples of the aromatic hydrocarbon ring-containing group include an aryl group having 6 to 20 carbon atoms and an arylalkyl group having 7 to 20 carbon atoms.

[0017] The aryl group having 6 to 20 carbon atoms may have a monocyclic structure, a fused ring structure, or two linked aromatic hydrocarbon rings. Examples of the aryl group having a fused ring structure having 6 to 20 carbon atoms include hydrocarbon-type aromatic fused ring groups having 7 to 20 carbon atoms, which are structures in which two or more aromatic hydrocarbon rings are fused together.

[0018] Examples of the aryl group having a monocyclic structure and having 6 to 20 carbon atoms include phenyl, tolyl, xylyl, ethylphenyl, 2,4,6-trimethylphenyl, etc. Examples of the hydrocarbon-type aromatic fused ring group having 7 to 20 carbon atoms include naphthyl, anthracenyl, phenanthryl, pyrenyl, fluorenyl, and indenofluorenyl.

[0019] The aryl group in which two aromatic hydrocarbon rings are linked may be one in which two aromatic hydrocarbon rings of a monocyclic structure are linked together, one in which an aromatic hydrocarbon ring of a monocyclic structure and an aromatic hydrocarbon ring of a fused ring structure are linked together, or one in which an aromatic hydrocarbon ring of a fused ring structure and an aromatic hydrocarbon ring of a fused ring structure are linked together. Examples of the linking group that links two aromatic hydrocarbon rings include a single bond, a sulfide group (—S—), and a carbonyl group. Examples of the aryl group in which two monocyclic aromatic hydrocarbon rings are linked together include biphenyl, diphenyl sulfide, and benzoylphenyl.

[0020] An arylalkyl group having 7 to 20 carbon atoms is a group in which one or more hydrogen atoms in an alkyl group are substituted with an aryl group. Examples of the arylalkyl group having 7 to 20 carbon atoms include benzyl, fluorenyl, indenyl, 9-fluorenylmethyl, α-methylbenzyl, α,α-dimethylbenzyl, phenylethyl, and naphthylpropyl groups.

[0021] The hydrocarbon group having 1 to 20 carbon atoms may have a substituent, and examples of the substituent include a halogen atom, a cyano group, a nitro group, a hydroxyl group, an amino group, a carboxy group, an epoxy group, a mercapto group, and an isocyanate group.

[0022] The heterocyclic group having 2 to 20 carbon atoms is a group obtained by removing one hydrogen atom from a heterocyclic compound. The heterocyclic group may have a monocyclic structure or a fused ring structure. Examples of the heterocyclic group having a fused ring structure having 2 to 20 carbon atoms include a heterocycle-containing fused ring group having 3 to 20 carbon atoms, which has a structure in which a heterocycle and a heterocycle or a hydrocarbon ring are fused together. Specific examples of heterocyclic groups include pyridyl, quinolyl, thiazolyl, tetrahydrofuranyl, dioxolanyl, tetrahydropyranyl, methylthiophenyl, hexylthiophenyl, benzothiophenyl, pyrrolyl, pyrrolidinyl, imidazolyl, imidazolidinyl, imidazolinyl, pyrazolyl, pyrazolidinyl, piperidinyl, piperazinyl, pyrimidinyl, furyl, thienyl, benzoxazol-2-yl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, morpholinyl, and the like. The heterocyclic group may have a substituent, and examples of the substituent include a halogen atom, a cyano group, a nitro group, a hydroxyl group, an amino group, a carboxy group, an epoxy group, a mercapto group, and an isocyanate group. In the present invention, heterocyclic groups having 2 to 10 carbon atoms are preferred because they have good curability.

[0023] The hydrocarbon group having 1 to 20 carbon atoms in which two or more methylene groups have been substituted with a divalent group selected from <Group A> does not have a structure in which the divalent groups are adjacent to each other.

[0024] In the present invention, when a hydrogen atom in the group is substituted with a substituent, the number of carbon atoms in the group refers to the number of carbon atoms in the group after the substitution. For example, when a hydrogen atom in the alkyl group having 1 to 20 carbon atoms is substituted, the number of carbon atoms of 1 to 20 refers to the number of carbon atoms after the hydrogen atom is substituted, not the number of carbon atoms before the hydrogen atom is substituted. In the present invention, the number of carbon atoms in a group in which a methylene group in a group with a predetermined number of carbon atoms is replaced with a divalent group defines the number of carbon atoms in the group before the substitution. For example, in the case of a group in which a methylene group in an alkyl group having 1 to 20 carbon atoms is replaced with a divalent group, the term "1 to 20 carbon atoms" refers to the number of carbon atoms before the methylene group in the alkyl group is replaced with the divalent group, not the number of carbon atoms after the replacement.

[0025] The compound of the present invention preferably has 1 to 3 groups represented by the general formula (I) in the molecule, more preferably 1 to 2, and particularly preferably 1, since this reduces cure shrinkage. For example, when the compound of the present invention contains an isocyanurate ring described below, it preferably has 1 to 3 groups represented by the general formula (I) in the molecule, more preferably 1 to 2, and particularly preferably 1.

[0026] R in the general formula (I) 1 and R 2 A compound in which is a hydrogen atom is preferred because it has excellent curability.

[0027] R in the general formula (I) 3 , R 4 , R 6 and R 7 Compounds in which is a hydrogen atom are preferred because they have little cure shrinkage and excellent curability.

[0028] R in the general formula (I) 5 A compound in which is a hydrogen atom is preferred because it has little cure shrinkage.

[0029] R in the general formula (I) 8 Compounds in which is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms are preferred because they have less cure shrinkage, and compounds in which is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms are preferred because they have even better cure properties.

[0030] The compound of the present invention preferably has a heterocycle because of reduced cure shrinkage, more preferably has a nitrogen-containing heterocycle, and particularly preferably has an isocyanurate ring.

[0031] The compound of the present invention preferably has two or more urethane bonds in the molecule because it reduces cure shrinkage, and more preferably has three or more urethane bonds in the molecule. Of these, it is preferable that the compound has a group represented by the following general formula (II) having a urethane bond and further has one or more other urethane bonds.

[0032] [ka] In the formula, R 11 and R 12 each independently represents a hydrogen atom or a methyl group, R 13 , R 14 , R 15 , R 16 and R 17 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group having 1 to 20 carbon atoms are substituted with a divalent group selected from the following <Group A>, * represents a bond. <Group A>: Carbon-carbon double bond, -O-, -S-, -CO-, -CO-O-, -SO2-

[0033] R in the general formula (II) 11 and R 12 A compound in which is a hydrogen atom is preferred because it has excellent curability.

[0034] R in the general formula (II) 13 ~R 16 Compounds in which is a hydrogen atom are preferred because they have little cure shrinkage and excellent curability.

[0035] R in the general formula (II) 17Compounds in which is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms are preferred because they have less cure shrinkage, and compounds in which is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms are preferred because they have even better cure properties.

[0036] The compound of the present invention preferably has a urethane value calculated by the following formula of 200 g / eq. to 400 g / eq., since this reduces cure shrinkage, and more preferably has a urethane value of 240 g / eq. to 300 g / eq. (Urethane value) = (molecular weight) / (number of urethane bonds in the molecule)

[0037] Among the compounds of the present invention, those having an isocyanurate ring include compounds represented by the following general formula (a).

[0038] [ka] In the formula, R 1 and R 2 each independently represents a hydrogen atom or a methyl group, R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 18 , R 19 , R 20 and R 21 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group having 1 to 20 carbon atoms are substituted with a divalent group selected from the following <Group A>, X 1 , X 2 and X 3 each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms, or a group in which one or more methylene groups in the divalent hydrocarbon group have been substituted with a divalent group selected from the following <Group A>, n and m each independently represent 0 or 1. <Group A>: Carbon-carbon double bond, -O-, -S-, -CO-, -CO-O-, -SO2-

[0039] Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms in the general formula (a) include groups in which one hydrogen atom has been removed from the groups exemplified as the hydrocarbon group having 1 to 20 carbon atoms in the general formula (I).

[0040] R in the general formula (a) 1 ~R 8 The preferred group is R 1 ~R 8 The preferred groups are the same as those given above.

[0041] In the general formula (a), n and m are 1, and R 5 , R 19 and R 2 A compound in which is a hydrogen atom has three urethane bonds in the molecule, and is preferred because it undergoes little cure shrinkage.

[0042] In the general formula (a), n and m are 1, and R 18 and R 20 Compounds in which is a hydrocarbon group having 1 to 20 carbon atoms are preferred because they have little cure shrinkage, and are more preferably alkyl groups having 1 to 20 carbon atoms or aryl groups having 6 to 20 carbon atoms, with alkyl groups having 1 to 10 carbon atoms or aryl groups having 6 to 10 carbon atoms being particularly preferred because they have good curability.

[0043] X in the general formula (a) 1 , X 2 and X 3 However, compounds having an alkylene group of 1 to 20 carbon atoms are preferred because they have small cure shrinkage, and because they have good curability, alkylene groups having 1 to 5 carbon atoms are more preferred, and alkylene groups having 1 to 3 carbon atoms are particularly preferred. Examples of alkylene groups having 1 to 3 carbon atoms include methylene, ethylene, isopropylene, and n-propylene.

[0044] X in the general formula (a) 1 , X 2 and X 3 When the alkylene group is an alkylene group having 1 to 20 carbon atoms, it is preferable that the alkylene group is a linear alkylene group, since this reduces shrinkage on cure.

[0045] Specific examples of the compound of the present invention include the following compounds.

[0046] [ka]

[0047] [ka]

[0048] The polymer of the present invention uses a compound having a group represented by the general formula (I) as a monomer, and can be produced by polymerizing the compound having a group represented by the general formula (I). The polymer may be a homopolymer of the compound, or a copolymer with another compound having an ethylenically unsaturated bond. The polymerization method is not particularly limited, and may be solution polymerization using a solvent, or bulk polymerization when the monomer is in a liquid state. The polymer of the present invention is preferred because it has excellent heat resistance.

[0049] The polymerization method for the polymer may be any method that can form a polymer with a desired molecular weight, and for example, a polymerization initiator can be used. The polymerization initiator used for the polymerization may be any radical polymerization initiator used for polymerizing a compound having an ethylenically unsaturated bond, and any conventionally known compound may be used. The radical polymerization initiator may be either a photoradical polymerization initiator or a thermal radical polymerization initiator.

[0050] Examples of the photoradical polymerization initiator include benzoins such as benzoin, benzoin methyl ether, benzoin propyl ether, and benzoin butyl ether; benzil ketals such as benzil dimethyl ketal; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1-benzyl-1-dimethylamino-1-(4'-morpholinobenzoyl)propane, 2-morpholyl-2-(4'-methylmercapto)benzoylpropane, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 1-hydroxy-1-benzoylcyclohexane, 2-hydroxy-2-benzoylpropane, 2-hydroxy-2-(4'-isopropyl)benzoylpropane, N,N-dimethylaminoacetophenone, 1,1-dichloroacetophenone, 4-butylbenzoyltrichloromethane, and 4-phenoxybenzo acetophenones such as 1-chloroanthraquinone, 2-amylanthraquinone, and other anthraquinones; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, methylbenzophenone, and 4,4'-dichlorobenzophenone Benzophenones such as 4,4'-bisdiethylaminobenzophenone, Michler's ketone, and 4-benzoyl-4'-methyldiphenyl sulfide; oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide; carbazoles such as 3-(2-methyl-2-morpholinopropionyl)-9-methylcarbazole; α-dicarbonyls such as benzyl and methyl benzoylformate;Oxygen compounds such as those described in JP 2000-80068 A, JP 2001-233842 A, JP 2005-97141 A, JP 2006-516246 A, Japanese Patent No. 3860170 A, Japanese Patent No. 3798008 A, WO2006 / 018973 A, JP 2011-132215 A, and WO2015 / 152153 A p-Methoxyphenyl-2,4-bis(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-naphthyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-butoxystyryl)-s-triazine Triazines such as triazine; benzoyl peroxide, 2,2'-azobisisobutyronitrile, ethyl anthraquinone, 1,7-bis(9'-acridinyl)heptane, thioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, diethylthioxanthone, benzophenone, phenyl biphenyl ketone, 4-benzoyl-4'-methyldiphenyl sulfide, 2-(p-butoxystyryl)-5-trichloromethyl-1,3,4-oxadiazole, 9-phenylacridine, 9,10-dimethylbenzphenazine, benzophenone / Michler's ketone, hexaarylbiimidazole / mercaptobenzimidazole, thioxanthone / amine, etc.;

[0051] Examples of the thermal radical polymerization initiator include azo compounds and organic peroxides. Examples of azo compounds include 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-methyl)dihydrochloride, 1,1'-azobis(1-acetoxy-1-phenylethane), 1,1'-azobis(cyclohexane-1-carboxamide), 1,1'-azobis(1-methyl-2-methylpropional ... Examples of suitable azo compounds include 2,2'-azobis(isobutyrate), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylpropionitrile), 2,2'-azobis(2-methylbutyronitrile), 1-[(1-cyano-1-methylethyl)azo]formamide, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, dimethyl 2,2'-azobis(2-methylpropionate), and 2,2'-azobis(N-butyl-2-methylpropionamide). Among these, azo compounds such as 2,2'-azobis(2-methylbutyronitrile) are preferred due to their high yield.

[0052] Examples of organic peroxides include benzoyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, di-tert-butyl peroxide, methyl ethyl ketone peroxide, 1,1-di(t-hexylperoxy)cyclohexane, 2,2-di(t-butylperoxy)butane, n-butyl 4,4-di(t-butylperoxy)valerate, 2,2-di(4,4-di(t-butylperoxy)cyclohexyl)propane, and p-menthane hydroperoxide.

[0053] Examples of commercially available thermal radical polymerization initiators include "AIBN" (2,2'-azobis(isobutyronitrile)), "V-40" (1,1'-azobis(cyclohexane-1-carbonitrile), "VAm-110" (2,2'-azobis(N-butyl-2-methylpropionamide), and "V-601" (dimethyl 2,2'-azobis(isobutyrate)), all manufactured by Wako Pure Chemical Industries, Ltd.; and "OTAZO-15" (1,1'-azobis(1-acetoxy-1-phenylethane) and "MAIB" (dimethyl 2,2'-azobisisobutyrate), all manufactured by Otsuka Chemical Co., Ltd.

[0054] The thermal radical polymerization initiator used preferably has a 10-hour half-life temperature of 40°C to 80°C, more preferably 50°C to 70°C, from the viewpoints of reaction efficiency and safety.

[0055] Examples of other compounds having an ethylenically unsaturated bond used in the case of a copolymer include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobutyl acrylate, N-octyl acrylate, isooctyl acrylate, isononyl acrylate, stearyl acrylate, methoxyethyl acrylate, dimethylaminoethyl acrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, tris(2-acryloyloxyethyl) isocyanurate, dipentaerythritol pentaacrylate, and the like. Examples of the acrylate compounds include acrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, and tricyclodecane dimethylol diacrylate; and methacrylate compounds such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, butyl methacrylate, tertiary butyl methacrylate, cyclohexyl methacrylate, trimethylolpropane trimethacrylate, and tris(2-methacryloyloxyethyl) isocyanurate.

[0056] A polymer copolymerized with at least one of an acrylate compound and a methacrylate compound as a monomer is preferred because it has excellent adhesion to a substrate. In order to reduce cure shrinkage, the ratio of the compound of the present invention to the total monomers is preferably 50 wt% or more, more preferably 75 wt% or more, and particularly preferably 90 wt% or more.

[0057] The polymerizable composition of the present invention contains the compound. A polymerizable composition containing the compound is preferred because it has small cure shrinkage. The polymerizable composition may contain the polymer and may also contain the polymerization initiator. The components constituting the polymerizable composition are as described above.

[0058] The content of the polymerization initiator is preferably 0.1 to 10 parts by mass, more preferably 1 to 5 parts by mass, relative to 100 parts by mass of the compound or the polymer, as this provides excellent curability.

[0059] The content of the radical polymerization initiator is preferably 0.5 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, and even more preferably 0.5 to 6 parts by mass, relative to 100 parts by mass of the "compound having an ethylenically unsaturated bond".

[0060] The polymerizable composition may contain a solvent. The solvent may be any solvent capable of dissolving or dispersing each component of the polymerizable composition (such as the compound of the present invention), and examples thereof include ketone-based solvents such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; ether-based solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, and dipropylene glycol dimethyl ether; ester-based solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, 3-methoxybutyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and Texanol; cellosolve-based solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; alcohol-based solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, and amyl alcohol; ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol monomethyl ether, Ether ester solvents such as propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, and ethoxyethyl propionate; BTX solvents such as benzene, toluene, and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane, and cyclohexane; terpene hydrocarbon oils such as turpentine oil, D-limonene, and pinene; mineral spirits, Swazol #310 (all manufactured by Cosmo Matsuyama Oil); and Solvesso #100 (all manufactured by Exxon Chemical). halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, and 1,2-dichloroethane; halogenated aromatic hydrocarbon solvents such as chlorobenzene; carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, and water, and these solvents can be used alone or in combination as a mixed solvent of two or more.Ether solvents are preferred, and 1,4-dioxane is particularly preferred, as they provide good yields.

[0061] The molecular weight can be controlled by controlling the monomer concentration. Polymerization at 0.01M to 1.0M is preferred because it allows control of the weight average molecular weight of the polymer. Controlling the monomer concentration to 0.01M to 0.5M is even more preferred because it allows for the production of a polymer with a narrow molecular weight distribution. Considering efficiency such as reaction time and polymer yield, it is particularly preferred to control the concentration to 0.05M to 0.3M.

[0062] The polymerizable composition may contain an ultraviolet absorber, such as a benzotriazole-based ultraviolet absorber, a triazine-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, a cyanoacrylate-based ultraviolet absorber, or inorganic particles that absorb ultraviolet light, such as titanium oxide particles. These ultraviolet absorbents may be used alone or in combination of two or more.

[0063] The polymerizable composition may contain various components depending on the purpose, for example, a hindered amine light stabilizer (HALS) for improving weather resistance, an antioxidant for improving heat resistance and weather resistance, or a radical polymerization inhibitor for improving storage stability.

[0064] When the polymerizable composition contains a polymerization initiator, the curing of the polymerizable composition can be carried out by generating radicals from the polymerization initiator. When the polymerization initiator is a photoradical polymerization initiator, radicals are generated by irradiation with light, and when the polymerization initiator is a thermal radical polymerization initiator, radicals are generated by heating.

[0065] Specific examples of the curing method include a method in which the polymerizable composition is applied to a substrate, dried as necessary, and then heated or irradiated with light such as ultraviolet light to form a cured film. The curing conditions may be appropriately determined depending on the types of monomer and initiator used.

[0066] When the polymerizable composition contains a photoradical polymerization initiator, a cured product can be produced by a production method including a light irradiation step. Examples of light sources include ultra-high pressure mercury lamps, high pressure mercury lamps, medium pressure mercury lamps, low pressure mercury lamps, mercury vapor arc lamps, xenon arc lamps, carbon arc lamps, metal halide lamps, fluorescent lamps, tungsten lamps, excimer lamps, germicidal lamps, light emitting diodes, and CRT light sources. Preferably, ultra-high pressure mercury lamps, mercury vapor arc lamps, carbon arc lamps, xenon arc lamps, and the like that emit light with a wavelength of 300 to 450 nm are used.

[0067] The polymerizable composition and cured product of the present invention can be used in a variety of applications, including curable paints, varnishes, curable adhesives, printed circuit boards, display devices (color filters in color display liquid crystal display panels for color displays such as color televisions, PC monitors, personal digital assistants, and digital cameras, color filters for various display applications, color filters for CCD image sensors, touch panels, electroluminescent display devices, plasma display panels, and black partition walls for organic EL), powder coatings, printing inks, printing plates, adhesives, gel coats, photoresists for electronics, electroplating resists, etching resists, solder resists, insulating films, black matrices, and resists for forming structures in the manufacturing process of LCDs, and resists for encapsulating electrical and electronic components. The compounds can be used in a variety of applications, such as compositions for forming three-dimensional objects by stereolithography, solder resists, magnetic recording materials, micromechanical components, waveguides, optical switches, plating masks, etching masks, color test systems, glass fiber cable coatings, screen printing stencils, materials for producing three-dimensional objects by stereolithography, holographic recording materials, image recording materials, fine electronic circuits, bleaching materials, bleaching materials for image recording materials, bleaching materials for image recording materials using microcapsules, photoresist materials for printed wiring boards, photoresist materials for UV and visible laser direct imaging systems, photoresist materials and protective films used to form dielectric layers in the sequential lamination of printed circuit boards.

[0068] The polymerizable composition of the present invention is particularly useful as an adhesive because it has excellent positional accuracy due to its small cure shrinkage and high adhesion, and is also particularly useful as a coating agent because it has small cure shrinkage and little deformation after curing.

[0069] The method for producing a cured product of the present invention includes a step of irradiating the polymerizable composition with light, and can be the same as the light irradiation step mentioned in the method for producing a cured product of the polymerizable composition described above. [Example]

[0070] EXAMPLES The present invention will be specifically explained below by showing examples and comparative examples, but the present invention is not limited to the following examples in any way.

[0071] (Intermediate Production Example 1) Tris(2-hydroxyethyl)isocyanurate (15.66 g; 60.00 mmol), imidazole (10.20 g; 149.8 mmol), and N,N-dimethylformamide (50 mL) were added to a 200 mL two-neck flask and stirred until a homogeneous solution was obtained. Next, a solution of tert-butyldimethylsilyl chloride (10.86 g; 72.00 mmol) in DMF (40 mL) was placed in a dropping funnel and attached to the two-neck flask, and the entire system was purged with nitrogen. The solution was slowly added dropwise from the dropping funnel in an ice bath. After the addition was complete, the reaction solution was stirred at room temperature for 12 hours and then quenched by adding 5% aqueous sodium carbonate (20 mL). The reaction solution was partitioned between ethyl acetate (400 mL) and 5% aqueous sodium carbonate (200 mL). The organic layer was dried over sodium sulfate for 2 hours, then filtered. The resulting filtrate was concentrated under reduced pressure to remove the solvent. Finally, the reaction residue was fractionated by silica gel column chromatography (eluent: hexane / ethyl acetate = 2 / 1 → 1 / 1 → 1 / 4) to obtain the desired Diol as a white solid (yield 7.90 g; 21.1 mmol, 35%). mp=70.2-72.1 o C. 1 H-NMR (400 MHz, CDCl3, at rt, ppm) δ 4.14 (t, J = 5.2 Hz, 4H), 4.06 (t, J = 6.0 Hz, 2H), 3.86-3.81 (m, 6H), 2.66 (s, 2H), 0.86 (s, 9H), 0.04 (s, 6H); 13 C-NMR (100 MHz, CDCl3, at rt, ppm) δ 150.48, 149.60, 60.58, 59.60, 45.29, 44.78, 25.89, 18.35, -5.37; -1 ) ν 3249, 2936, 2930, 2861, 2858, 1675, 1448, 1354, 1322, 1253, 1192, 1094, 991, 913, 836, 773. HRMS m / z: [M+H]+ Calcd for [C 15 H 30 N3O6Si1] + 376.19039; Found 376.19058.

[0072] [ka]

[0073] (Intermediate Production Example 2) Diol (1.50 g; 4.00 mmol) and dibutyltin dilaurate (152 mg; 0.240 mmol) were dissolved in dichloromethane (4.0 mL) in a 50 mL recovery flask and the atmosphere was purged with nitrogen. A solution of benzyl isocyanate (1.07 g; 8.04 mmol) in dichloromethane (4.0 mL) was slowly added via syringe, and the reaction mixture was allowed to react at 60 °C for 4 hours. Next, a 1 M solution of tetrabutylammonium fluoride in THF (4.4 mL; 4.4 mmol) was added to the reaction mixture and the mixture was allowed to react at room temperature for 2 hours. The reaction mixture was concentrated under reduced pressure to remove the solvent. The resulting residue was fractionated by silica gel column chromatography (eluent: hexane / ethyl acetate = 1 / 2 → 1 / 4) to obtain the desired BU(Bn)OH as a white solid (yield: 1.61 g; 3.05 mmol, 76%). mp=63.2-69.4 o C; 1 H-NMR (400 MHz, DMSO-d6, at rt, ppm) δ 7.67 (t, J = 6.2 Hz, 2H), 7.31-7.19 (m, 10H), 4.81 (s, 1H), 4.14 (t, J = 6.2 Hz, 8H), 3.98 (t, J = 5.4 Hz, 4H), 3.81 (t, J = 6.4 Hz, 2H), 3.51 (brs, 2H); 13C-NMR (100 MHz, DMSO-d6, at rt, ppm) δ 156.27, 148.89, 148.86, 139.59, 128.24, 126.96, 126.77, 60.47, 57.42, 44.31, 43.75, 41.67; IR (ATR, cm -1 ) ν 3340, 3028, 2962, 2926, 1674, 1522, 1450, 1358, 1315, 1236, 1134, 1039, 760, 696; HRMS m / z: [M+Na] + Calcd for [C 25 H 29 N5Na1O8] + 550.19138; Found 550.19204.

[0074] [ka]

[0075] Example 1 BU(Bn)OH (791 mg; 1.50 mmol) and dibutyltin dilaurate (19 mg; 0.030 mmol) were dissolved in dichloromethane (3.0 mL) in a 30 mL recovery flask and the atmosphere was purged with nitrogen. 1,1-(bisacryloyloxymethyl)ethyl isocyanate (395 mg; 1.65 mmol) was added to the solution via syringe and the mixture was allowed to react at 40 °C for 2 hours. The reaction solution was concentrated under reduced pressure to remove the solvent. The resulting residue was fractionated by silica gel column chromatography (eluent: hexane / ethyl acetate = 1 / 2), yielding the desired BU(Bn)DUA as a colorless, transparent liquid (yield: 1.11 g; 1.45 mmol, 97%). 1H-NMR (400 MHz, DMSO-d6, at rt, ppm) δ 7.65 (t, J = 6.0 Hz, 2H), 7.30-7.18 (m, 11H), 6.32 (dd, J = 1.6, 17.6 Hz, 2H), 6.14 (dd, J = 10.0, 10.8 Hz, 2H), 5.93 (dd, J = 1.2, 10.0 Hz, 2H), 4.21-3.94 (m, 20H), 1.24 (s, 3H); 13 C-NMR (100 MHz, DMSO-d6, at rt, ppm) δ 165.45, 156.08, 154.69, 148.89, 148.82, 133.68, 133.55, 131.69, 128.23, 128.12, 128.01, IR (ATR, cm -1 ) ν 3327, 2956, 1682, 1522, 1452, 1406, 1363, 1240, 1182, 1061, 982, 808, 762, 698, 602; HRMS m / z: [M+Na] + Calcd for [C 36 H 42 N6Na1O 13 ] + 789.27075; Found 789.27136.

[0076] Example 2 BU(Bn)DUA (307 mg; 0.400 mmol) and photoinitiator A (8.5 mg; 0.016 mmol) were dissolved in N,N-dimethylformaldehyde (0.80 mL) in a 10 mL recovery flask and the atmosphere was purged with nitrogen. The reaction mixture was stirred at room temperature and irradiated with 2000 mW of light at 365 nm for 6 hours. The reaction solution was poured into methanol to reprecipitate the product. The resulting precipitate was collected by suction filtration and dried at 100 °C and 0.10 MPa for 12 hours to obtain the desired Poly(BU(Bn)DUA) as a pale yellow solid (yield: 254 mg, 83%). Mn=25200, Mw=378000, Mw / Mn=15.00; 1 H-NMR (400 MHz, DMSO-d6, at rt, ppm) δ 7.62 (brs, 2H), 7.33-7.20 (brm, 11H), 4.27-3.98 (brm, 20H), 2.31 (brs, 1H), 1.68 (brs, 2H), 1.22 IR (ATR, cm -1 ) ν 3342, 3028, 2953, 1682, 1518, 1452, 1371, 1317, 1236, 1142, 1078, 1041, 762, 698.

[0077] [ka]

[0078] Example 3 BU(Bn)DUA (230 mg; 0.300 mmol) and photoinitiator A (6.3 mg; 0.012 mmol) were dissolved in N,N-dimethylformaldehyde (3.0 mL) in a 10 mL recovery flask and the atmosphere was purged with nitrogen. The reaction mixture was stirred at room temperature and irradiated with 2000 mW of light at 365 nm for 6 hours. The reaction solution was poured into methanol to reprecipitate the product. The resulting precipitate was collected by suction filtration and dried under conditions of 100 °C and 0.10 MPa for 12 hours to obtain the desired Poly(BU(Bn)DUA) as a pale yellow solid (yield: 180 mg, 78%). Mn=8600, Mw=14700, Mw / Mn=1.71; 1H-NMR (400 MHz, DMSO-d6, at rt, ppm) δ 7.62 (brs, 2H), 7.33-7.20 (brm, 11H), 4.27-3.98 (brm, 20H), 2.31 (brs, 1H), 1.68 (brs, 2H), 1.22 IR (ATR, cm -1 ) ν 3342, 3028, 2953, 1682, 1518, 1452, 1371, 1317, 1236, 1142, 1078, 1041, 762, 698.

[0079] Example 4 BU(Bn)DUA (153 mg; 0.200 mmol) and photoinitiator A (2.1 mg; 0.0040 mmol) were dissolved in N,N-dimethylformaldehyde (0.1 mL) in a 10 mL recovery flask and the atmosphere was purged with nitrogen. The reaction mixture was stirred at room temperature and irradiated with 2000 mW of light at 365 nm for 6 hours. The reaction solution was poured into methanol to reprecipitate the product. The resulting precipitate was collected by suction filtration and dried under conditions of 100 °C and 0.10 MPa for 12 hours, yielding the desired Poly(BU(Bn)DUA) as a pale yellow solid (144 mg, 94%). IR (ATR, cm -1 ) ν 3342, 3028, 2953, 1682, 1518, 1452, 1371, 1317, 1236, 1142, 1078, 1041, 762, 698.

[0080] (Comparative Example 1) Comparative polymer 1 was obtained in the same manner as in Example 3, except that bis(acryloyloxyethyl)hydroxyethyl isocyanurate (111 mg; 0.300 mmol) was used instead of BU(Bn)DUA (yield: 101 mg, 91%).

[0081] (Comparative Example 2) Comparative polymer 2 was obtained in the same manner as in Example 3, except that polyethylene glycol diacrylate (90.8 mg; 0.300 mmol) was used instead of BU(Bn)DUA (yield: 84.4 mg, 93%).

[0082] (Comparative Example 3) Comparative polymer 3 was obtained in the same manner as in Example 3, except that tricyclodecane dimethanol diacrylate (91.3 mg; 0.300 mmol) was used instead of BU(Bn)DUA (yield: 83.1 mg, 91%).

[0083] <Volume change rate> The volume change rates of the polymers obtained in Examples 3 to 5 and Comparative Examples 1 to 3 were measured as follows. The results are shown in Table 1. The densities of the monomer and polymer were measured under a helium atmosphere using a SHIMADZU AccuPyc 1330, and the volume change rate was calculated using the following formula: In the volume change rate, "-" indicates volume contraction, and "+" indicates volume expansion. [(density of monomer - density of polymer) / density of monomer] x 100 The smaller the volume change rate, the less curling the coating agent will have, which is preferable. The volume change rate is preferably +5% to -5%, and more preferably +1% to -1%.

[0084] [Table 1]

[0085] As shown in Table 1, the compound of the present invention has a small volume change rate when polymerized, and exhibits little shrinkage on curing.

Claims

1. A compound represented by the following general formula (a): 【Chemical 1】 In the formula, R 1 and R 2 each independently represent a hydrogen atom or a methyl group; R 3 , R 4 , R 5 , R 6 , R 7 and R 8 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group having 1 to 20 carbon atoms are substituted with a divalent group selected from the following <Group A>: R 18 , R 19 , R 20 and R 21 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; X 1 , X 2 and X 3 each independently represent a divalent hydrocarbon group having 1 to 20 carbon atoms, or a divalent hydrocarbon group in which one or more methylene groups have been substituted with a divalent group selected from the following <Group A>: n and m each independently represent 0 or 1. <Group A>: carbon-carbon double bond, —O—, —S—, —CO—, —CO—O—, —SO 2 —

2. A polymer comprising the compound according to claim 1 as a monomer.

3. A polymerizable composition comprising the compound according to claim 1.

4. An adhesive comprising the polymerizable composition according to claim 3 .

5. A coating agent comprising the polymerizable composition according to claim 3.

6. A cured product of the polymerizable composition according to claim 3.

7. A method for producing a cured product, comprising a step of irradiating the polymerizable composition according to claim 3 with light.

8. A method for producing a polymer, comprising polymerizing the compound according to claim 1.

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