TW201700524A - Composition - Google Patents

Abstract

The invention of the present application provides a composition having excellent adhesive properties, heat resistance and liquid storage stability, and more specifically provides a composition that is characterized by containing a mixture (1) of cationic polymerizable compounds, with the mixture (1) containing an aromatic ring-containing epoxy compound (1A) represented by general formula (I) as a primary component and further containing at least one compound selected from among an aliphatic epoxy compound (1B), an alicyclic epoxy compound (1C), and an oxetane compound (1D). (In the formula, R1, R2, R3 and R4 each independently denote a hydrogen atom, an alkyl group having 1-5 carbon atoms, an alkoxy group having 1-8 carbon atoms, an alkenyl group having 2-5 carbon atoms, or a halogen atom, and m is an integer between 0 and 10).

Description

combination

The present invention relates to a composition and a cured product obtained by irradiating the composition with an active energy ray. This composition is especially useful for adhesives.

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

For example, various cationically polymerizable compositions are disclosed in Patent Documents 1 to 3 below.

However, the cured product of the cationically polymerizable composition described in these documents is not sufficient in terms of adhesion or heat resistance.

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. Hei 10-279658

Patent Document 2: Japanese Patent Laid-Open Publication No. 2003-313274

Patent Document 3: Japanese Patent Laid-Open Publication No. 2010-229392

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

The present invention is based on the above findings and is achieved by providing a composition For the purpose, the composition is characterized in that it comprises a mixture (1) of a cationically polymerizable compound, and the mixture (1) contains an aromatic ring-containing epoxy compound represented by the following formula (I) (1A). The main component further contains at least one selected from the group consisting of 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 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, the carbon atoms of an alkoxy group having 1 to 8 carbon atoms of 2 to 5 Alkenyl or halogen atom, m is an integer from 0 to 10)

Further, the present invention 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 an adhesive containing the same will be described in detail based on preferred embodiments.

In the mixture (1) of the above cationically polymerizable compound used in the present invention, the cationically polymerizable compound constituting the mixture is polymerized or crosslinked by a cationic polymerization initiator activated by light irradiation. As the compound, as the cationically polymerizable compound, an epoxy compound, an oxetane compound, a cyclic lactone compound, or the like can be used. The cyclic acetal compound, the cyclic thioether compound, the spiroorthoester compound, the vinyl ether, etc., but it is necessary to contain the aromatic ring-containing epoxy compound (1A) represented by the above formula (I) as a main component. Further, it is also necessary to contain at least one of an aliphatic epoxy compound (1B), an alicyclic epoxy compound (1C), and an oxetane compound (1D). In addition, the main component means that a plurality of cationically polymerizable compounds are mixed and the total mass of the same type of cationically polymerizable compound is the highest.

In the aromatic ring-containing epoxy compound (1A) represented by the above formula (I), in the above formula (I), the number of carbon atoms represented by R ¹ , R ² , R ³ and R ⁴ is 1 The alkyl group of 5 may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a second butyl group, a tert-butyl group, an isobutyl group, a pentyl group, an isopentyl group or a third pentyl group. Examples of the alkoxy group having 1 to 8 carbon atoms represented by R ¹ , R ² , R ³ and R ⁴ include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group and a pentyl group. An oxy group, an isopentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group or the like, and the number of carbon atoms represented by R ¹ , R ² , R ³ and R ⁴ is 2 to 5 Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, and a propylene group. Examples of the halogen atom represented by R ¹ , R ² , R ³ and R ⁴ include fluorine, chlorine, bromine and iodine. Further, the halogen atoms in the present specification are the same as herein.

Examples of the formula (I) as represented by the aromatic ring-containing epoxy compound of (. 1A), an epoxy group when it becomes small in terms of the aspect, preferably R ^1, R ^2, R ³ and R ⁴ is hydrogen or In the case of a methyl group, it is particularly preferred that R ¹ , R ² , R ³ and R ⁴ are hydrogen.

Examples of the aliphatic epoxy compound (1B) include a monofunctional epoxy compound such as a glycidyl ether compound of an aliphatic alcohol or a glycidyl ester of an alkyl carboxylic acid, or an aliphatic polyol or an alkylene oxide adduct thereof. A polyfunctional epoxy compound such as a polyglycidyl ether compound or a polyglycidyl ester of an aliphatic long-chain polybasic acid. Typical examples of the compound include allyl glycidyl ether, butyl glycidyl ether, second butylphenyl glycidyl ether, 2-ethylhexyl glycidyl ether, and C12-13 mixed alkyl glycidyl ether. 1,4-butanediol diglycidyl Ether, 1,6-hexanediol diglycidyl ether, triglycidyl ether of glycerol, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, hexahydroglycidyl ether of dipentaerythritol, new a glycidyl ether of a polyhydric alcohol such as pentanediol diglycidyl ether, polyethylene glycol diglycidyl ether or polypropylene glycol diglycidyl ether, and an aliphatic polyol such as propylene glycol, trimethylolpropane or glycerin A polyglycidyl ether compound of a polyether polyol obtained by forming one or two or more kinds of alkylene oxides, or a diglycidyl ester of an aliphatic long-chain dibasic acid. Further, examples thereof include monoglycidyl ether of an aliphatic higher alcohol, glycidyl ester of a higher fatty acid, epoxidized soybean oil, octyl epoxy stearate, butyl epoxy stearate, epoxidized soybean oil, and epoxidized polybutylene. Diene, etc.

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

A commercially available product can be used as the aliphatic epoxy compound (1B), and examples thereof include DENACOL EX2-11, DENACOL EX-171, DENACOL EX-192, DENACOL EX-211, DENACOL EX-212, and 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); Epolight M-1230, Epolight 40E, Epolight 100E, Epolight 200E, Epolight 400E, Epolight 70P, Epolight 200P, Epolight 400P, Epolight 1500NP, Epolight 1600, Epolight 80MF, Epolight 100MF (total Wong Society Chemical Co., Ltd.) and so on.

The alicyclic epoxy compound (1C) may, for example, be a polyglycidyl ether compound of a polyol having at least one alicyclic ring, or a compound containing a cyclohexene or a cyclopentene ring by using an oxidizing agent. A compound containing a cyclohexene oxide or a cyclopentene oxide obtained by epoxidation. For example, hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexane methyl ester of 3,4-epoxycyclohexanecarboxylic acid, and 3,4-epoxy-1-methylhexanecarboxylic acid 3 can be mentioned. , 4-epoxy-1-methylcyclohexyl ester, 6-methyl-3,4-epoxycyclohexanecarboxylic acid 6-methyl-3,4-epoxycyclohexylmethyl ester, 3,4- Epoxy-3-methylcyclohexanecarboxylic acid 3,4-epoxy-3-methylcyclohexylmethyl ester, 3,4-epoxy-5-methylcyclohexanecarboxylic acid 3,4-epoxy 5-5-methylcyclohexylmethyl ester, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-1,3-di Alkane, bis(3,4-epoxycyclohexylmethyl) adipate, bis(3,4-epoxycyclohexylmethyl) adipate, methylene bis (3,4-epoxy ring) Hexane), propane-2,2-diylbis(3,4-epoxycyclohexane), 2,2-bis(3,4-epoxycyclohexyl)propane, dicyclopentadiene epoxide Compound, ethyl bis(3,4-epoxycyclohexanecarboxylate), dioctyl epoxy hexahydrophthalate, di(2-ethylhexyl) epoxy hexahydrophthalate, 1 - Epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, and the like.

The alicyclic epoxy compound (1C) is preferably a 3,4-epoxycyclohexanecarboxylic acid 3,4-epoxycyclohexyl group in terms of the viscosity of the adhesive and the heat resistance of the cured product. Methyl ester.

A commercially available product can be used as the alicyclic epoxy compound (1C), and examples thereof include Celloxide 2021P, Celloxide 2081, Celloxide 2000, and Celloxide 3000 (manufactured by Daicel Co., Ltd.).

Examples of the above oxetane compound (1D) include 3,7-bis(3-oxetanyl)-5-oxadecane and 1,4-bis[(3-ethyl-3). -oxetanylmethoxy)methyl]benzene, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-B Benzyl-3-oxetanylmethoxy)methyl]propane, ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, triethylene glycol bis(3-ethyl-3-oxo Heterocyclic butyl methyl)ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane , 1,6-double (3- a difunctional aliphatic oxetane compound such as ethyl-3-oxetanylmethoxy)hexane, 3-ethyl-3-[(phenoxy)methyl]oxetane, 3- Ethyl-3-(hexyloxymethyl)oxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-( a monofunctional oxetane compound such as hydroxymethyl)oxetane or 3-ethyl-3-(chloromethyl)oxetane, wherein in terms of reactivity and hardenability, Preferably, it is a difunctional aliphatic oxetane.

The oxetane compound (1D) is preferably 3-ethyl-{[(3-ethyloxetane-3) in terms of the viscosity of the adhesive and the heat resistance of the cured product. -yl)methoxy]methyl}oxetane.

A commercially available product can be used as the oxetane compound (1D), and examples thereof include ARON OXETANE EXOH, POX, OXA, OXT-101, OXT-211, OXT-212, and OXT-221 (manufactured by Toagosei Co., Ltd.). Wait.

In the mixture (1) of the above cationically polymerizable compound, the aromatic epoxy compound (1A), the aliphatic epoxy compound (1B), and the alicyclic epoxy compound (1C) represented by the above formula (I). And the mixing ratio of the oxetane compound (1D) is preferably 20 to 80 parts by mass based on 100 parts by mass of the mixture (1) of the above cationically polymerizable compound, the aromatic polyfunctional epoxy compound (1A). Preferably, it is 30 to 70 parts by mass, more preferably 30 to 60 parts by mass, and the above aliphatic epoxy compound (1B) is 0 to 70 parts by mass, preferably 5 to 60 parts by mass, more preferably 10 to 50 parts by mass. The alicyclic epoxy compound (1C) is 0 to 20 parts by mass, preferably 0.5 to 15 parts by mass, more preferably 1 to 10 parts by mass, and the oxetane compound (1D) is 0. ~70 parts by mass, preferably 5 to 60 parts by mass, more preferably 10 to 50 parts by mass. Among them, since the aromatic epoxy compound (1A) represented by the above formula (I) is a main component, the content thereof is the most valuable value compared with other compounds.

The cationically polymerizable compound may contain an aromatic ring-containing epoxy compound other than the aromatic ring-containing epoxy compound (1A) represented by the above formula (I) and the aromatic ring represented by the above formula (I). The epoxy compound (1A) is used in combination. As the aromatic ring-containing epoxidation Examples of the material include a glycidyl ether compound having at least one aromatic ring such as phenol, cresol or butanol or an alkylene oxide adduct thereof, for example, bisphenol A or bisphenol F, or the like. Further, a glycidyl ether compound or an epoxy novolac resin of a compound having an alkylene oxide; a glycidol having an aromatic compound having two or more phenolic hydroxyl groups such as resorcin or hydroquinone or catechol; Mono/polyglycidyl etherate of an aromatic compound having two or more alcoholic hydroxyl groups such as benzene dimethanol, phenylenediethanol or phenylbutanol; phthalic acid, terephthalic acid, trimellitic acid, etc. A glycidyl ester of a polybasic acid aromatic compound having two or more carboxylic acids, a glycidyl ester of benzoic acid such as benzoic acid or toluic acid or naphthoic acid, or an epoxide of styrene oxide or divinylbenzene. 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 formula (I) is relative to the aromatic ring-containing compound represented by the above formula (I). 100 parts by mass of the epoxy compound (1A) 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 may be any compound which can generate an acid by irradiation with an energy ray, and is preferably used as a ruthenium salt for releasing Lewis acid by irradiating an energy ray. Double salt, or a derivative thereof. As a representative of the compound, a salt of a cation and an anion represented by the following formula: p[A] ^q+ ‧s[B] ^t- (A represents a cationic species, B represents an anionic species, and q and t respectively Independently represents 1 or 2, p and s represent coefficients that maintain the charge as neutral).

Here, the cation [A] ^{q+ is} preferably 鎓, and its structure can be represented, for example, by the following formula: [(R ¹⁰ ) _a Q] ^q+ .

Further, here, R ¹⁰ is an organic group having 1 to 60 carbon atoms and may contain atoms other than carbon atoms. a is an integer from 1 to 5. Each of R R ^{10 is} independent and may be the same or different. Further, it is preferred that at least one of them is an organic group having an aromatic ring as described above. The Q group is selected from an atom or an atom group in a group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F, and N=N. Further, when the valence of Q in the cation [A] ^q+ is t, the relationship of q = at is satisfied (where N = N is regarded as the valence of 0).

Further, it is preferred that the anion [B] ^t- is a halide complex, and the structure thereof can be represented, for example, by the following formula: [LX _b ] ^t- .

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

Specific examples of the anion [LX _b ] ^t- of the above formula include tetrakis(pentafluorophenyl)borate, tetrakis(3,5-difluoro-4-methoxyphenyl)borate, and tetrafluoroethylene. Boric acid (BF ₄ ) ^- , hexafluorophosphate (PF ₆ ) ^- , hexafluoroantimonate (SbF ₆ ) ^- , hexafluoroarsenate (AsF ₆ ) ^- , hexachloroantimonate (SbCl ₆ ) ^- and the like.

Further, the anion [B] ^t- can also preferably be a structure represented by the following formula: [LX _b-1 (OH)] ^t- .

L, X, and b are the same as described above. Further, examples of other anions which can be used include perchlorate ion (ClO ₄ ) ^- , trifluoromethyl sulfite ion (CF ₃ SO ₃ ) ^- , fluorosulfonate ion (FSO ₃ ) ^- , tosylate Anion, trinitrobenzenesulfonate anion, camphorsulfonate, nonafluorobutanesulfonate, hexadecafluorooctanesulfonate, tetraarylborate, tetrakis(pentafluorophenyl)borate, and the like.

In the present invention, among the above-mentioned onium salts, the aromatic onium salts of the following (1) to (3) are particularly effective. These may be used alone or in combination of two or more.

(1) phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate, 4-methylphenyldiazonium hexafluorophosphate and the like aryl diazonium salt

(2) Diphenylphosphonium hexafluoroantimonate, bis(4-methylphenyl)phosphonium hexafluorophosphate, bis(4-t-butylphenyl)phosphonium hexafluorophosphate, tolylcumene Diarylsulfonium salt such as tetrakis(pentafluorophenyl)borate

(3) a phosphonium salt of a phosphonium cation, a hexafluoroantimonium ion or a tetrakis(pentafluorophenyl)borate ion represented by the following group I or group II;

Further, as another preferred one, (η ⁵ -2,4-cyclopentadien-1-yl)[(1,2,3,4,5,6-η)-(1-methyl) An iron-aromatic complex such as ethyl)phenyl]-iron-hexafluorophosphate or an aluminum such as tris(acetonitrile)aluminum, tris(ethylacetoneacetate)aluminum or tris(salicylic acid)aluminum a mixture of a substance and a decyl alcohol such as triphenyl stanol.

Among these, from the viewpoint of the practical surface and the light sensitivity, an aromatic onium salt, an aromatic onium salt, and an iron-aromatic hydrocarbon complex are preferably used.

The ratio of use of the cationic polymerization initiator (2) to the mixture (1) of the above cationically polymerizable compound is not particularly limited, and may be used in a substantially usual ratio within a range not detracting from the object of the present invention, for example, relative The cationic polymerization initiator (2) can be 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 cationically polymerizable compound. If the amount is too small, the hardening tends to be insufficient, and if it is too large, the physical properties such as the water absorption rate of the cured product and the strength of the cured product may be adversely affected. Happening.

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

In the compositions of the present invention, a decane coupling agent can be used as needed.

Examples of the decane coupling agent include dimethyl dimethoxy decane, dimethyl diethoxy decane, methyl ethyl dimethoxy decane, methyl ethyl diethoxy decane, and methyl trimethoxy. Alkyl decyl, methyl triethoxy decane, ethyl trimethoxy decane, ethyl trimethoxy decane, etc. alkyl functional alkoxy decane, vinyl trichloro decane, vinyl trimethoxy decane, vinyl three Alkenyl functional alkoxydecane, 3-methylpropenyloxypropyltriethoxydecane, 3-methylpropenyloxypropyltrimethoxy, such as ethoxy decane or allyltrimethoxydecane Baseline, 3-methylpropenyloxypropylmethyldiethoxydecane, 3-methylpropenyloxypropylmethyldimethoxydecane, 2-methylpropenyloxypropyltrimethyl Oxydecane, γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropylmethyldiethoxydecane, β-(3,4-epoxycyclohexyl)ethyltrimethoxy Epoxy functional alkoxydecane such as decane, N-β-(aminoethyl)-γ-aminopropyltrimethoxydecane, γ-aminopropyltriethoxydecane, N-benzene - anthracenyl functional alkoxydecane such as γ-aminopropyltrimethoxydecane, fluorenyl functional alkoxydecane such as γ-mercaptopropyltrimethoxydecane, titanium tetraisopropoxide or titanium tetra-n-butoxide Titanium chelates such as titanium alkoxides, dioctyloxytitanium bis(octanediol), diisopropoxy titanium bis(acetic acid ethyl acetate), chromium tetraacetyl phthalate, tributoxy A chromium chelate compound such as monoethyl phosphonium pyruvate or a chromium sulfonium compound such as tributoxylated monostearate or an isocyanate decane such as methyl triisocyanate decane.

The amount of the decane coupling agent to be used is not particularly limited, and 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 compositions of the present invention, a thermal polymerization initiator can be used as needed.

As the thermal polymerization initiator, examples of the compound which generates a cationic species or a Lewis acid by heating include an onium salt, a thiophene phosphonium salt, a tetrahydrothiophene phosphonium salt, a benzyl ammonium salt, a pyridinium salt, and the like. a salt such as a salt; a polyalkyl polyamine such as diethylenetriamine, triethylenetriamine or tetraethylenepentamine; 1,2-diaminocyclohexane, 1,4-diamino-3,6-di An alicyclic polyamine such as ethylcyclohexane or isophorone diamine; an aromatic polyamine such as m-xylylenediamine, diaminodiphenylmethane or diaminodiphenylphosphonium; The above polyamines are glycidyl ethers such as phenyl glycidyl ether, butyl glycidyl ether, bisphenol A-diglycidyl ether, bisphenol F-diglycidyl ether, or glycidyl esters of carboxylic acids. A polyepoxy addition modification produced by reacting various epoxy resins; and the organic polyamine is reacted with a carboxylic acid such as phthalic acid, isophthalic acid or dimer acid by a usual method. a amide-modified product; the above polyamines and aldehydes such as formaldehyde and at least one hydroformylation on the nucleus by phenol, cresol, xylenol, t-butylphenol, resorcinol or the like by a usual method Mannich modification produced by reacting phenols in reactive sites; polycarboxylic acids (oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, bismuth) acid, Diacid, dodecanedioic acid, 2-methylsuccinic acid, 2-methyladipate, 3-methyladipate, 3-methylglutaric acid, 2-methyloctanedioic acid, 3, An aliphatic dicarboxylic acid such as 8-dimethylsebacic acid, 3,7-dimethylsebacic acid, hydrogenated dimer acid or dimer acid; phthalic acid, terephthalic acid, isophthalic acid, An aromatic dicarboxylic acid such as naphthalene dicarboxylic acid; an alicyclic dicarboxylic acid such as cyclohexane dicarboxylic acid; a tricarboxylic acid such as trimellitic acid, trimesic acid, or a terpolymer of castor oil fatty acid; An acid anhydride such as a tetracarboxylic acid such as formic acid; dicyandiamide, an imidazole, a carboxylic acid ester, a sulfonic acid ester, an amine imide or the like.

As the thermal polymerization initiator, a commercially available product can be used, and examples thereof include Adeka Opton CP77, Adeka Opton CP66 (manufactured by Adeka Co., Ltd.), CI-2639, CI-2624 (manufactured by Nippon Soda Co., Ltd.), and San-Aid SI-60L. , San-Aid SI-80L, San-Aid SI-100L (manufactured by Sanshin Chemical Industry Co., Ltd.).

The amount of the above-mentioned thermal polymerization initiator is not particularly limited, and 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, When the composition of the present invention is hardened, it is preferably heated at 130 to 180 ° C for 20 minutes to 1 hour.

In the composition of the present invention, the properties of the cured product can also be improved by using a thermoplastic organic polymer as needed. Examples of the thermoplastic organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, poly(meth)acrylic acid, and styrene-(meth)acrylic acid. Copolymer, (meth)acrylic acid-methyl methacrylate copolymer, glycidyl (meth)acrylate-poly(methyl) methacrylate copolymer, polyvinyl butyral, cellulose ester, polypropylene Indoleamine, saturated polyester, and the like.

In the composition of the present invention, a solvent which can be used for dissolving or dispersing the components (1) to (4), which are generally used, can be used without particular limitation, and examples thereof include methyl ethyl ketone and methyl amyl ketone. , ketones such as diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone; diethyl ether, two An ether solvent such as an alkane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, propylene glycol monomethyl ether or dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate, acetic acid N-propyl ester, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, ester solvent such as TEXANOL; solvent-soluble cellulose such as ethylene glycol monomethyl ether or ethylene glycol monoethyl ether a solvent; an alcohol solvent such as methanol, ethanol, isopropanol or n-propanol, isobutanol or n-butanol or pentanol; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, An ether ester solvent such as propylene glycol-1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate or ethoxyethyl propionate; benzene, BTX solvent such as toluene or xylene; aliphatic hydrocarbon solvent such as hexane, heptane, octane or cyclohexane; terpene hydrocarbon oil such as turpentine, D-limonene or decene; mineral spirit, Swazol #310 (Cosmo Matsuyama Oil (share)), Solvesso #100 (Exxon Chemical (share)) and other paraffinic solvents; carbon chloride, chloroform, trichloroethylene, dichloromethane, 1,2-dichloroethane and other halogenated fats Hydrocarbon solvent; halogenated aromatic hydrocarbon solvent such as chlorobenzene; propylene carbonate, carbitol solvent, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N,N-dimethylformamidine The amine, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylhydrazine, water, and the like may be used alone or in combination of two or more.

Regarding the composition of the present invention, the viscosity is 1 to 200 mPa. s or less is preferable because it is excellent in hardenability and coatability.

The composition of the present invention is applied to a support substrate by a known method such as a roll coater, a curtain coater, or various printing or dipping. Further, it may be temporarily applied to a support substrate such as a film and then transferred to another support substrate, and the application method is not limited.

The material of the support base is not particularly limited, and a general user can be used, and for example, an inorganic material such as glass can be cited; diethyl phthalocyanine, triethyl fluorene cellulose (TAC), propylene glycol, butyl sulfonate , cellulose esters such as acetaminophen cellulose, nitrocellulose; polydecylamine; polyimine; polyurethane; epoxy resin; polycarbonate; polyethylene terephthalate , polyethylene naphthalate, polybutylene terephthalate, polytetramethylene terephthalate, poly-1,2-diphenoxyethane-4,4' - polyester such as ethylene dicarboxylate or polybutylene terephthalate; polystyrene; polyolefin such as polyethylene, polypropylene, polymethylpentene; polyvinyl alcohol (PVA), polyvinyl acetate, Vinyl compounds such as polyvinyl chloride and polyvinyl fluoride; acrylic resins such as polymethyl methacrylate and polyacrylate; polycarbonate; polyfluorene; polyether oxime; polyether ketone; polyether quinone imide; Ethylene, drop A polymer material such as an olefin resin or a cycloolefin polymer (COP).

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

Further, 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 the solid matter in the composition), other monomers or other cationic polymerizable polymerization may be added as needed. Starting agent, radical polymerization initiator, inorganic filler, organic filler, pigment, dye and other colorants, photosensitizer, defoamer, tackifier, surfactant, leveling agent, flame retardant, thixotropic Various resin additives such as a diluent, a diluent, a plasticizer, a stabilizer, a polymerization inhibitor, an ultraviolet absorber, an antioxidant, an antistatic agent, a flow regulator, and a subsequent accelerator.

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 beams, X-rays, radiation, high frequency, and the like, and ultraviolet rays are 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 composition of the present invention include optical materials such as glasses and imaging lenses, paints, coating agents, lining agents, inks, resists, liquid resists, adhesives, and printing plates. , insulating varnish, insulating sheet, laminated board, printed circuit board, semiconductor device, LED (Light Emitting Diode) package, liquid crystal injection port, organic EL (Electro Luminescence), light A sealing agent for a component, an electrical insulation, an electronic component, a separation film, a molding material, a putty, a glass fiber impregnating agent, a caulk, a semiconductor, a passivation film for a solar cell, an interlayer insulating film, and protection a film portion, a lens sheet used for a backlight of a liquid crystal display device, a lens portion of a lens sheet such as a Fresnel lens sheet or a lenticular lens sheet used for a screen such as a projection television, or a sheet using the same An optical lens such as a backlight, an optical lens such as a microlens, an optical element, an optical connector, an optical waveguide, or an injection molding agent for optical molding, and the like, for example, a substrate which can be used as a coating agent, and examples thereof include gold. Genus, wood, rubber, plastic, glass, ceramics, etc.

[Examples]

Hereinafter, the composition of the present invention and the cured product obtained by curing the composition will be more specifically described by way of Examples, Evaluation Examples and Comparative Examples, and the present invention is not limited by the examples and the like. Further, in the examples and comparative examples, the parts mean parts by mass.

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

According to the compounding composition shown in the following [Table 1] to [Table 4], each component was sufficiently mixed to obtain each of the compositions 1 to 16 and the comparative compositions 1 to 4.

As the cationically polymerizable compound, the following compounds (1A-1) and (1A'-1) to (1A'-2), (1B-1) to (1B-3), and (1C-1) to (1C) were used. -2), (1D-1)~(1D-2).

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

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)

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

Compound 1D-1: ARON OXETANE OXT-221 (manufactured by Toagosei Co., Ltd.)

Compound 1D-2: ARON OXETANE OXT-101 (manufactured by Toagosei Co., Ltd.)

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

Compound 2-1: a propylene carbonate 50% solution of a compound represented by [Chemical Formula 4] and a compound represented by [Chemical Formula 5]

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

The comparative compositions obtained in the above Examples 1 to 16 and the comparative compositions obtained in Comparative Examples 1 to 4 were subjected to the following evaluations. The results are shown in the above [Table 1] to [Table 4].

(adhesiveness)

The obtained compositions 1 to 16 and the comparative compositions 1 to 4 were applied to a single TAC film or a PMMA film, and then a PTFE (cycloolefin polymer) subjected to corona discharge treatment was used. The film was bonded, and a test piece was obtained by irradiating an energy of 1000 mJ/cm ² with a cold mirror type high-pressure Hg lamp. A 90 degree peel test of the obtained test piece was performed.

(Tg)

Each of the obtained compositions 1 to 16 and the comparative compositions 1 to 4 was applied onto a PET film by a bar coater at a thickness of 3 μm, and irradiated with a cold mirror type high-pressure Hg lamp at 2000 mJ/cm ^{2 .} Energy. The adhesive hardened material was taken out from the film after 24 hours, and the Tg was measured using a viscoelasticity measuring device (DMA7100) manufactured by Hitachi High-Tech Science Co., Ltd. The results are shown in [Table 1] to [Table 4].

(viscosity)

For each of the obtained compositions 1 to 16 and the comparative compositions 1 to 4, the viscosity was measured at 25 ° C using an E-type viscometer. The results are shown in [Table 1] to [Table 4].

It is clear from [Table 1] to [Table 4] that the composition of the present invention is excellent in adhesion and heat resistance.

Claims (6)

A composition comprising a mixture (1) of a cationically polymerizable compound, the mixture (1) comprising an aromatic ring-containing epoxy compound (1A) represented by the following formula (I) as The main component further contains at least one selected from the group consisting of 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 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and 2 to 5 carbon atoms; Alkenyl or halogen atom, m is an integer from 0 to 10). The composition of claim 1, wherein the aliphatic epoxy compound (1B) is a diglycidyl ether of an aliphatic diol having 1 to 6 carbon atoms. The composition of claim 1 or 2, which comprises 0.1 to 20 parts by mass of the cationic polymerization initiator (2), based on 100 parts by mass of the mixture (1) of the above cationically polymerizable compound. The composition of claim 1 or 2, wherein the cationic polymerization initiator is p[A] ^q+ ‧s[B] ^t- (A represents a cationic species, B represents an anionic species, and q and t each independently represent 1 or 2, p and s represent a salt of a cation and an anion represented by a coefficient that maintains a neutral charge. The composition of claim 1 or 2, which comprises 0.05 to 3 parts by mass of water, based on 100 parts by mass of the total amount of the composition (excluding the solvent). An adhesive comprising the composition of any one of claims 1 to 5.