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

Abstract

To provide urethane compounds that expand in volume when polymerized, and to provide polymerizable compositions with little volume change during curing.SOLUTION: Provided is an urethane compound represented by the general formula (I) in the figure. (In the formula, one or two of R1, R2, R3, R4, R5 and R6 are ethylenically unsaturated bond-containing groups or groups having ethylenically unsaturated bond-containing groups as substituents; and X1, X2 and X3 each independently represent a divalent hydrocarbon group having 1 to 20 carbon atoms, or the like.)SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] Urethane compounds containing urethane bonds and ethylenically unsaturated bonds are UV-curable and are therefore widely used in coatings, adhesives, UV-curable paints, resists, etc. In these applications, there is often a trade-off between curability and low cure shrinkage, and achieving both has been a challenge.

[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 urethane compound which expands in volume when polymerized, and to provide a polymerizable composition which undergoes little change in volume upon curing.

Means for Solving the Problems

[0006] As a result of intensive studies, the present inventors have found that a specific urethane compound having a benzene ring structure expands in volume during curing. Therefore, when used in combination with an existing radically polymerizable compound that contracts in volume (curing shrinkage) during curing, the volume change when made into a polymer is suppressed, and the present invention has been completed.

[0007] <A. Urethane Compound> The present invention is a urethane compound represented by the following general formula (I).

[0008]

Chemical formula

[0009] The polymerizable composition using the urethane compound of the present invention undergoes little change in volume upon curing, and is therefore useful as a coating agent or adhesive. DETAILED DESCRIPTION OF THE INVENTION

[0010] The urethane compound of the present invention is represented by the above general formula (I) and has at least one ethylenically unsaturated bond-containing group in the molecule.

[0011] The ethylenically unsaturated bond-containing group is a group having a carbon-carbon double bond at its terminal, and examples thereof include a vinyl group, a vinyloxy group, an allyl group, an allyloxy group, an allylamino group, an isopropenyl group, an isopropenyloxy group, an isopropenylamino group, an acryloyl group, an acryloyloxy group, an acrylamide group, a methacryloyl group, a methacryloyloxy group, and a methacrylamide group.

[0012] A urethane compound in which the ethylenically unsaturated bond-containing group is an acryloyloxy group or a methacryloyloxy group is preferred because of its excellent curability, and an acryloyloxy group is more preferred because of its even more excellent curability.

[0013] A urethane compound in which the total number of acryloyloxy groups and methacryloyloxy groups present in the molecule is 1 is preferred because it has a small volume change.

[0014] The hydrocarbon group having 1 to 20 carbon atoms 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.

[0015] 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.

[0016] 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.

[0017] 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.

[0018] 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.

[0019] 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.

[0020] 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.

[0021] 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.

[0022] 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.

[0023] 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.

[0024] Examples of the substituent that the hydrocarbon group having 1 to 20 carbon atoms may have include the above-mentioned ethylenically unsaturated bond-containing group, a halogen atom, a halogenated alkyl group having 1 to 3 carbon atoms, a cyano group, a nitro group, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, an amino group, a carboxy group, an epoxy group, a mercapto group, and an isocyanate group.

[0025] Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms include divalent groups obtained by removing one hydrogen atom from the hydrocarbon group having 1 to 20 carbon atoms, such as alkylene groups having 1 to 20 carbon atoms and arylene groups having 6 to 20 carbon atoms.

[0026] 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.

[0027] 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 after 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 after the methylene group in the alkyl group is replaced with the divalent group, not the number of carbon atoms before the replacement.

[0028] R in the general formula (I) 1 , R 2 and R 3 A urethane compound in which one or two of the above are ethylenically unsaturated bond-containing groups is preferred because it results in a polymerizable composition that undergoes little volume change during curing and has high curability.

[0029] When the ethylenically unsaturated bond-containing group is a hydrocarbon group having 3 to 20 carbon atoms and having an ethylenically unsaturated bond, or a group in which one or more methylene groups in the hydrocarbon group having 3 to 20 carbon atoms and having an ethylenically unsaturated bond have been substituted with a divalent group selected from the above <Group A>, it is preferable because a polymerizable composition having a small volume change during curing and high curability can be obtained.

[0030] R 1 , R 2 and R 3 Urethane compounds in which one of the groups is an ethylenically unsaturated bond-containing group are preferred because they result in a polymerizable composition that undergoes less volume change upon curing, and urethane compounds in which the group is a hydrocarbon group having 4 to 10 carbon atoms are particularly preferred.

[0031] In particular, R in the general formula (I) 1 , R 2 and R 3 A urethane compound in which one or two of R are an acryloyloxy group or a methacryloyloxy group, or a hydrocarbon group having 3 to 20 carbon atoms and having such a group as a substituent is preferred because it has a smaller volume change during curing and can provide a polymerizable composition with higher curability. 1 , R 2 and R 3 Preferably, one of the groups is an acryloyloxy group or a methacryloyloxy group, or a hydrocarbon group having 3 to 10 carbon atoms and having such a group as a substituent.

[0032] R in the general formula (I) 4 , R 5 and R 6 However, urethane compounds containing hydrogen atoms are preferred because they provide polymerizable compositions that undergo little change in volume upon curing.

[0033] X in the general formula (I) 1 , X 2 and X 3A compound in which the alkylene group has 1 to 20 carbon atoms is preferred because a polymerizable composition with a small volume change during curing can be obtained, and it is more preferred that the alkylene group has 1 to 5 carbon atoms.

[0034] X in the general formula (I) 1 X 2 and X 3 When they are alkylene groups having 1 to 20 carbon atoms, it is preferred that the alkylene group is a linear alkylene group because the volume change during curing of the resulting polymerizable composition is small.

[0035] Specific examples of the urethane compound of the present invention include the following compounds.

[0036]

Chemical formula

[0037]

Chemical formula

[0038] [[ID=…]] [[ID=…]]

Chemical formula

[0039]

Chemical formula

[0040]

Chemical formula

[0041]

Chemical formula

[0042] <00…]]] <B. Polymer> The polymer of the present invention is one containing a urethane compound represented by the general formula (I) as a monomer. The polymer may be a homopolymer of the urethane compound, or a copolymer with a radically polymerizable compound other than the urethane compound. The polymer of the present invention is preferred because it has excellent adhesion to substrates.

[0043] When synthesizing the polymer of the present invention, 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 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 monomer concentration to 0.05M to 0.3M.

[0044] The polymerization initiator used for the polymerization may be any radical polymerization initiator used for the polymerization of a radically polymerizable compound, 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.

[0045] The radical polymerizable compound is a compound having a radically polymerizable reactive group, and is preferably a compound containing an ethylenically unsaturated bond because of its high reactivity. The radical polymerizable compound may be used alone or in combination of two or more kinds. The urethane compound of the present invention is a type of radically polymerizable compound.

[0046] The radical polymerizable compound other than the urethane compound is preferably an unsaturated carboxylic acid ester compound, more preferably a (meth)acrylate. In this specification, "(meth)acrylate" means acrylate or methacrylate, and "(meth)acrylic" means acrylic or methacrylic.

[0047] Examples of monofunctional (meth)acrylates include isoamyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, isomylstyryl (meth)acrylate, isostearyl (meth)acrylate, 2-ethylhexyl-diglycol (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-(meth)acryloyloxyethyl hexahydrophthalate, butoxyethyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, methoxydiethylene glycol (meth)acrylate, and methoxypolyethylene. Examples of the acrylates include propylene glycol (meth)acrylate, methoxypropylene glycol (meth)acrylate, phenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acryloyloxyethyl-2-hydroxyethyl phthalate, and t-butylcyclohexyl (meth)acrylate.

[0048] Examples of polyfunctional (meth)acrylates include triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, bisphenol A PO adduct di(meth)acrylate, and hydroxypivalic acid neopentyl glycol di(meth)acrylate. Examples of the acrylate include difunctional (meth)acrylates such as poly(meth)acrylate, polytetramethylene glycol di(meth)acrylate, polyethylene glycol diacrylate, and tripropylene glycol diacrylate, and trifunctional or higher (meth)acrylates such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, glycerin propoxy tri(meth)acrylate, and pentaerythritol ethoxy tetra(meth)acrylate.

[0049] 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.;

[0050] 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-carbonitrile), dimethyl 2,2'-azobis(isobutyrate), 2,2'-azobis(4-methoxy-2,4-dimethyl) Examples of suitable azo compounds include 2,2'-azobis(2-methylbutyronitrile), 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.

[0051] 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.

[0052] 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)), "V-601" (dimethyl 2,2'-azobis(isobutyrate)) manufactured by Wako Pure Chemical Industries, Ltd., "OTAZO-15" (1,1'-azobis(1-acetoxy-1-phenylethane)), "MAIB" (dimethyl 2,2'-azobisisobutyrate) manufactured by Otsuka Chemical Co., Ltd., and the like.

[0053] As the thermal radical polymerization initiator to be used, those having a 10-hour half-life temperature of 40°C to 80°C are preferable, and those having a 10-hour half-life temperature of 50°C to 70°C are more preferable, from the viewpoints of reaction efficiency and safety.

[0054] In the case of the copolymer, since a polymerizable composition with a small volume change during curing can be obtained, it is preferable that the ratio of the urethane compound of the present invention be 50 wt% or more, more preferably 75 wt% or more, and particularly preferably 90 wt% or more in all the radically polymerizable compounds.

[0055] <C. Polymerizable composition> The polymerizable composition of the present invention contains the above urethane compound. The polymerizable composition containing the compound is preferable because it has a small volume change during curing. Further, the polymerizable composition preferably contains the polymerization initiator. Each component constituting the polymerizable composition is as described above.

[0056] In addition to the urethane compound of the present invention, the polymerizable composition of the present invention can be used in combination with a radically polymerizable compound other than the urethane compound of the present invention.

[0057] The content of the polymerization initiator is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, and still more preferably 1 to 6 parts by mass with respect to 100 parts by mass of all the radically polymerizable compounds including the urethane compound, because of good curability.

[0058] The content of the radical polymerizable compound (including the urethane compound of the present invention) in the polymerizable composition of the present invention is preferably 30 parts by mass to 99.9 parts by mass per 100 parts by mass of the solid content of the polymerizable composition in order to obtain good curability, and is preferably 40 parts by mass to 99.5 parts by mass in order to obtain even better curability, and particularly preferably 50 parts by mass to 99 parts by mass. The solid content refers to the components remaining after excluding the solvent, which will be described later, from the polymerizable composition.

[0059] The content of the urethane compound of the present invention is preferably 30 parts by mass or more, more preferably 40 parts by mass or more, and particularly preferably 50 parts by mass or more, per 100 parts by mass of all radically polymerizable compounds in total, because volume change is small.

[0060] The polymerizable composition may contain a solvent, which is a compound that is liquid at 25° C. and 1 atmosphere, and does not belong to the above radical polymerizable compounds and polymerization initiators.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 and polar solvents are preferred because they provide good yields, and 1,4-dioxane and dimethylformamide are particularly preferred. The content of the solvent is preferably adjusted so that the monomer concentration is 0.10M to 1.0M.

[0061] 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.

[0062] 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.

[0063] 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.

[0064] 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.

[0065] When the polymerizable composition contains a photo radical polymerization initiator, a cured product can be produced by a production method having a step of irradiating light. Examples of the light source include an ultra-high pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a mercury vapor arc lamp, a xenon arc lamp, a carbon arc lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, an excimer lamp, a germicidal lamp, a light emitting diode, a CRT light source, etc. Preferably, an ultra-high pressure mercury lamp, a mercury vapor arc lamp, a carbon arc lamp, a xenon arc lamp, etc. that emit light with a wavelength of 300 to 450 nm are used.

[0066] The polymerizable composition of the present invention can reduce the volume change during curing by using the urethane compound of the present invention that expands in volume during curing and an existing radical polymerizable compound that shrinks during curing, so it has excellent positional accuracy and high adhesion, and is particularly useful as an adhesive. In addition, since the volume change during curing is small and the deformation after curing is small, it is also particularly useful as a coating agent.

[0067] <D. Adhesive> Since the polymerizable composition of the present invention has a small volume change before and after curing, it can be preferably used as an adhesive with excellent positional accuracy. Among the above applications, it is particularly useful as an adhesive for fixing a camera lens or a CD image sensor.

[0068] <E. Coating agent> Since the polymerizable composition of the present invention has a small volume change before and after curing, it can be preferably used as a coating agent with little deformation after curing. Among the above applications, it is particularly useful as a coating agent such as a surface coating agent for a touch panel device.

[0069] <F. Cured product> Since the polymerizable composition and cured product of the present invention have a small volume change before and after curing, they can be used in curable paints, varnishes, curable adhesives, printed circuit boards, display devices (color filters in liquid crystal display panels for color displays such as color TVs, PC monitors, portable information terminals, and digital cameras, color filters for various display applications, color filters for CCD image sensors, touch panels, electroluminescent display devices, plasma display panels, black partitions of organic ELs), powder coatings, printing inks, printing plates, adhesives, gel coats, photoresists for electronic engineering, electroplating resists, etching resists, solder resists, insulating films, black matrices, and resists for forming structures in the manufacturing process of LCDs, compositions for encapsulating electrical and electronic components, solder resists, magnetic recording materials, micro mechanical parts, waveguides, optical switches, plating masks, etching masks, color test systems, glass fiber cable coatings, stencils for screen printing, materials for manufacturing three-dimensional objects by stereolithography, materials for holographic recording, image recording materials, microelectronic circuits, decoloring materials, decoloring materials for image recording materials, decoloring materials for image recording materials using microcapsules, photoresist materials for printed wiring boards, photoresist materials for UV and visible laser direct imaging systems, and photoresist materials and protective films used for forming dielectric layers in the sequential lamination of printed circuit boards, and can be used in various applications such as these.

[0070] <G. Method for manufacturing cured product> The method for manufacturing the cured product of the present invention has a step of irradiating the polymerizable composition with light, and can be the same as the step of irradiating with light mentioned in the method for manufacturing the cured product of the above-mentioned polymerizable composition.

Examples

[0071] Hereinafter, the present invention will be specifically described by showing examples and comparative examples, but the present invention is not limited by the following examples and the like.

[0072]

Chemical formula

[0073] Example 1 In a 50 mL recovery flask, 1,3,5-tris(hydroxymethyl)benzene (Triol, 1.68 g; 10.0 mmol) and dibutyltin dilaurate (126 mg; 0.200 mmol) were dissolved in tetrahydrofuran (10 mL) and the atmosphere was purged with nitrogen. Hexyl isocyanate (2.80 g; 22.0 mmol) was slowly added to the reaction mixture via syringe and the mixture was allowed to react at 60 °C for 16 hours. The reaction residue was fractionated by silica gel column chromatography (eluent: hexane / ethyl acetate = 2 / 1 → 1 / 1 → 1 / 2) to obtain the desired BU(BzHexyl)OH as a white solid (yield: 1.50 g; 3.54 mmol, 35%). mp=87.6-88.5 o C; 1 H-NMR (400 MHz, CDCl3, at rt, ppm) δ 7.29 (s, 2H), 7.24 (s, 1H), 5.07 (s, 4H), 4.82 (s, 2H), 4.69 (d, J = 5.6 Hz, 2H), 3.17 (dt, J = 6.8, 14.0 Hz, 4H), 2.07 (t, J = 5.6 Hz, 1H), 1.51-1.46 (m, 4H), 1.34-1.29 (m, 12H), 0.88 (t, J = 6.8 Hz, 6H); 13 C-NMR (100 MHz, CDCl3, at rt, ppm) δ 156.44, 141.70, 137.49, 126.86, 126.28, 66.31, 65.00, 41.27, 31.58, 30.03, 26.54, 22.68, 14.15; IR (ATR, cm -1 ) ν 3305, 2945, 2926, 2856, 1686, 1533, 1456, 1252, 1142, 1043, 993, 852, 777; HRMS m / z: [M+Na] + Calcd for [C 23 H 38 N2Na1O5] +445.26784; Found 445.26767.

[0074] In a 30 mL recovery flask, BU(Bz Hexyl)OH (845 mg; 2.00 mmol) and dibutyltin dilaurate (25 mg; 0.040 mmol) were dissolved in THF (2.0 mL) and the atmosphere was purged with nitrogen. 2-Isocyanatoethyl acrylate (339 mg; 2.40 mmol) was added to the solution via syringe and the mixture was allowed to react at 60 °C for 2 hours. The reaction solution was concentrated under reduced pressure to remove the solvent, and the resulting residue was fractionated by silica gel column chromatography (eluent: hexane / ethyl acetate = 1 / 1) to obtain the target BU(Bz Hexyl)UA as a colorless, transparent liquid (yield: 1.08 g; 1.92 mmol, 96%). 1 H-NMR (400 MHz, CDCl3, at rt, ppm) δ 7.29 (s, 3H), 6.43 (dd, J = 1.2, 16.8 Hz, 1H), 6.12 (dd, J = 10.0, 17.2 Hz, 1H), 5.86 (dd, J = 1.2, 10.0 Hz, 1H), 5.13-5.08 (m, 6H), 4.90-4.59 (m, 3H), 4.25 (t, J = 5.4 Hz, 2H), 3.52 (dt, J = 5.2, 10.8 Hz, 2H), 3.18 (dt, J = 5.2, 10.8 Hz, 4H), 1.51-1.46 (m, 4H), 1.35-1.26 (m, 12H), 0.88 (t, J = 6.8 Hz, 3H); 13 C-NMR (100 MHz, CDCl3, at rt, ppm) δ 166.16, 156.38, 137.45, 137.06, 131.57, 128.00, 127.35, 66.42, 66.05, 41.21, 40.23, 31.54, 29.94, 26.50, 22.63, 14.11; IR (ATR, cm -1) ν 3319, 3269, 3140, 2941, 2927, 2856, 1724, 1687, 1612, 1541, 1458, 1406, 1336, 1254, 1190, 1149, 1088, 1039, 984, 845, 808, 766; HRMS m / z: [M+Na] + Calcd for [C 29 H 45 N3Na1O8] + 586.31043; Found 586.30988.

[0075] Example 2 In a 10 mL recovery flask, BU(Bz Hexyl)UA (282 mg; 0.500 mmol) and photoinitiator A (5.3 mg; 0.010 mmol) were dissolved in N,N-dimethylformaldehyde (1.0 mL) 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 8 hours. The reaction solution was then reprecipitated in methanol. 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(Bz)UA) as a pale yellow solid (yield: 275 mg; 0.488 mmol, 98%). Mn=10000, Mw=17100, Mw / Mn=1.71; 1 H-NMR (400 MHz, CDCl3, at rt, ppm) δ 7.09 (brs, 3H), 6.21 (brs, 1H), 5.76 (brs, 2H), 4.92 (brs, 6H), 4.07 (brs, 2H), 3.31 (brs, 2H), 3.12 (brs, 4H), 2.26 (brs, 1H) 1.94-1.26 (brm, 18H), 0.86 (brs, 6H); 13C-NMR (100 MHz, CDCl3, at rt, ppm) δ 173.29, 156.73, 137.41, 136.99, 127.53, 127.35, 125.63, 66.37, 66.02, 63.85, 41.29, 31.63, IR (ATR, cm -1 ) ν 3319, 3066, 2939, 2927, 2856, 1689, 1529, 1456, 1242, 1146, 1144, 1039, 1003, 862, 775.

[0076] [ka]

[0077] Example 3 In a 10 mL recovery flask, BU(BzHexyl)UA (282 mg; 0.500 mmol), tricyclodecane dimethanol diacrylate (TCDMDA, 76 mg; 0.250 mmol), and photoinitiator A (10.6 mg; 0.020 mmol) were dissolved in N,N-dimethylformaldehyde (1.5 mL) and purged with nitrogen. The reaction mixture was stirred at room temperature and irradiated with 2000 mW light at 365 nm for 8 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 copolymer 1 as a yellow solid (yield: 179 mg, 50%).

[0078] Example 4 In a 10 mL recovery flask, BU(BzHexyl)UA (282 mg; 0.500 mmol), TCDMDA (152 mg; 0.500 mmol), and photoinitiator A (15.8 mg; 0.030 mmol) were dissolved in N,N-dimethylformaldehyde (2.0 mL) and purged with nitrogen. The reaction mixture was stirred at room temperature and irradiated with 2000 mW light at 365 nm for 8 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 copolymer 2 as a yellow solid (yield: 180 mg, 41%).

[0079] (Comparative Example 1) Cyclohexanetriol (1.32 g; 10.0 mmol) and dibutyltin dilaurate (126 mg; 0.200 mmol) were dissolved in N,N-dimethylaminoformaldehyde (10.0 mL) in a 50 mL recovery flask, and the atmosphere was purged with nitrogen. To this solution, n-hexyl isocyanate (2.80 g; 22.0 mmol) was added via syringe, and the reaction was allowed to proceed at 60 °C for 16 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 = 3 / 1 → 1 / 1 → 1 / 2) to obtain the target BU(CH n-Hexyl)OH as a white solid (yield: 1.69 g; 4.37 mmol, 44%). mp=105.8-109.4 o C. 1 H-NMR (400 MHz, DMSO-d6, at rt, ppm) δ 7.06 (t, J = 5.8 Hz, 2H), 6.96 (t, J = 5.6 Hz, 2H), 4.89-4.75 (m, 3H), 4.51-4.43 (m, 2H), 4.07 (s, 1H), 3.55-3.49 (m, 1H), 2.92 (dt, J = 6.4, 6.8 Hz, 4H), 2.16-2.06 (m, 2H), 1.85 (d, J = 12.8 Hz, 1H), 1.40-1.08 (m, 19H), 0.84 (t, J = 6.8 Hz, 6H);13 C-NMR (100 MHz, DMSO-d6, at rt, ppm) δ 156.14, 156.02, 67.61, 64.34, 64.01, 41.38, 40.69, 38.38, 38.12, 31.51, 29.92, 29.87, 26.45, 22.60, 14.42; IR (ATR, cm -1 ) ν 3514, 3325, 2939, 2927, 2856, 1693, 1660, 1533, 1466, 1246, 1228, 1128, 1070, 1014, 891, 775. HRMS (ESI) m / z: [M+Na] + Calcd for [C 20 H 38 N2Na1O5] + 409.26784; Found 409.26850.

[0080] [ka]

[0081] BU(CH n-Hexyl)OH (773 mg; 2.00 mmol) and dibutyltin dilaurate (25.2 mg; 0.0400 mmol) were dissolved in tetrahydrofuran (2.0 mL) in a 20 mL recovery flask and the atmosphere was purged with nitrogen. 2-Isocyanatoethyl acrylate (339 mg; 2.40 mmol) was added to the solution via syringe and the mixture was allowed to react at 60 °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 / 1 → 1 / 2) to obtain the desired BU(CH n-Hexyl)UA as a colorless, transparent liquid (yield: 968 mg; 1.83 mmol, 92%). 1H-NMR (400 MHz, DMSO-d6, at r.t., ppm) δ 7.37 (t, J = 5.6 Hz, 1H), 7.30 (t, J = 5.6 Hz, 1H), 7.09 (t, J = 5.6 Hz, 2H), 7.04 (t, J = 5.6 Hz, 2H), 6.38 (dd, J = 1.6, 17.6 Hz, 1H), 6.18 - 6.10 (m, 1H), 5.93 - 5.89 (m, 1H), 5.03 - 5.01 (m, 1H), 4.79 - 4.74 (m, 1H), 4.59 - 4.53 (m, 2H), 4.08 (t, J = 5.6 Hz, 2H), 3.26 - 3.21 (m, 2H), 2.92 (dt, J = 6.0, 6.4 Hz, 4H), 2.19 - 2.17 (m, 2H), 1.95 - 1.92 (m, 1H), 1.54 (t, J = 10.8 Hz, 1H), 1.37 - 1.21 (m, 18H), 0.83 (t, J = 6.8 Hz, 6H); 13 C-NMR (100 MHz, CDCl3, at r.t., ppm) δ 166.20, 166.17, 155.78, 155.61, 155.50, 131.58, 128.13, 128.08, 69.02, 67.96, 67.89, 67.42, 63.70, 41.12, 40.24, 40.11, 37.51, 35.64, 31.57, 30.03, 26.52, 22.67, 14.14; IR (ATR, cm -1 ) ν 3319, 2941, 2927, 2856, 1693, 1522, 1456, 1408, 1240, 1192, 1132, 1011, 985, 781, 775. HRMS (ESI) m / z: [M+Na] + Calcd for [C 26 H 45 N3Na1O8] + 550.31043; Found 550.30937.

[0082] <000042⑨>

Chem.

[0083] (Comparative Example 2) BU(CH n-Hexyl)UA (264 mg; 0.500 mmol) and photoinitiator A (5.3 mg; 0.010 mmol) were dissolved in DMF (1.0 mL) in a 10 mL recovery flask and purged with nitrogen. The reaction mixture was stirred at room temperature and irradiated with 2000 mW light at 365 nm for 7 hours. The reaction solution was poured into a 1:1 methanol:water mixture 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 afford the desired Poly(BU(CH n-Hexyl)UA) as a pale yellow solid (yield: 244 mg; 0.462 mmol, 92%). 1 H-NMR (400 MHz, DMSO-d6, at rt, ppm) δ 6.99 (brs, 2H), 5.02-4.56 (brm, 3H), 4.09-3.96 (brm, 2H), 3.18 (brs, 2H), 2.93 (brs, 4H), 2.19-1.94 (brm, 4H), 1.54-1.21 (brm, 21H), 0.83 (brs, 6H); 13 C-NMR (100 MHz, CDCl3, at rt, ppm) δ 174.63, 155.99, 155.81, 68.84, 67.82, 67.34, 64.05, 63.59, 41.74, 41.07, 40.04, 37.45, 35.57, 31.56, 29.96, 26.54, 22.64, 14.11; -1 ) ν 3317, 2945, 2927, 2858, 1693, 1514, 1456, 1377, 1298, 1228, 1130, 1034, 1009, 773, 725.

[0084] (Comparative Example 3) Trimethylolethane (1.20 g; 10.0 mmol) and dibutyltin dilaurate (126 mg; 0.200 mmol) were dissolved in N,N-dimethylaminoformaldehyde (10.0 mL) in a 50 mL recovery flask, and the atmosphere was purged with nitrogen. To this solution, n-hexyl isocyanate (2.80 g; 22.0 mmol) was added via syringe, and the reaction was allowed to proceed at 60 °C for 12 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 = 2 / 1 → 1 / 1), affording the target BU(Tri n-Hexyl)OH as a colorless, transparent liquid (yield: 1.98 g; 5.29 mmol, 53%). 1 H-NMR (400 MHz, DMSO-d6, at rt, ppm), δ 7.05 (t, J = 5.8 Hz, 2H), 4.58 (t, J = 4.8 Hz, 1H), 3.79 (s, 4H), 3.24 (d, J = 4.4 Hz, 1H), 2.92 (dt, J = 6.0, 6.8 Hz, 4H), 1.37-1.22 (m, 16H), 0.86-0.81 (m, 9H); 13 IR (ATR, cm -1 ) ν 3317, 2927, 2856, 1686, 1533, 1458, 1246, 1142, 1041, 1012, 775. HRMS (ESI) m / z: [M+Na] + Calcd for [C 19 H 38 N2Na1O5] + 397.26784; Found 397.26833.

[0085] [ka]

[0086] BU(Tri n-Hexyl)OH (749 mg; 2.00 mmol) and dibutyltin dilaurate (25.2 mg; 0.0400 mmol) were dissolved in THF (2.0 mL) in a 20 mL recovery flask and the atmosphere was purged with nitrogen. 2-Isocyanatoethyl acrylate (339 mg; 2.40 mmol) was added to the solution via syringe and the mixture was allowed to react at 60 °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 = 2 / 1 → 1 / 1) to obtain the desired BU(Tri n-Hexyl)UA as a colorless, transparent liquid (yield: 951 mg; 1.84 mmol, 92%). 1 H-NMR (400 MHz, DMSO-d6, at rt, ppm) δ 7.34 (t, J = 5.4 Hz, 1H), 7.10 (t, J = 5.2 Hz, 2H), 6.33 (dd, J = 1.2, 17.6 Hz, 1H), 6.14 (dd, J = 10.4, 17.2 Hz, 1H), 5.93 (dd, J = 1.2, 10.4 Hz, 1H), 4.09 (t, J = 5.4 Hz, 2H), 3.85-3.79 (m, 6H), 3.24 (dt, J = 5.2, 6.0 Hz, 2H), 2.93 (q, J = 6.4Hz, 4H), 1.36-1.22 (m, 16H), 0.86-0.82 (m, 9H); 13 C-NMR (100 MHz, CDCl3, at rt, ppm) δ 166.11, 156.73, 156.43, 131.50, 128.00, 66.55, 66.17, 63.54, 41.79, 41.12, 40.15, 38.90, IR (ATR, cm -1) ν 3317, 2937, 2926, 2856, 1693, 1529, 1466, 1408, 1244, 1188, 1144, 1036, 810, 775. HRMS (ESI) m / z: [M+Na] + Calcd for [C 25 H 45 N3Na1O8] + 538.31043; Found 538.31143.

[0087] [ka]

[0088] Comparative Example 4 BU(Tri n-Hexyl)UA (258 mg; 0.500 mmol) and photoinitiator A (5.3 mg; 0.010 mmol) were dissolved in DMF (1.0 mL) in a 10 mL recovery flask and purged with nitrogen. The reaction mixture was stirred at room temperature and irradiated with 2000 mW light at 365 nm for 4 hours. The reaction solution was poured into a 1:1 methanol:water mixture 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(Tri n-Hexyl)UA) as a pale yellow solid (yield: 248 mg; 0.480 mmol, 96%). 1 H-NMR (400 MHz, CDCl3, at rt, ppm) δ 6.36 (brs, 1H), 5.64 (brs, 2H), 4.11-3.91 (brm, 8H), 3.36 (brs, 2H), 3.08 (brs, 4H), 2.52-2.28 (brs, 1H), 1.90-1.25 (brm, 18H), 0.90-0.84 (brm, 9H); 13C-NMR (100 MHz, CDCl3, at rt, ppm) δ 174.55, 157.09, 156.76, 66.55, 66.19, 64.13, 63.73, 41.90, 41.17, 39.98, 38.90, 29.93, 26.57, 22.64, 16.77, 14.10; IR (ATR, cm -1 ) ν 3315, 2941, 2926, 2856, 1693, 1529, 1450, 1414, 1333, 1240, 1147, 1111, 1022, 833, 773, 725.

[0089] (Comparative Example 5) In a 10 mL recovery flask, TCDMDA (304 mg; 1.00 mmol) and photoinitiator A (21.1 mg; 0.040 mmol) were dissolved in N,N-dimethylformaldehyde (1.0 mL) 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(TCDMDA) as a yellow solid (yield: 278 mg, 91%).

[0090] (Comparative Example 6) TAI (423 mg; 1.00 mmol) and photopolymerization initiator A (31.7 mg; 0.060 mmol) were added to a 10 mL recovery flask, melted at 50°C, stirred until homogeneous, and then purged with nitrogen. The reaction mixture was irradiated with 365 nm light at 2000 mW for 4 hours while stirring at room temperature. The resulting cured product was crushed and washed in methanol. 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(TAI) as a pale yellow solid (417 mg, 98%). 13C-NMR (CP-MAS) δ 175.04, 166.79, 150.22, 129.12, 62.04, 42.16, 33.65; IR (ATR, cm -1 ) ν 2958, 1705, 1682, 1446, 1362, 1255, 1153, 1057, 985, 810, 762.

[0091] [ka]

[0092] <Volume change rate> The volume change rates of the polymers obtained in Examples 2 to 4 and Comparative Examples 2, 4 to 6 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 +2.5% to -2.5%.

[0093] [Table 1]

[0094] As shown in Table 1, the urethane compound of the present invention expands in volume when polymerized. Therefore, by using the urethane compound of the present invention in combination with an existing radically polymerizable compound that shrinks on curing, it was possible to reduce the change in volume during curing.

Claims

1. A urethane compound represented by the following general formula (I): 【Chemical 1】 (In the formula, R １ , R ２ and R ３ each independently represents a hydrocarbon group having 1 to 20 carbon atoms or a group in which one or more methylene groups in the hydrocarbon group have been substituted with a divalent group selected from the following <Group A>, R ４ , R ５ and R ６ each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group have been substituted with a divalent group selected from the following <Group A>, However, R １ , R ２ , R ３ , R ４ , R ５ and R ６ one or two of the above are an ethylenically unsaturated bond-containing group, a hydrocarbon group having 3 to 20 carbon atoms and having an ethylenically unsaturated bond-containing group as a substituent, or a group in which one or more methylene groups in the hydrocarbon group 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 hydrocarbon group have been substituted with a divalent group selected from the following <Group A>, <Group A> is a carbon-carbon double bond, —O—, —S—, —CO—, —CO—O—, and —SO ２ - and Each of the hydrocarbon groups may have a substituent, and the substituent is an ethylenically unsaturated bond-containing group, a halogen atom, a halogenated alkyl group having 1 to 3 carbon atoms, a cyano group, a nitro group, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, an amino group, a carboxy group, an epoxy group, a mercapto group, or an isocyanate group.

2. 2. The urethane compound according to claim 1, wherein the ethylenically unsaturated bond-containing group is an acryloyloxy group or a methacryloyloxy group.

3. R １ , R ２ and R ３ or one or two of the above are an ethylenically unsaturated bond-containing group, a hydrocarbon group having 3 to 20 carbon atoms and having an ethylenically unsaturated bond-containing group as a substituent, or a group in which one or more methylene groups in the hydrocarbon group are substituted with a divalent group selected from <Group A>.

4. R ４ , R ５ and R ６ The urethane compound according to any one of claims 1 to 3, wherein is a hydrogen atom.

5. A polymer comprising the urethane compound according to any one of claims 1 to 4 as a monomer.

6. A polymerizable composition comprising the urethane compound according to any one of claims 1 to 4 and a polymerization initiator, In the formula (1), one or two of R 1 , R 2 and R 3 are an ethylenically unsaturated bond-containing group, a hydrocarbon group having 3 to 20 carbon atoms and having an ethylenically unsaturated bond-containing group as a substituent, or a group in which one or more methylene groups in the hydrocarbon group have been substituted with a divalent group selected from the <Group A>, In the formula (1), R １ , R ２ and R ３ wherein the number of carbon atoms of any of the above-listed groups that is not an ethylenically unsaturated bond-containing group, a hydrocarbon group having 3 to 20 carbon atoms and having an ethylenically unsaturated bond-containing group as a substituent, or a group in which one or more methylene groups in the hydrocarbon group are substituted with a divalent group selected from <Group A>, is independently 6 or more.

7. An adhesive comprising the polymerizable composition according to claim 6.

8. A coating agent comprising the polymerizable composition according to claim 6.

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

10. A method for producing a cured product, comprising a step of irradiating the polymerizable composition according to claim 6 with light.

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