CN108779321B - 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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CN108779321B
CN108779321B CN201780019743.5A CN201780019743A CN108779321B CN 108779321 B CN108779321 B CN 108779321B CN 201780019743 A CN201780019743 A CN 201780019743A CN 108779321 B CN108779321 B CN 108779321B
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CN108779321A (en
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松土和彦
渡边智志
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Adeka Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
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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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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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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
    • C08G59/20—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
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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
    • C08G59/20—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
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    • 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
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • C—CHEMISTRY; METALLURGY
    • 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)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)
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Abstract

The invention provides a curable composition, a method for producing a cured product, and a cured product thereof, wherein the cured product has a high glass transition temperature and excellent adhesion. The curable composition contains: a cationically polymerizable component (A), a cationically polymerizable initiator (B), a radically polymerizable component (C), a radically polymerizable initiator (D), and a polymer (E), wherein the polymer (E) has a weight average molecular weight of 1000 to 30000, and is selected from the group consisting of: a polymer obtained from a monomer represented by the following formula (I) wherein X is an alkyl group having 1 to 7 carbon atoms, or the like, a polymer obtained from a monomer represented by the following formula (II) wherein R is1X' is an alkyl group having 1 to 7 carbon atoms, etc., and the component (A) contains a glycidyl compound of a polyhydric alcohol having a molecular weight of 200 or more and an oxetane compound as essential components, and the component (C) contains a compound having an epoxy group and an ethylenically unsaturated group, an acrylate of an alcohol having 2 to 20 carbon atoms, etc. 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 cured product with a high glass transition temperature and excellent adhesion, a method for producing a cured product, and a cured product thereof.
Background
The curable composition is used in the fields of inks, coatings, various coating agents, adhesives, optical members, and the like. Various reports have been made on improvement of such a curable composition.
For example, the following patent documents 1 to 4 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 adhesiveness. Patent documents 2 and 3 propose a low-viscosity photocurable adhesive which exhibits adhesion rapidly after light irradiation even when a resin film having low moisture permeability is used as a protective film, exhibits excellent adhesion after a certain period of time with respect to various forces, does not cause a problem after a durability test, and has excellent adhesion after a moisture and heat resistance test. Further, patent document 4 proposes an active energy ray-polymerizable resin composition containing an unsaturated alicyclic epoxy ester compound, which can achieve both high heat resistance, a high refractive index, and transparency.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2014-105218
Patent document 2: japanese laid-open patent publication No. 2015-040283
Patent document 3: japanese patent laid-open publication No. 2015-143352
Patent document 4: japanese laid-open patent publication No. 2015-168757
Disclosure of Invention
Problems to be solved by the invention
However, even the curable compositions proposed in patent documents 1 to 4 may not necessarily satisfy the requirements for curability and adhesion, and a novel curable composition that can highly satisfy 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 cured product with a high glass transition temperature and excellent adhesion, a method for producing a cured product, and a cured product thereof.
Means for solving the problems
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.
That is, the curable composition of the present invention is characterized by containing: a cationically polymerizable component (A), a cationically polymerizable initiator (B), a radically polymerizable component (C), a radically polymerizable initiator (D), and a polymer (E), wherein the polymer (E) has a weight average molecular weight of 1000 to 30000, and 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 monomers represented by the following formula (I), a polymer obtained from two or more monomers selected from monomers represented by the following formula (II), and a polymer obtained from a monomer represented by the following formula (I) and a monomer represented by the following formula (II),
Figure BDA0001810338840000021
(in the formula (I), X is C1-7 alkyl, C1-7 alkoxy, C6-12 aryl, C6-12 aryloxy or C6-10 alicyclic hydrocarbon group, or the group of these groups in which the hydrogen atom is substituted by more than 1 group selected from the group consisting of epoxy, oxetanyl, hydroxyl and carboxyl),
Figure BDA0001810338840000031
(in the formula (II), R1Represents a hydrogen atom, a methyl group or a halogen atom, X' represents 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 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) contains, as essential components, a glycidyl compound of a polyol or a glycidyl compound of a polyol alkylene oxide adduct having a molecular weight of 200 or more (A1) and an oxetane compound (A2),
the radical polymerizable component (C) contains, as an essential component, a compound (C1) having an epoxy group and an ethylenically unsaturated group, or an acrylate ester of an alcohol having 2 to 20 carbon atoms or a methacrylate ester of an alcohol having 2 to 20 carbon atoms (C2). Here, the weight average molecular weight means: the weight average molecular weight was measured by GPC in a Tetrahydrofuran (THF) solvent and determined in terms of styrene.
The curable composition of the present invention preferably further contains an alicyclic epoxy compound (a3) as the cationically polymerizable component (a). In the curable composition of the present invention, the polyol in the glycidyl compound of a polyol or glycidyl compound of a polyol alkylene oxide adduct (a1) having a molecular weight of 200 or more is preferably a polyol having a condensed ring. Further, the curable composition of the present invention preferably comprises: 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 by an epoxy group. Further, it is preferable that: 30 to 70 parts by mass of the cationic polymerizable component (A), 0.001 to 10 parts by mass of the cationic polymerization initiator (B), 30 to 60 parts by mass of the radical polymerizable component (C), 1 to 10 parts by mass of the radical polymerization initiator (D), 1 to 20 parts by mass of the polymer (E), and 100 parts by mass of the total of the cationic polymerizable component (A), the radical polymerizable component (C), and the polymer (E).
The method for producing a cured product of the present invention is characterized by irradiating or heating the curable composition of the present invention with an active energy ray.
The cured product of the present invention is characterized as 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 cured product with a high glass transition temperature and excellent adhesion, 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 for adhesives.
Detailed Description
The curable composition of the present invention will be described in detail below.
The curable composition of the present invention contains: a cationically polymerizable component (A), a cationically polymerizable initiator (B), a radically polymerizable component (C), a radically polymerizable initiator (D), and a polymer (E), wherein the polymer (E) has a weight average molecular weight of 1000 to 30000, and 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 monomers represented by the following formula (I), a polymer obtained from two or more monomers selected from monomers represented by the following formula (II), and a polymer obtained from a monomer represented by the following formula (I) and a monomer represented by the following formula (II). The curable composition of the present invention contains a cationic polymerizable component (A) containing a glycidyl compound of a polyol or a glycidyl compound of a polyol alkylene oxide adduct having a molecular weight of 200 or more (A1) and an oxetane compound (A2) as essential components, and a radical polymerizable component (C) containing an epoxy group and an ethylenically unsaturated group (C1), an acrylic acid ester of an alcohol having 2 to 20 carbon atoms, or a methacrylic acid ester of an alcohol having 2 to 20 carbon atoms (C2) as essential components.
Figure BDA0001810338840000041
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 is substituted by 1 or more groups selected from the group consisting of an epoxy group, an oxetanyl group, a hydroxyl group and a carboxyl group.
Figure BDA0001810338840000051
Here, in the formula (II), R1Represents a hydrogen atom, a methyl group or a halogen atom, and X' represents 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 is substituted by 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 which undergoes a polymerization or crosslinking reaction by a cationic polymerization initiator activated by irradiation with an energy ray or heating. Examples thereof include: epoxy compounds, oxetane compounds, vinyl ether compounds, and the like.
The cationically polymerizable component (a) of the curable composition of the present invention contains a glycidyl compound of a polyol or a polyol alkylene oxide adduct having a molecular weight of 200 or more (a1) and an oxetane compound (a2) as essential components, and as other epoxy compounds, an alicyclic epoxy compound (A3), an aromatic epoxy compound (a4), and the like can be used.
Examples of the glycidyl compound of a polyol or a polyol alkylene oxide adduct having a molecular weight of 200 or more (a1) include a glycidyl compound obtained by glycidylating a polyol or a polyol alkylene oxide adduct, and the molecular weight of the glycidyl compound is 200 or more.
Examples of the glycidyl compound of the polyol or the glycidyl compound of the polyol alkylene oxide adduct having a molecular weight of 200 or more (a1) include: 1, 4-butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol tetraglycidyl ether, dipentaerythritol hexaglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, dicyclopentadiene dimethanol diglycidyl ether and other polyhydric alcohol glycidyl ethers, and also polyglycidyl etherates of polyether polyols obtained by adding 1 or 2 or more alkylene oxides to aliphatic polyhydric alcohols such as propylene glycol, trimethylolpropane and glycerol, and diglycidyl esters of aliphatic long-chain dibasic acids.
As the glycidyl compound of a polyol or the glycidyl compound of a polyol alkylene oxide adduct (a1), there can be further mentioned: monoglycidyl ether of aliphatic higher alcohol, glycidyl ester of higher fatty acid, epoxidized soybean oil, epoxidized octyl stearate, epoxidized butyl stearate, epoxidized soybean oil, epoxidized polybutadiene, and the like.
The glycidyl compound of a polyol having a molecular weight of 200 or more or the glycidyl compound of a polyol alkylene oxide adduct (a1) is preferable because it has a saturated condensed ring because curability and adhesion of a cured product are improved.
As the glycidyl compound of the polyol or the glycidyl compound of the polyol alkylene oxide adduct having a molecular weight of 200 or more (a1), commercially available ones can be used, and examples thereof include: 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, and DENACOL EX-931 (NACOL ChemseX Corporation); eplight M-1230, Eplight 40E, Epolight 100E, Epolight 200E, Epolight 400E, Epolight 70P, Epolight 200P, Epolight 400P, Epolight 1500NP, Eplight 1600, Eplight 80MF, Eplight 100MF (Co., Ltd.), ADEKA Glycol ED-503G, ADEKA Glycol ED-506, ADEKA Glycol ED-523T, ADEKA RESIN EP-4088S, ADEKA RESIN EP-4080E (manufactured by ADEKA Co., Ltd.), and the like.
Examples of the oxetane compound (a2) include: 3, 7-bis (3-oxetanyl) -5-oxo-nonane, 1, 4-bis [ (3-ethyl-3-oxetanylmethoxy) methyl ] benzene, 1, 2-bis [ (3-ethyl-3-oxetanylmethoxy) methyl ] ethane, 1, 3-bis [ (3-ethyl-3-oxetanylmethoxy) methyl ] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmeth) ether, 1, 4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1, 3-bis (3-oxetanylmethoxy) propane, 1, 3-bis (3-ethylcyclobutane) propane, or a mixture thereof, Difunctional aliphatic oxetane compounds such as 1, 6-bis (3-ethyl-3-oxetanylmethoxy) hexane, monofunctional oxetane compounds such as 3-ethyl-3- [ (phenoxy) methyl ] oxetane, 3-ethyl-3- (hexyloxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (hydroxymethyl) oxetane and 3-ethyl-3- (chloromethyl) oxetane, and the like. These can be used alone in 1 or a combination of 2 or more. Among the oxetane compounds (a2), a polyfunctional oxetane compound is preferable because a cured product thereof has a high glass transition temperature.
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 Takayama petrochemical Co., Ltd.); ARON OXETANE OXT-121, OXT-221, EXOH, POX, OXA, OXT-101, OXT-211, OXT-212 (manufactured by TOYO SYNTHETIC CO., LTD.), ETERNACOLL OXBP, OXTP (manufactured by UYO Kyowa Co., Ltd.), etc.
The alicyclic epoxy compound (a3) means that an oxirane ring is directly bonded to a saturated ring without a bonding group. Specific examples of the alicyclic epoxy compound (a3) include: a cyclohexene oxide obtained by epoxidizing a polyglycidyl etherate or cyclohexene of a polyhydric alcohol having at least 1 alicyclic ring, a cyclopentene ring-containing compound, or a cyclopentene oxide-containing compound, with an oxidizing agent. Examples thereof include: 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexylformate, 3, 4-epoxy-1-methylcyclohexyl-3, 4-epoxy-1-methylhexylcarboxylate, 6-methyl-3, 4-epoxycyclohexylmethyl-6-methyl-3, 4-epoxycyclohexylformate, 3, 4-epoxy-3-methylcyclohexylmethyl-3, 4-epoxy-3-methylcyclohexylcarboxylate, 3, 4-epoxy-5-methylcyclohexylmethyl-3, 4-epoxy-5-methylcyclohexylcarboxylate, bis (3, 4-epoxycyclohexylmethyl) adipate, 3, 4-epoxy-6-methylcyclohexylcarboxylate, bis (phenylcarbamoyl) carboxylate, methylenebis (3, 4-epoxycyclohexane), propane-2, 2-diyl-bis (3, 4-epoxycyclohexane), 2-bis (3, 4-epoxycyclohexyl) propane, dicyclopentadiene diepoxide, ethylenebis (3, 4-epoxycyclohexylformate), dioctylphthalate oxide, di-2-ethylhexyl hexahydrophthalate oxide, 1-epoxyethyl-3, 4-epoxycyclohexane, 1, 2-epoxy-2-epoxyethylcyclohexane, α -pinene oxide, limonene dioxide, and the like. The alicyclic epoxy compound (a3) is preferably 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexyl formate or 3, 4-epoxy-1-methylcyclohexyl-3, 4-epoxy-1-methylhexyl formate from the viewpoint of improving adhesion.
As the alicyclic epoxy compound (a3), commercially available ones can be used, and examples thereof include: CELLOXIDE 2021P, CELLOXIDE 2081, CELLOXIDE 2000, CELLOXIDE 3000 (manufactured by Daicel Corporation), and the like.
The aromatic epoxy compound (a4) is an epoxy compound containing an aromatic ring, and specific examples of the aromatic epoxy compound (a4) include: mono/polyglycidyl etherates of polyhydric phenols having at least 1 aromatic ring such as phenol, cresol, butylphenol and the like or alkylene oxide adducts thereof, for example: a glycidyl etherate of bisphenol a, bisphenol F, or a compound obtained by further adding an alkylene oxide to these compounds, or a novolak epoxy resin; mono/polyglycidyl etherates of aromatic compounds having 2 or more phenolic hydroxyl groups such as resorcinol, hydroquinone, and catechol; glycidyl etherate of aromatic compound having 2 or more alcoholic hydroxyl groups such as phenyl dimethanol, phenyl diethanol, and phenyl dibutanol; 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, styrene oxides, and epoxides of divinylbenzene.
As the aromatic epoxy compound (a4), commercially available products can be used, and examples thereof include: 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 (manufactured by Nagase ChemteX Corporation); OGSOL PG-100, OGSOL EG-200, OGSOL EG-210, OGSOL EG-250(Osaka Gas Chemicals Co., Ltd.); HP4032, HP4032D, HP4700 (manufactured by DIC corporation); ESN-475V (New Nippon iron King chemical Co., Ltd.); EPIKOTE YX8800 (manufactured by Mitsubishi chemical Co., Ltd.); MARPROOF G-0105SA and MARPROOF G-0130SP (manufactured by Nissan oil Co., Ltd.); EPICLON N-665, EPICLON HP-7200 (available from DIC corporation); EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, XD-1000, NC-3000, EPPN-501H, EPPN-501HY, EPPN-502H, NC-7000L (manufactured by Nippon Kagaku Co., Ltd.); ADEKA RESIN EP-4000, ADEKA RESIN EP-4005, ADEKA RESIN EP-4100 and ADEKA RESIN EP-4901 (manufactured by ADEKA); TECHMORE VG-3101L (Printech Co., Ltd.). The aromatic epoxy compound (a4) is preferably a polyfunctional aromatic epoxy compound because it has excellent curability.
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 cationically polymerizable component (a), the ratio of the glycidyl compound of the polyol or the glycidyl compound of the polyol alkylene oxide adduct having a molecular weight of 200 or more (a1), the oxetane compound (a2), the alicyclic epoxy compound (A3), the aromatic epoxy compound (a4) and the vinyl ether compound used is, based on 100 parts by mass of the cationically polymerizable component (a): 40 to 70 parts by mass of a glycidyl compound of a polyol or a glycidyl compound of a polyol alkylene oxide adduct having a molecular weight of 200 or more (A1), 30 to 60 parts by mass of an oxetane compound (A2), 0 to 50 parts by mass of an alicyclic epoxy compound (A3), 0 to 30 parts by mass of an aromatic epoxy compound (A4), and 0 to 20 parts by mass of a vinyl ether compound are preferable because 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 that can release a substance that initiates cationic polymerization by irradiation with an energy ray or heating, and is preferably an onium salt, that is, a double salt, or a derivative thereof that releases a lewis acid by irradiation with an energy ray. Typical examples of the compounds include salts of cations and anions represented by the following general formulae.
[A]r+[B]r-
Here the cation [ A ]]r+Preferably, the onium salt has a structure represented by the following general formula.
[(R2)aQ]r+
Further, here, R2Is an organic group having 1 to 60 carbon atoms and optionally containing atoms other than a plurality of carbon atoms. a is an integer of 1 to 5. a number of R2Each independently may be the same or different. At least 1 of the organic groups is preferably an organic group having an aromatic ring as described above. Q is selected from the group consisting of S, N, Se, Te,P, As, Sb, Bi, O, I, Br, Cl, F, N ═ N. In addition, a cation [ A ]]r+In (2), when the valence of Q is Q, it is necessary to satisfy the relationship of r-a-Q (where N-N is considered as valence 0).
In addition, an anion [ B ]]r-The halide complex is preferably represented by the following general formula.
[LYb]r-
Here, L is a metal or semimetal (metaloid) As a central atom of the halide complex, and B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co, and the like. Y is a halogen atom. b is an integer of 3 to 7. In addition, an anion [ B ]]r-When the valence of L in (b) is p, the relationship of r ═ b-p must be satisfied.
As anions of the above formula [ LYb]r-Specific examples of (3) include: tetrakis (pentafluorophenyl) borate, tetrakis (3, 5-difluoro-4-methoxyphenyl) borate, tetrafluoroborate (BF)4)-Hexafluorophosphate radical (PF)6)-Hexafluoroantimonate (SbF)6)-Hexafluoroarsenate (AsF)6)-Hexachloroantimonate (SbCl)6)-And the like.
In addition, an anion [ B ]]r-Also, a structure represented by the following general formula can be preferably used.
[LYb-1(OH)]r-
L, Y, b are the same as described above. Examples of other anions that can be used include: perchlorate ion (ClO)4)-Trifluoromethyl sulfite ion (CF)3SO3)-Fluorosulfonate ion (FSO)3)-Tosylate anion, trinitrobenzene sulfonate anion, camphorsulfonate, nonafluorobutanesulfonate, hexadecafluorooctansulfonate, tetraarylborate, tetrakis (pentafluorophenyl) borate, and the like.
Among such onium salts, the use of the following aromatic onium salts (i) to (iii) is particularly effective for the curable composition of the present invention. Of these, 1 kind thereof may be used alone or 2 or more kinds thereof may be used in combination.
(i) Aryl diazonium salts such as phenyl diazonium hexafluorophosphate, 4-methoxybenzyl diazonium hexafluoroantimonate and 4-methylbenzyl diazonium hexafluorophosphate
(ii) Diaryliodonium salts such as diphenyliodonium hexafluoroantimonate, bis (4-methylphenyl) iodonium hexafluorophosphate, bis (4-tert-butylphenyl) iodonium hexafluorophosphate and tolylcumyliodione tetrakis (pentafluorophenyl) borate
(iii) Sulfonium salts such as sulfonium cation represented by the following group I or II, hexafluoroantimony ion, hexafluorophosphate ion, tetrakis (pentafluorophenyl) borate ion, and the like
< group I >)
Figure BDA0001810338840000111
< group II >
Figure BDA0001810338840000121
In addition, other preferable examples include: (η)5A mixture of an iron-arene complex such as 2, 4-cyclopentadien-1-yl [ (1,2,3,4,5, 6-. eta.) - (1-methylethyl) benzene ] -iron-hexafluorophosphate or the like, an aluminum complex such as tris (acetylacetonate) aluminum, tris (ethylacetoneacetate) aluminum, tris (salicylaldehyde) aluminum or the like, and a silanol such as triphenylsilanol; salts such as thiophenium salts, tetrahydrothiophenium salts, benzylammonium salts, pyridinium salts, and hydrazonium salts; polyalkyl polyamines such as diethylene triamine, triethylene triamine and tetraethylene pentamine; alicyclic polyamines such as 1, 2-diaminocyclohexane, 1, 4-diamino-3, 6-diethylcyclohexane, and isophoronediamine; aromatic polyamines such as m-xylylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone; the polyamines mentioned above, glycidyl ethers such as phenyl glycidyl ether, butyl glycidyl ether, bisphenol A-diglycidyl ether and bisphenol F-diglycidyl ether, and various rings such as glycidyl esters of carboxylic acids are reacted with each other by a conventional methodA modified product of a polyepoxide produced by the reaction of an epoxy resin; amidated modified products produced by reacting the above-mentioned organic polyamines with carboxylic acids such as phthalic acid, isophthalic acid and dimer acid 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, tert-butylphenol, or resorcinol 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, dodecanedioic acid, 2-methylsuccinic acid, 2-methyladipic acid, 3-methylglutaric acid, 2-methylsuberic acid, 3, 8-dimethylsebacic acid, 3, 7-dimethylsebacic acid, hydrogenated dimer acid, etc.), aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, etc., alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, etc.), tricarboxylic acids such as trimellitic acid, trimesic acid, trimers of castor oil fatty acids, tetracarboxylic acids such as pyromellitic acid, etc.); dicyandiamide, imidazoles, carboxylic esters, sulfonic esters, aminimides, and the like.
Among them, from the viewpoint of improving the use and light sensitivity, it is preferable to use: aromatic iodonium salts, aromatic sulfonium salts, and iron-arene complexes, and further preferably: the aromatic sulfonium salt having the following structure is contained in an amount of at least 0.1 mass% relative to 100 mass% of the cationic polymerization initiator (B).
Figure BDA0001810338840000131
Here, in the formula, R11、R12、R13、R14、R15、R16、R17、R18、R19And R20Each independently represents 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, R21、R22、R23And R24Are respectively independentAnd is hydrogen atom, halogen atom or alkyl group having 1 to 10 carbon atoms, R25Represents a hydrogen atom, a halogen atom, An alkyl group having 1 to 10 carbon atoms or any substituent selected from the following chemical formulae (A) to (C), Anq-Represents an anion having a valence of q, and p represents a coefficient for making the charge neutral.
Figure BDA0001810338840000141
Here, in the formula, R11、R12、R13、R14、R15、R16、R17、R18、R19、R20、R21、R22、R23、R24、R26、R27、R28、R29、R35、R36、R37、R38And R39Each independently represents 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, R30、R31、R32、R33And R34Each independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 10 carbon atoms.
In the compound represented by the above general formula (1), R is11、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、R38And R39Examples of the halogen atom include: fluorine, chlorine, bromine, iodine, and the like.
As 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、R38And R39Examples of the alkyl group having 1 to 10 carbon atoms 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, methoxyethoxyethylethyl, 3-methoxybutyl, 2-methylthioethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, difluoroethyl, trichloroethyl, dichlorodifluoroethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, decafluoropentyl, tridecafluorohexyl, pentadecafluoroheptyl, heptadecafluorooctyl, methoxymethyl, 1, 2-epoxyethyl, methoxyethyl, isopentyl, pentyl, isopentyl, hexyl, heptyl, nonyl, 2-methylthioethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichlorodifluoromethyl, methoxyethoxymethyl, methylthiomethyl, ethoxyethyl, butoxymethyl, t-butylthiomethyl, 4-pentenyloxymethyl, trichloroethoxymethyl, bis (2-chloroethoxy) methyl, methoxycyclohexyl, 1- (2-chloroethoxy) ethyl, 1-methyl-1-methoxyethyl, ethyldithioethyl, trimethylsilylethyl, t-butyldimethylsilyloxymethyl, 2- (trimethylsilyl) ethoxymethyl, t-butoxycarbonylmethyl, ethyloxycarbonylmethyl, ethylcarbonylmethyl, t-butoxycarbonylmethyl, acryloyloxyethyl, methacryloyloxyethyl, 2-methyl-2-adamantyloxycarbonylmethyl, acetoacetyl, 2-methoxy-1-propenyl, methyl-ethyl, n-butyl, Hydroxymethyl, 2-hydroxyethyl, 1-hydroxyethyl, 2-hydroxypropyl, 3-hydroxybutyl, 4-hydroxybutyl, 1, 2-dihydroxyethyl and the like.
As R11、R12、R13、R14、R15、R16、R17、R18、R19、R20、R21、R22、R23、R24、R26、R27、R28、R29、R35、R36、R37、R38And R39Examples of the alkoxy group having 1 to 10 carbon atoms include: methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, sec-butyloxy, tert-butyloxy, isobutyloxy, pentyloxy, isopentyloxy, tert-pentyloxy, hexyloxy, cyclohexyloxy, cyclohexylmethyloxy, tetrahydrofuryloxy, tetrahydropyranyloxy, 2-methoxyethyloxy, 3-methoxypropyloxy, 4-methoxybutyloxy, 2-butoxyethyloxy, methoxyethoxyethyloxy, 3-methoxybutyloxy, 2-methylthioethyloxy, trifluoromethyloxy and the like.
As R11、R12、R13、R14、R15、R16、R17、R18、R19、R20、R21、R22、R23、R24、R26、R27、R28、R29、R35、R36、R37、R38And R39Examples of the ester group having 2 to 10 carbon atoms include: methoxycarbonyl, ethoxycarbonyl, isopropyloxycarbonyl, phenoxycarbonyl, acetoxy, propionyloxy, butyryloxy, chloroacetyloxy, dichloroacetoxy, trichloroacetoxy, trifluoroacetyloxy, t-butylcarbonyloxy, methoxyacetoxy, benzoyloxy and the like.
The cationic polymerization initiator (B) is used in an amount of 0.001 to 10 parts by mass, preferably 0.1 to 10 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 too small, curing tends to be insufficient, and if too large, the curing may adversely affect various physical properties such as water absorption of the cured product and strength of the cured product.
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 acrylate ester of an alcohol having 2 to 20 carbon atoms or a methacrylate ester of an alcohol having 2 to 20 carbon atoms (C2).
Examples of the compound (C1) having an epoxy group and an ethylenically unsaturated group include: the epoxy acrylate or epoxy methacrylate is specifically an acrylate obtained by reacting an aromatic epoxy resin, an alicyclic epoxy resin, an aliphatic epoxy resin, or the like, which is conventionally known, with acrylic acid or methacrylic acid. 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 of an alcohol having 2 to 20 carbon atoms (C2) include: an acrylic ester or a methacrylic ester obtained by reacting an aromatic or aliphatic alcohol having at least 1 hydroxyl group in the molecule and 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, isoamyl 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-ethylhexyl acrylate, ethyl acrylate, butyl acrylate, 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 hexamethacrylate, epsilon-caprolactone-modified dipentaerythritol hexamethacrylate, 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 compound other than (C1) or (C2) which is polymerized or crosslinked by a radical polymerization initiator activated by irradiation with energy rays or heating may be used, and examples thereof include: allyl carbamate compounds, unsaturated polyester compounds, styrene compounds, and the like. The ratio of the component (C1) to the component (C2) in the radically polymerizable component (C) is preferably 50% by mass or more.
The radical initiator (D) of 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) of 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 monomers represented by the above formula (I), a polymer obtained from two or more monomers selected from 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 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, from the viewpoint of curability, 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.
Examples of the alkoxy group having 1 to 7 carbon atoms represented by X in the 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, from the viewpoint of curability, 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.
Examples of the aryl group having 6 to 12 carbon atoms represented by X in the 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 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 formula (I) include: cyclohexyl, methylcyclohexyl, norbornyl, dicyclopentyl, bicyclooctyl, trimethylbicycloheptyl, tricyclooctyl, tricyclodecyl, spirooctyl, spirodicyclopentyl, adamantyl, isobornyl and the like.
With respect to these alkyl groups, alkoxy groups, aryl groups, aryloxy groups and alicyclic hydrocarbon groups, the hydrogen atoms in these groups may also be substituted with 1 or more groups selected from the group consisting of epoxy groups, oxetanyl groups, hydroxyl groups and carboxyl groups.
In the above formula (I), when a part of X is substituted with an epoxy group or an oxetanyl group, examples of the monomer represented by the formula (I) include monomers represented by the following formulae (1) to (3).
Figure BDA0001810338840000181
Here, in the formula (1), R3Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and m is an integer of 1 to 6.
Figure BDA0001810338840000182
Here, in the formula (2), R4Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n is an integer of 1 to 6.
Figure BDA0001810338840000183
Here, in the formula (3), R5Represents 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), as R1Examples of the halogen atom include: fluorine, chlorine, bromine, iodine, and the like.
In the formula (II), 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, and the same groups as those of the formula (I) are exemplified.
In the above formula (II), when a part of X' is substituted with an epoxy group or an oxetanyl group, examples of the monomer represented by the formula (II) include those represented by the following formulae (4) to (6).
Figure BDA0001810338840000191
Here, in the formula (4), R1Same as the above formula (II), R6Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and t is an integer of 1 to 6.
Figure BDA0001810338840000192
Here, in the formula (5), R1Same as the above formula (II), R7Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and q is an integer of 1 to 6.
Figure BDA0001810338840000193
Here, in formula (6), R1Same as the above formula (II), R8Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and y is an integer of 1 to 6.
In the polymer (E), the use ratio of the monomers constituting the polymer is preferably as follows because the adhesiveness is improved: 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, it is preferable that, with respect to 100 parts by mass of the total of the cationically polymerizable component (a), the radically polymerizable component (C), and the polymer (E): 30 to 70 parts by mass of the cationic polymerizable component (A), 0.001 to 10 parts by mass of the cationic polymerization initiator (B), 30 to 60 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). If the compounding ratio is not the above ratio, the curability and adhesion of the cured product may be deteriorated.
In the curable composition of the present invention, a sensitizer and/or a sensitization auxiliary may be further used as necessary. The sensitizer is a compound which exhibits the 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). In addition, the sensitizing auxiliary is a compound which further promotes the action of the sensitizing agent.
Examples of the sensitizer and the sensitization aid include: anthracene compounds, naphthalene compounds, and the like.
Examples of the anthracene compound include those represented by the following formula (7).
Figure BDA0001810338840000201
Here, in formula (7), R50And R51Each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxyalkyl group having 2 to 12 carbon atoms, R52Represents 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 thereof include: 9, 10-dimethoxyanthracene, 9, 10-diethoxyanthracene, 9, 10-dipropoxyanthracene, 9, 10-diisopropoxylanthracene, 9, 10-dibutoxyanthracene, 9, 10-dipentyloxylanthracene, 9, 10-dihexyloxyanthracene, 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-dimethoxyanthracene, 2-methyl-or 2-ethyl-9, 10-diethoxyanthracene, 2-methyl-or 2-ethyl-9, 10-dipropoxyanthracene, 9, 10-diisopropoxylanthracene, 2-methyl-or 2-ethyl-9, 10-diisopropoxylanthracene, 2-methyl-or 2-ethyl-9, 10-dibutoxyanthracene, 2-methyl-or 2-ethyl-9, 10-dipentyloxylanthracene, 2-methyl-or 2-ethyl-9, 10-dihexyloxyanthracene, etc.
Examples of the naphthalene-based compound include those represented by the following formula (8).
Figure BDA0001810338840000211
Here, in the formula (8), R53And R54Each independently represents an alkyl group having 1 to 6 carbon atoms.
Specific examples of the naphthalene-based compound represented by the above formula (8) include the following compounds.
Examples thereof 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 use ratio of the sensitizer and the sensitization auxiliary to the cationically polymerizable component (a) is not particularly limited, and may be generally used in a usual use ratio within a range not to impair the object of the present invention, and for example, from the viewpoint of improving curability, it is preferable that the sensitizer and the sensitization auxiliary are each 0.1 to 3 parts by mass with respect to 100 parts by mass of the cationically polymerizable component (a).
In the curable composition of the present invention, a silane coupling agent may be used as necessary. As the silane coupling agent, for example, there can be used: alkyl-functional alkoxysilanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltrimethoxysilane, alkenyl-functional alkoxysilanes such as vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, and allyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 2-methacryloxypropyltrimethoxysilane, gamma-glycidyloxypropyltrimethoxysilane, and the like, Epoxy-functional alkoxysilanes such as gamma-glycidoxypropylmethyldiethoxysilane and beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, amino-functional alkoxysilanes such as N-beta (aminoethyl) -gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane and N-phenyl-gamma-aminopropyltrimethoxysilane, mercapto-functional alkoxysilanes such as gamma-mercaptopropyltrimethoxysilane, alkoxytitanium compounds such as tetraisopropoxytitanium and tetra-N-butoxytitanium, titanium chelate compounds such as dioctyloxy bis (octylglycolate) titanates and diisopropoxyl bis (ethylacetoacetate) titanates, zirconium chelate compounds such as zirconium tetraacetylacetonate and zirconium tributoxydmonoacetylacetonate, zirconium acylate compounds such as zirconium tributoxydisulatate, etc., titanium oxide compounds such as magnesium oxide, magnesium oxide, Isocyanate silanes such as methyl triisocyanate silane.
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 per 100 parts by mass of the total amount of solids in the curable composition.
In the curable composition of the present invention, the properties of the cured product can be improved by using a thermoplastic organic polymer as needed. 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) acrylic acid copolymer, polyvinyl butyral, cellulose ester, polyacrylamide, saturated polyester, and the like.
The curable composition of the present invention may further contain, as necessary: an ultraviolet absorber; a compound which is inactive at normal temperature, and exhibits ultraviolet absorbability by being activated by removing a protective group by heating to a predetermined temperature, irradiation with light, acid, or the like.
In addition, various resin additives such as polyols, inorganic fillers, organic fillers, colorants such as pigments and dyes, antifoaming agents, thickeners, surfactants, leveling agents, flame retardants, thixotropic agents, diluents, plasticizers, stabilizers, polymerization inhibitors, ultraviolet absorbers, antioxidants, antistatic agents, flow control agents, and adhesion promoters may be added as necessary within a range not to impair the effects of the present invention.
The curable composition of the present invention is not particularly limited, and a solvent which can dissolve or disperse the components (a), (B), (C), (D) and (E) can be used. Examples of the solvent include: ketones such as methyl ethyl ketone, methyl pentanone, 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, and dipropylene glycol dimethyl ether; ester-based 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-based hydrocarbon oils such as turpentine, D-limonene and pinene; paraffin solvents such as mineral spirits, Swasol #310(Cosmo Matsuyama Oil co., ltd.), SOLVESSO #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, a carbitol solvent, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, water, and the like. These solvents may be used in a mixed solvent of 1 or 2 or more.
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, and more preferably 3 parts by mass or less. If the water content is too high, cloudiness or component precipitation may occur, which is not preferable.
The curable composition of the present invention can be applied to a support substrate by a known means such as a roll coater, a curtain coater, various printing, and dipping. Further, the transfer agent may be applied to a support substrate such as a film once and then transferred to another support substrate, and the application method is not particularly limited.
The material of the support substrate is not particularly limited, and a commonly used material 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; a polyimide; a 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' -dicarboxylate, and polybutylene terephthalate; 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; polysulfones; polyether sulfone; a polyether ketone; a polyetherimide; high polymer materials such as polyoxyethylene, norbornene resin, cycloolefin polymer (COP) and the like. The support base may be subjected to surface activation treatment such as corona discharge treatment, flame treatment, ultraviolet treatment, high-frequency ray treatment, glow discharge treatment, reactive plasma treatment, or laser treatment.
In the method for curing the curable composition of the present invention by irradiation with an energy ray, examples of the energy ray include: ultraviolet rays, electron beams, X-rays, radioactive rays, high-frequency rays, and the like, and most preferable in terms of economy is ultraviolet rays. Examples of the light source of ultraviolet rays include: ultraviolet laser, mercury lamp, xenon laser, metal halide lamp, and the like.
The method for curing the curable composition of the present invention by heating is carried out under conditions of 70 to 250 ℃ for 1 to 100 minutes. The pressurization and Post-baking (PEB) may be performed after the Pre-baking (PAB) or the baking may be performed at different multi-stage temperatures. The heating conditions vary depending on the kind and mixing ratio of each component, and are, for example, 5 to 15 minutes in the case of using a dryer at 70 to 180 ℃ and 1 to 5 minutes in the case of using a hot plate. Then, in order to cure the coating film, the cured film can be obtained by performing a heat treatment at 180 to 250 ℃, preferably 200 to 250 ℃, for 30 to 90 minutes in a dryer, and for 5 to 30 minutes in a hot plate.
Specific applications of the curable composition of the present invention or a cured product thereof include: adhesive, optical material represented by glasses and imaging lenses, coating material, coating agent, lining agent, ink, resist, liquid resist, printing plate, color television, PC monitor, portable information terminal, digital camera, display element such as organic EL and touch panel, insulating varnish, insulating sheet, laminate, printed circuit board, sealant for semiconductor device/LED package/liquid crystal injection port/organic EL/optical element/electric insulation/electronic component/separation film, molding material, putty, glass fiber impregnant, gap filler, passivation film for semiconductor and solar cell, interlayer insulation film, protective film, prism lens sheet used for backlight of liquid crystal display device, fresnel lens sheet used for screen of projection television, lens portion of lens sheet such as lenticular lens sheet, and the like, And optical lenses such as back lights and microlenses, optical elements, optical connectors, optical waveguides, and casting agents for optical molding, which use such sheets.
Examples of the display device include: if necessary, a transparent support may be provided with a device for forming each layer such as an undercoat layer, an antireflection layer, a polarizer layer, a retardation layer, a birefringence layer, a light scattering layer, a hard coat layer, a lubricating layer, and a protective layer, and a film made of the cured product of the present invention may be used for each layer.
Examples
The present invention will be described in further detail below with reference to examples and the like, but the present invention is not limited to these examples.
Examples 1 to 15 and comparative examples 1 to 3
The respective components were sufficiently mixed at the compounding ratios shown in the following [ Table 1] to [ Table 3], to obtain the curable compositions of examples 1 to 15 and the curable compositions of comparative examples 1 to 3, respectively. The units of examples and comparative examples are parts by mass.
As the cationically polymerizable component (A), the following compounds (A1-1) to (A1-3), (A2-1) to (A3-1) were used.
Compound (A1-1): ADEKA RESIN EP-4088L (manufactured by ADEKA corporation)
Compound (A1-2): 1, 6-hexanediol diglycidyl ether
Compound (A1-3): neopentyl glycol diglycidyl ether
Compound (A2-1): ARON OXETANE OXT-221 (manufactured by TOYOBA SYNTHETIC CO., LTD.)
Compound (A3-1): CELLOXIDE 2021P (alicyclic epoxy: manufactured by Daicel Corporation)
As the cationic polymerization initiator (B), the following compound (B-1) was used.
Compound B-1: a 50% solution of propylene carbonate in a mixture of a compound represented by the following formula (9) and a compound represented by the following formula (10)
Figure BDA0001810338840000251
Figure BDA0001810338840000261
As the radically polymerizable component (C), the following compounds (C2-1) to (C2-4) were used.
Compound (C2-1): 1, 6-hexanediol diacrylate
Compound (C2-2): dicyclodecane dimethanol diacrylate
Compound (C2-3): ethoxylated isocyanuric acid triacrylate
Compound (C2-4): tetrahydrofurfuryl acrylate
As the radical polymerization initiator (D), the following compound (D-1) was used.
Compound (D-1): IRGACURE 184 (manufactured by BASF corporation)
As the polymer (E), the following compounds (E-1) and (E-2) were used.
Compound (E-1): copolymer of methyl methacrylate 75 parts by mass and glycidyl methacrylate 25 parts by mass (weight average molecular weight 7000)
Compound (E-2): copolymer (weight average molecular weight 8000) of 35 parts by mass of methyl methacrylate, 35 parts by mass of styrene and 30 parts by mass of glycidyl methacrylate
The obtained curable compositions of examples 1 to 15 and comparative examples 1 to 3 were evaluated for glass transition temperature (Tg), elastic modulus, and adhesion according to the following procedure. The results are shown in [ Table 1] to [ Table 3 ].
(glass transition temperature and modulus of elasticity at 80 ℃ C.)
The curable compositions of examples 1 to 15 and comparative examples 1 to 3 were coated on a polyethylene terephthalate (PET) film by a bar coater to a thickness of 30 μm, and irradiated with a metal halide lamp at 3000mJ/cm2The energy of (a). After 24 hours, the cured adhesive was taken out from the film, and Tg and elastic modulus at 80 ℃ were measured using a viscoelasticity measuring apparatus (DMA7100) manufactured by Hitachi High-Technologies Corporation.
(Adhesivity)
The compositions 1 to 15 of the examples and the compositions 1 to 3 of the comparative examples obtained above were each coated on one corona-treated PMMA Film (Techno chemical Co., Ltd.: Technology 125S001), and then, another COP (cycloolefin Polymer, model Zeonor Film 14-060) Film subjected to corona discharge treatment was laminated using a laminator, and an electrodeless ultraviolet lamp was used to irradiate the Film through the COP Film at a rate of 1000mJ/cm2The light was adhered to obtain a test piece. The obtained test piece was subjected to a 90-degree peel test.
[ Table 1]
Figure BDA0001810338840000271
[ Table 2]
Figure BDA0001810338840000281
[ Table 3]
Figure BDA0001810338840000291
As is clear from [ Table 1] to [ Table 3], the curable composition of the present invention has a high glass transition temperature of the cured product and excellent adhesion.
Figure BDA0001810338840000292

Claims (7)

1. A curable composition comprising:
a cationically polymerizable component (A), a cationically polymerizable initiator (B), a radically polymerizable component (C), a radically polymerizable initiator (D), and a polymer (E), wherein the polymer (E) has a weight average molecular weight of 1000 to 30000, and 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 a monomer represented by the formula (I) and a monomer represented by the formula (II),
Figure FDA0002924876840000011
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 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,
Figure FDA0002924876840000012
in the formula (II), R1Represents a hydrogen atom, a methyl group or a halogen atom, X' represents 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 is substituted with at least 1 kind of group selected from the group consisting of an epoxy group, an oxetanyl group, a hydroxyl group and a carboxyl group,
the cationically polymerizable component (A) comprises a glycidyl compound of a polyol or a glycidyl compound of a polyol alkylene oxide adduct having a molecular weight of 200 or more (A1) and an oxetane compound (A2) as essential components, wherein the polyol in the glycidyl compound of a polyol or a glycidyl compound of a polyol alkylene oxide adduct having a molecular weight of 200 or more (A1) is a polyol having saturated condensed rings,
the radical polymerizable component (C) contains, as an essential component, a compound (C1) having an epoxy group and an ethylenically unsaturated group, or an acrylate ester of an alcohol having 2 to 20 carbon atoms or a methacrylate ester of an alcohol having 2 to 20 carbon atoms (C2).
2. The curable composition according to claim 1, further comprising an alicyclic epoxy compound (A3) as the cationically polymerizable component (A).
3. The curable composition according to claim 1, wherein the polymer (E) is a polymer obtained from a monomer represented by the formula (I) wherein X is an aryl group having 6 to 12 carbon atoms and a monomer represented by the formula (II) wherein X' is an alkyl group having 1 to 7 carbon atoms, the alkyl group being substituted with an epoxy group.
4. The curable composition according to claim 1, wherein the amount of the cationic polymerizable component (A) is 30 to 70 parts by mass, the amount of the cationic polymerization initiator (B) is 0.001 to 10 parts by mass, the amount of the radical polymerizable component (C) is 30 to 60 parts by mass, the amount of the radical polymerization initiator (D) is 1 to 10 parts by mass, the amount of the polymer (E) is 1 to 20 parts by mass, and the total of the cationic polymerizable component (A), the radical polymerizable component (C) and the polymer (E) is 100 parts by mass.
5. A method for curing a curable composition, which comprises irradiating the curable composition according to any one of claims 1 to 4 with an active energy ray.
6. A method for curing a curable composition, which comprises 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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