JP6762745B2 - Curable composition - Google Patents

Description

The present invention is a cationically curable composition, more specifically, a curable composition suitable for a cationically curable adhesive used for electronic parts and the like, and the curable composition is irradiated with active energy rays or The present invention relates to a method of curing by irradiation and heating, and a cured product obtained by curing the composition.

The cation-curing type curable composition is a resin composition that is cured by irradiation with active energy rays, particularly ultraviolet rays, and its characteristics are excellent storage stability, faster curing than thermosetting type, and radical curing. Compared to molds, curing inhibition by oxygen does not occur, curing control is easy and suitable for delayed curing applications, the physical properties and adhesive strength of the cured product are high, and the workability of the thin film is excellent. Therefore, the composition is used in the fields of inks, paints, various coating agents, adhesives, optical members, etc. by taking advantage of this characteristic.

In particular, the curable composition used as an adhesive for electronic materials is required to have stable performance over a long period of time. Therefore, the cured product of the curable composition used for the said application is required to have high reliability in environmental tests and durability tests such as weather resistance, moisture resistance, heat resistance, and voltage resistance.

For example, Patent Documents 1 to 5 disclose various cationically curable compositions or cured products thereof that are cured by irradiation with active energy rays. However, according to these documents, a composition having high toughness and adhesive strength of the cured product and excellent moisture resistance and durability has not been obtained.

Japanese Unexamined Patent Publication No. 2006-316213 Japanese Unexamined Patent Publication No. 2008-10171 Japanese Unexamined Patent Publication No. 2012-567971 Japanese Patent No. 4276407 Japanese Patent No. 5640031

An object to be solved by the present invention is to provide a curable composition in which the cured product has high toughness and adhesive strength and excellent moisture resistance and durability.

As a result of diligent efforts to solve the above problems, a curable composition containing a cationically polymerizable component (A) and a cationically polymerizable initiator (B) has been obtained.
The cationically polymerizable component (A) contains one or more selected from the aromatic polyfunctional epoxy compound (A1) and one or more selected from the aliphatic epoxy compound (A2).
The aliphatic epoxy compound (A2) contains one or more selected from the group consisting of an alicyclic glycidyl compound represented by the following general formula (I) and a hydrogenated bisphenol type epoxy compound.
The cationically polymerizable component (A) has a mass ratio of the aromatic polyfunctional epoxy compound (A1) and the aliphatic epoxy compound (A2) in the range of 10:90 to 50:50 for the former: the latter.
The cationic polymerization initiator (B) contains one or more sulfonium borate salts and contains.
The sulfonium borate salt is one or two selected from a salt composed of a combination of a sulfonium cation represented by the following general formula (IIa) or (IIb) and a borate anion represented by the following general formula (III). Contains the above,
It has been found that the curable composition and the cured product thereof solve the above-mentioned problems.

(In the formula, X is an aliphatic hydrocarbon having 3 to 14 carbon atoms having an alicyclic structure having 3 to 6 carbon atoms, or a structure in which 2 or 3 alicyclic structures having 3 to 6 carbon atoms are condensed. Represents an aliphatic hydrocarbon having 3 to 14 carbon atoms.
J represents an oxygen atom or -COO-
m represents 0 or 1 and represents
n represents 1, 2 or 3. )

(In the formula, R ^{1 to} R ³ are independently hydrogen atom, hydroxyl group, halogen group, nitro group, carboxyl group, linear or branched alkyl group having 1 to 12 carbon atoms, and carbon atom number 1. ~ 12 linear or branched alkoxy groups, linear or branched hydroxyalkyl groups with 1 to 12 carbon atoms, linear or branched ketone groups with 1 to 12 carbon atoms, carbon atoms Represents an aryl group having 6 to 20, an aryl ether group having 6 to 20 carbon atoms, an aryl thioether group having 6 to 20 carbon atoms, or an aryl ketone group having 6 to 20 carbon atoms.
In the aryl group, the aryl ether group, the aryl thio ether group, and the aryl ketone group represented by R ^{1 to} R ³ , one or two or more hydrogen atoms in the aromatic ring are hydroxyl groups, halogen groups, or nitro. Groups, carboxyl groups, linear or branched alkyl groups with 1 to 12 carbon atoms, linear or branched alkoxy groups with 1 to 12 carbon atoms, linear or branched with 1 to 12 carbon atoms Branched chain hydroxyalkyl groups, aryl groups with 6 to 20 carbon atoms, aryl ether groups with 6 to 20 carbon atoms, aryl thioether groups with 6 to 20 carbon atoms, or aryl ketone groups with 6 to 20 carbon atoms. May have been replaced
The alkyl group or alkoxy group represented by R ^{1 to} R ³ which may substitute the aryl group, the aryl ether group, the aryl thioether group and the aryl ketone group is the substituted aryl group, the aryl. It may be bonded to the aromatic ring of the ether group, the arylthio ether group and the arylketone group to form a fused ring of a 5- or 6-membered ring.
R ^{4 to} R ⁷ independently have a hydrogen atom, a hydroxyl group, a halogen group, a nitro group, a carboxyl group, a linear or branched alkyl group having 1 to 12 carbon atoms, and a direct chain having 1 to 12 carbon atoms. It represents a chain-like or branched-chain alkoxy group, a linear or branched-chain hydroxyalkyl group having 1 to 12 carbon atoms, or a linear or branched-chain ketone group having 1 to 12 carbon atoms. )

(In the formula, R ^{8 to} R ¹¹ each independently represent a substituted phenyl group, and 1 to 5 of the five hydrogen atoms in the aromatic ring of the phenyl group are substituted with a fluorine atom. The hydrogen atom not substituted with a fluorine atom in the phenyl group is a hydroxyl group, a halogen group other than fluorine, a linear or branched alkyl group having 1 to 12 carbon atoms, or a linear chain having 1 to 12 carbon atoms. It may be substituted with a linear or branched alkoxy group, a linear or branched hydroxyalkyl group having 1 to 12 carbon atoms, or a linear or branched hydroxyl group having 1 to 12 carbon atoms. is there.)

Further, in the present invention, the cationically polymerizable component (A) is one or more selected from the aromatic polyfunctional epoxy compound (A1), or one selected from the aliphatic epoxy compound (A2). Or, it contains two or more kinds and one or two or more kinds selected from the alicyclic epoxy compound (C).
The alicyclic epoxy compound (C) has one or more cyclohexene oxide groups and one or both cyclopentene oxide groups in the molecule in total, and has an ethylene oxide structure in total of two or more in the molecule. Contains one or more selected from the group consisting of compounds having
The cationically polymerizable component (A) is such that the alicyclic epoxy compound (C) is 0. 0 parts by mass of the total of the aromatic polyfunctional epoxy compound (A1) and the aliphatic epoxy compound (A2). It has been found that a curable composition and a cured product thereof containing 5 to 35 parts by mass solves the above-mentioned problems and obtains a higher effect on toughness.

By using the curable composition of the present invention, it is possible to provide a cationically curable adhesive having high toughness and adhesive strength of the cured product and excellent moisture resistance and durability.

Hereinafter, the curable composition of the present invention will be described in detail.

In the present invention, the aromatic polyfunctional epoxy compound (A1) and the aliphatic epoxy compound (A2), which are constituents of the cationically polymerizable component (A), are irradiated with active energy rays or irradiated with active energy rays. A specific epoxy compound that undergoes a polymerization or cross-linking reaction by action with a cationic polymerization initiator (B) activated by heating.

In the present invention, the aromatic polyfunctional epoxy compound (A1) is a compound having an aromatic ring in its unit structure and further having two or more epoxy groups in one molecule, and is used for curable compositions. It can be appropriately selected depending on the situation, and one type may be used alone, or two or more types may be used in combination in any combination.

Specific examples of the aromatic polyfunctional epoxy compound (A1) include, but are not limited to, bisphenol A diglycidyl ether, bisphenol AF diglycidyl ether, and bisphenol AP diglycidyl. Ether, bisphenol B diglycidyl ether, bisphenol BP diglycidyl ether, bisphenol C diglycidyl ether, bisphenol E diglycidyl ether, bisphenol F diglycidyl ether, bisphenol G diglycidyl ether, bisphenol M diglycidyl ether, bisphenol S diglycidyl ether, Bisphenol compounds such as bisphenol P diglycidyl ether, bisphenol PH diglycidyl ether, bisphenol TMC diglycidyl ether, bisphenol Z diglycidyl ether, 4,4'-oxydiphenol diglycidyl ether, 4,4'-biphenol diglycidyl ether, etc. An epoxy compound obtained by glycidyl etherification of the above, an epoxy compound obtained by glycidyl etherification of the hydroxyl group of a compound obtained by further adding an alkylene oxide to a bisphenol compound, and these epoxy compounds and bisphenol A, bisphenol E, bisphenol F, bisphenol S, biphenol. Epoxy compounds obtained by copolymerizing bisphenol compounds such as bisphenol compounds (hereinafter collectively referred to as bisphenol type epoxy compounds); novolak type epoxy compounds obtained by polymerizing phenols and hydroxybenzaldehydes and converting them into glycidyl ether; resorcinol diglycidyl ether, hydroquinone di Glycidyl ether, catechol diglycidyl ether, 1,6-diglycidyloxynaphthalene, 2,2', 7,7'-tetraglycidyloxy-1,1'-binaphthalene, 4,4', 4''-trishydroxytri An epoxy compound obtained by converting the hydroxyl groups of an aromatic compound having two or more phenolic hydroxyl groups into glycidyl ether, such as phenylmethane triglycidyl ether; phenyldimethanol diglycidyl ether, phenyldiethanol diglycidyl ether, and phenyldibutanol diglycidyl ether. An epoxy compound obtained by glycidyl etherification of the hydroxyl group of an aromatic compound having two or more alcoholic hydroxyl groups, such as; phthalic acid diglycidyl ester, terephthalic acid diglycidyl ester. , Trimeritic acid triglycidyl ester, etc., a glycidyl ester compound obtained by glycidyl esterifying a carboxylic acid of a polybasic acid aromatic compound having two or more carboxylic acids; 1,3-divinylbenzenedioxide, 1,4- Examples thereof include an epoxy compound obtained by oxidizing a vinyl group of an aromatic compound having two or more vinyl groups such as divinylbenzene dioxide.

Commercially available products can be used as the aromatic polyfunctional epoxy compound (A1). For example, Denacol EX-121, Denacol EX-145, Denacol EX-146, Denacol EX-201, Denacol EX-711, Denacol EX. -721, on-coat EX-1020, on-coat EX-1030, on-coat EX-1040, on-coat EX-1050, on-coat EX-1051, on-coat EX-1010, on-coat EX-1011, on-coat 1012 (Nagase) Chemtex); Ogsol PG-100, Ogsol EG-200, Ogsol EG-210, Ogsol EG-250 (Osaka Gas Chemical); Epicron 830, Epicron 840, Epicron HP-4032, Epicron HP-4032D, Epicron HP-4700, Epicron N-665, Epicron N-770, Epicron HP-7200 (manufactured by DIC); Epototo YD-128, Epototo YD-6020, YDF-170, YDPN-638, YDCN-700-5, YH- 434, YD-172, YDC-1312, YSLV-80XY, YSLV-120TE, YP-50S, YP-70, FX-316, YPS-007A30, ESN-475V (manufactured by Nippon Steel & Sumitomo Metal Corporation); jER828, jER1001, jER806 , JER154, jER157S70, jER1031S, jERYX4000, jERYX8800 (manufactured by Mitsubishi Chemical Co., Ltd.); Marproof G-0105SA, Marproof G-0130SP (manufactured by Nippon Oil Co., Ltd.); RE-303S-L, RE-310S, EOCN-1020, EOCN -102S, EOCN-103S, EOCN-104S, XD-1000, NC-2000-L, NC-3000, EPPN-201, EPPN-501H, EPPN-501HY, EPPN-502H, NC-7000L (manufactured by Nippon Kayaku Co., Ltd.) ); Adecaredin EP-4000, Adecaledin EP-4005, Adecaledin EP-4100, Adecaledin EP-4901 (manufactured by ADEKA); TECHMORE VG-3101L (manufactured by Printec) and the like.

In the present invention, as the aromatic polyfunctional epoxy compound (A1), a bisphenol type epoxy compound is preferable, and a bisphenol A type epoxy compound is more preferable, in terms of high adhesive strength and high moisture resistance and durability. Further, a bisphenol type epoxy compound and a novolak type epoxy compound are preferable, and a bisphenol A type epoxy compound and a novolac type epoxy compound are more preferable, in terms of high toughness of the cured product and high moisture resistance durability.

In the present invention, the aliphatic epoxy compound (A2) is an aliphatic epoxy compound having a specific structure and does not contain the alicyclic epoxy (C) and the aromatic ring described below. One or more selected from the group consisting of the alicyclic glycidyl ether compound represented by the general formula (I) and the hydrogenated bisphenol type epoxy compound obtained by hydrogenating the aromatic ring of the bisphenol type epoxy compound. It refers to the aliphatic epoxy compound contained, and can be appropriately selected depending on the use of the curable composition, and one type may be used alone or two or more types may be used in combination in any combination.

In the alicyclic glycidyl ether compound represented by the general formula (I), the aliphatic hydrocarbon group having 3 to 14 carbon atoms having an alicyclic structure represented by X and having 3 to 6 carbon atoms is used. For example, cyclopropane, cyclopentane, cyclohexane, cycloheptan, cyclooctane, cyclononane, cyclodecane, cycloundecane, cyclododecane, methylcyclopropane, ethylcyclopropane, 2,2-dimethylcyclopropane, 1,1,2,2-tetra Methylcyclopropane, 1,3-dimethylcyclopentane, ethylcyclopentane, isopropylcyclopentane, pentylcyclopentane, methylcyclohexane, ethylcyclohexane, 1-ethyl-2methylcyclohexane, 1-ethyl-3methylcyclohexane, 1-ethyl- 4 Methylcyclohexane, 1,3-dimethylcyclohexane, 1,2-diethylcyclohexane, 1,3-diethylcyclohexane, 1,4-dimethylcyclohexane, propylcyclohexane, isopropylcyclohexane, butylcyclohexane, isobutylcyclohexane, tert-butylcyclohexane, hexyl Cyclohexane, heptylcyclohexane, octylcyclohexane, 1-isopropyl-4-methylcyclohexane, 1,3,5-trimethylcyclohexane, 1,2,3-trimethylcyclohexane, 1,2,4-trimethylcyclohexane, 1,1,3- Examples thereof include trimethylcyclohexane, 1,1,4-trimethylcyclohexane and 1,1,3,5-tetramethylcyclohexane.
Further, in the alicyclic glycidyl ether compound represented by the general formula (I), the alicyclic structure having 3 to 6 carbon atoms represented by X has a structure in which 2 or 3 alicyclic structures are condensed and has 3 to 3 carbon atoms. Examples of the 14 aliphatic hydrocarbon groups include bicyclo [2.2.1] heptane, bicyclo [3.2.0] heptane, bicyclo [4.1.0] heptane, and bicyclo [4.3.0] nonane. , Dodecahydrofluorene, tetrahydrodicyclopentadiene, tricyclo [5.2.1.0 ^2,6 ] decane, tricyclo [6.2.1.0 ^2,7 ] undecane, tetracyclo [6.2.1.1. ^3,6 . 0 ^2,7 ] Dodecane, noradadamantane, adamantane, 1,3-dimethyladamantane, 1-ethyladamantane, 2-ethyladamantane, 1,3,5-trimethyladamantane, decahydronaphthalene, diamantane and the like can be mentioned.

Specific examples of the alicyclic glycidyl ether compound represented by the general formula (I) in the aliphatic epoxy compound (A2) are described below, and are not limited to, but are representative compounds. As a glycidyl ether compound of an aliphatic condensed ring compound such as dicyclopentadiene dimethanol diglycidyl ether, adamantan dimethanol diglycidyl ether; 1,2-bis (glycidyloxy) cyclohexane, 1,3-bis (glycidyloxy). Of aromatic compounds having two or more phenolic hydroxyl groups, such as cyclohexane, 1,4-bis (glycidyloxy) cyclohexane, 1,4-bis (glycidyloxy) decalin, 1,6-bis (glycidyloxy) decalin, etc. An alicyclic epoxy compound having a structure obtained by hydrogenating a glycidyl ether compound; 2 alcoholic hydroxyl groups such as 1,4-bis (glycidyloxymethyl) cyclohexane and 1,4-bis (glycidyloxybutyl) cyclohexane. An epoxy compound having a structure obtained by hydrogenating an aromatic compound glycidyl ether compound having one or more; 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 1,4-cyclohexanedicarboxylic acid diglycidyl ester, 1,3,5 Examples thereof include alicyclic glycidyl ester compounds such as -cyclohexane tricarboxylic acid triglycidyl ester.

In the above aliphatic epoxy compound (A2), specific examples of the hydrogenated bisphenol type epoxy compound are described below, and the hydrogenated bisphenol A diglycidyl ether and the hydrogenated bisphenol AF diglycidyl are not limited thereto. Ether, hydrogenated bisphenol B diglycidyl ether, hydrogenated bisphenol C diglycidyl ether, hydrogenated bisphenol E diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol G diglycidyl ether, hydrogenated bisphenol M diglycidyl ether, Hydrogenated bisphenol S diglycidyl ether, hydrogenated bisphenol P diglycidyl ether, hydrogenated bisphenol TMC diglycidyl ether, hydrogenated bisphenol Z diglycidyl ether, bis [4- (glycidyloxy) cyclohexyl] ether, 4,4'-bicyclo Hexanol diglycidyl ether and the like can be mentioned.

As the aliphatic epoxy compound (A2), a commercially available product can be used, for example, Denacol EX-252 (manufactured by Nagase ChemteX Corporation); Epolite 4000 (manufactured by Kyoeisha Chemical Co., Ltd.); jERYX-8034 (manufactured by Mitsubishi Chemical Co., Ltd.). ); ST-3000 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.); Adeka Resin EP-4080S, Adeka Resin EP-4085S, Adeka Resin EP-4088S (manufactured by ADEKA), and the like.

In the present invention, the aliphatic epoxy compound (A2) is selected from one or more selected from the group consisting of the following compounds (IVa), (IVb) and hydrogenated bisphenol type epoxy compounds in terms of high adhesive strength. It is preferable to contain it.

In the present invention, as the aliphatic epoxy compound (A2), the glycidyl ether compound of the aliphatic condensed ring compound and the glycidyl ether compound of the aromatic compound having two or more alcoholic hydroxyl groups are hydrogenated because of the high adhesive strength. The epoxy compound having the structure obtained above and the hydrogenated bisphenol type epoxy compound are preferable, and dicyclopentadiene dimethanol diglycidyl ether, 1,4-bis (glycidyloxymethyl) cyclohexane, and hydrogenated bisphenol A type epoxy compound are preferable. More preferred. Further, in terms of high moisture resistance and durability, an epoxy compound having a structure obtained by hydrogenating an aliphatic condensed ring compound glycidyl ether compound, an aromatic compound glycidyl ether compound having two or more alcoholic hydroxyl groups, and an epoxy compound. Hydrogenated bisphenol type epoxy compounds are preferred, dicyclopentadiene dimethanol diglycidyl ether, 1,4-bis (glycidyloxymethyl) cyclohexane, and hydrogenated bisphenol A type epoxy are more preferred, and hydrogenated bisphenol A type epoxy is further preferred. preferable.

In the present invention, the cationically polymerizable component (A) has a mass ratio of the aromatic polyfunctional epoxy compound (A1) and the aliphatic epoxy compound (A2) to be high in toughness and adhesive strength, and has good moisture resistance and durability. In that respect, the former: the latter is preferably in the range of 10:90 to 50:50 and preferably in the range of 10:90 to 40:60. Further, the cationically polymerizable component (A) has a mass ratio of the aromatic polyfunctional epoxy compound (A1) and the aliphatic epoxy compound (A2) to be high in toughness and adhesive strength. : 90 to 40:60 is preferable, and 20:80 to 30:70 is more preferable. Further, the cationically polymerizable component (A) is the former: the latter in that the mass ratio of the aromatic polyfunctional epoxy compound (A1) and the aliphatic epoxy compound (A2) is high in adhesive strength and moisture resistance durability. The range is preferably in the range of 10:90 to 40:60, more preferably in the range of 20:80 to 40:60.

Further, the content of the cationically polymerizable component (A) in the curable composition of the present invention is high in toughness and adhesive strength, and has good moisture resistance and durability. The total mass of the functional epoxy compound (A1) and the aliphatic epoxy compound (A2) is preferably 10 to 99.9% by mass, more preferably 30 to 99.9% by mass, and 50 to 99. It is more preferably 9% by mass.

In the present invention, the cationic polymerization initiator (B) refers to a specific compound capable of releasing a substance that initiates cationic polymerization by irradiation or heating with active energy rays, and more specifically, of the active energy rays. A sulfonium borate salt composed of a combination of a specific sulfonium cation and a specific borate anion that releases Lewis acid by irradiation or irradiation and heating with active energy rays, and can be appropriately selected depending on the use of the curable composition. Yes, one type may be used alone, or two or more types may be used in combination in any combination.

In the present invention, the structure of the sulfonium cation can be represented by the following general formula (IIa) or general formula (IIb).

(In the formula, R ^{1 to} R ³ are independently hydrogen atom, hydroxyl group, halogen group, nitro group, carboxyl group, linear or branched alkyl group having 1 to 12 carbon atoms, and carbon atom number 1. ~ 12 linear or branched alkoxy groups, linear or branched hydroxyalkyl groups with 1 to 12 carbon atoms, linear or branched ketone groups with 1 to 12 carbon atoms, carbon atoms Represents an aryl group having 6 to 20, an aryl ether group having 6 to 20 carbon atoms, an aryl thioether group having 6 to 20 carbon atoms, or an aryl ketone group having 6 to 20 carbon atoms.
In the aryl group, the aryl ether group, the aryl thio ether group, and the aryl ketone group represented by R ^{1 to} R ³ , one or two or more hydrogen atoms in the aromatic ring are hydroxyl groups, halogen groups, or nitro. Groups, carboxyl groups, linear or branched alkyl groups with 1 to 12 carbon atoms, linear or branched alkoxy groups with 1 to 12 carbon atoms, linear or branched with 1 to 12 carbon atoms Branched chain hydroxyalkyl groups, aryl groups with 6 to 20 carbon atoms, aryl ether groups with 6 to 20 carbon atoms, aryl thioether groups with 6 to 20 carbon atoms, or aryl ketone groups with 6 to 20 carbon atoms. May have been replaced
The alkyl group or alkoxy group represented by R ^{1 to} R ³ which may substitute the aryl group, the aryl ether group, the aryl thioether group and the aryl ketone group is the substituted aryl group, the aryl. It may be bonded to the aromatic ring of the ether group, the arylthio ether group and the arylketone group to form a fused ring of a 5- or 6-membered ring.
R ^{4 to} R ⁷ independently have a hydrogen atom, a hydroxyl group, a halogen group, a nitro group, a carboxyl group, a linear or branched alkyl group having 1 to 12 carbon atoms, and a direct chain having 1 to 12 carbon atoms. It represents a chain-like or branched-chain alkoxy group, a linear or branched-chain hydroxyalkyl group having 1 to 12 carbon atoms, or a linear or branched-chain ketone group having 1 to 12 carbon atoms. )

Further, in the present invention, the borate anion can be represented by the following general formula (III).

(In the formula, R ^{8 to} R ¹¹ each independently represent a substituted phenyl group, and 1 to 5 of the five hydrogen atoms in the aromatic ring of the phenyl group are substituted with a fluorine atom. The hydrogen atom not substituted with a fluorine atom in the phenyl group is a hydroxyl group, a halogen group other than fluorine, a linear or branched alkyl group having 1 to 12 carbon atoms, or a linear chain having 1 to 12 carbon atoms. It may be substituted with a linear or branched alkoxy group, a linear or branched hydroxyalkyl group having 1 to 12 carbon atoms, or a linear or branched hydroxyl group having 1 to 12 carbon atoms. is there.)

Examples of the halogen group represented by R ^{1 to} R ⁷ include fluorine, chlorine, bromine and iodine.

Examples of the linear or branched alkyl group having 1 to 12 carbon atoms represented by R ^{1 to} R ⁷ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, and tertiary butyl. Examples thereof include linear or branched alkyl groups such as amyl, isoamyl, tertiary amyl, hexyl, heptyl, n-octyl, isooctyl, tertiary octyl, 2-ethylhexyl, nonyl, isononyl, decyl, undecyl and dodecyl.

Examples of the linear or branched alkoxy group having 1 to 12 carbon atoms represented by R ^{1 to} R ⁷ include methoxy, ethoxy, propoxy, isopropoxy, butoxy, secondary butyloxy, tertiary butyloxy, isobutoxy and amyloxy. , Third amyloxy, hexyloxy, cyclohexyloxy, octyloxy, tertiary octyloxy, benzyloxy, α-methylbenzyloxy, α, α-dimethylbenzyloxy and the like.

The linear or branched hydroxyalkyl group having 1 to 12 carbon atoms represented by R ^{1 to} R ⁷ is a hydroxy group substitution of the linear or branched alkyl group having 1 to 12 carbon atoms. Examples thereof include hydroxy group substituents of the above alkyl groups such as hydroxyethyl, 2-hydroxypropyl and 3-hydroxypropyl.

The linear or branched alkyl group having 1 to 12 carbon atoms represented by R ^{1 to} R ⁷ includes the linear or branched alkyl group having 1 to 12 carbon atoms and having the number of carbon atoms. Examples thereof include a group having a structure in which any one of the linear or branched alkyl groups 1 to 11 is substituted with a carbonyl group, and specific examples thereof include a methanoyl group, an ethanoyl group, a propanoyl group, and an isopropa. Noyl group, butanoyl group, isobutanoyl group, second butanoyl group, third butanoyl group, pentanoyl group, second pentanoyl group, third pentanoyl group, hexanoyl group, heptanoil group, octanoyl group, second octanoyl group, third octanoyl group , 2-Ethylhexanoyl group, nonanoyl group, isononanoyl group, decanoyl group, undecanoyl group and the like.

Examples of the aryl group having 6 to 20 carbon atoms represented by R ^{1 to} R ³ include phenyl, naphthyl, anthracenyl, phenanthryl, fluorenyl, indenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl and 4-. Vinylphenyl, 3-iso-propylphenyl, 4-iso-propylphenyl, 4-butylphenyl, 4-iso-butylphenyl, 4-tert-butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl , 4- (2-ethylhexyl) phenyl, 4-stearylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-Dimethylphenyl, 2,4-di-tert-butylphenyl, 2,5-di-tert-butylphenyl, 2,6-di-tert-butylphenyl, 2,4-di-tert-pentylphenyl , 2,5-Di-tert-amylphenyl, 2,5-di-tert-octylphenyl, 2,4-dikmylphenyl, 4-cyclohexylphenyl, (1,1'-biphenyl) -4-yl, 2 , 4,5-trimethylphenyl, ferrocenyl and the like.

The aryl ether group having 6 to 20 carbon atoms represented by R ^{1 to} R ³ is a group having a structure in which any one of the aryl groups having 6 to 20 carbon atoms is replaced with an oxygen atom. Specifically, phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 1-anthranyloxy group, 1-phenanthrenyloxy group, 9-fluorenyloxy group, 1-inde. Nyloxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 4-vinylphenoxy group, 3-iso-propylphenoxy group, 4-iso-propylphenoxy group, 4-butylphenoxy group, 4-iso-butylphenoxy group, 4-tert-butylphenoxy group, 4-hexylphenoxy group, 4-cyclohexylphenoxy group, 4-octylphenoxy group, 4- (2-ethylhexyl) phenoxy group, 4-stearylphenoxy group, 2,3-Dimethylphenoxy group, 2,4-dimethylphenoxy group, 2,5-dimethylphenoxy group, 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2, 4-Di-tert-butylphenoxy group, 2,5-di-tert-butylphenoxy group, 2,6-di-tert-butylphenoxy group, 2,4-di-tert-pentylphenoxy group, 2,5- Di-tert-amylphenoxy group, 2,5-di-tert-octylphenoxy group, 2,4-dikmylphenoxy group, 4-cyclohexylphenoxy group, (1,1'-biphenyl) -4-yl, 2, Examples thereof include a 4,5-trimethylphenoxy group and a ferroceniroxy group.

Examples of the arylthio ether group having 6 to 20 carbon atoms represented by R ^{1 to} R ³ include a sulfur atom substitution product of the oxygen atom of the aryl ether group having 6 to 20 carbon atoms, and specifically, phenylthio. Group, 1-naphthylthio group, 2-naphthylthio group, 1-anthranylthio group, 1-phenanthrenylthio group, 9-fluorenylthio group, 1-indenylthio group, 2-methylphenylthio group, 3-methylphenylthio group, 4-Methylphenylthio group, 4-vinylphenylthio group, 3-iso-propylphenylthio group, 4-iso-propylphenylthio group, 4-butylphenylthio group, 4-iso-butylphenylthio group, 4- tert-Butylphenylthio group, 4-hexylphenylthio group, 4-cyclohexylphenylthio group, 4-octylphenylthio group, 4- (2-ethylhexyl) phenylthio group, 4-stearylphenylthio group, 2,3-dimethyl Phenylthio group, 2,4-dimethylphenylthio group, 2,5-dimethylphenylthio group, 2,6-dimethylphenylthio group, 3,4-dimethylphenylthio group, 3,5-dimethylphenylthio group, 2 , 4-di-tert-butylphenylthio group, 2,5-di-tert-butylphenylthio group, 2,6-di-tert-butylphenylthio group, 2,4-di-tert-pentylphenylthio group , 2,5-di-tert-amylphenylthio group, 2,5-di-tert-octylphenylthio group, 2,4-dicumylphenylthio group, 4-cyclohexylphenylthio group, (1,1'- Biphenyl) -4-yl, 2,4,5-trimethylphenylthio group, ferrosenylthio group and the like.

As the aryl ketone group having 6 to 20 carbon atoms represented by R ^{1 to} R ³ , the carbonyl of the oxygen atom of the aryl ether group having 6 to 19 carbon atoms among the above-mentioned aryl ether groups having 6 to 20 carbon atoms. Examples thereof include benzoyl groups, 1-naphthoyl groups, 2-naphthoyl groups, 1-anthranilloyl groups, 1-phenanthrenoyl groups, 9-fluorenoyl groups, 1-indenoyl groups, 2-. Methylbenzoyl group, 3-methylbenzoyl group, 4-methylbenzoyl group, 4-vinylbenzoyl group, 3-iso-propylbenzoyl group, 4-iso-propylbenzoyl group, 4-butylbenzoyl group, 4-iso-butylbenzoyl group Group, 4-tert-butylbenzoyl group, 4-hexylbenzoyl group, 4-cyclohexylbenzoyl group, 4-octylbenzoyl group, 4- (2-ethylhexyl) benzoyl group, 4-stearylbenzoyl group, 2,3-dimethylbenzoyl group Group, 2,4-dimethylbenzoyl group, 2,5-dimethylbenzoyl group, 2,6-dimethylbenzoyl group, 3,4-dimethylbenzoyl group, 3,5-dimethylbenzoyl group, 2,4-di-tert- Butylbenzoyl group, 2,5-di-tert-butylbenzoyl group, 2,6-di-tert-butylbenzoyl group, 2,4-di-tert-pentylbenzoyl group, 2,5-di-tert-amylbenzoyl Group, 2,5-di-tert-octylbenzoyl group, 2,4-dicumylbenzoyl group, 4-cyclohexylbenzoyl group, (1,1'-biphenyl) -4-yl, 2,4,5-trimethylbenzoyl Examples include groups and ferrocenoyl groups.

Halogen groups, linear or branched alkyl groups having 1 to 12 carbon atoms, which may substitute aryl groups, aryl ether groups, aryl thioether groups and aryl ketone groups represented by R ^{1 to} R ³ . Linear or branched alkoxy groups with 1 to 12 carbon atoms, linear or branched hydroxyalkyl groups with 1 to 12 carbon atoms, aryl groups with 6 to 20 carbon atoms, 6 to 6 carbon atoms Examples of the 20 aryl ether group, the aryl thioether group having 6 to 20 carbon atoms, and the aryl ketone group having 6 to 20 carbon atoms include those described above.

The aryl group, the aryl ether group, the aryl group represented by R ^{1 to} R ³ in which the alkyl group or alkoxy group that may substitute the aryl group, the aryl ether group, the aryl thioether group and the aryl ketone group is substituted. Examples of the fused ring of the 5- or 6-membered ring formed by bonding the arylthio ether group and the aromatic ring of the arylketone group include a cyclopentane ring, an oxacyclopentane ring, a thiacyclopentane ring, a cyclopentanone ring, and a cyclohexane ring. Examples thereof include an oxacyclohexane ring, a thiacyclohexane ring, and a cyclohexanone ring.

A halogen group represented by R ^{8 to} R ¹¹ that may replace the substituted phenyl group, a linear or branched alkyl group having 1 to 12 carbon atoms, and a direct chain having 1 to 12 carbon atoms. The chain-like or branched-chain alkoxy group, the linear or branched-chain hydroxyalkyl group having 1 to 12 carbon atoms, or the linear or branched-chain ketone group having 1 to 12 carbon atoms are described above. Things can be mentioned.

Specific examples of the borate anion of the above general formula (III) are described below, and the representative compounds include, but are not limited to, tetrakis (pentafluorophenyl) borate and tetra (3,5-difluoro-). 4-Methoxyphenyl) borate and the like can be mentioned.

In the present invention, borate anions are tetrakis (pentafluorophenyl) borate and tetra (3,5-difluoro-4-) in that the cured product has high toughness, high adhesive strength, and high moisture resistance. Phenyl) borate is preferred, and tetrakis (pentafluorophenyl) borate is more preferred.

Further, in the present invention, one kind of sulfonium borate salt represented by the following general formula (V) can be used alone or in terms of high toughness of the cured product, high adhesive strength, and high moisture resistance and durability. It is more effective to use two or more types in combination in terms of high toughness of the cured product, high adhesive strength, and high moisture resistance and durability.

(In the formula, R ^{12 to} R ¹⁷ are each independently a hydrogen atom, a hydroxyl group, a halogen group, a nitro group, a carboxyl group, a linear or branched alkyl group having 1 to 12 carbon atoms, and 1 carbon atom. Represents a linear or branched alkoxy group of ~ 12, a linear or branched hydroxyalkyl group having 1 to 12 carbon atoms, or a linear or branched ketone group having 1 to 12 carbon atoms. ,
R ¹⁸ is a hydrogen atom, a hydroxyl group, a halogen group, a nitro group, a carboxyl group, a linear or branched alkyl group having 1 to 12 carbon atoms, and a linear or branched alkoxy having 1 to 12 carbon atoms. Group, linear or branched hydroxyalkyl group with 1 to 12 carbon atoms, linear or branched ketone group with 1 to 12 carbon atoms, aryl group with 6 to 20 carbon atoms, number of carbon atoms Represents an aryl ether group of 6 to 20, an aryl thioether group of 6 to 20 carbon atoms, or an aryl ketone group of 6 to 20 carbon atoms.
Represented by R ^18, the aryl group, the aryl ether group, the thioether group and the aryl ketone group, one of the hydrogen atoms of the aromatic ring or two or more, a hydroxyl group, a halogen group, a nitro group , Carboxyl group, linear or branched alkyl group with 1 to 12 carbon atoms, linear or branched alkoxy group with 1 to 12 carbon atoms, linear or branched with 1 to 12 carbon atoms A chain hydroxyalkyl group, an aryl group having 6 to 20 carbon atoms, an aryl ether group having 6 to 20 carbon atoms, an aryl thioether group having 6 to 20 carbon atoms, or an aryl ketone group having 6 to 20 carbon atoms. May have been replaced
Represented by R ^18, the aryl group, the aryl ether group, the thioether group, and an aryl group which may be substituted with the aryl ketone group, an aryl ether group, aryl thioether group, and aryl ketone groups are substituted It may be bonded to an aryl group, an aryl ether group, an aryl thioether group, and an aromatic ring of an aryl ketone to form a fused ring of a 5- or 6-membered ring. )

Examples of the halogen group represented by R ^{12 to} R ¹⁸ include the same halogen groups exemplified as the halogen group represented by R ^{1 to} R ⁷ .
The linear or branched chain alkyl group having 1 to 12 carbon atoms represented by R ^{12 to} R ¹⁸ is a linear or branched chain having 1 to 12 carbon atoms represented by R ^{1 to} R ^7. The same as those exemplified as the state alkyl group can be mentioned.
The linear or branched alkoxy group having 1 to 12 carbon atoms represented by R ^{12 to} R ¹⁸ is a linear or branched chain having 1 to 12 carbon atoms represented by R ^{1 to} R ^7. The same ones as exemplified as the state alkoxy group can be mentioned.
As the linear or branched hydroxyalkyl group having 1 to 12 carbon atoms represented by R ^{12 to} R ¹⁸ , the linear or branched having 1 to 12 carbon atoms represented by R ^{1 to} R ⁷ is used. Examples thereof include the same chain hydroxyalkyl groups as those exemplified.
The linear or branched chain ketone group having 1 to 12 carbon atoms represented by R ^{12 to} R ¹⁸ is a linear or branched chain having 1 to 12 carbon atoms represented by R ^{1 to} R ^7. The same as those exemplified as the state ketone group can be mentioned.
Examples of the aryl group having 6 to 20 carbon atoms represented by R ¹⁸ include the same aryl groups represented by R ^{1 to} R ³ having 6 to 20 carbon atoms.
Examples of the aryl ether group having 6 to 20 carbon atoms represented by R ¹⁸ include the same as those exemplified as the aryl ether group having 6 to 20 carbon atoms represented by R ^{1 to} R ³ .
The aryl thioether group having 6 to 20 carbon atoms represented by R ^18, include the same as those exemplified as the arylthio ether group having 6 to 20 carbon atoms represented by R ¹ to R ^3.
Examples of the aryl ketone group having 6 to 20 carbon atoms represented by R ¹⁸ include the same aryl ketone groups represented by R ^{1 to} R ³ having 6 to 20 carbon atoms.

Represented by R ^18, an aryl group, an aryl ether group, aryl thioether group, and an aryl group which may be substituted an aryl ketone group, an aryl ether group, aryl thioether group, and an aryl ketone group, an aryl group substituted , Aryl ether group, aryl thioether group, and 5 or 6-membered fused ring formed by bonding with the aromatic ring of aryl ketone include cyclopentane ring, oxacyclopentane ring, thiacyclopentane ring, cyclopentanone ring, and the like. Cyclohexane ring, oxacyclohexane ring, thiacyclohexane ring, cyclohexanone ring can be mentioned.

An aryl group represented by R ¹⁸ , an aryl ether group, an aryl thio ether group, and an aryl ketone group may be substituted, a halogen group, a linear or branched alkyl group having 1 to 12 carbon atoms, and a number of carbon atoms. 1-12 linear or branched alkoxy groups, 1-12 linear or branched hydroxyalkyl groups with 1-12 carbon atoms, aryl groups with 6-20 carbon atoms, aryls with 6-20 carbon atoms Examples of the ether group, the arylthio ether group having 6 to 20 carbon atoms, and the arylketone group having 6 to 20 carbon atoms are the same as those represented by R ^{1 to} R ³ , respectively.

Further, in the present invention, as the above-mentioned cationic polymerization initiator (B), one kind of a sulfonium borate salt composed of a combination of a sulfonium cation selected from the following group I or group II and a tetrakis (pentafluorophenyl) borate anion is used alone. Alternatively, it is more effective to use two or more kinds in combination in terms of high toughness of the cured product, high adhesive strength, and high moisture resistance and durability.

In the present invention, the content of the cationic polymerization initiator (B) is 100 parts by mass of the cationic polymerization component (A) in that the cured product has high toughness, high adhesive strength, and high moisture resistance durability. On the other hand, the cationic polymerization initiator (B) is preferably contained in an amount of 0.001 to 15 parts by mass, more preferably 0.1 to 10 parts by mass. If it is too small, curing tends to be insufficient, and if it is too large, it may adversely affect various physical properties such as the water absorption rate of the cured product and the strength of the cured product.

Further, in the present invention, the cationically polymerizable component (A) further contains an alicyclic epoxy compound (C) in addition to the aromatic polyfunctional epoxy compound (A1) and the aliphatic epoxy compound (A2). May be good.

In the present invention, the alicyclic epoxy compound (C) does not contain an aromatic ring, has one or both of a cyclohexene oxide group and a cyclopentene oxide group in the molecule, and has a total of one or two or more in the molecule, and ethylene. A cationic polymerization initiator (containing one or more selected from compounds having a total of two or more oxide structures in the molecule and activated by irradiation with active energy rays or irradiation and heating with active energy rays). It is a compound that causes a polymerization or cross-linking reaction by the action with B).

The cyclohexene oxide group and the cyclopentene oxide group refer to epoxy groups represented by the following chemical formulas (Va) and (Vb), respectively.

The alicyclic epoxy compound (C) can be appropriately selected depending on the intended use of the curable composition, and one type may be used alone or two or more types may be used in combination in any combination.

Specific examples of the alicyclic epoxy compound (C) are described below, and are not limited to, for example, 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, 3,4-epoxy-6-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), propane-2,2-diyl-bis (3,4-epoxycyclohexane), 2, , 2-bis (3,4-epoxycyclohexyl) propane, dicyclopentadiene diepoxyside, ethylenebis (3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate , 1-Epoxyethyl-3,4-Epoxycyclohexane, 1,2-Epoxy-2-epoxyethylcyclohexane, α-pinenooxide, limonendioxide and the like.

As the alicyclic epoxy compound (C), a commercially available product can be used, which is described below and is not limited to this. For example, celoxide 2021P, celoxide 2081, celoxide 2000, celoxide 3000 (Daicel). (Manufactured by the company); Limonene dioxide (manufactured by Tomoe Engineering Co., Ltd.) and the like.

In the present invention, the alicyclic epoxy compound (C) includes 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and 3,4-epoxy in terms of high toughness and high moisture resistance. -1-Methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate or 2,2-bis (3,4-epoxycyclohexyl) propane is preferred, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane Carboxylate or 2,2-bis (3,4-epoxycyclohexyl) propane is more preferred.

In the present invention, the content of the alicyclic epoxy compound (C) is high in toughness and excellent in moisture resistance and durability, and in the cationically polymerizable component (A), the aromatic polyfunctional epoxy compound (A1) and The alicyclic epoxy compound (C) is preferably contained in an amount of 0.5 to 35 parts by mass, more preferably 3 to 30 parts by mass, based on a total of 100 parts by mass of the aliphatic epoxy compound (A2). It is more preferably contained in an amount of 5 to 20 parts by mass.

Further, the curable composition of the present invention contains, if necessary, a cationically polymerizable epoxy other than the aromatic polyfunctional epoxy compound (A1), the aliphatic epoxy compound (A2) and the alicyclic epoxy compound (C). Compounds (hereinafter referred to as other epoxy compounds) (D) can be added.

In the present invention, the other epoxy compound (D) is one selected from an aromatic polyfunctional epoxy compound (A1), an aliphatic epoxy compound (A2), and an epoxy compound that does not correspond to the alicyclic epoxy compound (C). Alternatively, it is a compound consisting of two or more kinds and which causes a polymerization or cross-linking reaction by action with a cationic polymerization initiator (B) activated by irradiation with active energy rays or irradiation and heating with active energy rays. is there.
The other epoxidation products can be appropriately selected depending on the use of the curable composition, and one type may be used alone or two or more types may be used in combination in any combination.

The other epoxy compound (D) described below is not limited to this, and typical compounds include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and the like. Triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, diglycidyl ether of neopentyl glycol, etc. Polyglycidyl ether of polyhydric alcohol; Polyglycidyl ether of polyether polyol obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as propylene glycol, trimethylpropane, glycerin; aliphatic length Diglycidyl ester of chain dibasic acid; monoglycidyl ether of aliphatic higher alcohol; monoglycidyl ether of aromatic polyether alcohol obtained by adding alkylene oxide to phenol, cresol, butylphenol, and monoglycidyl ether of higher fatty acid. Examples thereof include glycidyl ester; octyl epoxy stearate, butyl epoxy stearate; epoxidized soybean oil; epoxidized polybutadiene.

As the other epoxy compound (D), a commercially available product can be used, which is described below and is not limited to, for example, Denacol EX-121, Denacol EX-171, and 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-612 , Denacol EX-614, Denacol EX-622, Denacol EX-810, Denacol EX-811, Denacol EX-850, Denacol EX-851, Denacol EX-821, Denacol EX-830, Denacol EX-832, Denacol EX-841 , Denacol EX-861, Denacol EX-911, Denacol EX-941, Denacol EX-920, Denacol EX-931 (manufactured by Nagase ChemteX); Epolite M-1230, Epolite 40E, Epolite 100E, Epolite 200E, Epolite 400E, Epolite 70P, Epolite 200P, Epolite 400P, Epolite 1500NP, Epolite 1600, Epolite 80MF, Epolite 100MF (manufactured by Kyoeisha Chemical Co., Ltd.), Adeka Glycyllol ED-503, Adeka Glycyrrol ED-503G, Adeka Glycyllol ED-506, Adeka Glycy Roll ED-523T, BF-1000, FC-3000 (manufactured by ADEKA); Epoxy PB3600, Epolide PB4700 (manufactured by Daicel); Bond First 2C, Bond First E, Bond First CG5001, Bond First CG5004, Bond First 2B, Bond First 7B, Bond First 7L, Bond First 7M, Bond First VC40 (manufactured by Sumitomo Chemical Co., Ltd.); JP-100, JP-200 (manufactured by Nippon Soda Co., Ltd.); Poly bd R-45HT, Poly bd R-15HT (Idemitsu Kosan Co., Ltd.) (Manufactured by); Ricon 657 (manufactured by Alchema Corporation) and the like.

In the present invention, the content of the other epoxy compound (D) is the aromatic polyfunctional epoxy compound (A1) and the aliphatic epoxy compound (A2) among the cationically polymerizable components (A) because of their high adhesiveness. The other epoxy compound (D) is preferably contained in an amount of 0.5 to 39.5 parts by mass, more preferably 0.5 to 35 parts by mass, and 0.5 to 35 parts by mass with respect to a total of 100 parts by mass. It is more preferable to contain 20 parts by mass. If it is too large, the toughness of the cured product will be reduced, and the moisture resistance and durability may be adversely affected.

Further, an oxetane compound can be added to the curable composition of the present invention, if necessary.

In the present invention, the oxetane compound is a molecule not contained in the aromatic polyfunctional epoxy compound (A1), the aliphatic epoxy compound (A2), the alicyclic epoxy compound (C), and other epoxy compounds (D). Initiation of cationic polymerization consisting of one or more selected from compounds having one or more oxetane groups and activated by irradiation with active energy rays or irradiation and heating with active energy rays. It is a compound that causes a polymerization or cross-linking reaction by the action with the agent (B).
The oxetane compound can be appropriately selected depending on the use of the curable composition, and one type may be used alone or two or more types may be used in combination in any combination.

The above-mentioned oxetane compounds are described below, and are not limited to these, and typical compounds include 3,7-bis (3-oxetanyl) -5-oxa-nonane and 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 glycolbis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycolbis (3-ethyl-3-oxetanylmethyl) ether, 1 , 4-Bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, 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. Can be mentioned.

As the oxetane compound, a commercially available product can be used, which is described below and is not limited to this, for example, Aron oxetane EXOH, POX, OXA, OXT-101, OXT-111, OXT-212. , OXT-221 (manufactured by Toagosei Co., Ltd.) and the like.

In the present invention, the content of the oxetane compound is 100 parts by mass in total of the aromatic polyfunctional epoxy compound (A1) and the aliphatic epoxy compound (A2) among the cationically polymerizable components (A) in that the adhesive strength is high. On the other hand, the content of the other aliphatic compound (A4) is preferably 0.5 to 39.5 parts by mass, more preferably 0.5 to 35 parts by mass, and 0.5 to 20 parts by mass. Is even more preferable. If it is too much, the toughness of the cured product will be reduced, and the moisture resistance may be adversely affected.

Further, a cationic thermal polymerization initiator (E) can be added to the curable composition of the present invention, if necessary. The cationic thermal polymerization initiator (E) may be any compound as long as it can generate cations by heat, and one or more of them may be used at the same time, and is particularly limited. Although not, it is preferable that the double salt, which is an onium salt that releases Lewis acid by heat, or a derivative thereof, has good heat resistance of the cured product obtained by curing the curable composition. Typical examples of such compounds include the following general formulas.
[X] ^{t +} [Y] ^t-
Examples of salts of cations and anions represented by.

Here, the cation [X] ^{t +} is not particularly limited, but is preferably onium that releases Lewis acid by heat, and its structure is, for example, the following general formula [(R ¹⁸ ) _a Q]. ^{t +}
Can be represented by.

Further, here, R ¹⁸ is 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. In a number of R ¹² are each independently, it may be the same or different. Further, it is preferable that at least one of a R ¹² is an organic group having an aromatic ring as described above because the resin has good curability. Q is an atom or atomic group selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F, N = N. Further, when the valence of Q in the cation [X] ^{t +} is q, it is necessary that the relationship t = a−q holds (however, N = N is treated as 0 valence).

The anion [Y] ^t- is not particularly limited, but a halide complex is preferable in that the resin has good curability, and the structure thereof is, for example, the following general formula [LZ _b ]. ^t-
Can be represented by.

Further, here, L is a metal or metalloid that is the 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. Z is a halogen atom. b is an integer of any of 3 to 7. Further, when the valence of L in the anion [Y] ^t- is p, it is necessary that the relationship t = bp is established.

Specific examples of the anion [LZ _b ] ^t- of the above general formula include tetrakis (pentafluorophenyl) borate [(C ₆ F ₅ ) ₄ B] ^- , tetrafluoroborate (BF ₄ ) ^- , and hexafluorophosphate. (PF ₆₎ ^-, hexafluoroantimonate (SbF ₆₎ ^-, hexafluoroarsenate (AsF ₆₎ ^-, hexachloroantimonate (SbCl ₆₎ ^-, and the like.

The anion [Y] ^t- is the following general formula [LZ _b-1 (OH)] ^t-
The structure represented by is also preferably used. L, Z, b, and t are the same as above. Other anions that can be used include perchlorate ion (ClO ₄ ) ^- , trifluoromethyl sulfite ion (CF ₃ SO ₃ ) ^- , fluorosulfonic acid ion (FSO ₃ ) ^- , and toluene sulfonic acid anion. , Trinitrobenzene sulfonic acid anion, camphor sulfonate, nonafluorobutane sulfonate, hexadecafluorooctanesulfonate, tetraarylborate, tetrakis (pentafluorophenyl) borate and the like.

Commercially available products can also be used as the thermal polymerization initiator. For example, compounds represented by the following chemical formulas, specific names thereof are Sun Aid SI-B2A (Chemical Formula 1), Sun Aid SI-B3A (Chemical Formula 2), and Sun Aid. SI-B3 (Chemical Formula 3), Sun Aid SI-B4 (Chemical Formula 4), Sun Aid SI-60 (Chemical Formula 5), Sun Aid SI-80 (Chemical Formula 6), Sun Aid SI-100 (Chemical Formula 7), Sun Aid SI-110 (Chemical Formula 7) 8), Sun Aid SI-150 (Chemical formula 9) (manufactured by Sanshin Kagaku Kogyo Co., Ltd.), Adecapton CP-66 (Chemical formula 10), Adeca Opton CP-77 (Chemical formula 11) (manufactured by ADEKA) and the like. These can be used alone or in combination of two or more.

In the present invention, the ratio of the thermal polymerization initiator (E) used is that the cured product has high toughness and adhesive strength, and has good moisture resistance and durability, with respect to 100 parts by mass of the cationically polymerizable component (A). The thermal polymerization initiator (E) is preferably 0.001 to 15 parts by mass, more preferably 0.1 to 10 parts by mass. If it is too small, curing tends to be insufficient, and if it is too large, it may adversely affect various physical properties such as water absorption rate and strength of the cured product.

In addition, the properties of the cured product can be improved by adding an ultraviolet absorber to the curable composition of the present invention, if necessary.

As the ultraviolet absorber, known ones can be used without particular limitation, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5, 2-Hydroxybenzophenones such as 5'-methylenebis (2-hydroxy-4-methoxybenzophenone); 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) ) Bentriazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5- Chlorobenzotriazole, 2- (2-hydroxy-3,5-dicumylphenyl) benzotriazole, 2,2'-methylenebis (4-tert-octyl-6-benzotriazolylphenol), 2- (2-hydroxy Polyethylene glycol ester of -3-tert-butyl-5-carboxyphenyl) benzotriazole, 2- [2-hydroxy-3- (2-acryloyloxyethyl) -5-methylphenyl] benzotriazole, 2- [2-hydroxy -3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-octylphenyl] benzotriazole, 2- [2-Hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] -5-chlorobenzotriazole, 2- [2-hydroxy-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-Hydroxy-3-tert-butyl-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-tert-amyl-5- (2-methacryloyloxyethyl) phenyl ] Bentriazole, 2- [2-hydroxy-3-tert-butyl-5- (3-methacryloyloxypropyl) phenyl] -5-chlorobenzotriazole, 2- [2-hydroxy-4- (2-methacryloyloxymethyl) ) Phenyl] benzotriazole, 2- [2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropyl) phenyl] benzotriazole, 2- [2 -Hydroxy-4- (3-methacryloyloxypropyl) phenyl] 2- (2-hydroxyphenyl) benzotriazoles such as benzotriazole; 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1 , 3,5-Triazine, 2- (2-Hydroxy-4-hexyloxyphenyl) -4,6-diphenyl-1,3,5-Triazine, 2- (2-Hydroxy-4-octoxyphenyl) -4 , 6-Bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (3-C12-13 mixed alkoxy-2-hydroxypropoxy) phenyl] -4,6 -Bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-acryloyloxyethoxy) phenyl] -4,6-bis (4-methylphenyl)- 1,3,5-triazine, 2- (2,4-dihydroxy-3-allylphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4,6 -Tris (2-hydroxy-3-methyl-4-hexyloxyphenyl) -1,3,5-triazine and other 2- (2-hydroxyphenyl) -4,6-diaryl-1,3,5-triazines Phenylsalicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, octyl (3,5-di-tert-butyl-4-hydroxy) Benzoate, dodecyl (3,5-di-tert-butyl-4-hydroxy) benzoate, tetradecyl (3,5-di-tert-butyl-4-hydroxy) benzoate, hexadecyl (3,5-di-tert-butyl- Benzoates such as 4-hydroxy) benzoate, octadecyl (3,5-di-tert-butyl-4-hydroxy) benzoate, behenyl (3,5-di-tert-butyl-4-hydroxy) benzoate; 2-ethyl- Substituted oxanilides such as 2'-ethoxyoxanilide, 2-ethoxy-4'-dodecyloxanilide; ethyl-α-cyano-β, β-diphenylacrylate, methyl-2-cyano-3-methyl-3-3 Cyanoacrylates such as (p-methoxyphenyl) acrylate; various metal salts or metal chelates, particularly nickel, chromium salts, chelates and the like can be mentioned.

Commercially available products can also be used as the above-mentioned ultraviolet absorber, for example, TINUVIN PS, TINUVIN99-2, TINUVIN234, TINUVIN384-2, TINUVIN571, TINUVIN900, TINUVIN928, TINUVIN1130, TINUVIN400, TINUVIN405, TINUVIN460, TINUVIN4 ADEKA STAB LA29, ADEKA STAB LA31, ADEKA STAB LA36, ADEKA STAB LA46, ADEKA STAB LA-F70, ADEKA STAB 1413 (manufactured by ADEKA, registered trademark) and the like.

In the present invention, the ratio of the ultraviolet absorber used is preferably 0.001 to 20 parts by mass, preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the cationically polymerizable component (A). Is more preferable. If it is too small, the ultraviolet absorbing ability is low, and if it is too large, it may adversely affect various physical properties such as transparency of the cured product.

Further, the curable composition of the present invention is inactive at room temperature, if necessary, and the protecting group is desorbed by heating to a predetermined temperature, light irradiation, acid or the like, and is activated to exhibit an ultraviolet absorbing ability. It is also possible to use the compound to be used.

Further, the properties of the cured product can be improved by adding one or more antioxidants to the curable composition of the present invention, if necessary.

As the antioxidant, known ones can be used without particular limitation. For example, specific products represented below include ADEKA STAB AO-20 (Chemical Formula No. 24) and ADEKA STAB AO-30 (Chemical Formula No. 24). .25), ADEKA STAB AO-40 (Chemical Formula No. 26), ADEKA STAB AO-50 (Chemical Formula No. 27), ADEKA STAB AO-60 (Chemical Formula No. 28), ADEKA STAB AO-80 (Chemical Formula No. 29), ADEKA STAB AO -330 (Chemical Formula No. 30) (all manufactured by ADEKA Corporation, registered trademark) and the like can be preferably used.

In addition, the chemical formula No. represented below. In 24 to 30, tBu represents a third butyl group.

Further, in the curable composition of the present invention, one or more kinds of a sensitizer and a sensitizer aid can be further used, if necessary. The sensitizer is a compound that exhibits maximum absorption at a wavelength longer than the maximum absorption wavelength indicated by the cationic polymerization initiator (B) and promotes the polymerization initiation reaction by the cationic polymerization initiator (B). The sensitizer is a compound that further promotes the action of the sensitizer.

Examples of the sensitizer and the sensitizer aid include anthracene compounds and naphthalene compounds.

As the anthracene compound, known compounds can be used without particular limitation, and examples thereof include those represented by the following general formula (VIa).

(In the formula, R ²⁴ and R ²⁵ independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxyalkyl group having 2 to 12 carbon atoms, and R ²⁶ is a hydrogen atom or 1 carbon atom. Represents an alkyl group of ~ 6)

Specific examples of the anthracene-based compound represented by the above general formula (VIa) include the following compounds.

9,10-dimethoxyanthracene,
9,10-diethoxyanthracene,
9,10-Dipropoxyanthracene,
9,10-diisopropoxyanthracene,
9,10-Dibutoxyanthracene,
9,10-Dipentyloxyanthracene,
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,
2-Methyl- or 2-Ethyl-9,10-diisopropoxyanthracene,
2-Methyl- or 2-Ethyl-9,10-dibutoxyanthracene,
2-Methyl- or 2-Ethyl-9,10-dipentyloxyanthracene,
2-Methyl- or 2-ethyl-9,10-dihexyloxyanthracene, etc.

As the naphthalene-based compound, known compounds can be used without particular limitation, and examples thereof include those represented by the following general formula (VIb).

(In the formula, R ²⁷ and R ²⁸ each independently represent an alkyl group having 1 to 6 carbon atoms).

Specific examples of the naphthalene-based compound represented by the above general formula (VIb) include the following compounds.

4-Methoxy-1-naphthol,
4-ethoxy-1-naphthol,
4-propoxy-1-naphthol,
4-Butyloxy-1-naphthol,
4-hexyloxy-1-naphthol,
1,4-dimethoxynaphthalene,
1-ethoxy-4-methoxynaphthalene,
1,4-Diethoxynaphthalene,
1,4-Dipropoxynaphthalene,
1,4-Dibutoxynaphthalene, etc.

In the present invention, the ratio of the sensitizer and the sensitizer to be used is not particularly limited, and the sensitizer and the sensitizing aid may be used in a generally normal ratio within a range that does not impair the object of the present invention. From the viewpoint of improving curability, it is preferable that the sensitizer and the sensitizer aid are each 0.1 to 3 parts by mass with respect to 100 parts by weight of (A).

Further, in the curable composition of the present invention, one or more kinds of acrylic monomer and radical polymerization initiator can be used, if necessary.

As the acrylic monomer, known ones can be used without particular limitation. For example, -2-hydroxyethyl acrylate, -2-hydroxypropyl acrylate, isobutyl acrylate, n-octyl acrylate, isooctyl acrylate can be used. , Isononyl acrylate, Stearyl acrylate, methoxyethyl acrylate, dimethylaminoethyl acrylate, zinc acrylate, 1,6-hexanediol diacrylate, trimethylpropantriacrylate, -2-hydroxyethyl methacrylate,-methacrylate- 2-Hydroxypropyl, butyl methacrylate, tertiary butyl methacrylate, cyclohexyl methacrylate, trimethyl propantrimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, bisphenol A diacrylate Examples thereof include glycidyl ether (meth) acrylate, bisphenol F diglycidyl ether (meth) acrylate, bisphenol Z diglycidyl ether (meth) acrylate, and tripropylene glycol di (meth) acrylate.

As the radical polymerization initiator, known ones can be used without particular limitation. For example, a ketone compound such as an acetophenone compound, a benzyl compound, a benzophenone compound, a thioxanthone compound, an oxime compound, or the like is used. be able to.

In addition, one or more silane coupling agents can be used in the curable composition of the present invention, if necessary.

As the silane coupling agent, known ones can be used without particular limitation, and for example, dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methyltrimethoxysilane, and methyltri. Alkyl-functional alkoxysilanes such as ethoxysilane, ethyltrimethoxysilane, ethyltrimethoxysilane, alkenyl-functional alkoxysilanes such as vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, 3-methacryloxy Bropiltriethoxysilane, 3-methacryloxybropyrtrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 2-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyl Epoxyfunctional alkoxysilanes such as trimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltri Amino-functional alkoxysilanes such as methoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, mercaptofunctional alkoxysilanes such as γ-mercaptopropyltrimethoxysilane, titanium tetraisopropoxide , Titanium alkoxides such as titanium tetranormalbutoxide, titanium chelates such as titanium dioctyloxybis (octylene glycolate), titanium diisopropoxybis (ethylacetoacetate), zircounium tetraacetylacetonate, zirconium tributoxy Zirconium chelates such as monoacetylacetonate, zirconium acylates such as zirconiumtributoxymonostearate, isocyanatesilanes such as methyltriisocyanatesilane, and the like can be used.

In the present invention, the amount of the silane coupling agent used is not particularly limited, but is usually in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass of the total amount excluding the solvent in the curable composition.

Further, the properties of the cured product can be improved by using one or more thermoplastic organic polymers in the curable composition of the present invention, if necessary.

As the thermoplastic organic polymer, known ones can be used without particular limitation. For example, polystyrene, polymethylmethacrylate, methylmethacrylate-ethylacrylate copolymer, methylmethacrylate-glycidylmethacrylate copolymer, poly ( Meta) acrylic acid, styrene- (meth) acrylic acid copolymer, (meth) acrylic acid-methyl methacrylate copolymer, glycidyl (meth) acrylate-polymethyl (meth) acrylate copolymer, polyvinyl butyral, cellulose ester, poly Examples thereof include acrylamide and saturated polyester.

In addition, the curable composition of the present invention includes the above-mentioned (A), (B) and (C), (D), (E), an oxetane compound, an ultraviolet absorber, an antioxidant, and a sensitizing agent, which are usually used. A solvent capable of dissolving or dispersing each component of a component that can be used as needed, such as an agent, a sensitizing aid, a silane coupling agent, and a thermoplastic organic polymer, can be used, and is known without particular limitation. Can be used, for example, ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone; ethyl ether, dioxane, tetrahydrofuran, 1,2- Ethereal solvents such as dimethoxyethane, 1,2-diethoxyethane, propylene glycol monomethyl ether, dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate, -n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, lactic acid Estel solvents such as ethyl, dimethyl succinate, texanol; cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; methanol, ethanol, iso- or n-propanol, iso- or n-butanol, amyl alcohol and the like. Alcohol-based solvents: ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethoxyethyl propionate, etc. Ether ester solvent; BTX solvent such as benzene, toluene, xylene; aliphatic hydrocarbon solvent such as hexane, heptane, octane, cyclohexane; terpene hydrocarbon oil such as terepine oil, D-lymonen, pinen; mineral Paraffinic solvents such as Spirit, Swazole # 310 (Cosmo Matsuyama Oil Co., Ltd.), Solbesso # 100 (Exxon Chemical Co., Ltd.); Halogenization of carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, 1,2-dichloroethane, etc. Aliper hydrocarbon solvent; halogenated aromatic hydrocarbon solvent such as chlorobenzene; propylene carbonate, carbitol solvent, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N, N-dimethylformamide, N, N-jime Examples thereof include tylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, water and the like, and these solvents can be used as one kind or a mixed solvent of two or more kinds.

The curable composition of the present invention has an improved curability, adhesive strength, and liquid storage stability, and therefore, the water content is preferably 5% by mass or less, and more preferably 3% by mass or less. Too much water is not preferable because it may cause cloudiness or precipitation of components.

Further, the curable composition of the present invention preferably has a viscosity of 1 to 5,000 mmPa · sec by an E-type viscometer, preferably 10 to 3,000 mmPa · sec, in terms of high adhesive strength. More preferably, it is 100 to 1,000 mmPa · sec. If the viscosity is too low, uneven coating may occur, which may reduce toughness, adhesive strength, and moisture resistance durability. If the viscosity is too high, handleability is poor, uniform application is difficult, and curing is not possible. It becomes complete and may reduce toughness, adhesive strength and moisture resistance durability. The viscosity of the curable composition is measured at 25 ° C.

The curable composition of the present invention can also be applied onto a support substrate by known means such as a roll coater, a curtain coater, various types of printing, and immersion. Further, once it is applied on a support substrate such as a film, it can be transferred onto another support substrate, and there is no limitation on the application method.

The material of the support substrate is not particularly limited, and a commonly used material can be used. For example, an inorganic material such as glass; diacetyl cellulose, triacetyl cellulose (TAC), propionyl cellulose, butyryl cellulose, acetyl propionyl, etc. can be used. Cellulose esters such as cellulose and nitrocellulose; polyamide; polyimide; polyurethane; epoxy resin; polycarbonate; polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxy Polyolefins such as ethane-4,4'-dicarboxylate and polybutylene terephthalate; Polyolefins; Polyolefins such as polyethylene, polypropylene and polymethylpentene; Vinyl compounds such as polyvinyl acetate, polyvinyl chloride and polyvinyl fluoride; Polymethylmethacrylate , Polycarbonate; Polycarbonate; Polysulfone; Polyethersulfone; Polyetherketone; Polyetherimide; Polyoxyethylene, Norbornene resin, Cycloolefin polymer (COP) and other polymer materials.
The support substrate may be subjected to surface activation treatment such as corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, and laser treatment.

Further, the curable composition in the present invention may contain, as necessary, colorants such as polyols, inorganic fillers, organic fillers, pigments and dyes, defoaming agents, thickeners, etc., as long as the effects of the present invention are not impaired. Add various resin additives such as surfactants, leveling agents, flame retardants, tinxing agents, diluents, plasticizers, stabilizers, polymerization inhibitors, antistatic agents, flow modifiers, adhesion accelerators, etc. Can be done.

The curable composition of the present invention or the adhesive of the present invention described later can be cured by irradiation with active energy rays.

Further, the curable composition of the present invention or the adhesive of the present invention described later can be cured by irradiation with active energy rays and heating.

In the present invention, in the method of curing the curable composition or adhesive by irradiation with active energy rays, or in the method of curing by irradiation and heating, the active energy rays include ultraviolet rays, electron beams, X-rays, and the like. Irradiation, high frequency, etc. can be mentioned, and ultraviolet rays are the most economically preferable. Examples of the ultraviolet light source include an ultraviolet laser, a high-pressure mercury lamp, a xenon laser, and a metal halide lamp.

In the present invention, in the method of curing by irradiation with active energy rays and the method of curing by irradiation and heating, the irradiation amount of active energy rays is 50 to 1000 mJ / min. If the irradiation amount is less than 50 mJ / min, the curing becomes insufficient, and if it exceeds 1000 mJ / min, the cured product may be deteriorated due to excessive irradiation with active energy rays, and the toughness and adhesive strength may be lowered.
Irradiation conditions vary depending on the type and blending ratio of each component, but are preferably 100 to 500 mJ / min, and more preferably 150 to 300 mJ / min.

In the present invention, in the method of curing the curable composition by irradiation with active energy rays and heating, the heating method is described below, and the heating method is not limited to, for example, an atmospheric pressure oven or a vacuum oven. , Hot plate, hot air, infrared irradiation, etc., and an appropriate heating method can be appropriately selected and used according to the use of the curable composition of the present invention.

In the present invention, in the method of curing the curable composition by irradiation with active energy rays and heating, suitable heating conditions are 60 to 200 ° C. for 10 to 180 minutes. If the temperature is lower than 60 ° C., the curing becomes insufficient, and if the temperature exceeds 180 ° C., the physical properties may be deteriorated due to thermal deterioration. Further, if the curing time is less than 10 minutes, the curing becomes insufficient, and if it exceeds 180 minutes, the physical properties may be deteriorated due to thermal deterioration.
The heating conditions vary depending on the type and blending ratio of each component, but are preferably 70 to 180 ° C. for 20 to 150 minutes, and more preferably 80 to 150 ° C. for 30 to 120 minutes.

Specific uses of the curable composition of the present invention and the cured product thereof include adhesives, glasses, optical materials typified by imaging lenses, paints, coating agents, lining agents, inks, resists, liquid resists, and printing. Plates, color TVs, PC monitors, mobile information terminals, digital cameras, organic EL, display elements such as touch panels, insulating varnish, insulating sheets, laminated boards, printed boards, for semiconductor devices, for LED packages, for liquid crystal inlets, organic Encapsulants, molding materials, putties, glass fiber impregnants, sealants for EL, optical elements, electrical insulation, electronic parts, separation films, etc., passivation films for semiconductors, solar cells, etc., layers Insulating film, protective film, prism lens sheet used for backlight of liquid crystal display device, Frenel lens sheet used for screen of projection TV, lens part of lens sheet such as lenticular lens sheet, or such sheet Examples thereof include the used backlight and the like, optical lenses such as microlenses, optical elements, optical connectors, optical waveguides, casting agents for optical modeling, and the like.

The curable composition of the present invention has high toughness and adhesive strength, and is excellent in moisture resistance and durability, so that it can be suitably used as an adhesive. When the curable composition of the present invention is used as an adhesive, the adhesive may consist only of the curable composition of the present invention, or in addition to the curable composition of the present invention, the present invention. It may contain a known component usually used in the technical field of. When the adhesive of the present invention contains other components in addition to the curable composition of the present invention, the content of the curable composition of the present invention in the adhesive of the present invention is preferably 10 to 99.9 mass. %, More preferably 30 to 99.9% by mass, still more preferably 50 to 99.9% by mass. The use of the adhesive of the present invention is not particularly limited, and it can be used for various purposes. Examples of the adherend include, but are not limited to, quartz glass, aluminosilicate glass, borosilicate glass, soda lime glass, sapphire glass, alumina, silicon nitride, boron nitride, and charcoal. Inorganic substances such as silicon, zinc oxide, zirconia and other ceramics, cement, gypsum, quartz, diamond and other minerals; those derived from animals and plants such as wood, fiber, paper, skin, hair and cells; iron, aluminum, platinum, Metals such as gold, silver, copper, nickel, titanium, zinc, silicon, stainless steel, steel, brass, duralmin, hasteroi, dichrome, inverse, solder; epoxy resin, phenol resin, polyallylate, cyanate resin, bismaleimide resin, benzo Oxazine resin, silicone resin, polyamide, polyimide, polyamideimide, polyacrylate, polyurethane, polyethylene, polyethylene terephthalate, polybutylene terephthalate, polyphenylene ether, polypropylene, polystyrene, polybutadiene, polyphenylene sulfide, polysulfone, polyethersulfone, polyetherketone, poly Resins such as ether ether ketone, polyvinyl alcohol, polyacetal, polyester, polyamide, polycarbonate, cellulose triacetate, cycloolefin polymer; etc. may be used for adhesion of the same types of adherends listed above. Although it may be used for adhesion between different types, it can be suitably used for adhesion between one type or between two types selected from glass, inorganic substances, metals and resins because of its high adhesiveness. It can be preferably used by adhering one kind or two kinds selected from the resins. Further, since it is excellent in moisture resistance and durability, it can be suitably used for electronic material applications.

Hereinafter, the present invention will be described in more detail with reference to Examples and the like, but the present invention is not limited to these Examples.

Hereinafter, the curable composition of the present invention and a cured product obtained by curing the curable composition will be specifically described with reference to Examples and Comparative Examples, and Examples and Comparative Evaluation Examples. The numerical values shown in the tables [Table 1] to [Table 3] below represent parts by mass.

[Examples 1 to 15]
Each component was sufficiently mixed with the formulations shown in [Table 1] to [Table 2] below to obtain curable compositions of Examples 1 to 15, respectively. When the viscosities of the curable compositions of Examples 1 to 15 were measured with an E-type viscometer, they were all within the range of 100 to 1000 mmPa · sec. The viscosity of each curable composition was measured at 25 ° C.

[Comparative Examples 1 to 5]
Each component was sufficiently mixed with the formulations shown in [Table 3] below to obtain curable compositions of Comparative Examples 1 to 5, respectively.

As the cationically polymerizable component (A), the following aromatic polyfunctional epoxy compounds (A1-1) to (A1-4) and aliphatic epoxy compounds (A2-1) to (A2-4) were used.
Compound A1-1: EPPN-201 (phenol novolac type epoxy: manufactured by Nippon Kayaku Co., Ltd.)
Compound A1-2: Adeka Resin EP-4100 (bisphenol A type epoxy compound: manufactured by ADEKA Corporation)
Compound A1-3: ADEKA REGIN EP-4000 (diglycidyl ether of bisphenol A alkylene oxide adduct: manufactured by ADEKA Corporation)
Compound A1-4: Epicron HP-7200 (dicyclopentadiene type novolac epoxy: manufactured by DIC Corporation)
Compound A2-1: jERYX-8034 (hydrogenated bisphenol A type epoxy compound: manufactured by Mitsubishi Chemical Corporation)
Compound A2-2: Adecaledin EP-4085 (1,4-bis (glycidyloxymethyl) cyclohexane: manufactured by ADEKA Corporation)
Compound A2-3: ADEKA REGIN EP-4088 (dicyclopentadiene dimethanol diglycidyl ether: manufactured by ADEKA Corporation)
Compound A2-4: Adeka Resin EP-4080 (hydrogenated bisphenol A type epoxy compound: manufactured by ADEKA Corporation)

The following compounds (B-1) to (B-2) were used as the cationic polymerization initiator (B), and (B'-1) was used as the comparative compound.
Compound B-1: Compound represented by [Chemical Formula 15]

Compound B-2: Compound represented by [Chemical Formula 16]

Compound B'-1: Compound represented by ([Chemical Formula 17])

The following compounds (C-1) to (C-2) were used as the alicyclic epoxy compound (C).
Compound C-1: 3,4-Epoxycyclohexylmethyl-3,4-Epoxycyclohexanecarboxylate Compound C-2: 2,2-Bis (3,4-Epoxycyclohexyl) Propane

The following compound (D-1) was used as the other aliphatic epoxy compound (D).
Compound D-1: Neopentyl glycol diglycidyl ether

The following compound (E-1) was used as the thermal polymerization initiator (E).
Compound E-1: Sun Aid SI-B3 (manufactured by Sanshin Chemical Industry Co., Ltd.)

The following silane coupling agent (F-1) was used as the additive (F).
Compound F-1: SILQUEST A186 SILANE (β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane: manufactured by Momentive Performance Materials Japan)

[Evaluation of cured product]
For Examples 1 to 15 and Comparative Examples 1 to 5, a cured product for evaluation was prepared according to the method described below, and the toughness, adhesive strength, and moisture resistance durability were evaluated. The evaluation method was an elastic modulus measurement test for toughness, a 3-point bending test for adhesive strength, and a 3-point bending test after the PCT test for moisture resistance durability. The evaluation results are shown in [Table 4] and [Table 5] below.

[Toughness evaluation]
For Examples 1 to 15 and Comparative Examples 1 to 5, a sample for elastic modulus measurement was prepared by the following method, and an elastic modulus measurement test was carried out.
(Preparation of sample for elastic modulus measurement)
Examples 1 to 15 and Comparative Examples 1 to 5 are each applied on a PET film to a thickness of 100 μm using a spacer, the PET film is aligned with the coated surface, and the PET film is further coated with a glass substrate. It is sandwiched from both sides and irradiated with light equivalent to 200 mJ / cm ² from the outside of the glass substrate on both sides with a high-pressure mercury lamp, and then heated in an atmospheric pressure oven at 100 ° C. for 30 minutes to cure. The cured product was taken out and cut into a width of 5 mm, a length of 20 mm, and a thickness of 100 μm, and the corresponding cured products 1a to 15a and Comparative Examples cured products 1a to 5a were obtained as samples for measuring the elastic modulus, respectively.
(Elastic modulus measurement test)
The elastic modulus of each of the elastic modulus measuring samples obtained as described above was measured by the dynamic viscoelasticity measuring device DMS6100 manufactured by SII. The measurement was carried out at a tensile measurement and a heating rate of 5 ° C./min, and the storage elastic modulus at a frequency of 10 Hz and 25 ° C. was used as the measured elastic modulus.

[Adhesive strength evaluation and moisture resistance durability evaluation]
For Examples 1 to 15 and Comparative Examples 1 to 5, three-point bending test samples (glass / PPS bonded sample and PPS / PPS bonded sample) were prepared by the following methods, and the obtained samples were evaluated for adhesive strength. The three-point bending test was carried out as it was, and the PCT test was carried out for the evaluation of moisture resistance durability, and the three-point bending test was carried out for the sample before and after the PCT test.
(Preparation of glass / PPS bonded sample)
Examples 1 to 15 and Comparative Examples 1 to 5 are applied to a non-alkali glass substrate (EagleXG: manufactured by Corning Inc.) having a length of 50 mm, a width of 25 mm, and a thickness of 1 mm, respectively, to a thickness of 20 to 30 μm with a bar coater. Then, a polyphenylene sulfide base material of the same size (Sustel PPS: manufactured by Tosoh Co., Ltd.) is laminated in the longitudinal direction so that the base materials overlap each other by 6 mm, and is equivalent to 200 mJ / cm ² from the glass base material side using a high-pressure mercury lamp. After that, it was heated in an atmospheric pressure oven at 100 ° C. for 30 minutes and cured to obtain the corresponding cured products 1b to 15b of Examples and 1b to 5b of Comparative Examples as glass / PPS bonded samples, respectively. .. In addition, Comparative Example 5 was not cured in the above curing step, and the sample could not be prepared.
(Preparation of PPS / PPS junction sample)
Two polyphenylene sulfide substrates of Examples 1 to 15 and Comparative Examples 1 to 5 were prepared, and one of the substrates was coated with a bar coater to a thickness of 20 to 30 μm, and a high-pressure mercury lamp was used. After irradiating the coated surface with light equivalent to 200 mJ / cm ² , the other polyphenylene sulfide base material is bonded in the longitudinal direction so that the base materials overlap each other by 6 mm, and then heated in an atmospheric pressure oven at 100 ° C. for 30 minutes. To obtain 1c to 15c of the corresponding cured products of Example and 1c to 5c of the cured products of Comparative Example, respectively, as PPS / PPS bonded samples. In addition, Comparative Example 5 was not cured in the above curing step, and the sample could not be prepared.
(PCT test)
Each of the three-point bending test samples and distilled water prepared above were placed in a pressure-resistant container, sealed, heated at 121 ° C. for 10 hours, and used as a three-point bending test sample after the PCT test. ~ 15b, Comparative Examples cured products 1b to 5b, Examples cured products 1c to 15c, and Comparative Examples cured products 1c to 5c, respectively, Example cured products 1b'to 15b', Comparative Example cured products 1b'to 5b', respectively. , Example cured products 1c'to 15c' and Comparative Examples cured products 1c' to 5c' were obtained.
(3-point bending test)
The three-point bending test samples before and after the PCT test were subjected to a three-point bending test with an Autograph AGS-10kNX manufactured by Shimadzu Corporation, and the fracture strength of the joint surface was measured. The measurement was carried out under the conditions of a distance between fulcrums of 20 mm and a jig moving speed of 50 mm / min. Regarding Comparative Example 1, the fracture strengths of the joint surfaces of the comparatively cured products 1b'and 1c', which were samples after the PCT test, were significantly reduced, and the three-point bending test could not be performed. Further, with respect to Comparative Example 3, the joint surfaces of the comparatively cured products 3b'and 3c', which were samples after the PCT test, were completely peeled off, and the three-point bending test could not be performed. Further, with respect to Comparative Example 4, the fracture strength of the joint surface of the comparatively cured product 4b', which is a sample after the PCT test of the glass / PPS bonded sample, was significantly reduced, and the three-point bending test could not be performed. Further, in the PPS / PPS bonded sample, the adhesive strength of the comparative cured product 4c, which is a sample before the PCT test, and the comparative cured product 4c', which is a sample after the PCT test, are significantly reduced, and a three-point bending test is performed. could not.

In the above [Table 4] and the following [Table 5], the elastic modulus was evaluated as follows.
− 2.5 GPa or less + 2.6 to 3.0 GPa
++ 3.1-3.5 GPa
+++ 3.6 GPa or more

In the above [Table 4] and the following [Table 5], the evaluation of fracture strength was as follows.
− 1.5 MPa or less + 1.6 to 2.5 MPa
++ 2.6-3.5 MPa
+++ 3.6 MPa or more

From the above [Table 4], in the curable composition of the present invention, the cured product obtained by curing the cured product was excellent in toughness, adhesive strength, and moisture resistance and durability. On the other hand, in Comparative Example 1, when a larger amount of the aromatic polyfunctional epoxy compound (A1) was blended than in the curable composition of the present invention, as compared with Example 5, glass / PPS bonding and PPS / PPS bonding were performed. In all cases, the breaking strength was remarkably reduced and the adhesive strength was low. Further, in Comparative Example 2, the elastic modulus was remarkably lowered and the toughness was low unless the aromatic polyfunctional epoxy compound (A1) was blended as compared with Example 5. Further, from Comparative Example 3, when the aliphatic epoxy compound (A2) is not used for the present invention and is replaced with the alicyclic epoxy compound (C), the fracture strength after the PCT test is remarkably lowered and the moisture resistance durability is low. It was a thing. Further, from Comparative Example 4, when the aliphatic epoxy compound (A2) was not used for the present invention and was replaced with another aliphatic epoxy compound (D), both toughness and adhesive strength were low. Further, from Comparative Example 5, when the cationic polymerization initiator (B) was not used for the present invention and was replaced with a cationic polymerization initiator not corresponding to the present invention, the curing was insufficient and a cured product could not be obtained. From the above results, it is clear that the curable composition of the present invention is excellent in toughness, adhesive strength and moisture resistance durability for the cured product.

Further, from the above [Table 5], when the curable composition of the present invention further contains the alicyclic epoxy compound (C), the composition has high fracture strength, moisture resistance and durability, and further excellent toughness. It is clear that.

Claims (9)

A curable composition containing a cationically polymerizable component (A) and a cationically polymerizable initiator (B).
The cationically polymerizable component (A), one or more selected from aromatic polyfunctional epoxy compound (A1), one or more selected from the fat-aliphatic epoxy compound (A2), and alicyclic Containing one or more selected from the formula epoxy compound (C) ,
The aliphatic epoxy compound (A2) contains one or more selected from the group consisting of an alicyclic glycidyl compound represented by the following general formula (I) and a hydrogenated bisphenol type epoxy compound.
The cationically polymerizable component (A) has a mass ratio of the aromatic polyfunctional epoxy compound (A1) and the aliphatic epoxy compound (A2) in the range of 10:90 to 50:50 for the former: the latter.
The alicyclic epoxy compound (C) has one or more cyclohexene oxide groups and one or both cyclopentene oxide groups in the molecule, and has a total of two or more ethylene oxide structures in the molecule. Contains one or more selected from the group consisting of compounds having
As for the cationically polymerizable component (A), the alicyclic epoxy compound (C) was added to 0. 0 parts by mass of the total of the aromatic polyfunctional epoxy compound (A1) and the aliphatic epoxy compound (A2). Contains 5 to 35 parts by mass,
The cationic polymerization initiator (B) contains one or more sulfonium borate salts and contains.
The sulfonium borate salt is one or two selected from a salt composed of a combination of a sulfonium cation represented by the following general formula (IIa) or (IIb) and a borate anion represented by the following general formula (III). A curable composition containing the above.
(In the formula, X is an aliphatic hydrocarbon group having 3 to 14 carbon atoms having an alicyclic structure having 3 to 6 carbon atoms, or 2 or 3 alicyclic structures having 3 to 6 carbon atoms condensed. Represents an aliphatic hydrocarbon group having a structure and having 4 to 14 carbon atoms.
J represents an oxygen atom or -COO-
m represents 0 or 1 and represents
n represents 1, 2 or 3. )
(In the formula, R ^{1 to} R ³ are independently hydrogen atom, hydroxyl group, halogen group, nitro group, carboxyl group, linear or branched alkyl group having 1 to 12 carbon atoms, and carbon atom number 1. ~ 12 linear or branched alkoxy groups, linear or branched hydroxyalkyl groups with 1 to 12 carbon atoms, linear or branched ketone groups with 1 to 12 carbon atoms, carbon atoms Represents an aryl group having 6 to 20, an aryl ether group having 6 to 20 carbon atoms, an aryl thioether group having 6 to 20 carbon atoms, or an aryl ketone group having 6 to 20 carbon atoms.
In the aryl group, the aryl ether group, the aryl thio ether group, and the aryl ketone group represented by R ^{1 to} R ³ , one or two or more hydrogen atoms of the aromatic ring are hydroxyl groups, halogen groups, or nitro. Groups, carboxyl groups, linear or branched alkyl groups with 1 to 12 carbon atoms, linear or branched alkoxy groups with 1 to 12 carbon atoms, linear or branched with 1 to 12 carbon atoms Branched chain hydroxyalkyl groups, aryl groups with 6 to 20 carbon atoms, aryl ether groups with 6 to 20 carbon atoms, aryl thioether groups with 6 to 20 carbon atoms, or aryl ketone groups with 6 to 20 carbon atoms. May have been replaced
The alkyl group or alkoxy group represented by R ^{1 to} R ³ which may substitute the aryl group, the aryl ether group, the aryl thioether group and the aryl ketone group is the substituted aryl group, the aryl. It may be bonded to the aromatic ring of the ether group, the arylthio ether group and the arylketone group to form a fused ring of a 5- or 6-membered ring.
R ^{4 to} R ⁷ independently have a hydrogen atom, a hydroxyl group, a halogen group, a nitro group, a carboxyl group, a linear or branched alkyl group having 1 to 12 carbon atoms, and a direct chain having 1 to 12 carbon atoms. It represents a chain-like or branched-chain alkoxy group, a linear or branched-chain hydroxyalkyl group having 1 to 12 carbon atoms, or a linear or branched-chain ketone group having 1 to 12 carbon atoms. )
(In the formula, R ^{8 to} R ¹¹ each independently represent a substituted phenyl group, and 1 to 5 of the five hydrogen atoms in the aromatic ring of the phenyl group are substituted with a fluorine atom. The hydrogen atom not substituted with a fluorine atom in the phenyl group is a hydroxyl group, a halogen group other than fluorine, a linear or branched alkyl group having 1 to 12 carbon atoms, or a linear chain having 1 to 12 carbon atoms. It may be substituted with a linear or branched alkoxy group, a linear or branched hydroxyalkyl group having 1 to 12 carbon atoms, or a linear or branched hydroxyl group having 1 to 12 carbon atoms. is there.) The curable composition according to claim 1, wherein the aromatic polyfunctional epoxy compound (A1) contains one or more selected from the group consisting of a bisphenol type epoxy compound and a novolak type epoxy compound. object. The aliphatic epoxy compound (A2), the following compound (IVa), or claim 1, characterized in that it contains one or more kinds selected from the group consisting of (IVb) and hydrogenated bisphenol type epoxy compounds 2. The curable composition according to 2.
The alicyclic epoxy compound (C) is one selected from the group consisting of compounds having a total of one or two or more cyclohexene oxide groups in the molecule and a total of two or more epoxy groups in the molecule. The curable composition according to any one of claims 1 to 3 , wherein the curable composition contains two or more of them. The invention according to any one of claims 1 to 4 , wherein the cationic polymerization initiator (B) contains one or more selected from the sulfonium borate salts represented by the following (V). Curable composition.
(In the formula, R ^{12 to} R ¹⁷ are each independently a hydrogen atom, a hydroxyl group, a halogen group, a nitro group, a carboxyl group, a linear or branched alkyl group having 1 to 12 carbon atoms, and 1 carbon atom. Represents a linear or branched alkoxy group of ~ 12, a linear or branched hydroxyalkyl group having 1 to 12 carbon atoms, or a linear or branched ketone group having 1 to 12 carbon atoms. ,
R ¹⁸ is a hydrogen atom, a hydroxyl group, a halogen group, a nitro group, a carboxyl group, a linear or branched alkyl group having 1 to 12 carbon atoms, and a linear or branched alkoxy having 1 to 12 carbon atoms. Group, linear or branched hydroxyalkyl group with 1 to 12 carbon atoms, linear or branched ketone group with 1 to 12 carbon atoms, aryl group with 6 to 20 carbon atoms, number of carbon atoms Represents an aryl ether group of 6 to 20, an aryl thioether group of 6 to 20 carbon atoms, or an aryl ketone group of 6 to 20 carbon atoms.
Represented by R ^18, the aryl group, the aryl ether group, the thioether group and the aryl ketone group, one of the hydrogen atoms of the aromatic ring or two or more, a hydroxyl group, a halogen group, a nitro group , Carboxyl group, linear or branched alkyl group with 1 to 12 carbon atoms, linear or branched alkoxy group with 1 to 12 carbon atoms, linear or branched with 1 to 12 carbon atoms A chain hydroxyalkyl group, an aryl group having 6 to 20 carbon atoms, an aryl ether group having 6 to 20 carbon atoms, an aryl thioether group having 6 to 20 carbon atoms, or an aryl ketone group having 6 to 20 carbon atoms. May have been replaced
Represented by R ^18, the aryl group, the aryl ether group, the thioether group, and an aryl group which may be substituted with the aryl ketone group, an aryl ether group, aryl thioether group, and aryl ketone groups are substituted It may be bonded to the aromatic ring of the aryl group, the aryl ether group, the aryl thioether group, and the aryl ketone group to form a fused ring of a 5- or 6-membered ring. ) An adhesive comprising the curable composition according to any one of claims 1 to 5 . A method for curing the curable composition according to any one of claims 1 to 5 or the adhesive according to claim 6 by irradiation with active energy rays. A method for curing the curable composition according to any one of claims 1 to 5 or the adhesive according to claim 6 by irradiation with active energy rays and heating. The curable composition according to any one of claims 1 to 5 or a cured product obtained by curing the adhesive according to claim 6 .