CN110114376B - Curable composition, method for producing cured product, cured product thereof, and adhesive using same - Google Patents

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

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CN110114376B
CN110114376B CN201880005553.2A CN201880005553A CN110114376B CN 110114376 B CN110114376 B CN 110114376B CN 201880005553 A CN201880005553 A CN 201880005553A CN 110114376 B CN110114376 B CN 110114376B
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bis
acridine
ester
mass
parts
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CN110114376A (en
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松土和彦
关新之介
板野和幸
长坂一辉
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Adeka Corp
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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
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • 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
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00

Abstract

Provided are a curable composition which enables to obtain a cured product having low viscosity and excellent adhesion, a method for producing a cured product, a cured product thereof, and an adhesive using the same. The curable composition contains: 50 to 80 parts by mass of a radical polymerizable component (A), 1 to 10 parts by mass of a radical polymerization initiator (B), 20 to 50 parts by mass of a cationic polymerizable component (C), and 1 to 10 parts by mass of a cationic polymerization initiator (D), wherein the total of the radical polymerizable component (A) and the cationic polymerizable component (C) is 100 parts by mass, and the cationic polymerizable component (C) contains a glycidyl ether of an alcohol having 11 or more carbon atoms.

Description

Curable composition, method for producing cured product, cured product thereof, and adhesive using same
Technical Field
The present invention relates to a curable composition, a method for producing a cured product, a cured product thereof, and an adhesive using the curable composition, and more particularly, to a curable composition that can give a cured product having low viscosity and excellent adhesion, a method for producing a cured product, a cured product thereof, and an adhesive using the curable composition.
Background
Curable compositions are used in the fields of inks, paints, various coating agents, adhesives, optical members, and the like, and energy-ray curable compositions containing a cationically polymerizable component and a radically polymerizable component, and cured products thereof have been proposed.
For example, patent document 1 proposes an adhesive composition for polarizing plates, which has improved initial curability and adhesiveness. Patent document 2 proposes an active energy ray-curable composition capable of forming a cured product which is reduced in curling properties while maintaining high surface hardness and has excellent transparency. Further, patent literature proposes an adhesive composition which is excellent in curability, adhesiveness, and water resistance and which can be suitably used for production of IT-related products.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2014-037477
Patent document 2: japanese patent laid-open publication No. 2016-102193
Patent document 3: international publication No. 2014/178239
Disclosure of Invention
Problems to be solved by the invention
However, the curable compositions proposed in these patent documents 1 to 3 are not necessarily sufficient in viscosity and adhesion of the cured product thereof to a substrate, and further improvement is desired in the present situation.
Accordingly, an object of the present invention is to provide a curable composition which can give a cured product having low viscosity and excellent adhesion, a method for producing the cured product, a cured product thereof, and an adhesive using the curable composition.
Means for solving the problems
The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that a composition having a predetermined composition can solve the above problems, and have completed the present invention.
That is, the curable composition of the present invention is characterized by containing: 50 to 80 parts by mass of a radical polymerizable component (A), 1 to 10 parts by mass of a radical polymerization initiator (B), 20 to 50 parts by mass of a cation polymerizable component (C), and 1 to 10 parts by mass of a cation polymerization initiator (D), wherein the total of the radical polymerizable component (A) and the cation polymerizable component (C) is 100 parts by mass,
the cationically polymerizable component (C) contains a glycidyl ether of an alcohol having 11 or more carbon atoms.
In the curable composition of the present invention, the radically polymerizable component (a) preferably contains: an acrylic acid ester of an alcohol having 2 to 60 carbon atoms or a methacrylic acid ester of an alcohol having 2 to 60 carbon atoms (A1), or an acrylic acid ester of a phenol compound or a methacrylic acid ester of a phenol compound (A2).
The method for producing a cured product of the present invention is characterized in that the curable composition of the present invention is cured by irradiation with an active energy ray or cured by heating.
Further, the cured product of the present invention is characterized by being formed from the curable composition of the present invention.
Further, the adhesive of the present invention is characterized by being formed from the curable composition of the present invention.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, there can be provided: a curable composition which gives a cured product having low viscosity and excellent adhesion, a method for producing the cured product, a cured product thereof, and an adhesive using the curable composition.
Detailed Description
The curable composition of the present invention will be described in detail below.
The curable composition of the present invention contains: 50 to 80 parts by mass of a radical polymerizable component (A), 1 to 10 parts by mass of a radical polymerization initiator (B), 20 to 50 parts by mass of a cation polymerizable component (C) and 1 to 10 parts by mass of a cation polymerization initiator (D), wherein the total of the radical polymerizable component (A) and the cation polymerizable component (C) is 100 parts by mass. In the curable composition of the present invention, the cationically polymerizable component (C) contains a glycidyl ether of an alcohol having 11 or more carbon atoms. By adopting such a composition, a curable composition that can give a cured product having low viscosity and excellent adhesion is obtained.
The radical polymerizable component (a) is not particularly limited as long as it is a compound which can be polymerized or crosslinked by a radical polymerization initiator activated by irradiation with active energy rays or heating, and a known one can be used. Examples of the acrylic acid ester of an alcohol having 2 to 60 carbon atoms or the methacrylic acid ester of an alcohol having 2 to 60 carbon atoms (A1), the acrylic acid ester of a phenol compound or the methacrylic acid ester of a phenol compound (A2), acrylamide or methacrylamide, a vinyl compound, polyolefin, an allyl urethane compound, an unsaturated polyester compound, and a styrene compound.
Examples of the acrylic acid ester of an alcohol having 2 to 60 carbon atoms or the methacrylic acid ester of an alcohol having 2 to 60 carbon atoms (A1) include acrylic acid esters or methacrylic acid esters 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, and specific examples thereof include 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, acrylic acid esters of aliphatic alcohols having 2 to 60 carbon atoms, and acrylic acid or methacrylic acid esters obtained by reacting an alkylene oxide adduct thereof with acrylic acid or methacrylic acid, Neopentyl glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, epsilon-caprolactone-modified dipentaerythritol hexaacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, isoamyl methacrylate, lauryl methacrylate, stearyl methacrylate, isooctyl methacrylate, tetrahydrofurfuryl methacrylate, isobornyl methacrylate, benzyl methacrylate, 1, 3-butanediol dimethacrylate, 1, 4-butanediol dimethacrylate, 1, 6-hexanediol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol diacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, and propylene glycol diacrylate, 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. Here, the acrylic acid ester of an alcohol having 2 to 60 carbon atoms or the methacrylic acid ester of an alcohol having 2 to 60 carbon atoms means an acrylic acid ester obtained by adding an acryloyl group or a methacryloyl group to an alcohol, and has 2 to 60 carbon atoms.
As the acrylic acid Ester of an alcohol having 2 to 60 carbon atoms or methacrylic acid Ester of an alcohol having 2 to 60 carbon atoms (A1), commercially available ones can be used, and examples thereof include NK Ester AM-90G, NK Ester AM-130G, NK Ester A-SA, NK Ester S-1800A, NK Ester 701A, NK Ester A-200, NK Ester A-400, NK Ester A-600, NK Ester A-1000, NK Ester A-DCP, NK Ester A-DOD-N, NK Ester A-HD-N, NK Ester APG-100, NK Ester APG-200, NK Ester APG-400, NK Ester APG-700, NK Ester A-PTMG-65, NK Ester A-9300-1CL, and the like, NK Ester A-GLY-20E, NK Ester A-TMM-3L, NK Ester A-TMM-3LM-N, NK Ester A-TMPT, NK Ester AD-TMP, NK Ester ATM-35E, NK Ester A-TMMT, NK Ester A-9550, NK Ester A-DPH, NK Ester M-90G, NK Ester M-230G, NK Ester S, NK Ester SA, NK Ester 1G, NK Ester 2G, NK Ester 3G, NK Ester 4G, NK Ester 9G, NK Ester 14G, NK Ester 23G, NK Ester DCP, NK Ester DOD-N, NK Ester HD-N, NK Ester NOD-N, NK Ester NPG, NK Ester 1206PE, NK Ester 701, NK Ester 9PG, NK Ester TMPT (manufactured by shinkamura Kagaku K.K.); HEA, HPA, 4-HBA, AIB, TBA, NOAA, INAA, Viscoat #197, IDAA, LA, STA, ISTA (manufactured by Osaka organic chemical industries, Ltd.), LIGHT ACRYLATE IAA, LIGHT ACRYLATE L-A, LIGHT ACRYLATE S-A, LIGHT ACRYLATE EC-A, LIGHT ACRYLATE MTG-A, LIGHT ACRYLATE EHDG-AT, LIGHT ACRYLATE 130A, LIGHT ACRYLATE DPM-A, LIGHT ACRYLATE IB-XA, Lightester HOA (N), Lightester HOP-A (N), LIGHT ACRYLATE HOB-A, HOA-MS (N), LIGHT ACRYLATE HOA-HH (N), LIGHT ACRYLATE 3EG-A, LIGHT ACRYLATE 4EG-A, LIGHT ACRYLATE 9EG-A, LIGHT ACRYLATE 14EG-A, LIGHT ACRYLATE PTMGA-250, LIGHT ACRYLATE NP-A, LIGHT ACRYLATE MPD-A, LIGHT ACRYLATE 1,6HX-A, LIGHT ACRYLATE 1,9ND-A, LIGHT ACRYLATE DCP-A, LIGHT ACRYLATE HPP-A, Lightester G-201P, LIGHT ACRYLATE TMP-A, LIGHT ACRYLATE PE-3A, LIGHT ACRYLATE PE-4A, LIGHT ACRYLATE DPE-6A (Kyoeisha chemical Co., Ltd.); KAYARAD NPGDA, KAYARAD PEG400DA, KAYARAD FM-400, KAYARAD R-167, KAYARAD HX-220, KAYARAD HX-620, KAYARAD R-604, KAYARAD R-684, KAYARAD GPO-303, KAYARAD TMPTA, KAYARAD PET-30 (manufactured by Nippon Kagaku Co., Ltd.), etc.
Examples of the acrylate or methacrylate ester of a phenol compound (a2) include phenol compounds having at least 1 aromatic ring such as phenol, cresol, butylphenol, resorcinol, hydroquinone and catechol, mono/polyacrylate or methacrylate esters of alkylene oxide adducts thereof, and diacrylate or dimethacrylate esters of bisphenol a, bisphenol F and compounds obtained by further adding alkylene oxide thereto.
As the above-mentioned acrylic acid ESTER of phenol compound or methacrylic acid ESTER of phenol compound (A2), commercially available ones such as NK ESTER A-LEN-10, NK ESTER AMP-20GY, NK ESTER A-B1206PE, NK ESTER ABE-300, NK ESTER A-BPE-10, NK ESTER A-BPE-20, NK ESTER A-BPE-30, NK ESTER A-BPE-4, NK ESTER A-EF BPE, NK ESTER A-BPE-3, NK ESTER PHE-1G, NK ESTER BPE-80N, NK ESTER BPE-100, ESTER BPE-200, NK ESTER E-500, NK ESTER BPE-900, ESNK TERER BPE-1300N (manufactured by shin chemical Co., Ltd.); LIGHT ACRYLATE PO-A, LIGHT ACRYLATE P2H-A, LIGHT ACRYLATE P-200A (KyoeishA chemical Co., Ltd.); KAYARADR-128H, KAYARADR-551, KAYARADR-712 (available from Nippon Kagaku K.K.), etc.
In the radically polymerizable component (a), the proportion of the component (a1) is preferably 50 to 100% by mass, and more preferably 60 to 100% by mass, because the cured product has improved curability and adhesion. (A2) The proportion of the component (B) is preferably 0 to 50% by mass, more preferably 0 to 30% by mass.
In the curable composition of the present invention, the curability and the adhesiveness of the cured product are improved, and therefore the radical polymerizable component (a) is preferably 50 to 80 parts by mass, more preferably 50 to 65 parts by mass, based on 100 parts by mass of the total of the radical polymerizable component (a) and the cation polymerizable component (C).
Examples of the radical polymerization initiator (B) used in the present invention include a photo radical polymerization initiator and a thermal radical polymerization initiator.
The photopolymerization initiator preferably includes acetophenone compounds, benzil compounds, benzophenone compounds, thioxanthone compounds, bisimidazole compounds, acridine compounds, acylphosphine compounds, and oxime ester compounds.
Examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4' -isopropyl-2-hydroxy-2-methylpropiophenone, 2-hydroxymethyl-2-methylpropiophenone, 2-dimethoxy-1, 2-diphenylethan-1-one, p-dimethylaminoacetophenone, p-tert-butyldichloroacetophenone, p-tert-butyltrichloroacetophenone, p-azidobenzylideneacetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinoacetone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, and, Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one, and the like.
Examples of the benzil compound include benzil and the like.
Examples of the benzophenone-based compound include benzophenone, methyl benzoylbenzoate, Michler's ketone, 4' -bisdiethylaminobenzophenone, 4 '-dichlorobenzophenone, and 4-benzoyl-4' -methyldiphenyl sulfide.
Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2, 4-diethylthioxanthone.
Examples of the bisimidazole compound include hexaarylbisimidazole (a dimer of HABI and triaryl-imidazole), specifically, 2 ' -bis (2-chlorophenyl) -4,4 ', 5,5 ' -tetrakis (4-ethoxycarbonylphenyl) -1,2 ' -biimidazole, 2 ' -bis (2-bromophenyl) -4,4 ', 5,5 ' -tetrakis (4-ethoxycarbonylphenyl) -1,2 ' -biimidazole, 2 ' -bis (2-chlorophenyl) -4,4 ', 5,5 ' -tetraphenyl-1, 2 ' -biimidazole, 2 ' -bis (2, 4-dichlorophenyl) -4,4 ', 5,5 ' -tetraphenyl-1, 2 ' -biimidazole, 2 ' -bis (2,4, 6-trichlorophenyl) -4,4 ', 5,5 ' -tetraphenyl-1, 2 ' -biimidazole, 2 ' -bis (2-bromophenyl) -4,4 ', 5,5 ' -tetraphenyl-1, 2 ' -biimidazole, 2 ' -bis (2, 4-dibromophenyl) -4,4 ', 5,5 ' -tetraphenyl-1, 2 ' -biimidazole, 2 ' -bis (2,4, 6-tribromophenyl) -4,4 ', 5,5 ' -tetraphenyl-1, 2 ' -biimidazole, 2,4,5,2 ', 4 ', 5 ' -hexaphenylbiimidazole, 2 ' -bis (2-chlorophenyl) -4,5,4 ', 5' -tetraphenylbisimidazole, 2 '-bis (2-bromophenyl) -4,5, 4', 5 '-tetraphenylbisimidazole, 2' -bis (2, 4-dichlorophenyl) -4,5,4 ', 5' -tetraphenylbisimidazole, 2 '-bis (2-chlorophenyl) -4,5, 4', 5 '-tetrakis (3-methoxyphenyl) biimidazole, 2' -bis (2-chlorophenyl) -4,5,4 ', 5' -tetrakis (3,4, 5-trimethoxyphenyl) -biimidazole, 2,5,2 ', 5' -tetrakis (2-chlorophenyl) -4,4 '-bis (3, 4-dimethoxyphenyl) biimidazole, 2' -bis (2, 6-dichlorophenyl) -4,5,4 ', 5 ' -tetraphenylbisimidazole, 2 ' -bis (2-nitrophenyl) -4,5,4 ', 5 ' -tetraphenylbisimidazole, 2 ' -di-o-tolyl-4, 5,4 ', 5 ' -tetraphenylbisimidazole, 2 ' -bis (2-ethoxyphenyl) -4,5,4 ', 5 ' -tetraphenylbisimidazole and 2,2 ' -bis (2, 6-difluorophenyl) -4,5,4 ', 5 ' -tetraphenylbisimidazole, 5 ' -tetrakis (p-iodophenyl) biimidazole, 2 ' -bis (o-chlorophenyl-4, 4 ', 5,5 ' -tetrakis (m-methoxyphenyl) biimidazole), 2 ' -bis (p-methylthiophenyl) -4,5,4 ', 5' -diphenyl-1, 1 '-biimidazole, bis (2,4, 5-triphenyl) -1, 1' -biimidazole, 5 '-tetrakis (p-chloronaphthyl) biimidazole, 1, 2' -, 1,4 '-, 2, 4' -covalently bonded tautomers disclosed in Japanese patent publication No. Sho 45-37377, compounds described in WO00/52529, and the like.
The acridine-based compound includes acridine, 9-phenylacridine, 9- (p-methylphenyl) acridine, 9- (p-ethylphenyl) acridine, 9- (p-isopropylphenyl) acridine, 9- (p-n-butylphenyl) acridine, 9- (p-tert-butylphenyl) acridine, 9- (p-methoxyphenyl) acridine, 9- (p-ethoxyphenyl) acridine, 9- (p-acetylphenyl) acridine, 9- (p-dimethylaminophenyl) acridine, 9- (p-cyanophenylphenyl) acridine, 9- (p-chlorophenyl) acridine, 9- (p-bromophenyl) acridine, 9- (m-methylphenyl) acridine, 9- (m-n-propylphenyl) acridine, 9- (m-isopropylphenyl) acridine, 9- (m-n-butylphenyl) acridine, 9- (m-butylphenyl) acridine, 9- (p-butylphenyl) acridine, 9- (m-tert-butylphenyl) acridine, 9- (m-methoxyphenyl) acridine, 9- (m-ethoxyphenyl) acridine, 9- (m-acetylphenyl) acridine, 9- (m-dimethylaminophenyl) acridine, 9- (m-diethylaminophenyl) acridine, 9- (cyanophenyl) acridine, 9- (m-chlorophenyl) acridine, 9- (m-bromophenyl) acridine, 9-methylacridine, 9-ethylacridine, 9-n-propylacridine, 9-isopropylacridine, 9-cyanoethylacridine, 9-hydroxyethylacridine, 9-chloroethylacridine, 9-bromoacridine, 9-hydroxyacridine, 9-nitroacridine, 9-aminoacridine, 9-methoxyacridine, 9-ethoxyacridine, 9-nitroacridine, 9-chloroacridine, etc, 9-n-propoxycaridine, 9-isopropoxyacridine, 9-chloroethoxyacridine, 4, 6-bis (dimethylamino) acridine, 10-acridine acetate, 10-methylacetamide acridine, 3, 6-dimethylacridine, 7, 13-bis (dimethylamino) acridine, 3, 6-dimethyl-10-acridine acetate, 3, 5-dimethyl-10-methylacetamide acridine, 7, 13-dimethyl-10-acridine acetate, 7, 13-dimethyl-10-methylacridine acetate, 1, 7-bis (9-acridinyl) heptane, 1, 5-bis (9-acridinyl) pentane, 1, 3-bis (9-acridinyl) propane, 4, 6-bis (dimethylamino) acridine, acridine acetate, acridine 10-dimethyl-10-methylacetate, acridine acetate, acridine, or its salts, 2, 7-Bibenzoyl-9-phenylacridine, 2, 7-bis (. alpha. -hydroxybenzyl) -9-phenylacridine, 2, 7-bis (. alpha. -acetoxybenzyl) -9-phenylacridine, 2, 7-dimethyl-9- (4-methylphenyl) acridine, 2, 7-dimethyl-9-phenylacridine, 2, 7-bis (3, 4-dimethyl-benzoyl) -9- (3, 4-dimethylphenyl) acridine, 2, 7-bis (. alpha. -acetoxy-4-tert-butylbenzyl) -9- (4-tert-butylphenyl) acridine, 2, 7-dimethyl-9- (3, 4-dichlorophenyl) acridine, 2, 7-bis (alpha-acetoxy-4-tert-butylbenzyl) acridine, 2, 7-dimethyl-9- (3, 4-dichlorophenyl) acridine, 2, 7-bis (alpha-hydroxybenzyl) -9-phenylacridine, 2, 7-dimethyl-9-4-phenylacridine, 2, 7-bis (alpha-acetoxybenzyl) -9-methyl-4-phenyl) acridine, 2, 7-bis (alpha-acetoxybenzyl) acridine, 4-methyl-phenyl) acridine, 2, 7-bis (alpha-hydroxy-benzyl) acridine, 2, 4-methyl-phenyl) acridine, 2, 7-bis (alpha-methyl) acridine, 2, 7-4-methyl, 2, 7-bis (alpha-methyl) acridine, 4-ethyl) acridine, 2, 7-bis (alpha-methyl, 4-ethyl) acridine, 2, 4-ethyl, 4-methyl, 2, 4-benzyl) acridine, 2, 4-bis (alpha-ethyl) acridine, 4-methyl, 2, 4-ethyl, 2, 4-benzyl) acridine, 2, 4-benzyl, 2, 4-bis (alpha-bis (2, 4-benzyl) acridine, 2, 4-bis (alpha-benzyl) acridine, 4-benzyl) acridine, 2, 4-bis (alpha-benzyl) acridine, 4-benzyl) acridine, 2,2, 7-dimethyl-9- (4-benzoylphenyl) acridine, 2, 7-bis (2-chlorobenzoyl) -9- (2-chlorophenyl) acridine, 2- (. alpha. -hydroxy-3-bromobenzyl) -6-methyl-9- (3-bromophenyl) acridine, 2, 5-bis (4-tert-butylbenzoyl) -9- (4-tert-butylphenyl) acridine, 1, 4-bis (2, 7-dimethyl-9-acridinyl) benzene, 2, 7-bis (. alpha. -phenylaminocarbonyloxy-3, 4-dimethylbenzyl) -9- (3, 4-dimethylphenyl) acridine and 2, 7-bis (3, 5-dimethyl-4-hydroxy-4' -fluorodiphenylmethyl) -9- (4-fluorophenyl) acridine, 9, 10-dihydroacridine, 1-methylacridine, 4-methylacridine, 2, 3-dimethylacridine, 1-phenylacridine, 4-phenylacridine, 1-benzylacridine, 4-benzylacridine, 1-chloroacridine, 2, 3-dichloroacridine, 10-butyl-2-chloroacridine-9 (10H) -one, 10-propyl-2-chloroacridine-9 (10H) -one, 10-butyl-2-chloroacridine-9 (10H) -one, 1, 2-bis (9-acridinyl) ethane, 1, 3-bis (9-acridinyl) propane, 1, 4-bis (9-acridinyl) butane, 1, 6-bis (9-acridinyl) hexane, 1, 7-bis (9-acridinyl) heptane, 1, 8-bis (9-acridinyl) octane, 1, 9-bis (9-acridinyl) nonane, 1, 10-bis (9-acridinyl) decane, 1, 11-bis (9-acridinyl) undecane, 1, 12-bis (9-acridinyl) dodecane, 1, 14-bis (9-acridinyl) tetradecane, 1, 16-bis (9-acridinyl) hexadecane, 1, 18-bis (9-acridinyl) octadecane, 1, 20-bis (9-acridinyl) eicosane, 1, 3-bis (9-acridinyl) -2-thiapropane, 1, 5-bis (9-acridinyl) -3-thiapentane, 1, 20-bis (9-acridinyl) eicosane, 7-methyl-benzo [ c ] acridine, 7-ethyl-benzo [ c ] acridine, 7-propyl-benzo [ c ] acridine, 7-butyl-benzo [ c ] acridine, 7-pentyl-benzo [ c ] acridine, 7-hexyl-benzo [ c ] acridine, 7-heptyl-benzo [ c ] acridine, 7-octyl-benzo [ c ] acridine, 7-nonyl-benzo [ c ] acridine, 7-decyl-benzo [ c ] acridine, 7-undecyl-benzo [ c ] acridine, 7-dodecyl-benzo [ c ] acridine, 7-tridecyl-benzo [ c ] acridine, 7-tetradecyl-benzo [ c ] acridine, 7-pentadecyl-benzo [ c ] acridine, 7-tetradecyl-benzo [ c ] acridine, and the like, 7-hexadecyl-benzo [ c ] acridine, 7-heptadecyl-benzo [ c ] acridine, 7-octadecyl-benzo [ c ] acridine, 7-nonadecyl-benzo [ c ] acridine, 1-bis (7-benzo [ c ] acridinyl) methane, 1, 2-bis (7-benzo [ c ] acridinyl) ethane, 1, 3-bis (7-benzo [ c ] acridinyl) propane, 1, 4-bis (7-benzo [ c ] acridinyl) butane, 1, 5-bis (7-benzo [ c ] acridinyl) pentane, 1, 6-bis (7-benzo [ c ] acridinyl) hexane, 1, 7-bis (7-benzo [ c ] acridinyl) heptane, 1, 8-bis (7-benzo [ c ] acridinyl) octane, and the like, 1, 9-bis (7-benzo [ c ] acridinyl) nonane, 1, 10-bis (7-benzo [ c ] acridinyl) decane, 1, 11-bis (7-benzo [ c ] acridinyl) undecane, 1, 12-bis (7-benzo [ c ] acridinyl) dodecane, 1, 13-bis (7-benzo [ c ] acridinyl) tridecane, 1, 14-bis (7-benzo [ c ] acridinyl) tetradecane, 1, 15-bis (7-benzo [ c ] acridinyl) pentadecane, 1, 16-bis (7-benzo [ c ] acridinyl) hexadecane, 1, 17-bis (7-benzo [ c ] acridinyl) heptadecane, 1, 18-bis (7-benzo [ c ] acridinyl) octadecane, 1, 19-bis (7-benzo [ c ] acridinyl) nonadecane, 1, 20-bis (7-benzo [ c ] acridinyl) eicosane, 7-phenyl-benzo [ c ] acridine, 7- (2-chlorophenyl) -benzo [ c ] acridine, 7- (4-methylphenyl) -benzo [ c ] acridine, 7- (4-nitrophenyl) -benzo [ c ] acridine, 1, 3-bis (7-benzo [ c ] acridinyl) benzene, 1, 4-bis (7-benzo [ c ] acridinyl) benzene, 7- [ 1-propen-3-yl (benzo [ c ] acridine) ], 7- [ 1-ethylpentyl- (benzo [ c ] acridine) ], 7- [ 8-heptadecenyl- (benzo [ c ] acridine) ], 7, 8-diphenyl-1, 14-bis (7-benzo [ c ] acridinyl) tetradecane, 1, 2-bis (7-benzo [ c ] acridinyl) ethene, 1-methyl-1, 2-bis (7-benzo [ c ] acridinyl) ethene, 7-styryl-benzo [ c ] acridine, 7- (1-propenyl) -benzo [ c ] acridine, 7- (1-pentenyl) -benzo [ c ] acridine, 9- (2-pyridyl) acridine, 9- (3-pyridyl) acridine, 9- (4-pyrimidinyl) acridine, 9- (2-pyrazinyl) acridine, 9 (5-methyl-2-pyrazinyl) acridine, 9- (2-quinoline) acridine, 1, 2-bis (7-benzo [ c ] acridinyl) ethene, 1-methyl-1, 2-bis (7-benzo [ c ] acridinyl) ethene, 9- (1-propenyl) -benzo [ c ] acridine, 9- (2-pyridyl) acridine, 9- (4-pyridyl) acridine, 9- (2-pyrazinyl) acridine, 2-quinoline) acridine, 2-acridine, and a pharmaceutically acceptable salt thereof, 9- (2-pyridyl) -2-methyl-acridine, 9- (2-pyridyl) -2-ethyl-acridine, 9- (3-pyridyl) -2-methyl-acridine, 9- (3-pyridyl) -2, 4-diethyl-acridine, 3, 6-diamino-acridine sulfonate, 3, 6-bis- (dimethylamino) -acridine sulfonate, 3, 6-diamino-10-methyl-acridinium chloride, 9-acridine carboxylic acid, and the like.
Examples of the acylphosphine-based compound include 2,4, 6-trimethylbenzoyldiphenylphosphine oxide (Lucirin TPO; manufactured by BASF), methyl isobutyryl-methylphosphinate, methyl isobutyryl-phenylphosphinate, methyl pivaloyl-phenylphosphinate, methyl 2-ethylhexanoyl-phenylphosphinate, isopropyl pivaloyl-phenylphosphinate, methyl p-toluoyl-phenylphosphinate, methyl o-toluoyl-phenylphosphinate, methyl 2, 4-dimethylbenzoyl-phenylphosphinate, isopropyl p-tert-butylbenzoyl-phenylphosphinate, methyl acryloyl-phenylphosphinate, isobutyryl-diphenylphosphine oxide, 2-ethylhexanoyl-diphenylphosphine oxide, o-toluoyl-diphenylphosphine oxide, N-toluyl-diphenylphosphine oxide, N-toluoyl-phenylphosphine oxide, N-propylbenzoyldiphenylphosphinate, N-propyldiphenylphosphinate, N-oxide, N-propyldiphenylphosphinate, p-propyldiphenylphosphinate, p-propyldiphenylphosphinate, p-propytene oxide, p-prophos-propytene oxide, p-propyipropyipropyipropyipropyipropyipropyipropyipropyipropyipropyipropyipropyipropyipropyipropyipropyipropyipropyipropyipropyipropyipropyipropyipropyipropyipropyipropyipropyipropyipropyipropyipropyipropyipropyipropyipropyipropyi, P-tert-butylbenzoyl-diphenylphosphine oxide, 3-pyridylcarbonyl-diphenylphosphine oxide, acryloyl-diphenylphosphine oxide, benzoyl-diphenylphosphine oxide, pivaloyl-phenylphosphinic acid vinyl ester, adipoyl-bis-diphenylphosphine oxide, pivaloyl-diphenylphosphine oxide, p-toluoyl-diphenylphosphine oxide, 4- (tert-butyl) -benzoyl-diphenylphosphine oxide, 2-methylbenzoyl-diphenylphosphine oxide, 2-methyl-2-ethylhexanoyl-diphenylphosphine oxide, 1-methyl-cyclohexanoyl-diphenylphosphine oxide, pivaloyl-phenylphosphinic acid methyl ester and pivaloyl-phenylphosphinic acid isopropyl ester, 4-octylphenylphosphine oxide, methyl ester, and isopropyl ester, Terephthaloyl-bis-diphenylphosphine oxide, 1-methyl-cyclohexylcarbonyldiphenylphosphine oxide, dihydroxybenzoyl-diphenylphosphine oxide, bis (2,4, 6-trimethylbenzoyl) -2, 4-diisobutyoxyphenylphosphine oxide, bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide (Irgacure 819; manufactured by BASF Co., Ltd.), bis (2,4, 6-trimethylbenzoyl) -2, 5-dimethylphenylphosphine oxide, bis (2, 6-dichloro-3, 4, 5-trimethoxybenzoyl) -4-ethoxyphenylphosphine oxide, bis (2,4, 6-trimethylbenzoyl) -2, 4-benzoylphosphine oxide, bis (p-benzoylphosphine oxide, bis (I) oxide, bis (I-benzoylphosphine oxide, bis (I), bis (I-benzoylphosphine oxide, 2,4, 6-trimethylbenzoyl) -2, 6-p-benzoylphosphine oxide, 6-tolylphosphine oxide, 4, 5-tolylphosphine oxide, bis (I), Bis (2-methyl-1-naphthoyl) -2, 5-dimethylphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -4-ethoxyphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -2-naphthylphosphine oxide, bis (2-methyl-1-naphthoyl) -4-propylphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -2, 5-dimethylphenylphosphine oxide, bis (2-methoxy-1-naphthoyl) -4-ethoxyphenylphosphine oxide, bis (2-chloro-1-naphthoyl) -2, 5-dimethylphenylphosphine oxide, bis (2, 6-dimethoxybenzoyl) -2,4, 4-trimethylpentylphosphine oxide, bis (2,4, 6-trimethylbenzoyl) -2, 4-dioctyloxyphenylphosphine oxide, bis (2,4, 6-trimethylbenzoyl) -2, 4-diisopropoxyphenylphosphine oxide, bis (2,4, 6-trimethylbenzoyl) -2, 4-dihexyloxyphenylphosphine oxide, bis (2,4, 6-trimethylbenzoyl) -2-propoxy-4-methylphenylphosphine oxide, bis (2,4, 6-trimethylbenzoyl) -2, 4-diisopentyloxyphenylphosphine oxide, bis (2, 6-dichlorobenzoyl) phenylphosphine oxide, bis (2, 6-dichlorobenzoyl) -2, 5-dimethylphenylphosphine oxide, bis (2, 6-dichlorobenzoyl) -phenylphosphine oxide, bis (2, 6-dichlorobenzoyl) -4-biphenylphosphine oxide, bis (2, 6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis (2, 6-dichlorobenzoyl) -2-naphthylphosphine oxide, bis (2, 6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis (2, 6-dimethoxybenzoyl) -2,4, 4-trimethyl-pentylphosphine oxide (CGI403), 6-trimethylbenzoyl-ethyl-phenyl-phosphonite (SPEEDCURE TPO-L; manufactured by Lambson).
Examples of the oxime ester compound include ethanone-1- [ 9-ethyl-6- (2-methylbenzoyl-9H-carbazol-3-yl ] -1- (O-acetyl oxime), 1- [ 9-ethyl-6-benzoyl-9H-carbazol-3-yl-octane-1-ketoxime-O-acetate, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -ethane-1-ketoxime-O-benzoate, 1- [ 9-n-butyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl ] -ethane-1- ketoxime-O-benzoate, ethanone-1- [ 9-ethyl-6- (2-methyl-4-tetrahydrofurylbenzoyl) -9H-carbazol-3-yl ] -1- (O-acetyloxime), ethanone-1- [ 9-ethyl-6- (2-methyl-4-tetrahydropyranoylbenzoyl) -9H-carbazol-3-yl ] -1- (O-acetyloxime), ethanone-1- [ 9-ethyl-6- (2-methyl-5-tetrahydrofurylbenzoyl) -9H-carbazol-3-yl ] -1- (O-acetyloxime, Ethanone-1- [ 9-ethyl-6- { 2-methyl-4- (2, 2-dimethyl-1, 3-dioxolanyl) methoxybenzoyl } -9H-carbazol-3-yl ] -1- (O-acetyl oxime), ethanone-1- [ 9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazol-3-yl ] -1- (O-acetyl oxime), and the like.
Examples of the thermal radical polymerization initiator include azo initiators such as 2,2 '-azobisisobutyronitrile, 2' -azobis (methyl isobutyrate), 2 '-azobis-2, 4-dimethylvaleronitrile, and 1, 1' -azobis (1-acetoxy-1-phenylethane); peroxide initiators such as benzoyl peroxide, di-t-butyl benzoyl peroxide, t-butyl peroxypivalate and bis (4-t-butylcyclohexyl) peroxydicarbonate, and persulfates such as ammonium persulfate, sodium persulfate and potassium persulfate. These may be used singly or in combination of two or more.
In the curable composition of the present invention, the curability and the adhesion of the cured product are improved, and therefore, the radical polymerization initiator (B) is preferably 1 to 10 parts by mass, more preferably 2 to 5 parts by mass, based on 100 parts by mass of the total of the radical polymerizable component (a) and the cation polymerizable component (C).
The cationic polymerizable component (C) is a compound which is activated by irradiation with active energy rays or heating of a cationic polymerization initiator to cause a polymerization reaction or a crosslinking reaction, and in addition to a glycidyl ether of an alcohol having 11 or more carbon atoms as an essential component, an aromatic epoxy compound (C1), an aliphatic epoxy compound (C2), an alicyclic epoxy compound (C3), an oxetane compound (C4), a vinyl ether compound (C5), a polymer (C6) having a weight average molecular weight of 1,000 to 30,000 selected from the following polymers (hereinafter also referred to as polymer (C6)), and the like can be used: 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), or a polymer obtained from a monomer selected from monomers represented by the following formula (I) and monomers represented by the following formula (II).
Figure BDA0002110418360000131
(wherein X represents 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 BDA0002110418360000132
(in the formula, 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. )
Examples of the glycidyl ether of an alcohol having 11 or more carbon atoms include glycidyl ethers of polyhydric alcohols such as triglycidyl ether of glycerol, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, and diglycidyl ether of dicyclopentadiene dimethanol, and polyglycidyl ethers of polyether polyols obtained by adding 1 or 2 or more kinds of alkylene oxides to aliphatic polyhydric alcohols such as propylene glycol, trimethylolpropane, and glycerol. Here, the glycidyl ether of an alcohol having 11 or more carbon atoms means that the number of carbon atoms of the residue portion of the glycidyl ether obtained by adding a glycidyl group to an alcohol is 11 or more carbon atoms. The glycidyl ether of an alcohol having 11 or more carbon atoms is preferred because of improved curability and adhesion of the cured product.
As the glycidyl ether of the alcohol having 11 or more carbon atoms, commercially available products can be used, and examples thereof include Denacol EX-171, Denacol EX-192, Denacol EX-830, Denacol EX-832, Denacol EX-841, Denacol EX-861, and Denacol EX-931 (manufactured by Nagasechemtex); epolite M-1230, Epolite 400E, Epolite 400P, (Co., Ltd.), Adeka Glycerol ED-506, ADEKA RESIN E in comparison with 4088S (manufactured by ADEKA Co., Ltd.), and the like.
The aromatic epoxy compound (C1) is an epoxy compound containing an aromatic ring. Specific examples of the aromatic epoxy compound (C1) include mono/polyglycidyl etherate of polyhydric phenol having at least 1 aromatic ring such as phenol, cresol, and butylphenol, or an alkylene oxide adduct thereof, glycidyl etherate of bisphenol a, bisphenol F, or a compound obtained by further adding an alkylene oxide thereto, and epoxy novolac resin; mono/polyglycidyl etherates of aromatic compounds having 2 or more phenolic hydroxyl groups such as resorcinol, hydroquinone, and catechol; glycidyl etherates of aromatic compounds 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, and epoxides of styrene oxide or divinylbenzene.
As the aromatic epoxy compound (C1), 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, On Cort EX-1020, On Cort EX-1030, On Cort EX-1040, On Cort EX-1050, On Cort EX-1051, On Cort EX-1010, On Cort EX-1011, and On Cort 1012 (manufactured by Nagasemtex Co., Ltd.); 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 (manufactured by Tokyo Kagaku K.K.); YX8800 (manufactured by mitsubishi chemical corporation); mar proof G-0105SA and Mar proof G-0130SP (manufactured by Nichiki 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 corporation); ADEKA RESIN EP-4000, ADEKA RESIN EP-4005, ADEKA RESIN EP-4100 and ADEKA RESIN EP-4901 (manufactured by ADEKA); TECHMORE VG-3101L (PURINTEKKU Co., Ltd.). The aromatic epoxy compound (C1) is preferably a polyfunctional compound because of its excellent curability.
The aliphatic epoxy compound (C2) is an epoxy compound not classified into an aromatic epoxy compound (C1) and an alicyclic epoxy compound (C3) described later. Specific examples of the aliphatic epoxy compound (C2) include polyfunctional epoxy compounds such as a glycidyl ether compound of an aliphatic alcohol, a monofunctional epoxy compound such as a glycidyl ester of an alkyl carboxylic acid, a polyglycidyl ether compound of an aliphatic polyol or an alkylene oxide adduct thereof, and a polyglycidyl ester of an aliphatic long-chain polybasic acid. Typical examples of the compound include glycidyl ethers of polyhydric alcohols such as allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, 1, 4-butanediol diglycidyl ether, and neopentyl glycol diglycidyl ether, and diglycidyl esters of aliphatic long-chain dibasic acids. Further, there may be mentioned monoglycidyl ether of aliphatic higher alcohol, glycidyl ester of higher fatty acid, epoxidized soybean oil, octyl epoxystearate, butyl epoxystearate, epoxidized polybutadiene and the like. As the aliphatic epoxy compound (C2), glycidyl ethers of aliphatic alcohols other than the glycidyl ether of an alcohol having 11 or more carbon atoms, and polyglycidyl ethers of aliphatic polyols or alkylene oxide adducts thereof are preferred because of their improved viscosity, coatability, and reactivity.
As the aliphatic epoxy compound (C2), commercially available compounds, 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-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-920 (produced by Denacol EX-Inc.); epolite M-1230, Epolite 40E, Epolite 100E, Epolite 200E, Epolite 400 38400 400E, Epolite 70P, Epolite 200P, Epolite 400P, Epolite 1500NP, Epolite 1600, Epolite 80MF, Epolite 100MF (manufactured by Kyoho chemical Co., Ltd.), Adeka Glycerol ED-503G, Adeka Glycerol ED-506, Adeka Glycerol ED-523T, ADEKA RESIN EP-4088S (manufactured by ADEKA Co., Ltd.), and the like.
The alicyclic epoxy compound (C3) refers to a compound in which an oxirane ring is directly bonded to a saturated ring without a bonding group. Specific examples of the alicyclic epoxy compound (C3) include a polyglycidyl ether of a polyol having at least 1 alicyclic ring, and a cyclohexene oxide-or cyclopentene oxide-containing compound obtained by epoxidizing a cyclohexene-or cyclopentene ring-containing compound with an oxidizing agent. Examples thereof include hydrogenated bisphenol A diglycidyl ether, 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexanecarboxylate, 3, 4-epoxy-1-methylcyclohexyl-3, 4-epoxy-1-methylhexanecarboxylate, 6-methyl-3, 4-epoxycyclohexylmethyl-6-methyl-3, 4-epoxycyclohexanecarboxylate, 3, 4-epoxy-3-methylcyclohexylmethyl-3, 4-epoxy-3-methylcyclohexanecarboxylate, 3, 4-epoxy-5-methylcyclohexylmethyl-3, 4-epoxy-5-methylcyclohexanecarboxylate, bis (3, 4-epoxycyclohexylmethyl) adipate, and the like, 3, 4-epoxy-6-methylcyclohexanecarboxylate, methylenebis (3, 4-epoxycyclohexane), propane-2, 2-diyl-bis (3, 4-epoxycyclohexane), 2-bis (3, 4-epoxycyclohexyl) propane, dicyclopentadiene diepoxide, ethylenebis (3, 4-epoxycyclohexanecarboxylate), dioctylphthalate oxide, di-2-ethylhexyl hexahydrophthalate oxide, 1-oxiranyl-3, 4-epoxycyclohexane, 1, 2-epoxy-2-oxiranylcyclohexane, alpha-pinene oxide, limonene dioxide and the like.
The alicyclic epoxy compound (C3) is preferably hydrogenated bisphenol a diglycidyl ether, 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexanecarboxylate or 3, 4-epoxy-1-methylcyclohexyl-3, 4-epoxy-1-methylhexanecarboxylate, from the viewpoint of improving adhesiveness.
As the alicyclic epoxy compound (C3), commercially available products can be used, and examples thereof include CELOXIDE 2021P, CELOXIDE 2081, CELOXIDE 2000 and CELOXIDE 3000 (manufactured by Daicel Corporation).
Examples of the oxetane compound (C4) include 3, 7-bis (3-oxetanyl) -5-oxa-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-oxetanylmethyl) ether, 1, 4-bis (3-ethyl-3-oxetanylmethoxy) butane, Difunctional aliphatic oxetane compounds such as 1, 6-bis (3-ethyl-3-oxetanylmethoxy) hexane, etc., 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, 3-ethyl-3- (chloromethyl) oxetane, etc. These can be used alone or in combination of 2 or more, polyfunctional oxetane compounds because of cured product curing and adhesion is high, so the optimization.
As the Oxetane compound (C4), commercially available products can be used, and examples thereof include ARON Oxetane OXT-121, OXT-221, EXOH, POX, OXA, OXT-101, OXT-211, OXT-212 (manufactured by Toyo Kabushiki Kaisha), ETERNACOLL OXBP, and OXTP (manufactured by Ushixing K.K.).
Examples of the vinyl ether compound (C5) 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.
As the vinyl ether compound (C5), commercially available products can be used, and examples thereof include 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether and 4-hydroxybutyl vinyl ether (manufactured by PELTO CHEMICAL CO., LTD.).
The content of the glycidyl ether of an alcohol having 11 or more carbon atoms in the cationically polymerizable component (C) is preferably 25 to 45 parts by mass, and more preferably 28 to 43 parts by mass, based on 100 parts by mass of the total of the radically polymerizable component (a) and the cationically polymerizable component (C), because the adhesiveness and low moisture permeability of the cured product are improved. Further, when the proportions of the aromatic epoxy compound (C1), the aliphatic epoxy compound (C2), the alicyclic epoxy compound (C3), the oxetane compound (C4), the vinyl ether compound (C5) and the polymer (C6) used are 1 to 20 parts by mass of the aromatic epoxy compound (C1), 20 to 40 parts by mass of the aliphatic epoxy compound (C2), 0 to 20 parts by mass of the alicyclic epoxy compound (C3), 10 to 30 parts by mass of the oxetane compound (C4), 0 to 20 parts by mass of the vinyl ether compound (C5) and 0 to 15 parts by mass of the polymer (C6) relative to 100 parts by mass of the total of the radically polymerizable component (A) and the cationically polymerizable component (C), in addition to the glycidyl ether of an alcohol having 11 or more carbon atoms as an essential component, the viscosity, coatability, reactivity and curability are improved, and is therefore preferred. The amount of the component (C) is 20 to 50 parts by mass based on 100 parts by mass of the total of the components (A) and (C).
In addition to the radical polymerizable component (a) and the cation polymerizable component (C), a compound having an epoxy group and an ethylenically unsaturated group may be used. Examples of these compounds include epoxy acrylates and epoxy methacrylates, and specifically, acrylates obtained by reacting conventionally known aromatic epoxy resins, alicyclic epoxy resins, aliphatic epoxy resins, and the like with acrylic acid or methacrylic acid. Among these epoxy acrylates or epoxy methacrylates, particularly preferred are acrylates or methacrylates of glycidyl ethers of alcohols.
The cationic polymerization initiator (D) in the curable composition of the present invention is not particularly limited as long as it is a compound capable of releasing a substance that initiates cationic polymerization by irradiation with active energy rays or heating, and a double salt of an onium salt that releases a lewis acid by irradiation with active energy rays or a derivative thereof is preferable. Representative examples of the compounds include those represented by the following general formula
[A]r+[B]r-
Salts of the cations and anions shown.
Thus, the cation [ A ]]r+Preferably, the onium is one whose structure can be represented by, for example, the following general formula.
[(R2)aQ]r+
Further, here, R2Is an organic group having 1 to 60 carbon atoms and may contain atoms other than carbon atoms. a is an integer of 1 to 5. a number of R2Each of which may be independently the same or different. In addition, at least 1 is preferably the aromatic ring with the organic group. 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+When the valence of Q in (b) is Q, it is necessary that the relationship of r-a-Q is satisfied (where 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, r is required to satisfy the relationship b-p.
As anions of the above formula [ LYb]r-Specific examples of (1) include halogen ions and perchloric acid ions (ClO)4)-Tetrafluoroboric acid ion (BF)4)-Hexafluorophosphate ion (PF)6)-Hexafluoroantimonate (SbF)6)-Hexafluoroarsenate (AsF)6)-Hexachloroantimonate (SbCl)6)-Inorganic ions are subjected to plasma treatment; trifluoromethanesulfonic acid ion, methanesulfonic acid ion, butanesulfonic acid ion, fluorosulfonic acid ion (FSO)3)-Benzenesulfonic acid anion, toluenesulfonic acid ion, trinitrobenzenesulfonic acid ion, camphorsulfonic acid ion, nonafluorobutanesulfonic acid ionSulfonic acid ions such as acid ions and hexadecafluorooctane sulfonic acid ions; a borate ion such as a tetraarylborate ion or a tetrakis (pentafluorophenyl) borate ion; carboxylic acid ions such as methane carboxylic acid ion, ethane carboxylic acid ion, propane carboxylic acid ion, butane carboxylic acid ion, octane carboxylic acid ion, trifluoromethane carboxylic acid ion, benzene carboxylic acid ion, and p-toluene carboxylic acid ion; trifluoromethyl sulfite ion (CF)3SO3)-Methyl sulfate ion (CH)3OSO3)-Bis (trifluoromethanesulfonyl) imide ion, tris (trifluoromethanesulfonyl) methide ion, (CF)3CF2)3PF3 -、((CF3)2C6H3)4B-、(C6F5)4Ga-、((CF3)2C6H3)4Ga-In addition, examples selected from the following groups can be given.
Figure BDA0002110418360000201
In addition, an anion [ B ]]r-Also, those having 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 perchloric acid ion (ClO)4)-Trifluoromethyl sulfite ion (CF)3SO3)-Fluorosulfonic acid ion (FSO)3)-Tosylate anion, trinitrobenzene sulfonate anion, camphorsulfonate, nonafluorobutanesulfonate, hexadecafluorooctansulfonate, tetraarylborate, tetrakis (pentafluorophenyl) borate, and the like.
Among such onium salts, the following aromatic onium salts (one) to (three) are 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.
Aryldiazonium salts such as (mono) phenyldiazonium hexafluorophosphate, 4-methoxybenzylazonylammonium hexafluoroantimonate and 4-methylbenzylazonylammonium hexafluorophosphate
Diaryliodonium salts such as (di) diphenyliodonium hexafluoroantimonate, di (4-methylphenyl) iodonium hexafluorophosphate, di (4-tert-butylphenyl) iodonium hexafluorophosphate and tolylcumylium tetrakis (pentafluorophenyl) borate
(III) sulfonium salts of sulfonium cations represented by the following group I or II with hexafluoroantimony ions, hexafluorophosphate ions, tetrakis (pentafluorophenyl) borate ions, and the like
< group I >
Figure BDA0002110418360000221
< group II >
Figure BDA0002110418360000231
In addition, as another preferable example, (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, an aluminum complex such as tris (acetylacetonate) aluminum, tris (ethylacetonoacetate) aluminum, tris (salicylaldehyde) aluminum, and a silanol such as triphenylsilanol; salts such as thiophenium salts, tetrahydrothiophenium (thiolanium) salts, benzylammonium salts, pyridinium salts, and hydrazinium salts; polyalkyl polyamines such as triethylene 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 obtained 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; the organic polyamine is reacted with carboxylic acid such as phthalic acid, isophthalic acid, dimer acid, etc. by a conventional methodAn amidated modified product produced by reacting an acid; mannich-modified products produced by reacting the polyamines with aldehydes such as formaldehyde and phenols having a nucleus with at least one hydroformylation reactive site such as phenol, cresol, xylenol, tert-butylphenol, and 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 and dimer acid; aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; tricarboxylic acids such as trimellitic acid, trimesic acid and trimer of castor oil fatty acid; tetracarboxylic acids such as pyromellitic acid); dicyandiamide, imidazoles, carboxylic esters, sulfonic esters, aminimides, and the like.
Among them, from the viewpoint of practical use and improvement in sensitivity, an aromatic iodonium salt, an aromatic sulfonium salt, and an iron-arene complex are preferably used, and more preferably, at least 0.1 mass% or more of an aromatic sulfonium salt having the following structure is contained in 100 mass% of the cationic polymerization initiator (D).
In the curable composition of the present invention, the cationic polymerization initiator (D) is used in a proportion of 1 to 10 parts by mass, preferably 2 to 5 parts by mass, based on 100 parts by mass of the total of the radical component (a) and the cationic polymerization component (C). If the amount is too small, curing tends to be insufficient, and if it is too large, various characteristics such as water absorption of the cured product and strength of the cured product may be adversely affected.
A sensitizer and/or a sensitization auxiliary may be further used in the curable composition of the present invention as needed. The sensitizer is a compound that exhibits a maximum absorption at a wavelength longer than the maximum absorption wavelength exhibited by the cationic polymerization initiator (D) and promotes the polymerization initiation reaction based on the cationic polymerization initiator (D). The sensitizing auxiliary is a compound that further promotes the action of the sensitizing agent.
Examples of the sensitizer and the sensitization assistant include anthracene compounds and naphthalene compounds.
Examples of the anthracene compound include compounds represented by the following formula (IIIa).
Figure BDA0002110418360000241
Here, in the formula (IIIa), R3And R4Each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxyalkyl group having 2 to 12 carbon atoms, R5Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Specific examples of the anthracene compound represented by the formula (IIIa) 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-dihexylooxyanthracene, 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, 2-methyl-or 2-ethyl-9, 10-diisopropoxylanthracene, 2-methyl-or 2-ethyl-9, 10-dibutoxyanthracene, 2-methyl-or 2-ethyl-9, 10-dipentyloxyacanthracene, 2-methyl-or 2-ethyl-9, 10-dihexyloxyanthracene, and the like.
Examples of the naphthalene-based compound include compounds represented by the following formula (IIIb).
Figure BDA0002110418360000251
Here, in the formula (IIIb), R6And R7Each independently represents an alkyl group having 1 to 6 carbon atoms.
Specific examples of the naphthalene-based compound represented by the above formula (IIIb) 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, and 1, 4-dibutoxynaphthalene.
The use ratio of the sensitizer and the sensitization auxiliary to the cationically polymerizable component (C) is not particularly limited, and may be generally used in a usual use ratio within a range not interfering with the object of the present invention, and for example, from the viewpoint of improving curability, it is preferable that the amount of the sensitizer and the sensitization auxiliary is 0.1 to 3 parts by mass or more, respectively, to 100 parts by mass of the cationically polymerizable component (C).
In the curable composition of the present invention, a silane coupling agent may be used as necessary. Examples of the silane coupling agent include 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, γ -glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, 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 titanium tetraisopropoxide and titanium tetra-N-butoxide, titanium chelates such as dioctyloxy bis (octyl glycolate) titanate, zirconium chelates such as zirconium tetraacetoacetate zirconium titanate and zirconium tributoxymetacetylacetonate, Zirconium acylates such as zirconium tributoxymetastearate, and isocyanate silanes such as methyltriisocyanosilane.
The amount of the silane coupling agent used 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 may be improved by using a thermoplastic organic polymer, if necessary. Examples of the thermoplastic organic polymer include polystyrene, polymethyl methacrylate, a methyl methacrylate-ethyl acrylate copolymer, a methyl methacrylate-glycidyl methacrylate copolymer, poly (meth) acrylic acid, a styrene- (meth) acrylic acid copolymer, a (meth) acrylic acid-methyl methacrylate copolymer, a glycidyl (meth) acrylate-polymethyl (meth) acrylate copolymer, polyvinyl butyral, a cellulose ester, a polyacrylamide, and a saturated polyester.
The curable composition of the present invention is not particularly limited, and a solvent capable of dissolving or dispersing the above-mentioned components (a), (B), (C) and (D) which are generally used may be used, and examples thereof include ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone and 2-heptanone; ether solvents such as ethyl 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 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate (texanol); cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; alcohol solvents such as methanol, ethanol, isopropanol or n-propanol, isopropanol 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(Exon chemical company); 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, and a mixed solvent of 1 or 2 or more of these solvents can be used.
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 large, cloudiness may occur and components may precipitate, which is not preferable.
In the curable composition of the present invention, if necessary, a compound which is inactive at normal temperature and exhibits an ultraviolet absorbing function by being heated to a predetermined temperature, irradiated with light, activated by acid or the like to remove a protecting group, may be further used.
Further, as long as the effects of the present invention are not impaired, various resin additives such as polyols, inorganic fillers, organic fillers, pigments, dyes and other colorants, antifoaming agents, thickeners, surfactants, leveling agents, flame retardants, thixotropic agents, diluents, plasticizers, stabilizers, polymerization inhibitors, ultraviolet absorbers, antioxidants, antistatic agents, flow control agents, adhesion promoters and the like may be added as necessary.
The curable composition of the present invention is applied to a support substrate by a known means such as roll coater, curtain coater, various printing, and dipping. Further, the transfer may be performed once on a support substrate such as a film and then transferred to another support substrate, and the method of application is not 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 cellulose diacetate, cellulose Triacetate (TAC), cellulose propionate, cellulose butyrate, cellulose acetate propionate, 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 treatment, glow discharge treatment, reactive plasma treatment, or laser treatment.
In the method of curing the curable composition of the present invention by irradiation with an active energy ray, the active energy ray includes ultraviolet rays, electron beams, X-rays, radiation rays, high frequency rays, and the like, and ultraviolet rays are economically most preferable. Examples of the light source of ultraviolet rays include an ultraviolet laser, a mercury lamp, a xenon laser, and a metal halide lamp.
The method for curing the curable composition of the present invention by heating is carried out at 70 to 250 ℃ for 1 to 100 minutes. After the Pre-baking (PAB; Pre applied bake), the post-baking (PEB) may be performed by applying pressure, or the baking may be performed at different multi-stage temperatures. The heating conditions vary depending on the kind and the blending ratio of the components, and are, for example, 70 to 180 ℃ for 5 to 15 minutes in the case of an oven or 1 to 5 minutes in the case of a hot plate. Thereafter, the coating film is cured by heat treatment at 180 to 250 ℃, preferably 200 to 250 ℃, for 30 to 90 minutes in the case of an oven, or for 5 to 30 minutes in the case of a hot plate, to obtain a cured film.
Specific applications of the curable composition or the cured product thereof of the present invention include adhesives, optical materials represented by glasses and imaging lenses, paints, coating agents, lining agents, inks, resists, liquid resists, printing plates, color televisions, PC monitors, portable information terminals, digital cameras, display elements such as organic EL and touch panels, insulating varnishes, insulating sheets, laminated plates, printed circuit boards, sealants for semiconductor devices, LED packages, liquid crystal injection ports, organic EL, optical elements, electrical insulators, electronic components, separation films, molding materials, putties (putty), glass fiber impregnants, fillers, passivation films for semiconductors and solar cells, interlayer insulating films, protective films, prisms used in backlights of liquid crystal display devices, fresnel lens sheets used in screens of projection televisions, and the like, Lens portions of lens sheets such as lenticular lens sheets, backlights using the same, optical lenses such as microlenses, optical elements, optical connectors, optical waveguides, and optical molding agents.
Examples of the display device include a device in which each layer such as an undercoat layer, an antireflection layer, a polarizing element layer, a retardation layer, a birefringence layer, a light scattering layer, a hard coat layer, a lubricating layer, and a protective layer is provided on a transparent support as required, and a film comprising the cured product of the present invention can be used for each layer.
Examples
The present invention will be described in more detail below with reference to examples and comparative examples. In the examples and comparative examples, parts are parts by mass.
Examples 1 to 11 and comparative examples 1 to 4
The respective components were thoroughly mixed according to the following formulations shown in [ Table 1] to [ Table 3] to obtain curable compositions of examples 1 to 11 and comparative examples 1 to 4. The viscosity and adhesion of each of the obtained curable compositions were evaluated in accordance with the following procedures.
(viscosity)
The viscosity of each of the obtained curable compositions was measured at 25 ℃ with an E-type viscometer. The results are also shown in [ Table 1] to [ Table 3 ].
(Adhesivity)
Each of the curable compositions thus obtained was coated on one acrylic film (TECNOOLOY 125S001, manufactured by SUMITOMO CHEMICAL CO., LTD.) subjected to corona discharge treatment, and then bonded to another COP (cycloolefin Polymer, model Zeonor film 14-060, manufactured by Zeon corporation, Japan) film subjected to corona discharge treatment using a laminator, and irradiated with 1000mJ/cm of the COP film through an electrodeless ultraviolet lamp2And then the substrates were bonded together to obtain a test piece. The obtained test piece was subjected to a 90-degree peel test. The initial adhesion force is a value after exposure for 3 minutes, and the adhesion force after curing is a value after 6 hours or more from exposure. The evaluation was carried out according to the following criteria.
< initial adhesion force >
O: indicating an adhesion of more than 0.5N/2 cm.
X: the adhesive strength was 0.5N/2cm or less.
< post-curing adhesion force >
O: indicating an adhesion of more than 1.5N/2 cm.
X: the adhesive strength was 1.5N/2cm or less.
(moisture permeability)
Each of the curable compositions thus obtained was coated on 1 acrylic film (TECNOOLOY 75S001, manufactured by Sumitomo chemical Co., Ltd.) subjected to corona discharge treatment, and then irradiated with 500mJ/cm of ultraviolet light using an electrodeless lamp2The test piece was obtained. The test piece was left in an atmosphere of 23 ℃ (humidity 50%) for 6 hours or more. The moisture permeability of the obtained test piece was measured by a water vapor permeability measuring device 7002 (manufactured by inc.). The test environment was set at 40 deg.C/90% RH. The evaluation was carried out according to the following criteria. The moisture permeability of the single acrylic film was 50g/m2/day。
Very good: is expressed as ≤ 40g/m2/day。
O: to represent<50g/m2/day。
X: indicates that not less than 50g/m2/day。
As the radical polymerizable component (A), the following compounds (A1-1) to (A1-5) and (A2-1) were used.
Compound a 1-1: 1, 6-hexanediol diacrylate
Compound a 1-2: viscoat #150 (tetrahydrofurfuryl acrylate; manufactured by Osaka Okagaku K.K.)
Compound a 1-3: NK ESTER A-DCP (Dicyclodecane dimethanol diacrylate; manufactured by Xinzhongcun chemical Co., Ltd.)
Compound a 1-4: NK ESTER APG-200 (tripropylene glycol diacrylate; manufactured by Xinzhongcun chemical Co., Ltd.)
Compound a 1-5: A-9300S (multifunctional acrylate; manufactured by Xinzhongcun chemical industry Co., Ltd.)
Compound A2-1: NK ESTER BPE-500 (ethoxylated bisphenol A dimethacrylate, manufactured by Newzhongcun chemical Co., Ltd.)
As the radical polymerization initiator (B), the following compound (B-1) was used.
Compound B1-1: irgacure 184 (manufactured by BASF corporation)
As the cation polymerizable component (C), the following compounds (C1-1), (C2-1) to (C2-4), (C3-1) and (C6-1) were used.
Compound C1-1: EP-4100 (bisphenol A type diglycidyl ether manufactured by ADEKA Co., Ltd.)
Compound C2-1: ADEKA RESIN EP-4088L (diglycidyl ether of an alcohol having 11 or more carbon atoms; manufactured by ADEKA K.K.)
Compound C2-2: 1, 4-butanediol diglycidyl ether
Compound C2-3: neopentyl glycol diglycidyl ether
Compound C2-4: epiclon HP-7200 (dicyclopentadiene type glycidyl ether; available from DIC)
Compound C3-1: CELOXIDE 2021P (alicyclic epoxy compound; manufactured by Daicel Corporation)
Compound C6-1: copolymer of methyl methacrylate (70 parts by mass) and glycidyl methacrylate (30 parts by mass) (weight-average molecular weight 8000)
As the cationic polymerization initiator (D), the following compound D-1 was used.
Compound D-1: propylene carbonate 50% solution of a mixture of 2 compounds represented by the following structure
Figure BDA0002110418360000321
[ Table 1]
Figure BDA0002110418360000331
[ Table 2]
Figure BDA0002110418360000341
[ Table 3]
Figure BDA0002110418360000351
As is clear from [ table 1] to [ table 3], the curable composition of the present invention is excellent in curability and adhesion of the cured product.

Claims (6)

1. A curable composition characterized by containing: 50 to 80 parts by mass of a radical polymerizable component (A), 1 to 10 parts by mass of a radical polymerization initiator (B), 20 to 50 parts by mass of a cation polymerizable component (C), and 1 to 10 parts by mass of a cation polymerization initiator (D), wherein the total of the radical polymerizable component (A) and the cation polymerizable component (C) is 100 parts by mass,
the cationically polymerizable component (C) contains a glycidyl ether of an alcohol having 11 or more carbon atoms, and the content of the glycidyl ether of an alcohol having 11 or more carbon atoms is 25 to 45 parts by mass with respect to 100 parts by mass of the total of the radically polymerizable component (A) and the cationically polymerizable component (C).
2. The curable composition according to claim 1, wherein the radically polymerizable component (a) comprises: an acrylic acid ester of an alcohol having 2 to 60 carbon atoms or a methacrylic acid ester of an alcohol having 2 to 60 carbon atoms (A1), or an acrylic acid ester of a phenol compound or a methacrylic acid ester of a phenol compound (A2).
3. A method for producing a cured product, characterized by curing the curable composition according to any one of claims 1 or 2 by irradiation with an active energy ray.
4. A method for producing a cured product, which comprises curing the curable composition according to claim 1 or 2 by heating.
5. A cured product of the curable composition according to claim 1 or 2.
6. An adhesive formed from the curable composition according to any one of claims 1 or 2.
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