CN108884297B - 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

Info

Publication number
CN108884297B
CN108884297B CN201780018739.7A CN201780018739A CN108884297B CN 108884297 B CN108884297 B CN 108884297B CN 201780018739 A CN201780018739 A CN 201780018739A CN 108884297 B CN108884297 B CN 108884297B
Authority
CN
China
Prior art keywords
compound
mass
parts
curable composition
polymerizable component
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201780018739.7A
Other languages
Chinese (zh)
Other versions
CN108884297A (en
Inventor
长坂一辉
大野泰延
松土和彦
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Adeka Corp
Original Assignee
Adeka Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Adeka Corp filed Critical Adeka Corp
Publication of CN108884297A publication Critical patent/CN108884297A/en
Application granted granted Critical
Publication of CN108884297B publication Critical patent/CN108884297B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • 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
    • C08G59/22—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
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • 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
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C08G59/245—Di-epoxy compounds carbocyclic aromatic
    • 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
    • C08G59/3218—Carbocyclic 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
    • C08G59/68—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 catalysts used
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • 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
    • C08K5/06—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Polyethers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention provides a curable composition having excellent viscosity and adhesiveness, a method for producing a cured product, and a cured product thereof. The composition comprises the following components in parts by mass based on 100 parts by mass of the components (A) and (C): 20 to 90 parts by mass of a cationic polymerizable component (A), 1 to 10 parts by mass of a cationic polymerization initiator (B), 1 to 30 parts by mass of a radical polymerizable component (C), and 0 to 10 parts by mass of a radical polymerization initiator (D), wherein the component (A) contains, as essential components, an aromatic epoxy compound (A1), a glycidyl compound of a polyol having a molecular weight of 200 or more or a glycidyl compound of a polyol alkylene oxide adduct (A2), and an oxetane compound (A3), the component (A1) is 35 to 50 parts by mass relative to 100 parts by mass of the total of the component (A) and the component (C), and the component (C) contains, as essential components, a compound having an epoxy group and an ethylenically unsaturated group (C1), an acrylic ester of an alcohol having 2 to 20 carbon atoms, or the like (C2).

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 excellent viscosity and 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 3 propose: an energy ray-curable composition containing a cationically polymerizable component and a radically polymerizable component, and a cured product thereof. Specifically, patent document 1 proposes: an adhesive composition for polarizing plates, which has excellent initial curability and adhesiveness. Patent document 2 proposes a low viscosity photocurable adhesive which, when used for producing a polarizing plate having a resin film with low moisture permeability as a protective film, exhibits excellent curability even when the humidity of the application environment is high, exhibits good adhesion after a certain period of time with respect to various forces, causes no problem after a durability test, and exhibits good adhesion after a moisture and heat resistance test. Further, patent document 3 proposes: an active energy ray-polymerizable resin composition which can achieve both high heat resistance, high refractive index, and transparency, said composition containing an unsaturated alicyclic epoxy ester compound.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2014-105218
Patent document 2: japanese patent laid-open publication No. 2015-143352
Patent document 3: 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 3 may not necessarily satisfy the requirements for curability and adhesion, and a novel curable composition that can satisfy both viscosity and adhesion at a high level is desired at present.
Accordingly, an object of the present invention is to provide a curable composition having excellent viscosity and 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, based on 100 parts by mass of the total of the cationically polymerizable component (a) and the radically polymerizable component (C): 20 to 90 parts by mass of the cationic polymerizable component (A), 1 to 10 parts by mass of the cationic polymerization initiator (B), 1 to 30 parts by mass of the radical polymerizable component (C), and 0 to 10 parts by mass of the radical polymerization initiator (D),
the cationically polymerizable component (A) contains an aromatic epoxy compound (A1), a glycidyl compound of a polyol having a molecular weight of 200 or more or a glycidyl compound of a polyol alkylene oxide adduct (A2), and an oxetane compound (A3) as essential components, the aromatic epoxy compound (A1) is 35 to 50 parts by mass based on 100 parts by mass of the total of the cationically polymerizable component (A) and the radically polymerizable component (C),
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).
In the curable composition of the present invention, the aromatic epoxy compound (a1) is preferably a polyfunctional aromatic epoxy compound. In the curable composition of the present invention, the oxetane compound (a3) is preferably a polyfunctional oxetane compound. Further, in the curable composition of the present invention, the acrylic ester of an alcohol having 2 to 20 carbon atoms or the methacrylic ester of an alcohol having 2 to 20 carbon atoms (C2) is preferably an acrylic ester or a methacrylic ester having a cyclic structure. Further, in the curable composition of the present invention, the cyclic structure is preferably at least one selected from the following groups.
Figure GDA0001806239830000031
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
The present invention can provide a curable composition having excellent viscosity and adhesion, a method for producing a cured product, and a cured product thereof. 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 20 to 90 parts by mass of a cationic polymerizable component (A), 1 to 10 parts by mass of a cationic polymerization initiator (B), 1 to 30 parts by mass of a radical polymerizable component (C), and 0 to 10 parts by mass of a radical polymerization initiator (D) so that the total of the cationic polymerizable component (A) and the radical polymerizable component (C) is 100 parts by mass. The curable composition of the present invention contains the cationically polymerizable component (a) 35 to 50 parts by mass of the aromatic epoxy compound (a1) per 100 parts by mass of the sum of the cationically polymerizable component (a) and the radically polymerizable component (C), as essential components, the aromatic epoxy compound (a1), the glycidyl compound of a polyol having a molecular weight of 200 or more or the glycidyl compound of a polyol alkylene oxide adduct (a2), and the oxetane compound (A3). 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).
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 an aromatic epoxy compound (a1), a glycidyl compound of a polyol having a molecular weight of 200 or more or a glycidyl compound of a polyol alkylene oxide adduct (a2), and an oxetane compound (A3) as essential components, and an alicyclic epoxy compound, a vinyl ether compound, and the like can be used as other epoxy compounds.
The aromatic epoxy compound (a1) is an epoxy compound containing an aromatic ring, and specific examples of the aromatic epoxy compound 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 (a1), 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 RESINEP-4100 and ADEKA RESIN EP-4901 (manufactured by ADEKA); TECHMORE VG-3101L (Printech Co., Ltd.). The aromatic epoxy compound (a1) is preferably a polyfunctional aromatic epoxy compound because it has excellent curability.
Examples of the glycidyl compound of a polyol or a polyol alkylene oxide adduct having a molecular weight of 200 or more (a2) 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 (a2) 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 (a2), 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 (a2) 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 (a2), 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, Epolight200P, Eplight 400P, Epolight 1500NP, Eplight 1600, Eplight 80MF, Eplight 100MF (available from Kyoho chemical Co., Ltd.), ADEKA Glycerol ED-503G, ADEKAGLYCIROL ED-506, ADEKA Glycerol ED-523T, ADEKA RESIN EP-4088S, ADEKA RESIN EP-4080E (available from ADEKA K.K.) and the like.
Examples of the oxetane compound (a3) 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 or in combination of 2 or more, polyfunctional oxetane compounds to improve the curing properties and adhesion of the cured product, so the preferred.
As the oxetane compound (a3), 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 OXETANEOXT-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 means that an oxirane ring is directly bonded to a saturated ring without a bonding group. Specific examples of the alicyclic epoxy compound 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: hydrogenated bisphenol A diglycidyl ether, 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexylformate, 3, 4-epoxy-1-methylcyclohexyl-3, 4-epoxy-1-methylhexyl formate, 6-methyl-3, 4-epoxycyclohexylmethyl-6-methyl-3, 4-epoxycyclohexylformate, 3, 4-epoxy-3-methylcyclohexylmethyl-3, 4-epoxy-3-methylcyclohexyl formate, 3, 4-epoxy-5-methylcyclohexylmethyl-3, 4-epoxy-5-methylcyclohexyl formate, bis (3, 4-epoxycyclohexylmethyl) adipate, hydrogenated bisphenol A diglycidyl ether, 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexylformate, 6-methyl-3, 4-epoxycyclohexylmethyl-6-methyl-3, 4-epoxycyclohexylformate, bis (3, 4-epoxycyclohexylmethyl), 3, 4-epoxy-6-methylcyclohexaneformate, 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 epoxide hexahydrophthalate, di-2-ethylhexyl phthalate epoxide hexahydrophthalate, 1-epoxyethyl-3, 4-epoxycyclohexane, 1, 2-epoxy-2-epoxyethylcyclohexane, α -pinene oxide, limonene dioxide and the like. Hydrogenated bisphenol a diglycidyl ether, 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexyl formate, or 3, 4-epoxy-1-methylcyclohexyl-3, 4-epoxy-1-methylhexyl formate is preferable as the alicyclic epoxy compound from the viewpoint of improving adhesiveness.
As the alicyclic epoxy compound, commercially available products can be used, 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 cationic polymerizable component (A), the use ratio of the aromatic epoxy compound (A1), the glycidyl compound of a polyol or polyol alkylene oxide adduct having a molecular weight of 200 or more (A2), the oxetane compound (A3), and the alicyclic epoxy compound and the vinyl ether compound is such that the aromatic epoxy compound (A1) is 30 to 80 parts by mass, the glycidyl compound of a polyol or polyol alkylene oxide adduct having a molecular weight of 200 or more (A2) is 10 to 30 parts by mass, the oxetane compound (A3) is 10 to 30 parts by mass, the alicyclic epoxy compound is 0 to 20 parts by mass, and the vinyl ether compound is 0 to 20 parts by mass, based on 100 parts by mass of the total of the cationic polymerizable component (A) and the radical polymerizable component (C), the viscosity, the coatability, the reactivity, and the curability are improved, and is therefore preferred.
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 an onium, the structure of which can be represented, for example, by the following general formula:
[(R1)aQ]r+
further, here, R1Is 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 R1Each independently may be the same or different. In addition, at least 1 is preferably the organic group having an aromatic ring as described above. 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. 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 regarded as having an atomic valence of 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 a 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)-Hexachloroantimonic acidRoot (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, trinitrobenzenesulfonate anion, camphorsulfonate, nonafluorobutanesulfonate, hexadecafluorooctane sulfonate, tetraarylborate, tetrakis (pentafluorophenyl) borate, etc.
Among such onium salts in the curable composition of the present invention, the aromatic onium salts (i) to (iii) below are particularly effective. 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 of sulfonium cations represented by the following group I or II, hexafluoroantimony ions, hexafluorophosphate ions, tetrakis (pentafluorophenyl) borate ions, and the like
< group I >)
Figure GDA0001806239830000101
< group II >
Figure GDA0001806239830000111
In addition, other preferable examples include: a mixture of an iron-arene complex such as (. eta.5-2, 4-cyclopentadien-1-yl) (1,2,3,4,5, 6-. eta.) - (1-methylethyl) benzene ] -iron-hexafluorophosphate, an aluminum complex such as tris (acetylacetonate) aluminum, tris (ethylacetoneacetic acid) aluminum, tris (salicylaldehyde) aluminum, 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; a modified polyepoxide prepared by reacting the above polyamine with various epoxy resins such as glycidyl ethers such as phenyl glycidyl ether, butyl glycidyl ether, bisphenol a-diglycidyl ether and bisphenol F-diglycidyl ether, or glycidyl esters of carboxylic acids by a conventional method; 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 GDA0001806239830000121
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 R24Each independently represents a hydrogen atom, a halogen atom or an 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 a substituent selected from any one of the following chemical formulae (A) to (C), Anq-Represents an anion having a valence of q, and p represents a coefficient for neutralizing the charge.
Figure GDA0001806239830000131
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 compounds represented by the above general formula, 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, tert-butylthiomethyl, 4-pentenyloxymethyl, trichloroethoxymethyl, bis (2-chloroethoxy) methyl, methoxycyclohexyl, 1- (2-chloroethoxy) ethyl, 1-methyl-1-methylOxyethyl, ethyldithioethyl, trimethylsilylethyl, t-butyldimethylsilyloxymethyl, 2- (trimethylsilyl) ethoxymethyl, t-butoxycarbonylmethyl, ethyloxycarbonylmethyl, ethylcarbonylmethyl, t-butoxycarbonylmethyl, acryloyloxyethyl, methacryloyloxyethyl, 2-methyl-2-adamantyloxycarbonylmethyl, acetoacetyl, 2-methoxy-1-propenyl, 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 and ethoxyAlkylcarbonyl, isopropyloxycarbonyl, phenoxycarbonyl, acetoxy, propionyloxy, butyryloxy, chloroacetyloxy, dichloroacetoxy, trichloroacetoxy, trifluoroacetyloxy, t-butylcarbonyloxy, methoxyacetoxy, benzoyloxy and the like.
The radically polymerizable component (C) of the curable composition of the present invention comprises, 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). (C2) Among them, an acrylate or a methacrylate having a cyclic structure is preferable, and more preferably, the cyclic structure is one or more selected from the following group.
Figure GDA0001806239830000151
Examples of the compound having an epoxy group and an ethylenically unsaturated group (C1) 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, 4-hydroxybutyl 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, caprolactone-modified dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, caprolactone-modified dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, and mixtures thereof, 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 hexamethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, pentaerythritol trimethacrylate, polyethylene glycol dimethacrylate, propylene glycol dimethacrylate, ethylene, Caprolactone-modified dipentaerythritol hexamethacrylate, ethoxylated isocyanuric acid triacrylate, ethoxylated isocyanuric acid trimethacrylate, -caprolactone-modified tris- (2-acryloyloxyethyl) isocyanurate, -caprolactone-modified tris- (2-methacryloyloxyethyl) isocyanurate, 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 activated by irradiation with an energy ray or heating and which undergoes a polymerization or crosslinking reaction by a radical polymerization initiator can be used, and examples thereof include: allyl urethane 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.
In the curable composition of the present invention, the cationic polymerizable component (a) is 20 to 90 parts by mass, the cationic polymerization initiator (B) is 1 to 10 parts by mass, preferably 1 to 6 parts by mass, the radical polymerizable component (C) is 1 to 30 parts by mass, and the radical polymerization initiator (D) is 0 to 10 parts by mass. If the compounding ratio is not the above ratio, the curability and adhesion of the cured product may be deteriorated. The total of the cationically polymerizable component (a) and the radically polymerizable component (C) is 100 parts by mass. The amount of the component (A1) is 35 to 50 parts by mass per 100 parts by mass of the total of the cationically polymerizable component (A) and the radically polymerizable component (C).
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 that exhibits the maximum absorption at a wavelength longer than the maximum absorption wavelength shown by the cationic polymerization initiator (B), promoting 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 (1).
Figure GDA0001806239830000171
Here, in the formula (1), 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 (1) 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 (2).
Figure GDA0001806239830000172
Here, in the formula (2), 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 (2) 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, it is preferable from the viewpoint of improving curability when the amount of each of the sensitizer and the sensitization auxiliary is 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, gamma-glycid, 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 tributoxymoacetonate, zirconium acylate compounds such as zirconium tributoxymetastearate, etc., titanium oxide compounds such as titanium oxide, etc., titanium oxide, etc., and the like, 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 solid content 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, is activated by heating to a predetermined temperature, irradiation with light, acid, or the like to release a protective group, and exhibits ultraviolet absorbability.
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.
In the curable composition of the present invention, a solvent which can dissolve or disperse the components (a), (B), (C) and (D) is not particularly limited and can be generally 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(CosmoMatsuyama 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, electrical 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, lens portion of optical film such as prism lens sheet, and optical film, 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 9 and comparative examples 1 to 5
The curable compositions of examples 1 to 9 and the curable compositions of comparative examples 1 to 5 were obtained by sufficiently mixing the respective components in the following blending ratios shown in [ table 1] and [ table 2 ]. The unit of the blending amount in examples and comparative examples is part by mass.
As the cationically polymerizable component (A), the following compounds (A1-1), (A2-1) and (A3-1) were used.
Compound (A1-1): bisphenol type diglycidyl ether
Compound (A2-1): neopentyl glycol diglycidyl ether
Compound (A3-1): ARON OXETANE OXT-221 (manufactured by TOYOBA SYNTHETIC CO., LTD.)
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 (3) and a compound represented by the following formula (4)
Figure GDA0001806239830000221
As the radical polymerizable component (C), the following compounds were used.
Compound (C1-1): EPOXY ESTER M-600A (of Kyoeisha chemical Co., Ltd.)
Compound (C1-2): EPOXY ESTER 70PA (of Kyoeisha chemical Co., Ltd.)
Compound (C1-3): EPOXY ESTER 200PA (of Kyoeisha chemical Co., Ltd.)
Compound (C2-1): 1, 6-hexanediol diacrylate
Compound (C2-2): acrylic acid 4-hydroxybutyl ester
Compound (C2-3): A-9300S (multifunctional acrylate; manufactured by Xinzhongcun chemical industries, Ltd.)
Compound (C2-4): viscoat #150 (tetrahydrofurfuryl acrylate; manufactured by Osaka organic chemical industry Co., Ltd.)
As the radical polymerization initiator (D), the following compound (D-1) was used.
Compound (D-1): IRGACURE 184 (manufactured by BASF corporation)
The obtained curable compositions of examples 1 to 9 and comparative examples 1 to 5 were evaluated for viscosity, adhesion, and curability according to the following procedures. The results are shown in [ Table 1] and [ Table 2 ].
(viscosity)
The viscosities of the obtained curable compositions of examples 1 to 9 and comparative examples 1 to 5 were measured at 25 ℃ with an E-type viscometer, respectively. The results are shown in [ Table 1] and [ Table 2 ].
(Adhesivity)
The curable compositions of examples 1 to 9 and comparative examples 1 to 5 obtained above were coated on one sheet of corona-treated PMMA Film (Technolloy 125S001, Sumitomo chemical Co., Ltd.), and then laminated with another sheet of COP (cycloolefin Polymer, model Zeonor Film 14-060, manufactured by Zeon Corporation) Film subjected to corona discharge treatment using a laminator, and irradiated with an electrodeless ultraviolet lamp 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.
(curing test)
The curable compositions of examples 1 to 9 and comparative examples 1 to 5 obtained above were applied toA TAC Film (Fujifilm Corporation: model FT-TD60ULP) was laminated with another COP (cycloolefin Polymer, model Zeonor Film 14-060) Film subjected to corona discharge treatment using a laminator, and the COP Film was irradiated with an electrodeless UV lamp at a thickness of 150mJ/cm2The curing rate was evaluated by irradiating the sheet for less than 30 seconds, and the sheet was evaluated as ○ when the sheet was peeled off and × when the sheet was easily peeled off even when the sheet was irradiated for 30 seconds or more.
[ Table 1]
Figure GDA0001806239830000241
[ Table 2]
Figure GDA0001806239830000251
Can not measure
As is clear from [ Table 1] and [ Table 2], the curable composition of the present invention is excellent in adhesiveness and tackiness.

Claims (8)

1. A curable composition characterized by containing, in an amount sufficient to cure,
which contains, based on 100 parts by mass of the total of the cationically polymerizable component (A) and the radically polymerizable component (C): 20 to 90 parts by mass of the cationic polymerizable component (A), 1 to 10 parts by mass of the cationic polymerization initiator (B), 1 to 30 parts by mass of the radical polymerizable component (C), and 0 to 10 parts by mass of the radical polymerization initiator (D),
the cationic polymerizable component (A) contains an aromatic epoxy compound (A1), a glycidyl compound of a polyol having a molecular weight of 200 or more or a glycidyl compound of a polyol alkylene oxide adduct (A2), and an oxetane compound (A3) as essential components, wherein the aromatic epoxy compound (A1) is 35 to 50 parts by mass based on 100 parts by mass of the total of the cationic polymerizable component (A) and the radically polymerizable component (C),
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, wherein the aromatic epoxy compound (A1) is a polyfunctional aromatic epoxy compound.
3. The curable composition according to claim 1, wherein the oxetane compound (A3) is a polyfunctional oxetane compound.
4. The curable composition according to claim 1, wherein the acrylic ester of an alcohol having 2 to 20 carbon atoms or the methacrylic ester of an alcohol having 2 to 20 carbon atoms (C2) is an acrylic ester or a methacrylic ester having a cyclic structure.
5. The curable composition according to claim 4,
the cyclic structure is one or more selected from the group consisting of,
Figure FDA0001806239820000021
6. a method for curing a curable composition, which comprises irradiating the curable composition according to any one of claims 1 to 5 with an active energy ray.
7. A method for curing a curable composition, which comprises heating the curable composition according to any one of claims 1 to 5.
8. A cured product of the curable composition according to any one of claims 1 to 5.
CN201780018739.7A 2016-03-31 2017-03-30 Curable composition, method for producing cured product, and cured product thereof Active CN108884297B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2016-070898 2016-03-31
JP2016070898 2016-03-31
PCT/JP2017/013284 WO2017170879A1 (en) 2016-03-31 2017-03-30 Curable composition, method for manufacturing cured product, and cured product thereof

Publications (2)

Publication Number Publication Date
CN108884297A CN108884297A (en) 2018-11-23
CN108884297B true CN108884297B (en) 2020-08-14

Family

ID=59965959

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201780018739.7A Active CN108884297B (en) 2016-03-31 2017-03-30 Curable composition, method for producing cured product, and cured product thereof

Country Status (5)

Country Link
JP (1) JP6883020B2 (en)
KR (1) KR102265025B1 (en)
CN (1) CN108884297B (en)
TW (1) TWI732844B (en)
WO (1) WO2017170879A1 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7008398B2 (en) * 2016-03-31 2022-01-25 株式会社Adeka Curable composition, method for producing cured product, and cured product thereof
KR102065717B1 (en) * 2016-12-26 2020-01-13 주식회사 엘지화학 Polarizer protecting film, polarizer plate comprising the same, liquid crystal display comprising the polarizer plate, and coating composition for polarizer protecting film
JP7373303B2 (en) * 2018-09-28 2023-11-02 住友化学株式会社 Optical laminates, polarizing plate composites, and image display devices

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI251123B (en) * 1999-09-17 2006-03-11 Hitachi Chemical Co Ltd Photosensitive resin composition, photosensitive element using the resin composition, method of manufacturing resist pattern, and method of manufacturing printed wiring board
US7781495B2 (en) * 2004-03-26 2010-08-24 Kaneka Corporation Composition curable by radical photo curing and cationic photo curing in combination
JP4667145B2 (en) * 2004-07-22 2011-04-06 三井化学株式会社 Photocurable resin composition and resin composition for plastics comprising the same
KR101434010B1 (en) * 2008-10-27 2014-08-25 제이에스알 가부시끼가이샤 Photosensitive insulating resin composition and cured product thereof
CN101776846B (en) * 2009-01-14 2012-07-18 北京光创物成材料科技有限公司 Light-cured component for laser stereo lithography
WO2012144260A1 (en) * 2011-04-19 2012-10-26 Dic株式会社 Cationic polymerizable adhesive and polarizing plate obtained using same
CN102385250A (en) * 2011-06-29 2012-03-21 南昌大学 Ultraviolet laser solidification rapid-prototyping photosensitive resin and manufacture method thereof
JP5240380B1 (en) * 2011-07-05 2013-07-17 Ｊｓｒ株式会社 Resin composition, polymer, cured film and electronic component
JP5976575B2 (en) * 2012-08-31 2016-08-23 富士フイルム株式会社 Curable composition for forming low refractive index film, method for producing optical member set, and method for producing curable composition
JP6103687B2 (en) 2012-11-22 2017-03-29 チェイル インダストリーズ インコーポレイテッド Adhesive composition for polarizing plate
CN104395788B (en) * 2013-06-18 2017-07-28 Lg化学株式会社 Polarizer and the image display device including the Polarizer
WO2015005211A1 (en) * 2013-07-09 2015-01-15 株式会社Adeka Cation-polymerizable composition
JPWO2015068454A1 (en) * 2013-11-07 2017-03-09 積水化学工業株式会社 Sealant for organic electroluminescence display element
KR101719883B1 (en) * 2013-12-25 2017-03-24 도아고세이가부시키가이샤 Photocurable adhesive composition, polarizer and process for producing same, optical member, and liquid-crystal display device
JP6337523B2 (en) 2014-03-07 2018-06-06 東洋インキＳｃホールディングス株式会社 Active energy ray polymerizable resin composition and laminate
JP6222637B2 (en) * 2014-03-19 2017-11-01 富士フイルム株式会社 Polymerizable nonlinear optical material, nonlinear optical film, optical element, light modulation element, and method of manufacturing nonlinear optical film

Also Published As

Publication number Publication date
JP6883020B2 (en) 2021-06-02
TWI732844B (en) 2021-07-11
TW201807140A (en) 2018-03-01
KR20180132635A (en) 2018-12-12
CN108884297A (en) 2018-11-23
KR102265025B1 (en) 2021-06-14
JPWO2017170879A1 (en) 2019-02-14
WO2017170879A1 (en) 2017-10-05

Similar Documents

Publication Publication Date Title
JP7071262B2 (en) Curable composition, method for producing cured product, and cured product thereof
KR102272147B1 (en) Curable composition, manufacturing method of cured product, and cured product thereof
CN108884297B (en) Curable composition, method for producing cured product, and cured product thereof
WO2017110951A1 (en) Curable composition, method for curing same, and cured product obtained thereby
JP2019026774A (en) Curable composition, method for producing cured product, and cured product thereof
CN108699320B (en) Curable composition, method for producing cured product, and cured product thereof
CN108779321B (en) Curable composition, method for producing cured product, and cured product thereof
JP7008398B2 (en) Curable composition, method for producing cured product, and cured product thereof
JP6949458B2 (en) Curable composition, method for producing cured product, and cured product thereof
KR102356381B1 (en) Curable composition, manufacturing method of cured product, and cured product thereof
JP2018172494A (en) Curable composition, method for producing cured product, cured product thereof, and adhesive using the same
JP2018012765A (en) Curable composition, method for producing cured product, cured product thereof, and adhesive

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant