KR20170133311A - Composition - Google Patents

Abstract

(식 중, R¹, R², R³ 및 R⁴는, 각각 독립적으로 수소 원자, 탄소 원자 수 1~5의 알킬기, 탄소 원자 수 1~8의 알콕시기, 탄소 원자 수 2~5의 알케닐기 또는 할로겐 원자를 나타내고, m은 0~10의 정수이다.)The present invention provides a composition having excellent adhesiveness, heat resistance and liquid storage stability, and more specifically, a composition comprising a mixture (1) of a cationic polymerizable compound, wherein the mixture (1) (1B), an alicyclic epoxy compound (1C), and an oxetane compound (1D), as a main component, and an aromatic ring-containing epoxy compound By weight of the composition.

(Wherein R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkene having 2 to 5 carbon atoms A halogen atom or a halogen atom, and m is an integer of 0 to 10.)

Description

Composition {COMPOSITION}

The present invention relates to a composition and a cured product obtained by irradiating the composition with active energy rays. The composition is particularly useful for adhesives.

The cationic polymerizable composition is used in the fields of inks, paints, various coating agents, adhesives, optical members and the like.

For example, the following Patent Documents 1 to 3 disclose various cationic polymerizable compositions.

However, the cured product of the cationic polymerizable composition described in these documents is not sufficient in adhesiveness or heat resistance.

Japanese Patent Application Laid-Open No. 10-279658 Japanese Patent Application Laid-Open No. 2003-313274 Japanese Patent Application Laid-Open No. 2010-229392

An object of the present invention is to provide a composition excellent in adhesiveness, heat resistance and liquid storage stability.

The present invention is based on the above finding and comprises a mixture (1) of a cationic polymerizable compound, wherein the mixture (1) comprises an aromatic ring-containing epoxy compound (1A) represented by the following general formula (I) And at least one selected from an aliphatic epoxy compound (1B), an alicyclic epoxy compound (1C), and an oxetane compound (1D) as a main component. It is.

(Wherein R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkene having 2 to 5 carbon atoms A halogen atom or a halogen atom, and m is an integer of 0 to 10.)

The present invention also provides an adhesive comprising the above composition.

Since the composition of the present invention is excellent in adhesiveness and heat resistance, it is particularly useful as an adhesive.

Hereinafter, the composition of the present invention and the adhesive comprising the composition will be described in detail based on preferred embodiments.

In the mixture (1) of the cationic polymerizable compound used in the present invention, the cationic polymerizable compound constituting the mixture is polymerized or crosslinked (crosslinked) by a cationic polymerization initiator activated by light An epoxy compound, an oxetane compound, a cyclic lactone compound, a cyclic acetal compound, a cyclic thioether compound, a spiroorthoester compound, a vinyl ether, and the like can be used as the cationic polymerizable compound. Containing epoxy compound (1A) represented by the general formula (I) as a main component. In addition, it is essential that it contains at least one of aliphatic epoxy compound (1B), alicyclic epoxy compound (1C) and oxetane compound (1D). The main component is a mixture of several kinds of cationic polymerizable compounds, which means that the total mass of the same kind of cationic polymerizable compounds is the largest.

In the aromatic ring-containing epoxy compound (1A) represented by the general formula (I), the alkyl group having 1 to 5 carbon atoms represented by R ¹ , R ² , R ³ and R ⁴ in the general formula (I) Butyl, isobutyl, amyl, iso-amyl, tert-amyl, and the like, and examples thereof include methyl, ethyl, propyl, isopropyl, butyl, sec-

Examples of the alkoxy group having 1 to 8 carbon atoms represented by R ¹ , R ² , R ³ and R ⁴ include methoxy, ethoxy, propyloxy, isopropyloxy, butoxy, pentyloxy, iso-pentyloxy, hexyloxy Heptyloxy, octyloxy, 2-ethylhexyloxy and the like,

Examples of the alkenyl group having 2 to 5 carbon atoms represented by R ¹ , R ² , R ³ and R ⁴ include vinyl, allyl, butenyl, and propenyl.

Examples of the halogen atom represented by R ¹ , R ² , R ³ and R ⁴ include fluorine, chlorine, bromine and iodine. The halogen atoms in this specification are all the same.

As the aromatic ring-containing epoxy compound (1A) represented by the general formula (I), R ¹ , R ² , R ³ and R ⁴ are preferably hydrogen or a methyl group in view of reducing the epoxy equivalent, Do.

Examples of the aliphatic epoxy compound (1B) include monofunctional epoxy compounds such as glycidyl ether compounds of aliphatic alcohols and glycidyl esters of alkylcarboxylic acids, polyglycidyl ether compounds of aliphatic polyhydric alcohols or alkylene oxide adducts thereof , Polyglycidyl esters of aliphatic long chain polybasic acids, and other polyfunctional epoxy compounds. Representative compounds include allyl glycidyl ether, butyl glycidyl ether, sec-butylphenyl glycidyl ether, 2-ethylhexyl glycidyl ether, C12-13 mixed alkyl glycidyl ether, 1,4-butanediol diglycidyl ether Cydyl ether, 1,6-hexanediol diglycidyl ether, triglycidyl ether of glycerin, triglycidyl ether of trimethylol propane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol , Neopentyl glycol diglycidyl ether, diglycidyl ether of polyethylene glycol, diglycidyl ether of polyhydric alcohol such as polyglycidyl ether of polypropylene glycol, aliphatic alcohols such as propylene glycol, trimethylol propane, glycerin and the like A polyglycidyl ether compound of a polyether polyol obtained by adding one or more alkylene oxides to a polyhydric alcohol, a diglycidyl ether of an aliphatic long chain dibasic acid It may be an ester. Also, monoglycidyl ethers of aliphatic higher alcohols, glycidyl esters of higher fatty acids, epoxidized soybean oil, octyl stearate, butyl stearate, epoxidized soybean oil, epoxidized polybutadiene and the like can be given.

As the aliphatic epoxy compound (1B), a diglycidyl ether of an aliphatic diol having 1 to 6 carbon atoms is preferable in view of the viscosity of the adhesive and the heat resistance of the cured product.

Examples of the aliphatic epoxy compound (1B) include commercially available products such as Denacol EX-121, Denacol EX-171, Denacol EX-192, Denacol EX-211, Denacol EX- Denacol EX-411, Denacol EX-411, Denacol EX-421, Denacol EX-512, Denacol EX-521, Denacol EX-611, Denacol EX-411, Denacol EX-821, Denacol EX-811, Denacol EX-850, Denacol EX-851, Denacol EX-821, Denacol EX-830 Denacol EX-932, Denacol EX-932, Denacol EX-932, Denacol EX-832, Denacol EX-841, Denacol EX-861, Denacol EX-911, Denacol EX- ; 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 Kagaku Co., Ltd.).

As the alicyclic epoxy compound (1C), a polyglycidyl ether compound of a polyhydric alcohol having at least one alicyclic ring or a cyclohexene oxide or a cyclopentene oxide-containing compound obtained by epoxidizing a cyclohexene or cyclopentane ring- . For example, hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl- Epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4- -3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 2- -Epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-methadioxane, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexylcarb Bis (3,4-epoxycyclohexyl) propane, propane-2,2-diyl-bis (3,4-epoxycyclohexane) Dicyclopentadiene diepoxide, ethylene bis (3,4-epoxyoxy Epoxyhexahydrophthalic acid di-2-ethylhexyl, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane And the like.

As the alicyclic epoxy compound (1C), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate is preferable in view of the viscosity of the adhesive and the heat resistance of the cured product.

As the alicyclic epoxy compound (1C), a commercially available product can be used. Examples of the alicyclic epoxy compound (1C) include Celloxide 2021P, Celloxide 2081, Celloxide 2000, and Celloxide 3000 (manufactured by Daicel Chemical Industries, Ltd.).

Examples of the oxetane compound (1D) include 3,7-bis (3-oxetanyl) -5-oxa-nonane, 1,4-bis [ ] Benzene, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [ (3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis Bifunctional aliphatic oxetane compounds such as 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane and 1,6-bis (3-ethyl-3-oxetanylmethoxy) Ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- ( (Hydroxymethyl) oxetane, 3-ethyl-3- (chloromethyl) oxetane, and the like. Of these, bifunctional aliphatic oxetane is preferred in view of reactivity and curability. Preferable.

As the oxetane compound (1D), 3-ethyl - {[(3-ethyloxetan-3-yl) methoxy] methyl} oxetane is particularly preferable in view of the viscosity of the adhesive and the heat resistance of the cured product.

As the oxetane compound (1D), a commercially available product can be used. Examples of the oxetane compound (1D) include oxides such as arox oxetane EXOH, POX, OXA, OXT-101, OXT-211, OXT-212 and OXT- .

A mixture of an aromatic epoxy compound (1A), an aliphatic epoxy compound (1B), an alicyclic epoxy compound (1C) and an oxetane compound (1D) represented by the general formula (I) The proportion of the aromatic polyfunctional epoxy compound (1A) is 20 to 80 parts by mass, preferably 30 to 70 parts by mass, more preferably 30 to 60 parts by mass, in 100 parts by mass of the mixture (1) of the cationic polymerizable compound (1C) is 0 to 70 parts by mass, preferably 5 to 60 parts by mass, more preferably 10 to 50 parts by mass, and the alicyclic epoxy compound (1C) is 0 to 70 parts by mass, More preferably 1 to 10 parts by mass, and the oxetane compound (1D) is contained in an amount of 0 to 70 parts by mass, preferably 5 to 60 parts by mass, more preferably 5 to 60 parts by mass, It is preferably 10 to 50 parts by mass. However, since the aromatic epoxy compound (1A) represented by the general formula (I) is the main component, its content is the largest as compared with other compounds.

As the cationic polymerizable compound, an aromatic ring-containing epoxy compound other than the aromatic ring-containing epoxy compound (1A) represented by the general formula (I) can be obtained by reacting an aromatic ring-containing epoxy compound (1A) represented by the general formula (I) Can be used together. Examples of the aromatic ring-containing epoxy compound include monohydric phenols having at least one aromatic ring such as phenol, cresol, and butylphenol, or glycidyl ether compounds of the alkylene oxide adduct thereof, such as bisphenol A, Glycidyl ether compounds or epoxy novolac resins of bisphenol F, or compounds obtained by addition of alkylene oxide thereto; Glycidyl ethers of aromatic compounds having two or more phenolic hydroxyl groups such as resorcinol, hydroquinone, and catechol; Mono / polyglycidyl ether compounds of aromatic compounds having two or more alcoholic hydroxyl groups such as benzene dimethanol, benzene diethanol and benzene dibutanol; Glycidyl esters of polybasic acid aromatic compounds having two or more carboxylic acids such as phthalic acid, terephthalic acid and trimellitic acid, glycidyl esters of benzoic acids such as benzoic acid, tolylic acid and naphthoic acid, styreneses such as styrene oxide or divinylbenzene And an epoxy compound. In this case, the content of the aromatic ring-containing epoxy compound other than the aromatic ring-containing epoxy compound (1A) represented by the above-mentioned general formula (I) is preferably 100 parts by mass or more per 100 parts by mass of the aromatic ring- Is preferably 90 parts by mass or less, more preferably 60 parts by mass or less.

The composition of the present invention may further contain a cationic polymerization initiator (2).

The cationic polymerization initiator (2) used in the present invention is not particularly limited as long as it is a compound capable of generating an acid upon irradiation with energy rays. Preferably, the cationic polymerization initiator (2) Or a derivative thereof. Representative of such compounds are compounds of the general formula < RTI ID = 0.0 >

p [A] ^{q +} s [B] ^t- (wherein A represents a cationic species, B represents an anionic species, q and t each independently represent 1 or 2, p and s represent a charge neutral , And salts of anions and cations represented by the following formulas.

Here, the cation [A] ^{q +} is preferably onium, and its structure is, for example,

_{^{[(R 10) a Q]}} q +

.

Here, R ¹⁰ is an organic group having 1 to 60 carbon atoms, which may contain several atoms other than carbon atoms. a is an integer between 1 and 5. a > R < ¹⁰ > may each independently be the same or different. It is also preferred that at least one is an organic group as described above having an aromatic ring. 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, Further, when the valence of Q in the cation [A] ^{q +} is t, it is necessary that q = at be satisfied (provided that N = N is treated as 0).

The anion [B] ^t- is preferably a halide complex, and its structure may be, for example,

[LX _b ] ^t-

.

In this case, L is a metal or a metalloid, which is a central atom of the halide complex, and B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, , Mn, Co, and the like. X is a halogen atom. b is an integer from 3 to 7. Further, when the valence of L in the anion [B] ^t- is p, it is necessary that the relationship r = bp is established.

Specific examples of the anion [LX _b ] ^t- of the above general formula include tetrakis (pentafluorophenyl) borate, tetra (3,5-difluoro-4-methoxyphenyl) borate, tetrafluoroborate ₄₎ ^- or the like ^-, phosphate (PF ₆₎ ^hexafluoro-, antimonate hexafluorophosphate (SbF ₆₎ ^-, it is Senate hexafluorophosphate (AsF ^_6), hexachloro antimonate (SbCl ₆₎ .

The anion [B] ^t- is represented by the following general formula,

[LX _{b - 1} (OH)] ^{t -}

Can also be preferably used. L, X, and b are as defined above. Other anions that can be used include perchlorate ion (ClO ₄ ) ^- , trifluoromethyl sulfite ion (CF ₃ SO ₃ ) ^- , fluorosulfonate ion (FSO ₃ ) ^- , toluenesulfonate anion, trinitrobenzenesulfonate anion , Camphorsulfonate, nonafluorobutanesulfonate, hexadecafluorooctanesulfonate, tetraarylborate, tetrakis (pentafluorophenyl) borate, and the like.

In the present invention, among these onium salts, it is particularly effective to use the following aromatic onium salts (a) to (c). Of these, one type may be used alone, or two or more types may be used in combination.

(A) aryldiazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate and 4-methylphenyldiazonium hexafluorophosphate;

(B) Diphenyliodonium hexafluoroantimonate, di (4-methylphenyl) iodonium hexafluorophosphate, di (4-tert-butylphenyl) iodonium hexafluorophosphate, trilumyl iodonium tetrakis Diaryl iodonium salts such as pentafluorophenylborate

(C) Sulfonium cations represented by the following Group I or Group II: sulfonium cations such as hexafluoroantimony ions and tetrakis (pentafluorophenyl)

Further, it is preferable that (η ⁵ -2,4-cyclopentadien-1-yl) [(1,2,3,4,5,6-η) - (1-methylethyl) benzene] Iron complexes such as tris (acetylacetonato) aluminum, tris (ethylacetonatoacetato) aluminum, tris (salicylaldehydato) aluminum, and triphenylsilanol And mixtures of silanols of the formula (I).

Of these, aromatic iodonium salts, aromatic sulfonium salts and iron-arene complexes are preferably used from the viewpoints of practical use and photosensitivity.

The ratio of the cationic polymerization initiator (2) to the mixture (1) of the cationic polymerizable compound is not particularly limited and may be generally used in a range of a normal use ratio within the range not hindering the object of the present invention. The amount of the cationic polymerization initiator (2) is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the mixture (1) of the cationic polymerizable compound. If the amount is too small, the curing tends to be insufficient, while if it is too large, adverse effects may be exerted on the physical properties such as the water absorption rate and the cured product strength of the cured product.

The composition of the present invention preferably contains 0.05 to 3 parts by mass of water relative to 100 parts by mass of the total amount of the composition (excluding the solvent).

In the composition of the present invention, a silane coupling agent may be used if necessary.

Examples of the silane coupling agent include dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyl Alkenyl functional alkoxysilanes such as vinyl trichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, and allyltrimethoxysilane, alkoxy functional alkoxysilanes such as trimethoxysilane, and 3-methacryloxypropyl tri Methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 2-methacryloxypropyltrimethoxysilane, Epoxyfunctional alkoxysilanes such as glycidoxypropyltrimethoxysilane,? -Glycidoxypropylmethyldiethoxysilane and? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-β (aminoethyl ) -γ-aminopropyl Amino functional alkoxysilanes such as methoxysilane,? -Aminopropyltriethoxysilane and N-phenyl-? -Aminopropyltrimethoxysilane, mercapto functional alkoxysilanes such as? -Mercaptopropyltrimethoxysilane , Titanium alkoxides such as titanium tetraisopropoxide and titanium tetra n-butoxide, titanium chelates such as titanium dioctyloxybis (octylene glycolate) and titanium diisopropoxybis (ethylacetate), and zirconium tetra Zirconium chelates such as acetylacetonate and zirconium tributoxymonoacetylacetonate; zirconium acylates such as zirconium tributoxymonostearate; and isocyanate silanes such as methyltriisocyanate silane.

The amount of the silane coupling agent to be used is not particularly limited, but is usually in the range of 1 to 20 parts by mass based on 100 parts by mass of the total amount of the solid matter in the composition.

In the composition of the present invention, a thermal polymerization initiator may be used if necessary.

The thermal polymerization initiator is a compound which generates a cationic species or a Lewis acid by heating, and includes salts of sulfonium salts, thiophenium salts, thioronium salts, benzylammonium, pyridinium salts and hydrazinium salts; Polyalkylpolyamines such as diethylenetriamine, triethylenetriamine, and tetraethylenepentamine; Alicyclic polyamines such as 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane and isophoronediamine; aromatic polyamines such as m-xylylenediamine, diaminodiphenylmethane and diaminodiphenylsulfone; The polyamines and glycidyl ethers such as phenyl glycidyl ether, butyl glycidyl ether, bisphenol A-diglycidyl ether, and bisphenol F-diglycidyl ether, or glycidyl esters of carboxylic acid Polyepoxy addition-modified products prepared by reacting various epoxy resins such as polyether polyols, polyether polyols, polyether polyols, An amidated modified product prepared by reacting the above organic polyamines with carboxylic acids such as phthalic acid, isophthalic acid and dimeric acid by a conventional method; A method of reacting phenols having at least one aldehyde reactive site in the nuclei such as aldehydes such as polyamines and formaldehyde and phenol, cresol, xylenol, tert -butylphenol and resorcinol by a conventional method, Denatures; It is possible to use polycarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 2-methylsuccinic acid, Aliphatic dicarboxylic acids such as methyl adipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, hydrogenated dimer acid and dimer acid; , Aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and naphthalene dicarboxylic acid, alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, and trimeric acid, trimesic acid, and trimer of castor fatty acid Tetracarboxylic acids such as pyromellitic acid and the like); Dicyandiamide, imidazoles, carboxylic acid esters, sulfonic acid esters, amine imides, and the like.

As the thermal polymerization initiator, commercially available products may be used. Examples of the thermal polymerization initiator include Adekaoptone CP77, Adekaoptone CP66 (ADEKA), CI-2639, CI-2624 (Nippon Soda Co.) , Sun Aid SI-80L, Sun Aid SI-100L (manufactured by San-Shin Kagaku Kogyo Co., Ltd.), and the like.

The amount of the thermal polymerization initiator to be used is not particularly limited, but is usually in the range of 0.001 to 10 parts by mass based on 100 parts by mass of the total amount of the solid matter in the composition. When the thermal polymerization initiator is used, It is preferable to heat at 130 to 180 ° C for 20 minutes to 1 hour.

The composition of the present invention may also improve the properties of the cured product by using a thermoplastic organic polymer, if necessary. Examples of the thermoplastic organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene- (meth) acrylic acid copolymer, Methacrylate copolymer, glycidyl (meth) acrylate-polymethyl (meth) acrylate copolymer, polyvinyl butyral, cellulose ester, polyacrylamide, and saturated polyester.

No particular limitation is imposed on the composition of the present invention, and a solvent capable of dissolving or dispersing the components (1) to (4) can be used. Examples of the solvent include methyl ethyl ketone, methyl amyl ketone, Ketones such as ethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; Ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, propylene glycol monomethyl ether and dipropylene glycol dimethyl ether; Esters such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and texanol; Cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Alcohol-based solvents such as methanol, ethanol, iso-or n-propanol, iso- or n-butanol, and amyl alcohol; Propylene glycol monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethoxyethyl propionate, etc. Ether-based solvent; BTX type solvents such as benzene, toluene and xylene; Aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; Terpene-based hydrocarbon oils such as terphenyl oil, D-limonene, and pinene; Paraffin solvents such as Mineral Spirit, Swazor # 310 (Kosomo Matsuyama Sekiyu Co., Ltd.), Solvesso # 100 (Exxon Chemical Co., Ltd.); Halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichlorethylene, methylene chloride, and 1,2-dichloroethane; Halogenated aromatic hydrocarbon solvents such as chlorobenzene; Propylene carbonate, carbitol-based solvent, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide , And water. These solvents may be used singly or as a mixed solvent of two or more kinds.

The composition of the present invention preferably has a viscosity of 1 to 200 mPa · s or less because of excellent curability and coating properties.

The composition of the present invention is applied on a supporting base by a known means such as a roll coater, a curtain coater, various printing, immersion or the like. In addition, it may be once transferred onto a support gas such as a film and then transferred onto another support gas, and there is no limitation on the application method thereof.

As the material of the support base, there is no particular limitation, and those which are usually used can be used. For example, inorganic materials such as glass; Cellulose esters such as diacetylcellulose, triacetylcellulose (TAC), propionylcellulose, butyrylcellulose, acetylpropionylcellulose, and nitrocellulose; Polyamide; Polyimide; Polyurethane; Epoxy resin; Polycarbonate; Polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4'-dicarboxylate, Polyesters such as rheneterephthalate; polystyrene; Polyolefins such as polyethylene, polypropylene and polymethylpentene; Vinyl compounds such as polyvinyl alcohol (PVA), polyvinyl acetate, polyvinyl chloride, and polyvinyl fluoride; Acrylic resins such as polymethyl methacrylate and polyacrylic acid ester; Polycarbonate; Polysulfone; Polyethersulfone; Polyether ketones; Polyetherimide; And polymer materials such as polyoxyethylene, norbornene resin and cycloolefin polymer (COP).

Further, the supporting substrate may be subjected to surface activation treatment such as corona discharge treatment, flame treatment, ultraviolet ray treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment and the like.

In addition, as long as the effect of the present invention is not impaired (preferably 50 parts by mass or less based on 100 parts by mass of the total amount of solids in the composition), other monomers, other cationic polymerizable polymerization initiators, A thickener, a surfactant, a leveling agent, a flame retardant, a stabilizer, a diluent, a plasticizer, a stabilizer, a polymerization inhibitor, an ultraviolet absorber, an antioxidant, an antistatic agent, a colorant, , A flow regulating agent, an adhesion promoter, and the like can be added.

The composition of the present invention is cured by irradiation with an active energy ray. Examples of the active energy ray include ultraviolet rays, electron rays, X rays, radiation, high frequency waves, and ultraviolet rays are most economically preferable. Examples of the ultraviolet light source include an ultraviolet laser, a mercury lamp, a xenon laser, and a metal halide lamp.

Specific examples of the application of the composition of the present invention include optical materials typified by glasses, image pickup lenses, paints, coating agents, lining agents, inks, resists, liquid resists, adhesives, printing plates, insulating varnishes, insulating sheets, Devices, LED packages, liquid crystal injection holes, organic EL devices, optical devices, electrical insulation materials, electronic parts, and separator films, molding materials, putties, glass fiber impregnants, fillers, semiconductors, solar cells A prism lens sheet used for a backlight of a liquid crystal display device, a fresnel lens sheet used for a screen of a projection TV or the like, a lenticular lens sheet, or the like A lens portion of a lens sheet, or an optical lens such as a backlight using such a sheet, a microlens, an optical element, an optical connector, an optical waveguide, For example, metal, wood, rubber, plastic, glass, ceramic products, and the like can be cited as examples of the substrate which can be applied as a coating agent.

Example

Hereinafter, the composition of the present invention and the cured product obtained by curing the composition will be described in detail by way of examples, evaluation examples and comparative examples, but the present invention is not limited to the examples and the like. In the examples and comparative examples, "parts" means parts by mass.

[Examples 1 to 16 and Comparative Examples 1 to 4]

The components shown in [Table 1] to [Table 4] below were thoroughly mixed to obtain Practical Compositions 1 to 16 and Comparative Compositions 1 to 4, respectively.

(1B-1) to (1B-3), (1C-1) to (1C-1) 2), (1D-1) to (1D-2) were used.

Compound 1A-1: EPOX-MK R1710 (bisphenol E type epoxy resin manufactured by PRINTECH)

Compound 1A'-1: EP-4901L (bisphenol F type epoxy resin manufactured by ADEKA)

Compound 1A'-2: EP-4100L (bisphenol A type epoxy resin manufactured by ADEKA)

Compound 1B-1: 1,4-butanediol diglycidyl ether

Compound 1B-2: Neopentyl glycol diglycidyl ether

Compound 1C-1: Celloxide 2021P (alicyclic epoxy compound manufactured by Daicel Chemical Industries, Ltd.)

Compound 1C-2: (4R) -1,2-epoxy-4- (2-methyloxylanyl) -1-methylcyclohexane

Compound 1D-1: Aronoxetane OXT-221 (product of Toagosei Co., Ltd.)

Compound 1D-2: Aronoxetane OXT-101 (product of Toagosei Co., Ltd.)

As the cationic polymerization initiator (2), the following compound (2-1) was used.

Compound 2-1: A 50% solution of propylene carbonate in a mixture of the compound represented by the first chemical formula shown below and the compound represented by the second chemical formula shown below

[Evaluation Examples 1 to 16 and Comparative Evaluation Examples 1 to 4]

The following evaluations were carried out on the composition obtained in Examples 1 to 16 and the comparative compositions obtained in Comparative Examples 1 to 4. The results are shown in [Table 1] to [Table 4].

(Adhesion)

Each of the obtained Practical Compositions 1 to 16 and Comparative compositions 1 to 4 was applied to one piece of a TAC film or a PMMA film and then stuck to a COP (cycloolefin polymer) film subjected to a corona discharge treatment using a laminator, A cold-mirror type high-pressure Hg lamp was irradiated with energy of 1000 mJ / cm 2 and adhered to obtain a test piece. A 90-degree peel test of the obtained test piece was carried out.

(Tg)

Each of the obtained Practical Compositions 1 to 16 and Comparative Compositions 1 to 4 was coated on a PET film to a thickness of 3 탆 with a bar coater and irradiated with energy of 2000 mJ / cm 2 using a cold mirror type high pressure Hg lamp I investigated. After 24 hours, the adhesive cured product was taken out from the film, and Tg was measured using a viscoelasticity measuring apparatus (DMA 7100) manufactured by Hitachi High-Tech Science Co., Ltd. The results are shown in [Table 1] to [Table 4].

(Viscosity)

Viscosities of 1 to 16 of the obtained practical compositions and 1 to 4 of the comparative compositions were measured at 25 캜 using an E-type viscometer. The results are shown in [Table 1] to [Table 4].

From [Table 1] to [Table 4], it is clear that the composition of the present invention is excellent in adhesiveness and heat resistance.

Claims (6)

Wherein the mixture (1) contains an aromatic ring-containing epoxy compound (1A) represented by the following general formula (I) as a main component and further contains an aliphatic epoxy compound (1B) ), An alicyclic epoxy compound (1C), and an oxetane compound (1D).

(Wherein R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkene having 2 to 5 carbon atoms A halogen atom or a halogen atom, and m is an integer of 0 to 10.) The method according to claim 1,
Wherein the aliphatic epoxy compound (1B) is a diglycidyl ether of an aliphatic diol having 1 to 6 carbon atoms. 3. The method according to claim 1 or 2,
Wherein the cationic polymerization initiator (2) is contained in an amount of 0.1 to 20 parts by mass based on 100 parts by mass of the mixture (1) of the cationic polymerizable compound. 4. The method according to any one of claims 1 to 3,
Wherein the cationic polymerization ^{initiator, p [A] q + ·} s [B] t- (A represents a cationic species, B represents an anion species, q and t independently represent 1 or 2, p and s Is a salt of a cation and an anion represented by the following formula (I). 5. The method according to any one of claims 1 to 4,
Wherein the composition contains 0.05 to 3 parts by mass of water relative to 100 parts by mass of the total amount of the composition (excluding the solvent). An adhesive comprising the composition according to any one of claims 1 to 5.