TWI738754B - Hardenable composition, method of manufacturing hardened material and hardened material - Google Patents

Abstract

The present invention provides a curable composition with a high glass transition temperature and excellent adhesion of a cured product, a method for manufacturing a cured product, and a cured product.

The curable composition of the present invention contains: 30 to 99 parts by mass of cationic polymerizable component (A), 0.1 to 10 parts by mass of cationic polymerization initiator (B), and 0 to 55 parts by mass of radical polymerizable component (C) , Free radical polymerization initiator (D) 0~10 parts by mass and selected from formula (I)

(In the formula, X is an alkyl group with 1 to 7 carbon atoms, etc.) A polymer derived from a monomer represented by the formula (II)

(In the formula, R ¹ represents a hydrogen atom, etc., X'is an alkyl group with 1 to 7 carbon atoms, etc.) represents the weight average molecular weight of the polymer obtained from the monomer, etc. The polymer has a weight average molecular weight of 1,000 to 30,000 (E) 1 to 30 Parts by mass, wherein the component (A) is a glycidyl compound of a polyol having a molecular weight of 200 or more and an alicyclic epoxy compound, and the component (C) is a compound having an epoxy group or the like.

Description

Hardenable composition, method of manufacturing hardened material and hardened material

The present invention relates to a curable composition, a method for manufacturing a cured product, and a cured product, and in detail, a curable composition with a high glass transition temperature and excellent adhesion, a method for manufacturing a cured product, and a cured product.

The curable composition is used in fields such as inks, paints, various coating agents, adhesives, and optical components. There are various reports on the improvement of this kind of curable composition.

For example, the following Patent Documents 1 to 3 propose energy ray curable compositions containing cationically polymerizable components and radically polymerizable components and their cured products. Specifically, Patent Document 1 proposes an adhesive composition for a polarizing plate that is excellent in initial curability and adhesiveness. In addition, Patent Document 2 proposes an active energy ray for plastic films that has excellent curability even with low viscosity, high environmental humidity during coating and curing, excellent adhesion to various plastic films, etc., and excellent colorlessness and transparency. Hardening type adhesive composition. In addition, Patent Document 3 proposes a low viscosity, excellent curability, excellent adhesion to various plastic films containing (meth)acrylic resins or cycloolefin polymers, etc., and excellent colorless and transparent properties for plastic films, etc. Energy line Hardening type adhesive composition.

[Prior technical literature] 〔Patent Documents〕

Patent Document 1: JP 2014-105218 A

Patent Document 2: Japanese Patent Application Publication No. 2015-057467

Patent Document 3: Japanese Patent Application Publication No. 2015-229744

However, even for the curable compositions proposed in Patent Documents 1 to 3, the curability and adhesiveness may not always be satisfied. The current situation is that it is desired to have a high degree of curability and adhesiveness. Hardening composition.

Therefore, the object of the present invention is to provide a curable composition having a high glass transition temperature of a cured product and excellent adhesion, a method for producing a cured product, and a cured product thereof.

The inventors of the present invention have intensively studied in order to solve the above-mentioned problems, and found that if it is a curable composition having a specific composition, the above-mentioned problems can be overcome, and the present invention has been completed.

That is, the curable composition of the present invention contains: 30 to 99 parts by mass of cationic polymerizable component (A), 0.1 to 10 parts by mass of cationic polymerization initiator (B), and radical polymerizable component (C) 0~55 parts by mass, 0~10 parts by mass of radical polymerization initiator (D), and selected from the following formula (I)

(In the formula, X is an alkyl group with 1 to 7 carbon atoms, an alkoxy group with 1 to 7 carbon atoms, an aryl group with 6 to 12 carbon atoms, an aryloxy group with 6 to 12 carbon atoms or carbon atoms The alicyclic hydrocarbon group of number 6 to 10, or the hydrogen atom in these groups is substituted by one or more groups selected from the group consisting of epoxy group, oxetanyl group, hydroxyl group and carboxyl group). The polymer obtained from the monomer of the following formula (II)

(In the formula, R ¹ represents a hydrogen atom, a methyl group or a halogen atom, and X'is an alkyl group with 1 to 7 carbon atoms, an aryl group with 6 to 12 carbon atoms or an alicyclic hydrocarbon group with 6 to 10 carbon atoms , Or the hydrogen atom in these groups is substituted by one or more groups selected from epoxy group, oxetanyl group, hydroxyl group and carboxyl group) represented by the polymer, selected A polymer obtained from two or more monomers of the monomer represented by the aforementioned formula (I), a polymer obtained from two or more monomers selected from the monomer represented by the aforementioned formula (II), or a polymer selected from the aforementioned formula (I) The monomer represented by the formula (II) and the polymer obtained from the monomer represented by the formula (II) form a group of a polymer having a weight average molecular weight of 1,000 to 30,000 (E) 1 to 30 parts by mass to make the aforementioned cationically polymerizable component (A) The total of the aforementioned radical polymerizable component (C) and the aforementioned polymer (E) is 100 parts by mass, and the aforementioned cationically polymerizable component (A) is a glycidyl product of a polyol having a molecular weight of 200 or more or The glycidyl compound (A1) and the alicyclic epoxy compound (A2) of the polyol alkylene oxide adduct are essential components. The radical polymerizable component (C) has an epoxy group and an ethylenic Saturated compound (C1), or acrylate of alcohol with 2 to 20 carbon atoms or methacrylate (C2) of alcohol with 2 to 20 carbon atoms are essential components. Here, the weight average molecular weight refers to the weight average molecular weight obtained by GPC measurement in tetrahydrofuran (THF) solvent and calculated in terms of styrene.

The curable composition of the present invention, wherein the glycidyl compound of a polyhydric alcohol with a molecular weight of 200 or more or the glycidyl compound (A1) of a polyhydric alcohol alkylene oxide adduct has a polyhydric alcohol having a condensed ring Polyols are preferred. In addition, in the curable composition of the present invention, the alicyclic epoxy compound (A2) is selected from 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylic acid Esters, 7-oxabicyclo[4.1.0]heptane, poly[oxy-(1-oxo-1,6-hexanediyl)] derivatives, adipic acid bis[(7-oxabi Cyclo[4.1.0]heptan-3-yl)methyl], 1,2-epoxy-4-vinylcyclohexane, 3,4-epoxycyclohexyl methyl methacrylate and limonene More than one kind of oxides is preferred. In addition, in the curable composition of the present invention, the polymer (E) is a polymer obtained from the monomer represented by the formula (I) and the monomer represented by the formula (II). X is an aryl group having 6 to 12 carbon atoms, X'in the aforementioned formula (II) is an alkyl group having 1 to 7 carbon atoms, and the aforementioned alkyl group is preferably substituted by an epoxy group.

The manufacturing method of the curable composition of the present invention is characterized by The curable composition of the present invention is irradiated with active energy rays or heated.

The cured product of the present invention is characterized by the cured product of the curable composition of the present invention.

According to the present invention, it is possible to provide a curable composition with a high glass transition temperature of the cured product and excellent adhesion, a method for manufacturing a cured product, and a cured product thereof. The curable composition of the present invention is particularly useful for adhesives.

Form of invention

The curable composition of the present invention will be described in detail below.

The curable composition of the present invention contains: 30 to 99 parts by mass of cationic polymerizable component (A), 0.1 to 10 parts by mass of cationic polymerization initiator (B), and 0 to 55 parts by mass of radical polymerizable component (C) Parts by mass, 0-10 parts by mass of the radical polymerization initiator (D), and polymers selected from the monomers represented by the following formula (I), and polymers derived from the monomers represented by the following formula (II) , A polymer obtained from two or more monomers selected from the monomer represented by the following formula (I), a polymer obtained from two or more monomers selected from the monomer represented by the following formula (II), or 1-30 parts by mass of polymer (E) with a weight average molecular weight of 1,000 to 30,000 selected from the group consisting of a monomer represented by the following formula (I) and a monomer represented by the following formula (II), The total of (A) component, (C) component, and (E) component is 100 parts by mass. In the curable composition of the present invention, cationic polymerizable Component (A) is based on the glycidyl compound of a polyol with a molecular weight of 200 or more or the glycidyl compound (A1) and alicyclic epoxy compound (A2) of polyol alkylene oxide adducts as essential components. The radical polymerizable component (C) is a compound (C1) having an epoxy group and an ethylenically unsaturated group, or an acrylate of an alcohol with 2 to 20 carbon atoms, or a methyl group of an alcohol with 2 to 20 carbon atoms Acrylate (C2) is an essential component.

Here, in formula (I), X is an alkyl group with 1 to 7 carbon atoms, an alkoxy group with 1 to 7 carbon atoms, an aryl group with 6 to 12 carbon atoms, and an aromatic group with 6 to 12 carbon atoms. An oxy group or an alicyclic hydrocarbon group with 6 to 10 carbon atoms, or hydrogen atoms in these groups are selected from one or more groups selected from the group consisting of epoxy, oxetanyl, hydroxyl, and carboxyl groups Replaced by.

Here, in formula (II), R ¹ represents a hydrogen atom, a methyl group or a halogen atom, and X'is an alkyl group with 1 to 7 carbon atoms, an aryl group with 6 to 12 carbon atoms or 6 to 10 carbon atoms The alicyclic hydrocarbon group or the hydrogen atom in these groups is substituted with one or more groups selected from the group consisting of epoxy group, oxetanyl group, hydroxyl group and carboxyl group.

The cationically polymerizable component (A) of the curable composition of the present invention is a compound that undergoes polymerization or crosslinking reaction by a cationic polymerization initiator activated by energy ray irradiation or heating. Examples include epoxy compounds, oxetane compounds, and vinyl ether compounds.

The cationically polymerizable component (A) of the curable composition of the present invention is based on the glycidyl compound (A1) of the polyol having a molecular weight of 200 or more or the glycidyl compound (A1) of the polyol alkylene oxide adduct and alicyclic ring The epoxy compound of the formula (A2) is an essential component, but other epoxy compounds such as aromatic epoxy compounds (A3) and the like can also be used. The ratio of the above-mentioned (A1) component and (A2) component in the cationically polymerizable component (A) is preferably 90% by mass or more.

The epoxy propyl product of the polyhydric alcohol with a molecular weight of 200 or more or the glycidyl product (A1) of the polyhydric alcohol alkylene oxide adduct can be exemplified by the epoxy It is propylated, and the molecular weight of the glycidate is preferably 200 or more.

The glycidyl product of the above-mentioned polyol having a molecular weight of 200 or more or the glycidyl product (A1) of the polyol alkylene oxide adduct includes 1,4-butanediol diglycidyl ether, 1, 6-Hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, triglycidyl ether of glycerol, triglycidyl ether of trimethylolpropane, tetraepoxy of sorbitol Propyl ether, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, dicyclopentadiene dimethanol diglycidyl ether, etc. Polyoxypropylene ether and polyoxypropylene etherate of polyether polyol obtained by addition of one or more kinds of alkylene oxide and aliphatic polyols such as propylene glycol, trimethylolpropane, glycerol, etc. , Diglycidyl ester of aliphatic long-chain dibasic acid.

The glycidyl compound of polyhydric alcohol or the glycidyl compound of polyhydric alcohol alkylene oxide adduct (A1), and further examples include the monoglycidyl ether of aliphatic higher alcohols or the glycidyl esters of higher fatty acids, cyclic Oxidized soybean oil, epoxy octyl stearate, epoxy butyl stearate, epoxidized soybean oil, epoxidized polybutadiene, etc.

The glycidyl compound (A1) of the polyol having a molecular weight of 200 or more or the glycidyl compound (A1) of the polyol alkylene oxide adduct contains saturated condensed rings, which can improve the hardenability and adhesion of the cured product, so Better.

Commercially available products can be used for the glycidyl product of the polyol having a molecular weight of 200 or more or the glycidyl product (A1) of the polyol alkylene oxide adduct, for example, Denacol EX-121, Denacol EX- 171, Denacol EX-192, Denacol EX-211, Denacol EX-212, Denacol EX-313, Denacol EX-314, Denacol EX-321, Denacol EX-411, Denacol EX-421, Denacol EX-512, Denacol EX- 521, Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX-622, Denacol EX-810, Denacol EX-811, Denacol EX-850, Denacol EX-851, Denacol EX-821, Denacol EX- 830, Denacol EX-832, Denacol EX-841, Denacol EX-861, Denacol EX-911, Denacol EX-941, Denacol EX-920, Denacol EX-931 (manufactured by Nagase Chemtex Corporation); EpoteM-1230, Epolite40E,Epolite100E,Epolite200E,Epolite400E,Epolite70P,Epolite200P,Epolite400P,Epolite1500NP,Epolite1600,Epolite80MF,Epolite100MF (Kyoeisha Chemical (Share) company), ADEKA GLYCIROLED-503, ADEKA GLYCIROLED-503G, ADEKA GLYCIROLED-506, ADEKA GLYCIROLED-523T, ADEKA ResinEP-4088S, ADEKA ResinEP-4080E ((share) ADEKA company), etc.

The above-mentioned alicyclic epoxy compound (A2) means that the ethylene oxide ring is directly bonded to a saturated ring without a bonding group. Specific examples of the alicyclic epoxy compound (A2) can be exemplified by using a polyglycidide etherate of a polyol having at least one alicyclic ring or a compound containing a cyclohexene or cyclopentene ring with an oxidizing agent Cyclohexene oxide or cyclopentene oxide-containing compound obtained by epoxidation. Examples include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy -1-methylhexane carboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexane carboxylate, 3, 4-Epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexane carboxylate, 3,4-epoxy-5-methylcyclohexylmethyl -3,4-Epoxy-5-methylcyclohexanecarboxylate, bis(3,4-epoxycyclohexylmethyl)adipate, 3,4-epoxy-6-methyl Cyclohexane carboxylate, methylene bis(3,4-epoxycyclohexane), propane-2,2-diyl-bis(3,4-epoxycyclohexane), 2, 2-bis(3,4-epoxycyclohexyl)propane, dicyclopentadiene diepoxide, ethylenebis(3,4-epoxycyclohexane carboxylate), epoxy six Dioctyl hydrogen phthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2- Epoxy-2-epoxyethylcyclohexane, α-pinene oxide, limonene dioxide, etc. The alicyclic epoxy compound (A2) is preferably 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylic acid from the viewpoint of improving adhesion Ester or 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexane carboxylate.

Commercial products can be used for the alicyclic epoxy compound (A2), and examples thereof include CELLOXID 2021P, CELLOXID 2081, CELLOXID 2000, and CELLOXID 3000 (manufactured by DAICEL Corporation).

The above-mentioned aromatic epoxy compound (A3) refers to an epoxy compound containing an aromatic ring, and specific examples of the aromatic epoxy compound include polyhydric phenols having at least one aromatic ring, such as phenol, cresol, and butylphenol, or The mono/polyglycidyl etherate of its alkylene oxide adducts can include, for example, bisphenol A, bisphenol F, or the glycidyl etherate or epoxy group of these compounds to which alkylene oxide is added. Novolac resin; mono/polyglycidyl etherate of aromatic compounds with more than two phenolic hydroxyl groups such as resorcinol, hydroquinone, catechol, etc.; phenyl dimethanol or phenyl diethanol, benzene Glycidyl etherate of aromatic compounds with two or more alcoholic hydroxyl groups, such as dibutanol; polybasic carboxylic acid, such as phthalic acid, terephthalic acid, trimellitic acid, etc. Glycidyl ester of acid aromatic compounds, glycidyl ester of benzoic acid, styrene oxide or epoxide of divinylbenzene, etc.

Commercial products can be used for the above-mentioned aromatic epoxy compound (A3), and examples include Denacol EX-146, Denacol EX-147, Denacol EX-201, Denacol EX-203, Denacol EX-711, Denacol EX-721, Oncoat EX -1020, Oncoat EX-1030, Oncoat EX-1040, Oncoat EX-1050, Oncoat EX-1051, Oncoat EX-1010, Oncoat EX-1011, Oncoat 1012(nagase Chemtex Corporation); OGSOLPG-100, OGSOLEG-200, OGSOLEG-210, OGSOLEG-250 (Osaka Gas Chemical Corporation); HP4032, HP4032D, HP4700 (DIC Corporation); ESN- 475V (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.); Epikote YX8800 (manufactured by Mitsubishi Chemical Co., Ltd.); Marproof G-0105SA, Marproof G-0130SP (manufactured by NOF Corporation); EPICLONN-665, EPICLONHP- 7200 (made by DIC Corporation); EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, XD-1000, NC-3000, EPPN-501H, EPPN-501HY, EPPN-502H, NC-7000L( Nippon Kayaku Co., Ltd.); ADEKA ResinEP-4000, ADEKA ResinEP-4005, ADEKA ResinEP-4100, ADEKA ResinEP-4901 (made by ADEKA Corporation); TECHMORE VG-3101L (made by Printec Corporation) Wait. Among the above-mentioned aromatic epoxy compounds, polyfunctional ones are preferred because they are excellent in curability.

The above-mentioned oxetane compounds include 3,7-bis(3-oxocyclobutyl)-5-oxa-nonane, 1,4-bis[(3-ethyl-3-oxocyclobutylmethoxy) Yl)methyl]benzene, 1,2-bis[(3-ethyl-3-oxocyclobutylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxobutylmethyl) Oxy)methyl)propane, ethylene glycol bis(3-ethyl-3-oxocyclobutylmethyl)ether, triethylene glycol bis(3-ethyl-3-oxocyclobutylmethyl)ether, tetraethylenedi Alcohol bis(3-ethyl-3-oxocyclobutylmethyl)ether, 1,4-bis(3-ethyl-3-oxobutylmethoxy)butane, 1,6-bis(3-ethyl- Difunctional aliphatic oxetane compounds such as 3-oxocyclobutylmethoxy)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 and other monofunctional oxetanes Compound etc. These can be used individually by 1 type or in combination of 2 or more types.

As the above-mentioned oxetane compound, a commercially available product containing a cationically polymerizable monomer as a main component can be used, and examples include 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, and 4-hydroxybutyl vinyl ether. (Manufactured by Maruzen Petrochemical Co., Ltd.); Aron Oxetane OXT-121, OXT-221, EXOH, POX, OXA, OXT-101, OXT-211, OXT-212 (manufactured by Toagosei Co., Ltd.), ETERNACOLLOXBP, OXTP (manufactured by Ube Industries Co., Ltd.), etc.

The above-mentioned vinyl ether compounds include, for example, diethylene glycol monovinyl ether, triethylene glycol divinyl ether, n-dodecyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, 2-chloroethyl Vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, triethylene glycol vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 1,6-cyclohexanedimethanol monovinyl ether , Ethylene glycol divinyl ether, 1,4-butanediol divinyl ether, 1,6-cyclohexanedimethanol divinyl ether, etc.

In the above-mentioned cationically polymerizable component (A), the glycidyl compound of the polyol having a molecular weight of 200 or more or the glycidyl compound of the polyol alkylene oxide adduct (A1), the alicyclic epoxy compound (A2) ), aromatic epoxy compound (A3), oxetane compound, and vinyl ether compound are used in proportions relative to 100 parts by mass of the cationically polymerizable component (A), the epoxy propyl group of a polyol with a molecular weight of 200 or more Epoxy propyl compound (A1) 10~99 mass parts, alicyclic epoxy compound or polyhydric alcohol alkylene oxide adduct (A2) 1 to 50 parts by mass, 0 to 80 parts by mass of aromatic epoxy compound (A3), 0 to 50 parts by mass of oxetane compound, and 0 to 20 parts by mass of vinyl ether compound can increase viscosity and coating Clothability, reactivity and hardening properties are preferred.

The cationic polymerization initiator (B) of the curable composition of the present invention refers to a compound that can release a substance that initiates cationic polymerization by energy ray irradiation or heating. It can be used, and it is preferably released by energy ray irradiation. The double salt of the onium salt of Lewis acid or its derivative. Representatives of this compound include the following general formula, [A] ^r+ [B] ^r-

Represents the salt of the cation and anion.

Here, the cation [A] ^{r+ is} preferably an onium, and its structure can be, for example, the following general formula [(R ² ) _a Q] ^r+

Express.

In addition, here, R ² is an organic group having 1 to 60 carbon atoms, and may contain several atoms other than carbon atoms. a is an integer from 1 to 5. R ^{2 of a} can be the same or different independently. In addition, at least one of them is preferably an organic group as described above having an aromatic ring. Q is an atom or group of atoms selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F, N=N. In addition, when the valence of Q in the cation [A] ^r+ is q, the relationship r=aq (but N=N is regarded as the valence 0) must be established.

In addition, the anion [B] ^{r- is} preferably a halide complex, and its structure can be, for example, the following general formula [LY _b ] ^r-

Express.

In addition, here, L is the metal or semimetal (Metalloid) of the central atom of the halide complex, which is B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co, etc. Y is a halogen atom. b is an integer of 3-7. In addition, when the valence of L in the anion [B] ^r- is regarded as p, the relationship r=bp must be established.

Specific examples of the anion [LY _b ] ^r- of the above general formula include tetrakis (pentafluorophenyl) borate, tetrakis (3,5-difluoro-4-methoxyphenyl) borate, and tetrafluoroboric acid root (BF ₄₎ ^-, hexafluorophosphate (PF ₆₎ ^-, hexafluoroantimonate (SbF ₆₎ ^-, hexafluoroarsenate (AsF ₆₎ ^-, hexachloro antimonate (SbCl ₆₎ ^- and the like.

In addition, the anion [B] ^r- also the following general formula _{[LY b-1 (OH)} ] r-

The constructor of the representation. L, Y, and b are the same as above. In addition, other usable anions include perchlorate ion (ClO ₄ ) ^- , trifluoromethyl sulfite ion (CF ₃ SO ₃ ) ^- , fluorosulfonic acid ion (FSO ₃ ) ^- , toluenesulfonic acid anion, Trinitrobenzene sulfonate anion, camphor sulfonate, nonafluorobutane sulfonate, hexafluorooctane sulfonate, tetraaryl borate, tetrakis (pentafluorophenyl) borate, etc.

In the curable composition of the present invention, among such onium salts, it is particularly effective to use the following aromatic onium salts (A) to (C). Among these, one type can be used alone or two or more types can be mixed and used.

(A) Phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate, 4-methylphenyldiazonium hexafluorophosphate and other aryl diazonium salts

(B) Diphenyl hexafluoroantimonate, bis(4-methylphenyl) hexafluorophosphate, bis(4-tert-butylphenyl) hexafluorophosphate, tolylcumene Diaryl iodonium salts such as pentafluorophenyl borate

(C) The following group I or group II represented by alumium cation and hexafluoroantimony ion, hexafluorophosphate ion, tetrakis (pentafluorophenyl) borate ion, etc.

Moreover, other preferable ones include (η ⁵ -2,4-cyclopentadien-1-yl) [(1,2,3,4,5,6-η)-(1-methylethyl) Benzene]-iron-hexafluorophosphate and other iron-arene complexes, or ginseng (acetone) aluminum, ginseng (acetate ethyl) aluminum, ginseng (salicylic aldehyde) aluminum and other aluminum complexes Mixtures with silanols such as triphenylsilanol; thiophenium salt, thiolanium, benzylammonium, pyridinium salt, hydrazinium salt, etc.; diethylenetriamine, tris Polyalkyl polyamines such as ethylene triamine and tetraethylene pentamine; 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane, isophor Alicyclic polyamines such as ketonediamines; aromatic polyamines such as m-xylylenediamine, diaminodiphenylmethane, diaminodiphenylmethane, etc.; the above-mentioned polyamines are made by general methods Glycidyl ethers such as phenyl glycidyl ether, butyl glycidyl ether, bisphenol A-diglycidyl ether, bisphenol F-diglycidyl ether, etc. or glycidyl ester of carboxylic acid The polyepoxy adduct modified product produced by the reaction of various epoxy resins such as epoxy resins; the above-mentioned organic polyamines are reacted with carboxylic acids such as phthalic acid, isophthalic acid, and dimer acid by a general method. The produced amide modified product; the above-mentioned polyamines, formaldehyde and other aldehydes, phenols, cresols, xylenol, tertiary butylphenol, resorcinol, etc., have at least one in the core by a general method Mannich modified product produced by phenolic reaction in the aldehyde reactive site; polycarboxylic acid (oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid) , Azelaic acid, sebacic acid, dodecanedioic acid, 2-methylsuccinic acid, 2-methyladipic acid, 3-methyladipic acid, 3-methylglutaric acid, 2-methyl Aliphatic dicarboxylic acids such as suberic acid, 3,8-dimethyl sebacic acid, 3,7-dimethyl sebacic acid, hydrogenated dimer acid, dimer acid; phthalic acid, terephthalic acid Aromatic dicarboxylic acids such as formic acid, isophthalic acid and naphthalenedicarboxylic acid; alicyclic dicarboxylic acids such as cyclohexane dicarboxylic acid; trimellitic acid, trimesic acid, castor oil Tricarboxylic acids such as trimers of fatty acids; tetracarboxylic acids such as pyromellitic acid, etc.) anhydrides; dicyandiamide, imidazoles, carboxylic acid esters, sulfonates, amide imides, etc.

Among these, from the viewpoint of practicality and improvement of photosensitivity, it is preferable to use aromatic iodonium salt, aromatic sulfonium salt, iron-arene complex; relative to 100% by mass of the cationic polymerization initiator (B), and More preferably, it contains at least 0.1% by mass or more of an aromatic sulfonium salt having the following structure.

Here, in the formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a halogen atom, and the number of carbon atoms from 1 to 10 alkyl group, C 1-10 alkoxy group or C 2-10 ester group, R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent a hydrogen atom, a halogen atom or the number of carbon atoms An alkyl group of 1 to 10, R ²⁵ represents a hydrogen atom, a halogen atom, an alkyl group of 1 to 10 carbon atoms, or any substituent selected from the following chemical formulas (A) to (C), An ^q- represents q For a valence anion, p represents a coefficient that makes the charge neutral.

Here, in the formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ each independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbon atoms, and 1 to 10 carbon atoms R ³⁰ , R ³¹ , R ³² , R ³³ and R ³⁴ each independently represent a hydrogen atom, a halogen atom or an alkyl group with 1 to 10 carbon atoms.

In the compound represented by the above general formula (1), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , Halogen represented by R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ Examples of the atom include fluorine, chlorine, bromine, and iodine.

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ represent alkyl groups with 1 to 10 carbon atoms, including Methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, isobutyl, pentyl, isopentyl, t-pentyl, hexyl, cyclohexyl, heptyl, Octyl, nonyl, ethyloctyl, 2-methoxyethyl, 3-methoxypropyl, 4-methoxybutyl, 2-butoxyethyl, methoxyethoxyethyl Group, methoxyethoxyethoxyethyl, 3-methoxybutyl, 2-methylthioethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloro Methyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, difluoroethyl, trichloroethyl, dichlorodifluoroethyl, pentafluoroethyl, heptafluoropropyl, nine Fluorobutyl, decafluoropentyl, tridecafluorohexyl, pentafluoroheptyl, heptafluorooctyl, methoxymethyl, 1,2-epoxyethyl, methoxyethyl, methoxy Ethoxymethyl, methylthiomethyl, ethoxyethyl, butoxymethyl, t-butylthiomethyl, 4-pentenoxymethyl, trichloroethoxymethyl, Bis(2-chloroethoxy)methyl, methoxycyclohexyl, 1-(2-chloroethoxy)ethyl, 1-methyl-1-methoxyethyl, ethyldithioethyl , Trimethylsilylethyl, t-butyldimethylsilyloxymethyl, 2-(trimethylsilyl)ethoxymethyl, t-butoxycarbonylmethyl, ethyl Oxycarbonylmethyl, ethylcarbonylmethyl, t-butoxycarbonylmethyl, acryloxyethyl, methacryloxyethyl, 2-methyl-2-adamantyloxycarbonylmethyl Group, acetoxyethyl, 2-methoxy-1-propenyl, hydroxymethyl, 2-hydroxyethyl, 1-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3-hydroxy Butyl, 4-hydroxybutyl, 1,2-dihydroxyethyl, etc.

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ represent alkoxy groups having 1 to 10 carbon atoms, including methoxy, ethoxy, propoxy, isopropoxy, Butoxy, s-butoxy, t-butoxy, isobutoxy, pentoxy, isopentoxy, t-pentoxy, hexyloxy, cyclohexyloxy, cyclohexylmethoxy , Tetrahydrofuranoxy, tetrahydropyranoxy, 2-methoxyethoxy, 3-methoxypropoxy, 4-methoxybutoxy, 2-butoxyethoxy, methoxy Group ethoxyethoxy, methoxyethoxyethoxyethoxy, 3-methoxybutoxy, 2-methylthioethoxy, trifluoromethoxy and the like.

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ represent ester groups with 2 to 10 carbon atoms, including methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, and phenoxy Carbonyl, acetoxy, propoxy, butoxy, chloroacetoxy, dichloroacetoxy, trichloroacetoxy, trifluoroacetoxy, t-butylcarbonyl Oxy, methoxyacetoxy, benzyloxy and the like.

The use ratio of the cationic polymerization initiator (B) is 0.1-10 parts by mass of the cationic polymerization initiator (B) relative to 100 parts by mass of the total of component (A), component (B) and component (C), preferably It is 1 to 6 parts by mass. When the amount is too small, the hardening is likely to be insufficient. When the amount is too large, it may adversely affect various physical properties such as the water absorption rate and the strength of the hardened product.

The radically polymerizable component (C) of the curable composition of the present invention is a compound having an epoxy group and an ethylenically unsaturated group (C1) or an acrylate of an alcohol with 2 to 20 carbon atoms or an acrylate with 2 to 20 carbon atoms. ~20 alcohol methacrylate (C2) is an essential ingredient.

The compound (C1) having an epoxy group and an ethylenically unsaturated group includes, for example, epoxy acrylate or epoxy methacrylate. Specifically, conventionally known aromatic epoxy resins and alicyclic Formula epoxy resins, aliphatic epoxy resins, etc., are acrylates obtained by reacting with acrylic acid or methacrylic acid. Among these epoxy acrylates or epoxy methacrylates, acrylate or methacrylate of glycidyl ether of alcohols is particularly preferred.

The above-mentioned acrylates of alcohols with 2 to 20 carbon atoms or methacrylates (C2) of alcohols with 2 to 20 carbon atoms include aromatic or aliphatic alcohols having at least one hydroxyl group in the molecule and their rings Acrylate or methacrylate obtained by reacting an oxane adduct with acrylic acid or methacrylic acid. Specifically, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isoamyl acrylate, lauryl acrylate, octadecyl acrylate, and isooctyl acrylate can be cited. Acrylate, tetrahydrofurfuryl propylene Acrylate, isobornyl acrylate, benzyl acrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, diethyl Glycol diacrylate, triethylene glycol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, Dipentaerythritol hexaacrylate, ε-caprolactone modified dipentaerythritol hexaacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, iso Amyl methacrylate, lauryl methacrylate, octadecyl methacrylate, isooctyl methacrylate, tetrahydrofurfuryl methacrylate, isobornyl methacrylate, benzyl Methacrylate, 1,3-Butanediol Dimethacrylate, 1,4-Butanediol Dimethacrylate, 1,6-Hexanediol Dimethacrylate, Diethylene Glycol Dimethacrylate Base acrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylolpropane trimethyl Acrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexamethacrylate, ε-caprolactone is modified dipentaerythritol hexamethacrylate, etc. Furthermore, among these acrylates or methacrylates, polyacrylates of polyols or polymethacrylates of polyols are particularly preferred.

The above-mentioned radically polymerizable component (C) may be a compound other than (C1) or (C2), which is polymerized or cross-linked by a radical polymerization initiator activated by energy ray irradiation or heating. For example, an allyl carbamate compound, an unsaturated polyester compound, a styrene compound, etc. are mentioned. The above (C1) component and (C2) component in the radical polymerizable component (C) The ratio of is preferably 50% by mass or more.

The radical initiator (D) of the curable composition of the present invention is not particularly limited, and conventional ones can be used. For example, ketone-based compounds such as acetophenone-based compounds, benzyl-based compounds, benzophenone-based compounds, and thioxanthone-based compounds, and oxime-based compounds can be used.

The polymer (E) of the curable composition of the present invention is selected from polymers derived from the monomer represented by the above formula (I), polymers derived from the monomer represented by the above formula (II), selected from the above formula ( I) A polymer obtained from two or more monomers of the monomer represented by the above formula (II), a polymer obtained from two or more monomers selected from the monomer represented by the above formula (II), and a monomer represented by the above formula (I) The weight average molecular weight is 1,000 to 30,000 in terms of polystyrene.

The alkyl group having 1 to 7 carbon atoms represented by X in the above formula (I) includes methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso -Butyl, pentyl, iso-pentyl, tert-pentyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 4-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, iso-heptyl, tert-heptyl, etc. Among them, from the viewpoint of hardening, the alkyl group with 1 to 4 carbon atoms or one or more groups selected from the group consisting of epoxy group, oxetanyl group, hydroxyl group and carboxyl group are partially substituted The alkyl group with 1 to 4 carbon atoms is preferred.

The alkoxy group having 1 to 7 carbon atoms represented by X in the above formula (I) includes methoxy, ethoxy, propoxy, iso-propoxy, butoxy, and sec-butoxy , Tert-butoxy, iso-butoxy, pentyloxy, iso-pentoxy, tert-pentoxy, hexyloxy, 2-hexyloxy, 3-hexyloxy, ring Hexyloxy, 4-methylcyclohexyloxy, heptyloxy, 2-heptyloxy, 3-heptyloxy, iso-heptyloxy, tert-heptyloxy, etc. Among these, from the viewpoint of curability, an alkoxy group having 1 to 4 carbon atoms or one or more groups selected from the group consisting of epoxy group, oxetanyl group, hydroxyl group, and carboxyl group are part of it. The substituted alkoxy group having 1 to 4 carbon atoms is preferred.

The aryl group having 6 to 12 carbon atoms represented by X in the above formula (I) includes phenyl, methylphenyl, naphthyl and the like.

The aryloxy group having 6 to 12 carbon atoms represented by X in the above formula (I) includes a phenoxy group, a methylphenoxy group, and a naphthoxy group.

The alicyclic hydrocarbon group with 6 to 10 carbon atoms represented by X in the above formula (I) includes cyclohexyl, methylcyclohexyl, norbornyl, dicyclopentyl, bicyclooctyl, and trimethylbicycloheptyl , Tricyclooctyl, tricyclodecyl, spirooctyl, spirobicyclopentyl, adamantyl, isobornyl, etc.

These alkyl groups, alkoxy groups, aryl groups, aryloxy groups and alicyclic hydrocarbon groups can be selected from the group consisting of epoxy, oxetanyl, hydroxy and carboxyl groups. A group of more than one group is substituted.

In the above formula (I), a part of X is a monomer represented by the formula (I) when it is substituted with an epoxy group or an oxetanyl group. Examples include the monomers represented by the following formulas (1) to (3) body.

Here, in formula (1), R ³ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and m is an integer of 1 to 6.

Here, in formula (2), R ⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n is an integer of 1 to 6.

Here, in formula (3), R ⁵ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and s is an integer of 1 to 6.

In the above formula (II), ^{the halogen atom represented by R 1} includes fluorine, chlorine, bromine, and iodine.

In the above formula (II), the alkyl group with 1 to 7 carbon atoms, the aryl group with 6 to 12 carbon atoms or the alicyclic hydrocarbon group with 6 to 10 carbon atoms of X'can be exemplified by the above formula (I) Same thing.

In the above formula (II), when a part of X'is substituted with an epoxy group or an oxetanyl group, the monomer represented by the formula (II) may be represented by the following formulas (4) to (6) By.

Here, in the formula (4), R ¹ is the same as the above formula (II), R ⁶ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and t is an integer of 1 to 6.

Here, in the formula (5), R ¹ is the same as the above formula (II), R ⁷ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and q is an integer of 1 to 6.

Here, in the formula (6), R ¹ is the same as the above formula (II), R ⁸ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and y is an integer of 1 to 6.

In the above-mentioned polymer (E), the use ratio of the monomers constituting the polymer is that the above-mentioned X is a carbon substituted with one or more groups selected from the group consisting of epoxy group, cyclobutane group, hydroxyl group and carboxyl group In the case of an alkyl group with 1 to 7 atoms, an aryl group with 6 to 12 carbon atoms, or an alicyclic hydrocarbon group with 6 to 10 carbon atoms, make the monomer represented by (I) or (II) above 10-100 mass % To use, because the adhesion is improved, so it is better.

In the curable composition of the present invention, the cationic polymerizable component (A) is 30 to 99 parts by mass, preferably 40 to 95 parts by mass, and the cationic polymerization initiator (B) is 0.1 to 10 parts by mass. It is preferably 1 to 8 parts by mass, the radical polymerizable component (C) is 0 to 55 parts by mass, and the radical polymerization initiator (D) is 0 to 10 parts by mass, preferably 0.1 to 8 parts by mass, The said polymer (E) is 1-30 mass parts. If the blending ratio is other than the above, the curability and adhesion of the cured product may be deteriorated.

In the curable composition of the present invention, a sensitizer and/or a sensitizer auxiliary may be further used as needed. The sensitizer is a compound that exhibits maximum absorption at a wavelength longer than the maximum absorption wavelength shown by the cationic polymerization initiator (B), and promotes the polymerization initiation reaction by the cationic polymerization initiator (B). In addition, the sensitization aid is a compound that further promotes the action of the sensitizer.

Examples of sensitizers and sensitization aids include anthracene-based compounds and naphthalene-based compounds.

Examples of the anthracene compound include those represented by the following formula (7).

Here, in formula (7), R ⁵⁰ and R ⁵¹ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxyalkyl group having 2 to 12 carbon atoms, and R ⁵² represents a hydrogen atom or An alkyl group with 1 to 6 carbon atoms.

Specific examples of the anthracene compound represented by the above formula (7) include the following compounds.

Examples include 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-diisopropoxyanthracene, 9,10-dibutyl Oxyanthracene, 9,10-dipentyloxyanthracene, 9,10-dihexoxyanthracene, 9,10-bis(2-methoxyethoxy)anthracene, 9,10-bis(2-ethyl Oxyethoxy)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-di Propoxyanthracene, 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.

Examples of the naphthalene-based compound include those represented by the following formula (8).

Here, in formula (8), R ⁵³ and R ⁵⁴ each independently represent an alkyl group having 1 to 6 carbon atoms.

When specific examples of the naphthalene-based compound represented by the above formula (8) are given, there are the following compounds.

Examples include 4-methoxy-1-naphthol, 4-ethoxy-1-naphthol, 4-propoxy-1-naphthol, 4-butoxy-1-naphthol, 4-hexyl Oxy-1-naphthol, 1,4-dimethoxynaphthalene, 1-ethoxy-4-methoxynaphthalene, 1,4-diethoxynaphthalene, 1,4-dipropoxynaphthalene , 1,4-Dibutoxynaphthalene, etc.

Relative to the above-mentioned cationically polymerizable component (A), sensitization The use ratio of the agent and the sensitization aid is not particularly limited, as long as it is within a range that does not hinder the purpose of the present invention, it may be used in a general use ratio, for example, relative to 100 parts by mass of the above-mentioned cationically polymerizable component (A). From the viewpoint of improving the hardenability, the sensitizer and the sensitizer auxiliary are preferably 0.1 to 3 parts by mass each.

In the curable composition of the present invention, a silane coupling agent can be used as needed. As the silane coupling agent, for example, dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, and methyltrimethoxysilane can be used. , Methyl triethoxy silane, ethyl trimethoxy silane, ethyl trimethoxy silane and other alkyl functional alkoxy silanes, vinyl trichlorosilane, vinyl trimethoxy silane, vinyl triethyl Alkenyl functional alkoxysilanes such as oxysilane, allyltrimethoxysilane, etc., 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane Methoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 2-methacryloxypropyltrimethyl Oxyoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyl diethoxysilane, β-(3,4-epoxycyclohexyl)ethyl Epoxy functional alkoxysilane such as trimethoxysilane, N-β(aminoethyl)-γ-aminopropyl trimethoxysilane, γ-aminopropyltriethoxysilane, N -Phenyl-γ-aminopropyltrimethoxysilane such as amino functional alkoxysilane, γ-mercaptopropyltrimethoxysilane such as mercapto functional alkoxysilane, tetraisopropane titanium oxide, Titanium alkoxides such as tetra-n-butane titanium oxide, titanium dioctyloxy bis (octyl glycolate), titanium diisopropoxy bis (ethyl acetyl acetate) and titanium chelate Zirconium chelate Materials, zirconium amides such as tributoxy zirconium monostearate, isocyanate silanes such as methyl triisocyanate silane, etc.

The amount of the silane coupling agent used is not particularly limited, but it is usually in the range of 0.01 to 20 parts by mass relative to 100 parts by mass of the total solid content in the curable composition.

In the curable composition of the present invention, by using a thermoplastic organic polymer as needed, the properties of the cured product can also be improved. Thermoplastic organic polymers, for example, polystyrene, polymethyl methacrylate, methyl methacrylate ethyl acrylate copolymer, methyl methacrylate glycidyl methacrylate copolymer, poly(methyl methacrylate) ) Acrylic acid, styrene-(meth)acrylic acid copolymer, (meth)acrylic acid-methyl methacrylate copolymer, glycidyl (meth)acrylate-polymethyl(meth)acrylate copolymer, Polyvinyl butyral, cellulose ester, polypropylene amide, saturated polyester, etc.

In the curable composition of the present invention, a UV absorber may be further used as needed, or it may be inactive at room temperature, and the protective group will be detached and activated by heating to a specific temperature/light irradiation/acid, etc., thereby exhibiting UV absorption Ability compound.

In addition, as long as the effects of the present invention are not impaired, coloring agents such as polyols, inorganic fillers, organic fillers, pigments, dyes, defoamers, thickeners, surfactants, leveling agents, and flame retardants can be added as needed. Various resin additives such as additives, thixotropic agents, diluents, plasticizers, stabilizers, polymerization inhibitors, ultraviolet absorbers, antioxidants, antistatic agents, flow regulators, adhesion promoters, etc.

The curable composition of the present invention is not particularly limited, and it can be Use a commonly used solvent that can dissolve or disperse the above-mentioned (A), (B), (C), (D), and (E) components. Examples of the solvent include ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; Ether solvents such as diethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, propylene glycol monomethyl ether, dipropylene glycol dimethyl ether, etc.; methyl acetate, Ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, 2,2,4-trimethyl-1,3 -Ester solvents such as pentanediol isobutyric acid (Texanol); cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; methanol, ethanol, iso- or n-propanol, iso- Or alcohol solvents such as n-butanol and pentanol; 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 and other ether ester solvents; benzene, toluene, xylene, etc. BTX solvents; hexane Aliphatic hydrocarbon solvents such as, heptane, octane, and cyclohexane; terpene hydrocarbon oils such as turpentine, D-limonene, pinene, etc.; mineral spirits, Swasol#310 (manufactured by Cosmo Songshan Petroleum Co., Ltd.) ), Solvesso#100 (Exxon Chemical Company) and other paraffinic solvents; halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, 1,2-dichloroethane, etc.; chlorine Halogenated aromatic hydrocarbon solvents such as benzene; propylene carbonate, carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N,N-dimethylformamide, N,N- Dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, water, etc. These solvents can be used singly or as a mixed solvent of two or more kinds.

The curable composition of the present invention improves curability, adhesiveness, and liquid storage stability, so the water content is preferably 5 parts by mass or less, and more preferably 3 parts by mass or less. When the moisture is too much, it will cause white turbidity or doubts about the composition, so it is not good.

The curable composition of the present invention is applied to the supporting substrate by known means such as roll coater, curtain coater, various printing, dipping, and the like. In addition, once applied to a supporting substrate such as a film, it can be transferred to another supporting substrate. The application method is not limited.

The material of the above-mentioned support matrix is not particularly limited, and ordinary users can be used, such as inorganic materials such as glass; diacetyl cellulose, triacetyl cellulose (TAC), acryl cellulose, butyric cellulose Cellulose esters of cellulose, acetyl propyl cellulose, nitrocellulose, etc.; polyamide; polyimide; polyurethane; epoxy resin; polycarbonate; polyterephthalate Ethylene formate, polyethylene naphthalate, polybutylene terephthalate, poly-1,4-cyclohexanedimethylene polyterephthalate, polyethylene-1,2- Polyesters such as diphenoxyethane-4,4'-dicarboxylate and polybutylene terephthalate; polystyrene; polyolefins such as polyethylene, polypropylene, and polymethylpentene; Vinyl compounds such as polyvinyl acetate, polyvinyl chloride, and polyvinyl fluoride; acrylic resins such as polymethyl methacrylate and polyacrylate; polycarbonate; polyether; polyether ketone; polyether ketone; poly Ether imine; polyoxyethylene, norbornene resin, cyclic olefin polymer (COP) and other polymer materials. In addition, surface activation treatments such as corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, and laser treatment may be performed on the above-mentioned support substrate.

In the method of curing the curable composition of the present invention by irradiating energy rays, the energy rays include ultraviolet rays, electron rays, X-rays, radiation rays, high frequency, etc., and ultraviolet rays are economically optimal. The light source of ultraviolet light can include ultraviolet laser, mercury lamp, xenon laser, metal halide lamp, etc.

The conditions of the method of curing the curable composition of the present invention by heating are 70 to 250° C. for 1 to 100 minutes. It can be pre-baked (PAB; Pre applied bake) and then pressurized to perform post-bake (PEB; Post exposure bake); it can also be baked at different temperatures in several stages. Although the heating conditions vary depending on the types and blending ratios of the ingredients, for example, at 70-180°C, the oven takes 5 to 15 minutes, and the hot plate takes 1 to 5 minutes. Then, in order to harden the coating film, heat treatment is performed at 180 to 250°C, preferably 200 to 250°C, in an oven for 30 to 90 minutes, and a hot plate for 5 to 30 minutes, to obtain a cured film.

Specific uses of the curable composition of the present invention or its cured product include adhesives, glasses, optical materials represented by photographic lenses, paints, coating agents, lining agents, inks, and resists. , Liquid resists, printing plates, color TVs, PC monitors, mobile information terminals, digital cameras, organic EL, touch panels and other display elements, insulating varnishes, insulating sheets, laminates, printed circuit boards, semiconductor devices/ LED encapsulation/liquid crystal injection port/organic EL/optical element/electrical insulation/electronic parts/separation film, etc. encapsulant, molding material, putty, glass fiber impregnant, wood powder filler, semiconductor use/ Passivation films for solar cells, interlayer insulating films, protective films, lenticular lens sheets used in backlights of liquid crystal display devices, Fresnel lens sheets used in screens of projection TVs, etc., biconvex Lens parts of lens sheets such as lens sheets, or backlights, etc. using such sheets, optical lenses such as microlenses, optical elements, optical connectors, optical waveguides, optical casting agents, etc.

The display device of the present invention can be enumerated on a transparent support provided with a primer layer, an anti-reflection layer, a polarizing element layer, a retardation layer, a birefringence layer, a light scattering layer, a hard coating layer, a lubricating layer, and a protective layer as required. For each layer, a film made of the cured product of the present invention can be used for each layer.

[Example]

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

[Examples 1-11, Comparative Example 1]

With the formulations shown in the following [Table 1] and [Table 2], each component was thoroughly mixed to obtain the curable composition of each of Examples 1 to 11 and the curable composition of Comparative Example 1. In addition, the units of Examples and Comparative Examples are parts by mass.

The following compounds (A1-1) to (A1-2) and (A2-1) to (A2-2) are used as the cationically polymerizable component (A).

Compound (A1-1): ADEKA Resin EP-4088L (manufactured by ADEKA Corporation)

Compound (A1-2): 1,6-hexanediol diglycidyl ether

Compound (A2-1): CELLOXID2021P (alicyclic epoxy group: manufactured by DAICEL Co., Ltd.)

Compound (A2-2): Limonene dioxide

Compound (A4-1): Aron Oxetane OXT-221 (manufactured by Toagosei Co., Ltd.)

The following compound (B-1) was used as the cationic polymerization initiator (B).

Compound (B-1): Propylene carbonate 50% solution of a mixture of the compound represented by the following formula (9) and the compound represented by the following formula (10)

The radical polymerizable component (C) uses the following compound (C2-1).

Compound (C2-1): 1,6-hexanediol diacrylate

Compound (C2-2): Ethoxylated isocyanuric acid triacrylate

Compound (C2-3): Tetrahydrofurfuryl acrylate

As the radical polymerization initiator (D), the following compound (D-1) was used.

Compound (D-1): IRGACURE184 (manufactured by BASF)

For the polymer (E), the following compound (E-1) was used.

Polymer (E-1): a copolymer of 75 parts by mass of methyl methacrylate and 25 parts by mass of glycidyl methacrylate (weight average molecular weight 7,000)

Polymer (E-2): a copolymer of 35 parts by mass of methacrylate, 35 parts by mass of styrene, and 30 parts by mass of glycidyl methacrylate (weight average molecular weight 8,000)

For each curable composition of Examples 1-11 and Comparative Example 1 obtained, the evaluation of glass transition temperature (Tg), elastic modulus, and adhesion was evaluated according to the following procedures. The results are recorded in [Table 1] and [Table 2].

(Glass transition temperature and elastic modulus)

The curable compositions of Examples 1 to 11 and Comparative Example 1 were respectively coated on a polyethylene terephthalate (PET) film with a coating bar to form a thickness of 30 μm, and irradiated with a metal halide lamp 3000mJ/cm ² energy. After 24 hours, the cured adhesive was taken out from the film, and a viscoelasticity measuring device (DMA7100) manufactured by Hitachi High-Tech Science was used to measure Tg and elastic modulus at 80°C.

(Viscosity)

For the obtained curable compositions of Examples 1-11 and Comparative Example 1, the viscosity at 25° C. was measured with an E-type viscometer. The results are recorded in [Table 1] and [Table 2].

(Adhesion)

The curable compositions of Examples 1-11 and Comparative Example 1 obtained above were each coated on a corona-treated PMMA film (manufactured by Sumitomo Chemical Co., Ltd.: Technolloy 125S001), and then used a laminator and another A piece of corona discharge treated COP (cycloolefin polymer, Japan Zeon Co., Ltd.: model Zeonor Film 14-060) film is laminated, and an electrodeless ultraviolet lamp is used to irradiate the COP film with equivalent to 1000mJ/cm ² Light was followed to obtain a test piece. A 90-degree peel test was performed on the obtained test piece. The results are shown in [Table 1] and [Table 2].

From [Table 1] to [Table 2], it is known that the cured product of the curable composition system of the present invention has a high glass transition temperature and excellent adhesion.

Claims (6)

A curable composition containing: 30 to 99 parts by mass of cationic polymerizable component (A), 0.1 to 10 parts by mass of cationic polymerization initiator (B), and 0 to 55 parts by mass of radical polymerizable component (C) , Free radical polymerization initiator (D) 0-10 parts by mass and selected from the following formula (I)

(In the formula, X is an alkyl group with 1 to 7 carbon atoms, an alkoxy group with 1 to 7 carbon atoms, an aryl group with 6 to 12 carbon atoms, an aryloxy group with 6 to 12 carbon atoms or carbon atoms The alicyclic hydrocarbon group of number 6 to 10, or the hydrogen atom in these groups is substituted by one or more groups selected from the group consisting of epoxy group, oxetanyl group, hydroxyl group and carboxyl group的) The polymer obtained from the monomer represented by the following formula (II)

(In the formula, R ¹ represents a hydrogen atom, a methyl group or a halogen atom, and X'is an alkyl group with 1 to 7 carbon atoms, an aryl group with 6 to 12 carbon atoms or an alicyclic hydrocarbon group with 6 to 10 carbon atoms , Or the hydrogen atom in these groups is substituted by one or more groups selected from the group consisting of epoxy group, oxetanyl group, hydroxyl group and carboxyl group).物, a polymer obtained from two or more monomers selected from the monomer represented by the aforementioned formula (I), a polymer obtained from two or more monomers selected from the monomer represented by the aforementioned formula (II), or selected The polymer obtained from the monomer represented by the aforementioned formula (I) and the monomer represented by the aforementioned formula (II) forms a group of 1 to 30 parts by mass of the polymer (E) with a weight average molecular weight of 1,000 to 30,000, so that the aforementioned cation The total of the polymerizable component (A), the aforementioned radical polymerizable component (C), and the aforementioned polymer (E) is 100 parts by mass, and the aforementioned cationic polymerizable component (A) is propylene oxide of a polyol with a molecular weight of 200 or more. The glycidyl compound or the glycidyl compound (A1) and the alicyclic epoxy compound (A2) of the polyol alkylene oxide adduct are essential components, and the aforementioned radical polymerizable component (C) has a ring The compound of oxy group and ethylenically unsaturated group (C1), or the acrylate of an alcohol with 2 to 20 carbon atoms or the methacrylate of an alcohol with 2 to 20 carbon atoms (C2) are essential components, among which the aforementioned molecular weight The polyol in the glycidyl product of a polyhydric alcohol of 200 or more or the glycidyl product (A1) of a polyol alkylene oxide adduct is a polyhydric alcohol having a condensed ring. The curable composition of claim 1, wherein the aforementioned alicyclic epoxy compound (A2) is selected from 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylic acid Esters, 7-oxabicyclo[4.1.0]heptane, poly[oxy-(1-oxo-1,6-hexanediyl)] derivatives, adipic acid bis[(7-oxadi Cyclo[4.1.0]heptan-3-yl)methyl], 1,2-epoxy-4-vinylcyclohexane, 3,4-epoxycyclohexyl methyl methacrylate and limonene One or more of the group of oxides. The curable composition of claim 1, wherein the aforementioned polymer (E) is a polymerization obtained from a monomer represented by the aforementioned formula (I) and a monomer represented by the aforementioned formula (II) In the aforementioned formula (I), X is an aryl group with 6 to 12 carbon atoms, and X'in the aforementioned formula (II) is an alkyl group with 1 to 7 carbon atoms. The aforementioned alkyl group is substituted by an epoxy group. . A hardening method of a hardening composition, which is to irradiate active energy rays to the hardening composition according to any one of claims 1 to 3. A hardening method of a hardening composition, which is to heat the hardening composition according to any one of claims 1 to 3. A hardened product, which is a hardened product of the hardenable composition according to any one of claims 1 to 3.