CN108884298B - Curable composition, method for producing cured product, and cured product thereof - Google Patents

Curable composition, method for producing cured product, and cured product thereof Download PDF

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CN108884298B
CN108884298B CN201780019466.8A CN201780019466A CN108884298B CN 108884298 B CN108884298 B CN 108884298B CN 201780019466 A CN201780019466 A CN 201780019466A CN 108884298 B CN108884298 B CN 108884298B
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CN108884298A (en
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松土和彦
渡边智志
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Adeka Corp
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4246—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof polymers with carboxylic terminal groups
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
    • C08G65/16—Cyclic ethers having four or more ring atoms
    • C08G65/18—Oxetanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
    • C—CHEMISTRY; METALLURGY
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    • C08K5/00—Use of organic ingredients
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    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

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  • Polymers & Plastics (AREA)
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  • Polyethers (AREA)
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Abstract

The invention provides a curable composition having a high glass transition temperature and excellent adhesion, a method for producing a cured product, and a cured product thereof. The composition contains 100 parts by mass of the total of the components (A) and (C): 45 to 90 parts by mass of a cationic polymerizable component (A), 0.001 to 15 parts by mass of a cationic polymerization initiator (B), 1 to 15 parts by mass of a radical polymerizable component (C), 1 to 10 parts by mass of a radical polymerization initiator (D), and 1 to 20 parts by mass of a polymer (E) selected from the group consisting of: a polymer obtained from a monomer represented by the following formula (I), a polymer obtained from a monomer represented by the following formula (II), wherein X is an alkyl group having 1 to 7 carbon atoms or the like, R 1 is a hydrogen atom or the like, X' is an alkyl group having 1 to 7 carbon atoms or the like, and the component (A) comprises a glycidyl compound or the like (A1) of a polyol and an oxetane compound (A2) as essential components, and the component (C) comprises a compound (C1) having an epoxy group and an ethylenically unsaturated group or the like as essential components.

Description

Curable composition, method for producing cured product, and cured product thereof
Technical Field
The present invention relates to a curable composition, a method for producing a cured product, and a cured product thereof, and more particularly to a curable composition having a high glass transition temperature and excellent adhesion, a method for producing a cured product, and a cured product thereof.
Background
Curable compositions are used in the fields of inks, paints, various coating agents, adhesives, optical members, and the like. Various reports have been made on improvement of such curable compositions.
For example, the following patent documents 1 to 3 propose: an energy ray-curable composition containing a cationically polymerizable component and a radically polymerizable component, or a cured product thereof. Specifically, patent document 1 proposes: an adhesive composition for polarizing plates which has excellent initial curability and adhesion. Patent document 2 proposes a low-viscosity photocurable adhesive which exhibits an adhesive force rapidly after light irradiation even when a resin film having low moisture permeability is used as a protective film, and which exhibits excellent adhesive force against various forces after a predetermined period of time, does not cause problems after a durability test, and exhibits excellent adhesive force after completion of a wet heat resistance test. Further, patent document 3 proposes: an active energy ray polymerizable resin composition which can achieve both high heat resistance and high refractive index and transparency, and which contains an unsaturated alicyclic epoxy ester compound.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open publication No. 2014-105218
Patent document 2: japanese patent application laid-open No. 2015-040283
Patent document 3: japanese patent laid-open No. 2015-168757
Disclosure of Invention
Problems to be solved by the invention
However, even the curable compositions proposed in patent documents 1 to 3 may not necessarily satisfy the requirements for curability and adhesion, and a novel curable composition capable of highly satisfying both curability and adhesion is desired in the present situation.
Accordingly, an object of the present invention is to provide a curable composition having a high glass transition temperature and excellent adhesion of a cured product, a method for producing a cured product, and a cured product thereof.
Solution for solving the problem
The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that the above problems can be solved by a curable composition having a specific composition, and have completed the present invention.
Specifically, the curable composition of the present invention is characterized by comprising, in terms of 100 parts by mass of the total of the cationic polymerizable component (a), the radical polymerizable component (C), and the polymer (E): 45 to 90 parts by mass of the cationic polymerizable component (A), 0.001 to 15 parts by mass of the cationic polymerization initiator (B), 1 to 15 parts by mass of the radical polymerizable component (C), 1 to 10 parts by mass of the radical polymerization initiator (D), and 1 to 20 parts by mass of the polymer (E), wherein the weight average molecular weight of the polymer (E) is 1000 to 30000, and the polymer (E) is selected from the group consisting of: a polymer obtained from a monomer represented by the following formula (I), a polymer obtained from a monomer represented by the following formula (II), a polymer obtained from two or more monomers selected from the monomers represented by the foregoing formula (I), a polymer obtained from two or more monomers selected from the monomers represented by the foregoing formula (II), and a polymer obtained from the monomers represented by the foregoing formula (I) and the monomers represented by the foregoing formula (II),
In the formula (I), X is an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms or an alicyclic hydrocarbon group having 6 to 10 carbon atoms, or a group in which a hydrogen atom in these groups is substituted with 1 or more groups selected from the group consisting of an epoxy group, an oxetanyl group, a hydroxyl group and a carboxyl group,
In the formula (II), R 1 represents a hydrogen atom, a methyl group or a halogen atom, X' is an alkyl group having 1 to 7 carbon atoms, an aryl group having 6 to 12 carbon atoms or an alicyclic hydrocarbon group having 6 to 10 carbon atoms, or a group in which a hydrogen atom in these groups is substituted with 1 or more groups selected from the group consisting of an epoxy group, an oxetanyl group, a hydroxyl group and a carboxyl group,
The cation polymerizable component (A) contains, as essential components, a glycidylate (A1) of a polyol or a glycidylate (A2) of a polyol alkylene oxide adduct,
The radical polymerizable component (C) contains, as an essential component, a compound (C1) having an epoxy group and an ethylenically unsaturated group, or an acrylic acid ester of a polyol having 2 to 20 carbon atoms or a methacrylic acid ester (C2) of a polyol having 2 to 20 carbon atoms. Here, the weight average molecular weight means: the weight average molecular weight was determined by GPC in Tetrahydrofuran (THF) solvent and converted to styrene.
The curable composition of the present invention preferably further contains an aromatic epoxy compound (A3) as the cationically polymerizable component (a). In the curable composition of the present invention, the aromatic epoxy compound (A3) is preferably a polyfunctional aromatic epoxy compound. Further, the curable composition of the present invention is preferably: the polymer (E) is a polymer obtained from a monomer represented by the formula (I) and a monomer represented by the formula (II), wherein X in the formula (I) is an aryl group having 6 to 12 carbon atoms, X' in the formula (II) is an alkyl group having 1 to 7 carbon atoms, and the alkyl group is substituted with an epoxy group.
The method for producing a cured product of the present invention is characterized by irradiating the curable composition of the present invention with active energy rays or heating the composition.
The cured product of the present invention is characterized in that it is a cured product of the curable composition of the present invention.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a curable composition having a high glass transition temperature and excellent adhesion of a cured product, a method for producing a cured product, and a cured product thereof can be provided. The curable composition of the present invention is particularly useful as an adhesive.
Detailed Description
The curable composition of the present invention will be described in detail below.
That is, the curable composition of the present invention is characterized by comprising: 45 to 90 parts by mass of a cationic polymerizable component (A), 0.001 to 15 parts by mass of a cationic polymerization initiator (B), 1 to 15 parts by mass of a radical polymerizable component (C), 1 to 10 parts by mass of a radical polymerization initiator (D), and 1 to 20 parts by mass of a polymer (E) having a weight average molecular weight of 1000 to 30000, the polymer (E) being selected from the group consisting of: a polymer obtained from a monomer represented by the following formula (I), a polymer obtained from a monomer represented by the following formula (II), a polymer obtained from two or more monomers selected from the monomers represented by the foregoing formula (I), a polymer obtained from two or more monomers selected from the monomers represented by the foregoing formula (II), and a polymer obtained from the monomers represented by the foregoing formula (I) and the monomers represented by the foregoing formula (II). In the curable composition of the present invention, the cationically polymerizable component (a) contains, as essential components, a glycidylate (A1) of a polyol or a glycidylate (A2) of a polyol alkylene oxide adduct, and the radical polymerizable component (C) contains, as essential components, a compound (C1) having an epoxy group and an ethylenically unsaturated group, or an acrylic ester of a polyol having 2 to 20 carbon atoms, or a methacrylic ester (C2) of a polyol having 2 to 20 carbon atoms.
In the formula (I), X is an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an alicyclic hydrocarbon group having 6 to 10 carbon atoms, or a group in which a hydrogen atom in these groups is substituted with 1 or more groups selected from the group consisting of an epoxy group, an oxetanyl group, a hydroxyl group and a carboxyl group.
In the formula (II), R 1 represents a hydrogen atom, a methyl group or a halogen atom, X' is an alkyl group having 1 to 7 carbon atoms, an aryl group having 6 to 12 carbon atoms or an alicyclic hydrocarbon group having 6 to 10 carbon atoms, or a group in which a hydrogen atom in these groups is substituted with 1 or more groups selected from the group consisting of an epoxy group, an oxetanyl group, a hydroxyl group and a carboxyl group.
The cationically polymerizable component (a) of the curable composition of the present invention is a compound that undergoes a polymerization or crosslinking reaction by a cationic polymerization initiator activated by irradiation with energy rays or heating. There may be mentioned: epoxy compounds, oxetane compounds, vinyl ether compounds, and the like.
The cationically polymerizable component (a) of the curable composition of the present invention contains, as essential components, a glycidylate (A1) of a polyol or a glycidylate (A2) of a polyol alkylene oxide adduct, and as other epoxy compounds, an aromatic epoxy compound (A3) and an alicyclic epoxy compound (A4) or the like can be used.
The glycidylate (A1) of the polyol or the polyol alkylene oxide adduct may be obtained by glycidylating the polyol or the polyol alkylene oxide adduct, and the molecular weight of the glycidylate is preferably 250 or more.
Examples of the glycidylate (A1) of the polyol or the glycidylate (A1) of the alkylene oxide adduct of the polyol include: 1, 4-butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, glycidyl ether of polyhydric alcohol such as dicyclopentadiene dimethanol diglycidyl ether, polyglycidyl etherified product of polyether polyol obtained by adding 1 or 2 or more alkylene oxides to aliphatic polyhydric alcohol such as propylene glycol, trimethylolpropane, glycerin, etc., and diglycidyl ester of aliphatic long chain dibasic acid.
The glycidylate (A1) of the polyol or the glycidylate (A1) of the alkylene oxide adduct of the polyol may be mentioned: monoglycidyl ethers of aliphatic higher alcohols, glycidyl esters of higher fatty acids, epoxidized soybean oil, octyl epoxy stearate, butyl epoxy stearate, epoxidized soybean oil, epoxidized polybutadiene, and the like.
The glycidylate (A1) of the polyol or the polyol alkylene oxide adduct is preferably one having a saturated condensed ring, since the curability and adhesion of the cured product are improved.
As the glycidylate of the above-mentioned polyol or the glycidylate (A1) of the alkylene oxide adduct of the polyol, commercially available products can be used, and examples thereof include those manufactured by ：DENACOL EX-121、DENACOL EX-171、DENACOL EX-192、DENACOL EX-211、DENACOL EX-212、DENACOL EX-313、DENACOL EX-314、DENACOL EX-321、DENACOL EX-411、DENACOL EX-421、DENACOL EX-512、DENACOL EX-521、DENACOL EX-611、DENACOL EX-612、DENACOL EX-614、DENACOL EX-622、DENACOL EX-810、DENACOL EX-811、DENACOL EX-850、DENACOL EX-851、DENACOL EX-821、DENACOL EX-830、DENACOL EX-832、DENACOL EX-841、DENACOL EX-861、DENACOL EX-911、DENACOL EX-941、DENACOL EX-920、DENACOL EX-931(Nagase ChemteX Corporation and manufactured by );Epolight M-1230、Epolight 40E、Epolight 100E、Epolight 200E、Epolight 400E、Epolight 70P、Epolight 200P、Epolight 400P、Epolight 1500NP、Epolight 1600、Epolight 80MF、Epolight 100MF( co-company, manufactured by ),ADEKA Glycirol ED-503、ADEKA Glycirol ED-503G、ADEKA Glycirol ED-506、ADEKA Glycirol ED-523T、ADEKA RESIN EP-4088S、ADEKA RESIN EP-4080E(ADEKA Co., ltd.).
Examples of the oxetane compound (A2) include: difunctional aliphatic oxetane compounds such as 3, 7-bis (3-oxetanyl) -5-oxo-nonane, 1, 4-bis [ (3-ethyl-3-oxetylmethoxy) methyl ] benzene, 1, 2-bis [ (3-ethyl-3-oxetylmethoxy) methyl ] ethane, 1, 3-bis [ (3-ethyl-3-oxetylmethoxy) methyl ] propane, ethyleneglycol bis (3-ethyl-3-oxetylmethyl) ether, triethyleneglycol bis (3-ethyl-3-oxetylmethyl) ether, tetraethyleneglycol bis (3-ethyl-3-oxetylmethyl) ether, 1, 4-bis (3-ethyl-3-oxetylmethoxy) butane, 1, 6-bis (3-ethyl-3-oxetylmethoxy) hexane, 3-ethyl-3- [ (phenoxy) methyl ] oxetane, 3-ethyl-3- (hexyloxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-hydroxyethyl-3- (oxetane) oxetane, and the like. Among them, difunctional aliphatic oxetane compounds are preferable because of improved adhesion. They may be used alone or in combination of 1 or more than 2.
As the oxetane compound (A2), commercially available products can be used, and examples thereof include: 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether (manufactured by Wash petrochemicals Co., ltd.); ARON OXETANE OXT-121, OXT-221, EXOH, POX, OXA, OXT-101, OXT-211, OXT-212 (manufactured by Toyama Kagaku Co., ltd.), ETERNACOLL OXBP, OXTP (manufactured by Yu Xingxing Co., ltd.), etc.
The aromatic epoxy compound (A3) is an epoxy compound containing an aromatic ring, and specific examples of the aromatic epoxy compound (A3) include: mono/polyglycidyl ethers of polyhydric phenols having at least 1 aromatic ring such as phenol, cresol, butylphenol and the like or alkylene oxide adducts thereof, for example: bisphenol a, bisphenol F, or glycidyl ethers of compounds having alkylene oxides added thereto, novolac epoxy resins; mono/polyglycidyl ethers of aromatic compounds having 2 or more phenolic hydroxyl groups such as resorcinol, hydroquinone and catechol; glycidyl ethers of aromatic compounds having at least 2 alcoholic hydroxyl groups, such as phenyldimethanol, phenyldiethanol and phenyldibutyl alcohol; and glycidyl esters of polybasic acid aromatic compounds having 2 or more carboxylic acids such as phthalic acid, terephthalic acid, and trimellitic acid, glycidyl esters of benzoic acid, and epoxides of styrene oxide or divinylbenzene.
As the aromatic epoxy compound (A3), commercially available ones can be used, and for example, ：DENACOL EX-146、DENACOL EX-147、DENACOL EX-201、DENACOL EX-203、DENACOL EX-711、DENACOL EX-721、ONCOAT EX-1020、ONCOAT EX-1030、ONCOAT EX-1040、ONCOAT EX-1050、ONCOAT EX-1051、ONCOAT EX-1010、ONCOAT EX-1011、ONCOAT 1012(Nagase ChemteX Corporation; OGSOL PG-100, OGSOL EG-200, OGSOL EG-210, OGSOL EG-250 (Osaka GAS CHEMICALS co., ltd.); HP4032 and HP4032D, HP4700 (manufactured by DIC Co., ltd.); ESN-475V (made by Nippon Kagaku Co., ltd.); EPIKOTE YX8800 (Mitsubishi chemical Co., ltd.); MARPROOF G-0105SA, MARPROOF G-0130SP (manufactured by Nikko Co., ltd.); EPICLON N-665, EPICLON HP-7200 (DIC Co., ltd.); EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, XD-1000, NC-3000, EPPN-501H, EPPN-501HY, EPPN-502H, NC-7000L (manufactured by Japanese chemical Co., ltd.); ADEKA RESIN EP-4000, ADEKA RESIN EP-4005, ADEKA RESIN EP-4100, ADEKA RESIN EP-4901 (manufactured by ADEKA corporation); TECHMORE VG-3101L (Printech co., ltd.) and the like. The aromatic epoxy compound (A3) is preferably a polyfunctional aromatic epoxy compound because of its excellent curability.
The alicyclic epoxy compound (A4) is a compound in which an oxirane ring is directly bonded to a saturated ring without a bonding group. Specific examples of the alicyclic epoxy compound (A4) include: cyclohexene oxide obtained by epoxidation of a polyglycidyl etherate of a polyol having at least 1 alicyclic ring or cyclohexene, a compound containing a cyclopentene ring, a compound containing a cyclopentene oxide by an oxidizing agent. Examples include: 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexylformate, 3, 4-epoxy-1-methylcyclohexyl-3, 4-epoxy-1-methylcyclohexylformate, 6-methyl-3, 4-epoxycyclohexylmethyl-6-methyl-3, 4-epoxycyclohexylformate, 3, 4-epoxy-3-methylcyclohexylmethyl-3, 4-epoxy-3-methylcyclohexylformate, 3, 4-epoxy-5-methylcyclohexylmethyl-3, 4-epoxy-5-methylcyclohexylformate, bis (3, 4-epoxycyclohexylmethyl) adipate, 3, 4-epoxy-6-methylcyclohexylformate, methylenebis (3, 4-epoxycyclohexane), propane-2, 2-diyl-bis (3, 4-epoxycyclohexane), 2-bis (3, 4-epoxycyclohexyl) propane, dicyclopentadiene diepoxide, ethylenebis (3, 4-epoxycyclohexylformate), epoxyhexa-phthalate, epoxydi-2-epoxyethyl-1, 4-epoxycyclohexane, pinene oxide, alpha-2-epoxycyclohexane, alpha, and the like. The alicyclic epoxy compound (A4), 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexylformate or 3, 4-epoxy-1-methylcyclohexyl-3, 4-epoxy-1-methylhexylformate, is preferable from the viewpoint of improving adhesion.
The alicyclic epoxy compound (A4) may be commercially available ones, and examples thereof include: CELLOXIDE 2021P, CELLOXIDE 2081, CELLOXIDE 2000, CELLOXIDE 3000 (manufactured by Daicel Corporation), and the like.
Examples of the vinyl ether compound include: diethylene glycol monovinyl ether, triethylene glycol divinyl ether, n-dodecyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, 2-chloroethyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, triethylene glycol vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 1, 6-cyclohexanedimethanol monovinyl ether, ethylene glycol divinyl ether, 1, 4-butanediol divinyl ether, 1, 6-cyclohexanedimethanol divinyl ether, and the like.
In the cation polymerizable component (a), the use ratio of the glycidylate of the polyol or the glycidylate of the polyol alkylene oxide adduct (A1), the oxetane compound (A2), the aromatic epoxy compound (A3), the alicyclic epoxy compound (A4) and the vinyl ether compound to 100 parts by mass of the cation polymerizable component (a) is: 50 to 80 parts by mass of a glycidylate of a polyol or a glycidylate (A1) of an alkylene oxide adduct of a polyol, 20 to 50 parts by mass of an oxetane compound (A2), 0 to 50 parts by mass of an aromatic epoxy compound (A3), 0 to 30 parts by mass of an alicyclic epoxy compound (A4) and 0 to 20 parts by mass of a vinyl ether compound are preferable, in which case the viscosity, coatability, reactivity and curability are improved.
The cationic polymerization initiator (B) of the curable composition of the present invention may be any polymerization initiator as long as it is a compound capable of releasing a substance that initiates cationic polymerization upon irradiation with energy rays or heating, and is preferably an onium salt that releases a lewis acid upon irradiation with energy rays, that is, a double salt, or a derivative thereof. Representative examples of the compounds include salts of cations and anions represented by the following general formula.
[A]r+[B]r-
Here, the cation [ A ] r+ is preferably an onium, and its structure can be represented by the following general formula, for example.
[(R2)aQ]r+
Further, here, R 2 is an organic group having 1 to 60 carbon atoms and may contain atoms other than a few carbon atoms. a is an integer of 1 to 5. The a R 2 groups are each independently the same or different. In addition, at least 1 of the organic groups having an aromatic ring is preferable. Q is an atom or group of atoms selected from the group consisting of S, N, se, te, P, as, sb, bi, O, I, br, cl, F, N =n. When the valence of Q in the cation [ a ] r+ is Q, it is necessary to establish a relationship of r=a-Q (where n=n is regarded as valence 0).
The anion [ B ] r- is preferably a halide complex, and its structure can be represented by the following general formula, for example.
[LYb]r-
Further, here, L is a metal or a semi-metal (Metalloid), B, P, as, sb, fe, sn, bi, al, ca, in, ti, zn, sc, V, cr, mn, co, or the like, which is a central atom of the halide complex. Y is a halogen atom. b is an integer of 3 to 7. When the valence of L in the anion [ B ] r- is p, the relationship of r=b-p needs to be established.
Specific examples of the anion [ LYb ] r- of the above general formula include: tetrakis (pentafluorophenyl) borate, tetrakis (3, 5-difluoro-4-methoxyphenyl) borate, tetrafluoroborate (BF 4)－, hexafluorophosphate (PF 6)－, hexafluoroantimonate (SbF 6)－, hexafluoroarsenate (AsF 6)－, hexachloroantimonate (SbCl 6)－, etc.).
The anion [ B ] r- may preferably have a structure represented by the following general formula.
[LYb-1(OH)]r-
L, Y, b are the same as described above. Further, as other anions which can be used, there may be mentioned: perchlorate ion (ClO 4)－, trifluoromethylsulfinate ion (CF 3SO3)－, fluorosulfonate ion (FSO 3)－, tosylate anion, trinitrobenzenesulfonate anion, camphorsulfonate, nonafluorobutanesulfonate, hexadecanoylsulfonate, tetraarylborate, tetrakis (pentafluorophenyl) borate, etc.).
Among such onium salts, the following aromatic onium salts (i) to (iii) are particularly effective in the curable composition of the present invention. Among them, 1 or 2 or more thereof may be used singly or in combination.
(I) Aryl diazonium salts such as phenyl diazonium hexafluorophosphate, 4-methoxyphenyl diazonium hexafluoroantimonate and 4-methylphenyl diazonium hexafluorophosphate
(Ii) Diaryl iodonium salts such as diphenyliodonium hexafluoroantimonate, bis (4-methylphenyl) iodonium hexafluorophosphate, bis (4-tert-butylphenyl) iodonium hexafluorophosphate, tolyltrimethyliodonium tetrakis (pentafluorophenyl) borate, and the like
(Iii) Sulfonium cations represented by the following group I or group II and sulfonium salts such as hexafluoroantimonic ions, hexafluorophosphate ions, tetrakis (pentafluorophenyl) borate ions, < group I >
< Group II >
Further, as other preferable substances, there may be mentioned: (eta 5 -2, 4-cyclopentadienyl-1-yl) [ (1, 2,3,4,5, 6-eta) - (1-methylethyl) benzene ] -iron-hexafluorophosphate and the like, tris (acetylacetonate) aluminum, tris (ethylacetonoacetate) aluminum, tris (salicylaldehyde) aluminum and the like, and silanol compounds such as triphenylsilanol; salts such as thiophenium salts, tetrahydrothiophenium salts, benzyl ammonium salts, pyridinium salts, and hydrazine salts; polyalkylpolyamines such as diethylenetriamine, triethylenetriamine and tetraethylenepentamine; alicyclic polyamines such as1, 2-diaminocyclohexane, 1, 4-diamino-3, 6-diethylcyclohexane and isophoronediamine; aromatic polyamines such as m-xylylenediamine, diaminodiphenylmethane and diaminodiphenylsulfone; polyepoxide addition modified products produced by reacting the above polyamines with various epoxy resins such as glycidyl ethers of phenyl glycidyl ether, butyl glycidyl ether, bisphenol a-diglycidyl ether, bisphenol F-diglycidyl ether, or glycidyl esters of carboxylic acids by a conventional method; amidated modified products produced by reacting the organic polyamines with carboxylic acids such as phthalic acid, isophthalic acid, dimer acid, etc. by a conventional method; a mannich modified product produced by reacting the polyamine with an aldehyde such as formaldehyde, and a phenol having at least one hydroformylation-reactive site in a core such as phenol, cresol, xylenol, t-butylphenol, resorcinol, etc., by a conventional method; anhydrides of polycarboxylic acids (aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanoic acid, 2-methylsuccinic acid, 2-methyladipic acid, 3-methylglutaric acid, 2-methylsuberic acid, 3, 8-dimethylsebacic acid, 3, 7-dimethylsebacic acid, hydrodimer acid, dimer acid, etc., aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, etc., alicyclic dicarboxylic acids such as cyclohexane dicarboxylic acid, etc., tricarboxylic acids such as trimellitic acid, trimesic acid, castor oil fatty acid, etc., tetracarboxylic acids such as pyromellitic acid, etc.); dicyandiamide, imidazoles, carboxylic acid esters, sulfonic acid esters, amine imides, and the like.
Among them, from the viewpoint of improving the use aspect and the light sensitivity, it is preferable to use: aromatic iodonium salts, aromatic sulfonium salts, iron-arene complexes, more preferably: the cationic polymerization initiator (B) contains at least 0.1 mass% or more of an aromatic sulfonium salt having the following structure relative to 100 mass% of the cationic polymerization initiator (B).
Here, in the formula, R 11、R12、R13、R14、R15、R16、R17、R18、R19 and R 20 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or An ester group having 2 to 10 carbon atoms, R 21、R22、R23 and R 24 each independently represent a hydrogen atom, a halogen atom, or An alkyl group having 1 to 10 carbon atoms, R 25 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or a substituent selected from any one of the following chemical formulas (a) to (C), an q- represents An anion having q-valent, and p represents a coefficient for making the charge neutral.
Here, ,R11、R12、R13、R14、R15、R16、R17、R18、R19、R20、R21、R22、R23、R24、R26、R27、R28、R29、R35、R36、R37、R38 and R 39 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an ester group having 2 to 10 carbon atoms, and R 30、R31、R32、R33 and R 34 each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms.
Among the compounds represented by the above general formula (1), as halogen atoms represented by R11、R12、R13、R14、R15、R16、R17、R18、R19、R20、R21、R22、R23、R24、R25、R26、R27、R28、R29、R30、R31、R32、R33、R34、R35、R36、R37、R38 and R 39, there are listed: fluorine, chlorine, bromine, iodine, and the like.
Examples of the alkyl group having 1 to 10 carbon atoms represented by R11、R12、R13、R14、R15、R16、R17、R18、R19、R20、R21、R22、R23、R24、R25、R26、R27、R28、R29、R30、R31、R32、R33、R34、R35、R36、R37、R38 and R 39 include: methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, pentyl, isopentyl, tert-pentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, ethyloctyl, 2-methoxyethyl, 3-methoxypropyl, 4-methoxybutyl, 2-butoxyethyl, methoxyethoxyethyl, methoxyethoxyethoxyethyl, 3-methoxybutyl, 2-methylthioethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, difluoroethyl, trichloroethyl, dichlorodifluoroethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, decafluoropentyl, tridecanfluorohexyl, pentadecafluoroheptyl, heptadecafluorooctyl, methoxymethyl, 1, 2-epoxyethyl, methoxyethyl, methoxyethoxymethyl, methylthiomethyl, ethoxyethyl, butoxymethyl, tert-butylthiomethyl, 4-pentenyloxymethyl, trichloroethoxymethyl, bis (2-chloroethoxymethyl), methoxycyclohexyl, 1- (2-chloroethoxy) ethyl, 1-ethyl-methoxymethyl, 1-methoxyethyl-methoxycarbonyl, tert-butyloxycarbonyl, 2-methoxycarbonyl, 2-methoxyethoxycarbonyl, 2-methoxyethoxymethyl, 2-methoxycarbonyl, methoxyethoxycarbonyl, 2-methoxyethoxymethyl, 2-methoxyethoxycarbonyl, adamantyloxymethyl, 2-methoxycarbonyl, ethoxycarbonyl, ethoxymethyl, 2-ethoxycarbonyl, 2-methoxy-1-propenyl, hydroxymethyl, 2-hydroxyethyl, 1-hydroxyethyl, 2-hydroxypropyl, 3-hydroxybutyl, 4-hydroxybutyl, 1, 2-dihydroxyethyl, and the like.
Examples of the alkoxy group having 1 to 10 carbon atoms represented by R11、R12、R13、R14、R15、R16、R17、R18、R19、R20、R21、R22、R23、R24、R26、R27、R28、R29、R35、R36、R37、R38 and R 39 include: methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, sec-butyloxy, tert-butyloxy, isobutyloxy, pentyloxy, isopentyloxy, tert-pentyloxy, hexyloxy, cyclohexyloxy, cyclohexylmethyloxy, tetrahydrofuranyloxy, tetrahydropyranyloxy, 2-methoxyethyloxy, 3-methoxypropyloxy, 4-methoxybutyloxy, 2-butoxyethyloxy, methoxyethoxyethyloxy, 3-methoxybutyloxy, 2-methylthioethyloxy, trifluoromethyloxy and the like.
Examples of the ester group having 2 to 10 carbon atoms represented by R11、R12、R13、R14、R15、R16、R17、R18、R19、R20、R21、R22、R23、R24、R26、R27、R28、R29、R35、R36、R37、R38 and R 39 include: methoxycarbonyl, ethoxycarbonyl, isopropyloxycarbonyl, phenoxycarbonyl, acetoxy, propionyloxy, butyryloxy, chloroacetoxy, dichloroacetoxy, trichloroacetoxy, trifluoroacetoxy, t-butylcarbonyloxy, methoxyacetoxy, benzoyloxy, and the like.
The proportion of the cationic polymerization initiator (B) used is 0.001 to 15 parts by mass, preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the total of the components (a) and (B) and (C). When the amount is too small, the curing tends to be insufficient, and when the amount is too large, various physical properties such as the water absorption rate of the cured product and the strength of the cured product may be adversely affected.
The radically polymerizable component (C) of the curable composition of the present invention contains, as an essential component, a compound (C1) having an epoxy group and an ethylenically unsaturated group, or an acrylic acid ester of an alcohol having 2 to 20 carbon atoms or a methacrylic acid ester (C2) of an alcohol having 2 to 20 carbon atoms.
Examples of the compound (C1) having the epoxy group and the ethylenically unsaturated group include: specifically, the epoxy acrylate or the epoxy methacrylate is an acrylate obtained by reacting an acrylic acid or a methacrylic acid with an aromatic epoxy resin, an alicyclic epoxy resin, an aliphatic epoxy resin, or the like, which have been conventionally known. Among these epoxy acrylates or epoxy methacrylates, particularly preferred are acrylates or methacrylates of glycidyl ethers of alcohols.
Examples of the acrylic acid ester of an alcohol having 2 to 20 carbon atoms or the methacrylic acid ester (C2) of an alcohol having 2 to 20 carbon atoms include: an aromatic or aliphatic alcohol having at least 1 hydroxyl group in the molecule, and an acrylic acid ester or a methacrylic acid ester obtained by reacting an alkylene oxide adduct thereof with acrylic acid or methacrylic acid. Specifically, there may be mentioned: 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isopentyl acrylate, lauryl acrylate, stearyl acrylate, isooctyl acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, benzyl acrylate, 1, 3-butanediol diacrylate, 1, 4-butanediol diacrylate, 1, 6-hexanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, epsilon-caprolactone modified dipentaerythritol hexaacrylate, 2-ethylhexyl methacrylate 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, isoamyl methacrylate, lauryl methacrylate, stearyl methacrylate, isooctyl methacrylate, tetrahydrofurfuryl methacrylate, isobornyl methacrylate, benzyl methacrylate, 1, 3-butanediol dimethacrylate, 1, 4-butanediol dimethacrylate, 1, 6-hexanediol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexamethyl, epsilon-caprolactone modified dipentaerythritol hexamethyl acrylic ester, and the like. Among these acrylates or methacrylates, polyacrylates of polyols or polymethacrylates of polyols are particularly preferable.
As the radical polymerizable component (C), a radical polymerization initiator other than (C1) or (C2) that is activated by irradiation with energy rays or heating to perform a polymerization or crosslinking reaction may be used, and examples thereof include: allyl urethane compounds, unsaturated polyester compounds, styrene compounds, and the like. The ratio of the component (C1) and the component (C2) in the radically polymerizable component (C) is preferably 50% by mass or more.
The radical initiator (D) in the curable composition of the present invention is not particularly limited, and a known radical initiator can be used. For example, it is possible to use: ketone compounds such as acetophenone compounds, benzil compounds, benzophenone compounds, and thioxanthone compounds, oxime compounds, and the like.
The polymer (E) in the curable composition of the present invention is selected from the group consisting of the following polymers, and has a weight average molecular weight of 1000 to 30000 in terms of polystyrene: a polymer obtained from a monomer represented by the above formula (I), a polymer obtained from a monomer represented by the above formula (II), a polymer obtained from two or more monomers selected from the monomers represented by the above formula (I), a polymer obtained from two or more monomers selected from the monomers represented by the above formula (II), and a polymer obtained from a monomer represented by the above formula (I) and a monomer represented by the above formula (II).
Examples of the alkyl group having 1 to 7 carbon atoms represented by X in the above formula (I) include: methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, pentyl, isopentyl, tert-pentyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 4-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, tert-heptyl, and the like. Among them, an alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms partially substituted with 1 or more groups selected from the group consisting of an epoxy group, an oxetanyl group, a hydroxyl group and a carboxyl group is preferable in view of curability.
Examples of the alkoxy group having 1 to 7 carbon atoms represented by X in the above formula (I) include: methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, sec-butyloxy, tert-butyloxy, isobutyloxy, pentyloxy, isopentyloxy, tert-pentyloxy, hexyloxy, 2-hexyloxy, 3-hexyloxy, cyclohexyloxy, 4-methylcyclohexyloxy, heptyloxy, 2-heptyloxy, 3-heptyloxy, isoheptyloxy, tert-heptyloxy and the like. Among them, an alkoxy group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms partially substituted with 1 or more groups selected from the group consisting of an epoxy group, an oxetanyl group, a hydroxyl group and a carboxyl group is preferable in view of curability.
Examples of the aryl group having 6 to 12 carbon atoms represented by X in the above formula (I) include: phenyl, methylphenyl, naphthyl, and the like.
Examples of the aryloxy group having 6 to 12 carbon atoms represented by X in the above formula (I) include: phenyloxy, methylphenyloxy, naphthyloxy, and the like.
Examples of the alicyclic hydrocarbon group having 6 to 10 carbon atoms represented by X in the above formula (I) include: cyclohexyl, methylcyclohexyl, norbornyl, dicyclopentyl, bicyclooctyl, trimethylbicycloheptyl, tricyclooctyl, tricyclodecyl, spirooctyl, spirodicyclopentyl, adamantyl, isobornyl, and the like.
For these alkyl, alkoxy, aryl, aryloxy, and alicyclic hydrocarbon groups, the hydrogen atom in these groups may also be substituted with 1 or more selected from the group consisting of epoxy, oxetanyl, hydroxy, and carboxyl groups.
In the above formula (I), when a part of X is taken out by an epoxy group or an oxetanyl group, examples of the monomer represented by the formula (I) include the monomers represented by the following formulas (1) to (3).
In the formula (1), R 3 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and m is an integer of 1 to 6.
In the formula (2), R 4 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n is an integer of 1 to 6.
In the formula (3), R 5 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and s is an integer of 1 to 6.
In the above formula (II), examples of the halogen atom represented by R 1 include: fluorine, chlorine, bromine, iodine, and the like.
In the above formula (II), examples of the alkyl group having 1 to 7 carbon atoms, the aryl group having 6 to 12 carbon atoms or the alicyclic hydrocarbon group having 6 to 10 carbon atoms of X' include the same groups as those in the above formula (I).
In the above formula (II), when a part of X' is substituted with an epoxy group or an oxetanyl group, the monomer represented by the formula (II) may be represented by the following formulas (4) to (6).
In the formula (4), R 1 is the same as in the above formula (II), R 6 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and t is an integer of 1 to 6.
In the formula (5), R 1 is the same as in the above formula (II), R 7 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and q is an integer of 1 to 6.
In the formula (6), R 1 is the same as in the above formula (II), R 8 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and y is an integer of 1 to 6.
In the above polymer (E), the adhesive properties are preferably improved when the ratio of the monomers constituting the polymer is as follows: when X is an alkyl group having 1 to 7 carbon atoms, an aryl group having 6 to 12 carbon atoms or an alicyclic hydrocarbon group having 6 to 10 carbon atoms, which is substituted with 1 or more groups selected from the group consisting of an epoxy group, an oxetanyl group, a hydroxyl group and a carboxyl group, the monomer represented by the above (I) or (II) is 10 to 100% by mass.
In the curable composition of the present invention, the cationic polymerizable component (a) is 45 to 90 parts by mass, the cationic polymerization initiator (B) is 0.001 to 15 parts by mass, the radical polymerizable component (C) is 1 to 15 parts by mass, the radical polymerization initiator (D) is 1 to 10 parts by mass, and the polymer (E) is 1 to 20 parts by mass, based on 100 parts by mass of the total of the cationic polymerizable component (a), the radical polymerizable component (C), and the polymer (E). If the ratio is not the above-mentioned blending ratio, there is a concern that curability and adhesion of the cured product may be deteriorated.
In the curable composition of the present invention, a sensitizer and/or a sensitizing auxiliary may be further used as needed. The sensitizer is a compound that exhibits maximum absorption at a wavelength longer than the maximum absorption wavelength shown by the cationic polymerization initiator (B) and promotes the polymerization initiation reaction based on the cationic polymerization initiator (B). The sensitizer is a compound that further promotes the action of the sensitizer.
Examples of the sensitizer and the sensitizing auxiliary include: anthracene-based compounds, naphthalene-based compounds, and the like.
Examples of the anthracene compound include those represented by the following formula (7).
In the formula (7), R 50 and R 51 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxyalkyl group having 2 to 12 carbon atoms, and R 52 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Specific examples of the anthracene compound represented by the above formula (7) include the following compounds.
Examples include: 9, 10-dimethoxy anthracene, 9, 10-diethoxy anthracene, 9, 10-dipropoxy anthracene, 9, 10-diisopropyl anthracene, 9, 10-dibutoxy anthracene, 9, 10-dipentyl anthracene, 9, 10-dihexyl xanthene, 9, 10-bis (2-methoxyethoxy) anthracene, 9, 10-bis (2-ethoxyethoxy) anthracene, 9, 10-bis (2-butoxyethoxy) anthracene, 9, 10-bis (3-butoxypropoxy) anthracene, 2-methyl-or 2-ethyl-9, 10-dimethoxy anthracene, 2-methyl-or 2-ethyl-9, 10-diethoxy anthracene, 2-methyl-or 2-ethyl-9, 10-dipropyl xanthene, 2-methyl-or 2-ethyl-9, 10-diisopropyl xanthene, 2-methyl-or 2-ethyl-9, 10-dibutoxy anthracene, 2-methyl-or 2-ethyl-9, 10-dipentyl xanthene, 2-methyl-or 2-ethyl-9, 10-diethoxy anthracene, etc.
Examples of the naphthalene compound include compounds represented by the following formula (8).
In the formula (8), R 53 and R 54 each independently represent an alkyl group having 1 to 6 carbon atoms.
Specific examples of the naphthalene compound represented by the above formula (8) include the following compounds.
Examples include: 4-methoxy-1-naphthol, 4-ethoxy-1-naphthol, 4-propoxy-1-naphthol, 4-butoxy-1-naphthol, 4-hexyloxy-1-naphthol, 1, 4-dimethoxynaphthalene, 1-ethoxy-4-methoxynaphthalene, 1, 4-diethoxynaphthalene, 1, 4-dipropoxynaphthalene, 1, 4-dibutoxynaphthalene, and the like.
The proportion of the sensitizer and the sensitizing auxiliary to the cationically polymerizable component (a) is not particularly limited, and may be used in a generally normal proportion within a range that does not hinder the object of the present invention, and for example, the sensitizer and the sensitizing auxiliary are preferably each 0.1 to 3 parts by mass relative to 100 parts by mass of the cationically polymerizable component (a) from the viewpoint of improving curability.
In the curable composition of the present invention, a silane coupling agent may be used as needed. As the silane coupling agent, for example, it is possible to use: alkyl functional alkoxysilanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, alkenylfunctional alkoxysilane such as allyltrimethoxysilane, 3-methacryloxypropyl triethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl methyldiethoxysilane, 3-methacryloxypropyl methyldimethoxysilane, 3-methacryloxypropyl epoxy functional alkoxysilanes such as 2-methacryloxypropyl trimethoxysilane, gamma-glycidoxypropyl methyldiethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, amino functional alkoxysilanes such as N-beta (aminoethyl) -gamma-aminopropyl trimethoxysilane, gamma-aminopropyl triethoxysilane, N-phenyl-gamma-aminopropyl trimethoxysilane, mercapto functional alkoxysilanes such as gamma-mercaptopropyl trimethoxysilane, alkoxytitans such as tetraisopropoxytitans and tetra-N-butoxytitans, dioctyl bis (glycolate) titanate, titanium chelates such as diisopropoxy bis (ethylacetoacetate) titanate, zirconium tetra-acetylacetonate, zirconium tri-butoxy monoacetylacetonate, zirconium chelates such as zirconium tri-butoxide, zirconium acylate such as zirconium tributoxide monostearate, isocyanate silane such as methyl triisocyanate silane, etc.
The amount of the silane coupling agent is not particularly limited, and is usually in the range of 0.01 to 20 parts by mass based on 100 parts by mass of the total amount of solids in the curable composition.
In the curable composition of the present invention, the thermoplastic organic polymer is used as needed, so that the properties of the cured product can be improved. Examples of the thermoplastic organic polymer include: polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, methyl methacrylate-glycidyl methacrylate copolymer, poly (meth) acrylic acid, styrene- (meth) acrylic acid copolymer, methyl (meth) acrylic acid-methyl methacrylate copolymer, glycidyl (meth) acrylate-poly (meth) methyl acrylate copolymer, polyvinyl butyral, cellulose ester, polyacrylamide, saturated polyester, and the like.
The curable composition of the present invention may be further used as needed: an ultraviolet absorber; a compound which is inactive at normal temperature, and which is activated by heating to a predetermined temperature, irradiation with light, or acid to release a protecting group, thereby exhibiting ultraviolet absorption ability.
Further, various resin additives such as a polyol, an inorganic filler, an organic filler, a pigment, a colorant such as a dye, an antifoaming agent, a thickener, a surfactant, a leveling agent, a flame retardant, a thixotropic agent, a diluent, a plasticizer, a stabilizer, a polymerization inhibitor, an ultraviolet absorber, an antioxidant, an antistatic agent, a flow regulator, an adhesion promoter, and the like may be added as necessary within a range not impairing the effect of the present invention.
The curable composition of the present invention is not particularly limited, and a solvent which can dissolve or disperse each of the above components (a), (B), (C), (D) and (E) can be used as commonly used. Examples of the solvent include: ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; ether solvents such as diethyl ether, dioxane, tetrahydrofuran, 1, 2-dimethoxyethane, 1, 2-diethoxyethane, propylene glycol monomethyl ether, dipropylene glycol dimethyl ether, and the like; ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and Texanol; cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; alcohol solvents such as methanol, ethanol, isopropanol or n-propanol, isobutanol or n-butanol, and pentanol; ether ester solvents such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol-1-monomethyl ether-2-acetate (PGMEA), 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, D-limonene, pinene, etc.; paraffin solvents such as mineral spirits, swasol #310 (Cosmo Matsuyama Oil co., ltd.) and solvosiso #100 (Exxon Mobil Corporation); halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride and 1, 2-dichloroethane; halogenated aromatic hydrocarbon solvents such as chlorobenzene; propylene carbonate, carbitol solvent, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, water and the like. The solvent may be used as a mixed solvent of 1 or 2 or more kinds.
The curable composition of the present invention has improved curability, adhesiveness, and liquid storage stability, and therefore the water content is preferably 5 parts by mass or less, more preferably 3 parts by mass or less. Excessive water is not preferable because of the fear of occurrence of cloudiness and precipitation of components.
The curable composition of the present invention can be applied to a supporting substrate by known means such as roll coater, curtain coater, printing, dipping, etc. In addition, the transfer may be performed onto a support substrate such as a film after being temporarily applied to another support substrate, and the application method thereof is not particularly limited.
The material of the support base is not particularly limited, and commonly used materials can be used, and examples thereof include: inorganic materials such as glass; cellulose esters such as diacetyl cellulose, triacetyl cellulose (TAC), propionyl cellulose, butyryl cellulose, levulinyl cellulose, and nitrocellulose; a polyamide; polyimide; polyurethane; an epoxy resin; a polycarbonate; polyesters such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, poly-1, 4-cyclohexanedimethanol terephthalate, polyethylene-1, 2-diphenoxyethane-4, 4' -dicarboxylic acid ester, and polybutylene terephthalate; a polystyrene; polyolefins such as polyethylene, polypropylene, polymethylpentene, and the like; vinyl compounds such as polyvinyl acetate, polyvinyl chloride and polyvinyl fluoride; acrylic resins such as polymethyl methacrylate and polyacrylate; a polycarbonate; polysulfone; polyether sulfone; polyether ketone; a polyetherimide; high molecular materials such as polyoxyethylene, norbornene resin, and cycloolefin polymer (COP). The support substrate may be subjected to surface activation treatment such as corona discharge treatment, flame treatment, ultraviolet treatment, high-frequency radiation treatment, glow discharge treatment, active plasma treatment, and laser treatment.
In the method of curing the curable composition of the present invention by irradiation with energy rays, examples of the energy rays include: ultraviolet rays, electron rays, X-rays, radiation rays, high-frequency rays, etc., and most preferably ultraviolet rays are economically advantageous. Examples of the light source of ultraviolet rays include: ultraviolet laser, mercury lamp, xenon laser, metal halide lamp, and the like.
The conditions in the method of curing the curable composition of the present invention by heating are 1 to 100 minutes at 70 to 250 ℃. The post-baking (PEB; post exposure bake) may be carried out after the pre-baking (PAB; PRE APPLIED bakes), or the baking may also be carried out at different multi-stage temperatures. The heating conditions vary depending on the kind and the compounding ratio of the components, and are, for example, 5 to 15 minutes in the case of a dryer at 70 to 180℃and 1 to 5 minutes in the case of a hot plate. Then, in order to cure the coating film, a cured film can be obtained by heat treatment at 180 to 250 ℃, preferably 200 to 250 ℃, for 30 to 90 minutes with a dryer, and for 5 to 30 minutes with a hot plate.
Specific applications of the curable composition of the present invention or the cured product thereof include: an optical material represented by an adhesive, spectacles, a lens for image pickup, a coating material, a coating agent, a lining agent, an ink, a resist, a liquid resist, a printing plate, a color television, a PC monitor, a portable information terminal, a digital camera, an organic EL, a display element such as a touch panel, an insulating varnish, an insulating sheet, a laminate, a printed board, a sealing agent such as a sealing agent for a semiconductor device, a packaging material for an LED, a liquid crystal injection port, an optical element, an electrical insulating material, an electronic component, a separating film, a molding material, putty, a glass fiber impregnating agent, a gap filler, a passivation film such as a semiconductor, a passivation film such as a solar cell, an interlayer insulating film, a protective film, a lens portion of a lens sheet such as a fresnel lens sheet or a lenticular lens sheet used for a backlight of a liquid crystal display device, an optical lens such as a backlight using such a sheet, an optical element such as a microlens, an optical element such as an optical element, an optical connector, an optical waveguide, a casting agent for optical modeling, and the like.
The display device of the present invention includes: the transparent support may be provided with a primer layer, an antireflection layer, a polarizing element layer, a retardation layer, a birefringent layer, a light scattering layer, a hard coat layer, a lubricant layer, a protective layer, and the like, as required, and a film composed of the cured product of the present invention may be used for each layer.
Examples
The present invention will be described in further detail with reference to examples, but the present invention is not limited to these examples.
Examples 1 to 20 and comparative examples 1 to 7
The curable compositions of examples 1 to 20 and the curable compositions of comparative examples 1 to 7 were obtained by thoroughly mixing the respective components by compounding as shown in the following tables 1 to 5. The unit of examples and comparative examples is parts by mass.
As the cationically polymerizable component (a), the following compounds were used.
Compound (A1-1): neopentyl glycol diglycidyl ether
Compound (A1-2): 1, 4-butanediol diglycidyl ether
Compound (A2-1): ARON OXETANE OXT-221 (manufactured by Toyama Synthesis Co., ltd.)
Compound (A3-1): bisphenol diglycidyl ether
Compound (A3-2): TECHMORE VG3101 (aromatic 3-functional epoxy: printech Co., ltd.)
As the cationic polymerization initiator (B), the following compound (B-1) was used.
Compound B-1: propylene carbonate 50% solution of a mixture of a compound represented by the following formula (9) and a compound represented by the following formula (10)
The following compounds were used as the radical polymerizable component (C).
Compound (C1-1): epoxy ester M-600A (co-Rong chemical Co., ltd.)
Compound (C1-2): epoxy ester 70PA (co-Rong chemical Co., ltd.)
Compound (C2-1): 1, 6-hexanediol diacrylate
As the radical polymerization initiator (D), the following compound (D-1) was used.
Compound (D-1): IRGACURE 184 (BASF corporation)
As the polymer (E), the following compound (E-1) was used.
Polymer (E-1): 75 parts by mass of methyl methacrylate and glycidyl methacrylate 25 copolymer (weight average molecular weight 7000)
As the polymer (E '), the following compounds (E ' -1) and (E ' -2) were used.
Compound (E' -1): 75 parts by mass of methyl methacrylate and glycidyl methacrylate 25 copolymer (weight average molecular weight 800)
Compound (E' -2: copolymer of 75 parts by mass of methyl methacrylate and glycidyl methacrylate 25 (weight-average molecular weight 35000)
The obtained curable compositions of examples 1 to 20 and comparative examples 1 to 7 were evaluated for glass transition temperature (Tg), elastic modulus, tackiness and adhesiveness according to the following procedures. The results are shown together in tables 1 to 5.
(Glass transition temperature and elastic modulus)
The curable compositions of examples 1 to 20 and comparative examples 1 to 7 were each coated on a polyethylene terephthalate (PET) film to a thickness of 30 μm by a bar coater, and irradiated with energy of 3000mJ/cm 2 by a metal halide lamp. After 24 hours, the cured adhesive was removed from the film, and Tg and elastic modulus at 80℃were measured using a viscoelasticity measuring device (DMA 7100) made of HITACHI HIGH-Technologies Corporation.
The obtained curable compositions of examples 1 to 20 and comparative examples 1 to 7 were each measured for viscosity at 25℃by an E-type viscometer. The results are shown together in tables 1 to 5.
(Adhesion)
The compositions of examples 1 to 20 and comparative examples 1 to 7 obtained above were each coated on one sheet of corona-treated PMMA Film (Technology 125S001, manufactured by Sumitomo chemical Co., ltd.), and then bonded to another sheet of COP (cycloolefin polymer, model number Zeonor Film 14-060, manufactured by Zeon Corporation) Film subjected to corona discharge treatment using a laminator, and the test piece was obtained by irradiating light corresponding to 1000mJ/cm 2 with an electrodeless ultraviolet lamp through the COP Film. The test piece obtained was subjected to a 90-degree peel test.
TABLE 1
TABLE 2
TABLE 3
TABLE 4
TABLE 5
As is clear from tables 1 to 5, the cured product of the curable composition of the present invention is excellent in curability and adhesion.

Claims (7)

1. A curable composition characterized by comprising 100 parts by mass of a total of a cationically polymerizable component (A), a radically polymerizable component (C) and a polymer (E): 65 to 90 parts by mass of the cation polymerizable component (A), 0.001 to 15 parts by mass of the cation polymerization initiator (B), 1 to 15 parts by mass of the radical polymerization component (C), 1 to 10 parts by mass of the radical polymerization initiator (D), and 1 to 20 parts by mass of the polymer (E), wherein the weight average molecular weight of the polymer (E) is 1000 to 30000, and the polymer (E) is selected from the group consisting of: a polymer obtained from a monomer represented by the following formula (I), a polymer obtained from a monomer represented by the following formula (II), a polymer obtained from two or more monomers selected from the monomers represented by the formula (I), a polymer obtained from two or more monomers selected from the monomers represented by the formula (II), and a polymer obtained from the monomer represented by the formula (I) and the monomer represented by the formula (II),
In the formula (I), X is an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms or an alicyclic hydrocarbon group having 6 to 10 carbon atoms, or a group in which a hydrogen atom in these groups is substituted with 1 or more groups selected from the group consisting of an epoxy group, an oxetanyl group, a hydroxyl group and a carboxyl group,
In the formula (II), R 1 represents a hydrogen atom, a methyl group or a halogen atom, X' is an alkyl group having 1 to 7 carbon atoms, an aryl group having 6 to 12 carbon atoms or an alicyclic hydrocarbon group having 6 to 10 carbon atoms, or a group in which a hydrogen atom in these groups is substituted with 1 or more groups selected from the group consisting of an epoxy group, an oxetanyl group, a hydroxyl group and a carboxyl group,
The cation polymerizable component (A) contains, as essential components, a glycidylate (A1) of a polyol or a glycidylate (A2) of a polyol alkylene oxide adduct,
The radical polymerizable component (C) contains, as an essential component, a compound (C1) having an epoxy group and an ethylenically unsaturated group, or an acrylic acid ester of a polyol having 2 to 20 carbon atoms or a methacrylic acid ester (C2) of a polyol having 2 to 20 carbon atoms,
The amount of the glycidylate (A1) of the polyol or the glycidylate (A2) of the polyol alkylene oxide adduct is 50 to 80 parts by mass and the amount of the oxetane compound (A2) is 20 to 50 parts by mass based on 100 parts by mass of the cationically polymerizable component (A).
2. The curable composition according to claim 1, further comprising an aromatic epoxy compound (A3) as the cationically polymerizable component (a).
3. The curable composition according to claim 2, wherein the aromatic epoxy compound (A3) is a polyfunctional aromatic epoxy compound.
4. The curable composition according to claim 1, wherein the polymer (E) is a polymer obtained from the monomer represented by the formula (I) and the monomer represented by the formula (II), X in the formula (I) is an aryl group having 6 to 12 carbon atoms, X' in the formula (II) is an alkyl group having 1 to 7 carbon atoms, and the alkyl group is substituted with an epoxy group.
5. A method for curing a curable composition, characterized by irradiating the curable composition according to any one of claims 1 to 4 with active energy rays.
6. A method for curing a curable composition, comprising heating the curable composition according to any one of claims 1 to 4.
7. A cured product of the curable composition according to any one of claims 1 to 4.
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