TW201706328A - Composition - Google Patents

Abstract

A composition which is characterized by containing, as a cationically polymerizable organic material mixture (1), an aromatic epoxy compound (1-1), an alicyclic epoxy compound (1-2A) or an aliphatic epoxy compound (1-2B), and a polyfunctional aliphatic oxetane compound (1-3), and which is also characterized in that the aromatic epoxy compound (1-1) is contained therein as a main component. It is preferable that at least one compound selected from the group consisting of glycidyl ethers of phenols, glycidyl etherified products of aromatic compounds having two or more alcoholic hydroxyl groups, glycidyl etherified products of polyhydric phenols, glycidyl esters of benzoic acids, glycidyl esters of polybasic acids, and epoxidized products of styrene oxide or divinylbenzene is contained as the aromatic epoxy compound (1-1).

Description

combination

This invention relates to a composition and an adhesive comprising the same.

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

For example, various photocurable adhesives are disclosed in Patent Documents 1 to 4 below.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2011-236389

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2012-149262

[Patent Document 3] International Publication No. 2008/111584

[Patent Document 4] International Publication No. 2015/005211

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

The present invention has been made in view of the above findings, and the object is achieved by providing a composition comprising an aromatic epoxy compound (1-1) as a (1) cationically polymerizable organic substance mixture. ) an alicyclic epoxy compound (1-2A) or an aliphatic epoxy compound (1-2B), and a polyfunctional aliphatic oxetane compound (1-3), and The aromatic epoxy compound (1-1) is a main component.

Further, the present invention provides an adhesive comprising the above composition.

The composition of the present invention is particularly useful as an adhesive because it is excellent in curability and adhesion.

Hereinafter, the composition of the present invention and an adhesive containing the same will be described in detail.

In the above (1) cationically polymerizable organic substance mixture used in the present invention, the cationically polymerizable organic substance constituting the mixture is caused by a cationic polymerization initiator activated by light irradiation to cause macromolecularization or crosslinking reaction. Compound. In the composition of the present invention, as the cationically polymerizable organic substance, an aromatic epoxy compound (1-1), an alicyclic epoxy compound (1-2A), and/or an aliphatic epoxy compound (1-2B) are used. And polyfunctional aliphatic oxetane compounds (1-3).

The aromatic epoxy compound (1-1) is an epoxy compound containing an aromatic ring, and specific examples of the aromatic epoxy compound include at least one aromatic ring such as phenol, cresol or butanol. a glycidyl etherate of a monophenol or an alkylene oxide adduct thereof, such as bisphenol A, bisphenol F, or a glycidyl etherate or epoxy novolac resin of a compound to which an alkylene oxide is further added a glycidyl ether of an aromatic compound having two or more phenolic hydroxyl groups such as resorcinol, hydroquinone or catechol; or two or more alcohols such as benzenedimethanol, phenylenediethanol or phenylbutanol; a glycidyl etherate of an aromatic compound of a hydroxyl group; a glycidyl ester of a polybasic aromatic compound having two or more carboxylic acids such as phthalic acid, terephthalic acid or trimellitic acid; benzoic acid or toluic acid; A glycidyl ester of benzoic acid such as naphthoic acid, an epoxide of styrene oxide or divinylbenzene, or the like.

In addition, the aromatic epoxy compound (1-1) contains a glycidyl ether selected from the group consisting of a glycidyl ether of a phenol, an aromatic compound having two or more alcoholic hydroxyl groups, and a glycidyl ether compound of a polyphenol. The case of at least one of glycidyl benzoate, glycidyl polybasic acid, styrene oxide or epoxide of divinylbenzene is preferred because the Tg of the composition is increased.

The aromatic epoxy compound (1-1) is preferred because it has an epoxy group equivalent of from 80 to 500 and is excellent in curability.

Commercially available products can be used as the aromatic epoxy compound (1-1), and examples thereof include DENACOL EX2-1, DENACOL EX-141, DENACOL EX-142, DENACOL EX-145, DENACOL EX-146, and 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 (manufactured by Nagase ChemteX); OGSOL PG-100, OGSOL EG-200, OGSOL EG-210, OGSOL EG-250 (manufactured by Osaka Gas Chemicals); HP4032, HP4032D, HP4700 (DIC Company made); ESN-475V (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.); Epikote YX8800 (manufactured by Mitsubishi Chemical Corporation); Marproof G-0105SA, Marproof G-0130SP (manufactured by Nippon Oil Co., Ltd.); EPICLON N-665, EPICLON HP- 7200 (manufactured by DIC Corporation); EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, XD-1000, NC-3000, EPPN-501H, EPPN-501HY, EPPN-502H, NC-7000L (Japanese Chemicals) Made by the company); Adeka Glycirol ED-501, Adeka Glycirol ED-509, Adeka Glycirol ED-529, Adeka Resin EP-4000, Adeka Resin EP- 4005, Adeka Resin EP-4100, Adeka Resin EP-4901 (manufactured by Adeka Co., Ltd.), TECHMORE VG-3101L (manufactured by Printec Co., Ltd.), and the like.

From the viewpoint of hardenability and adhesion, it is preferred to contain at least one multifunctional ring An oxygen compound is used as the above aromatic epoxy compound (1-1). The composition of the present invention preferably contains the polyfunctional aromatic epoxy compound (1-1) in an amount of 30 to 70 parts by mass, more preferably 35 to 60, in 100 parts by mass of the cationically polymerizable organic substance mixture. Parts by mass.

Specific examples of the alicyclic epoxy compound (1-2A) include a polyglycidyl ether compound of a polyol having at least one alicyclic ring, or a cyclohexene or cyclopentene ring using an oxidizing agent. A compound containing a cyclohexene oxide or a cyclopentene oxide obtained by epoxidation of a compound. 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-Methylcyclohexylmethyl ester, bis(3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexanecarboxylate, methylene double (3,4-epoxycyclohexane), propane-2,2-diylbis(3,4-epoxycyclohexane), 2,2-bis(3,4-epoxycyclohexyl)propane, Dicyclopentadiene diepoxide, exoethyl bis(3,4-epoxycyclohexanecarboxylate), dioctyl epoxy hexahydrophthalate, epoxy hexahydrophthalic acid di(2) -ethylhexyl)ester, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, α-pinene oxide, Limonene dioxide and the like.

As the alicyclic epoxy compound (1-2A), those having an epoxy group equivalent of 80 to 500 are preferred.

Commercially available products can be used as the alicyclic epoxy compound (1-2A), and examples thereof include Celloxide 2021P, Celloxide 2081, Celloxide 2000, and Celloxide 3000 (manufactured by Daicel Co., Ltd.).

The above aliphatic epoxy compound (1-2B) means an epoxy compound which is not classified into the above aromatic epoxy compound (1-1) or alicyclic epoxy compound (1-2A) as the aliphatic ring Specific examples of the oxygen compound 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, 2-ethylhexyl glycidyl ether, C12-13 mixed alkyl glycidyl ether, and 1,4-butanediol diglycidyl alcohol. 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 (1-2B) preferably has an epoxy group equivalent of from 80 to 500.

As the aliphatic epoxy compound (1-2B), a commercially available product can be used, and examples thereof include DENACOL EX2-11, 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); 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 (manufactured by Kyoeisha Chemical Co., Ltd.), Adeka Glycirol ED-503, Adeka Glycirol ED-503G, Adeka Glycirol ED-506, Adeka Glycirol ED-523T (manufactured by Adeka) and the like.

Further, the composition of the present invention preferably contains at least one polyfunctional epoxy compound as the above alicyclic epoxy compound (1-2A) or aliphatic epoxy compound (1-2B). Regarding the composition of the present invention, the cationically polymerizable organic substance mixture (1) is a polyfunctional alicyclic epoxy compound (1-2A) and/or a polyfunctional aliphatic epoxy compound (1-2B) in a mass of 100%. The total amount is preferably from 10 to 65 parts by mass, particularly preferably from 20 to 50 parts by mass. Further, the content of the polyfunctional alicyclic epoxy compound (1-2A) in 100 parts by mass of the cationically polymerizable organic substance mixture (1) is preferably 0 to 10 parts by mass, and a polyfunctional aliphatic epoxy compound ( The content of 1-2B) is preferably from 10 to 45 parts by mass.

The polyfunctional aliphatic oxetane compound (1-3) is suitably used in order to obtain a high Tg, and examples of the polyfunctional aliphatic oxetane compound (1-3) include 3,7- Bis(3-oxetanyl)-5-oxadecane, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, 1,2-double [ (3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycol Bis(3-ethyl-3-oxetanylmethyl)ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, tetraethylene glycol bis(3-ethyl-3 An oxetane compound such as oxetanylmethyl ether or the like.

As the polyfunctional aliphatic oxetane compound (1-3), a commercially available product containing a cationically polymerizable monomer as a main component can be used, and examples thereof include ARON OXETANE OXT-221 and ARON OXETANE OXT-121 (East Asia) Manufactured by a synthetic company; Etanacol OXBP, Etanacol OXTP, and Etanacol OXIPA (manufactured by Ube Industries, Ltd.).

In the above (1) cationically polymerizable organic substance mixture, the aromatic epoxy compound (1-1), the alicyclic epoxy compound (1-2A), the aliphatic epoxy compound (1-2B), and the like The ratio of use of the functional aliphatic oxetane compound (1-3) is as follows: In 100 parts by mass of the (1) cationically polymerizable organic substance mixture, the aromatic epoxy compound (1-1) is 35 to 80 parts by mass, alicyclic epoxy compound (1-2A) is 0 to 45 parts by mass, aliphatic epoxy compound (1-2B) is 0 to 45 parts by mass, polyfunctional aliphatic oxetane The compound (1-3) is 5 to 40 parts by mass, and the sum of the alicyclic epoxy compound (1-2A) and the aliphatic epoxy compound (1-2B) is not 0, and the aromatic epoxy compound (1-1) ) becomes the main component.

Here, the main component means a mixture of a plurality of cationically polymerizable organic substances, and the total mass of the same kind of compounds is the largest. For example, the composition of the following Example 4 contains 45 parts by mass of the aromatic epoxy compound (1-1-1), 5 parts by mass of the alicyclic epoxy compound (1-2A-1), and an aliphatic epoxy compound ( 1-2B-2) 30 parts by mass and 20 parts by mass of the polyfunctional aliphatic oxetane compound (1-3-1) as a cationically polymerizable organic substance. In this case, the aromatic epoxy compound having the highest content in the composition becomes a main component of the composition. In addition, in the fourth embodiment, it is assumed that 25 parts by mass of the aromatic epoxy compound (1-1-1) and 20 parts by mass of the aromatic epoxy compound (1-1-2) are substituted for the aromatic epoxy compound instead of the aromatic compound. In the case of 45 parts by mass of the group epoxy compound (1-1-1), the total content of 1-1-1 and 1-1-2 as the same type of aromatic epoxy compound is the largest in the composition, and thus the fragrance The family epoxy compound becomes the main component of the composition.

In the cationically polymerizable organic substance mixture of the above (1), a vinyl ether compound or a polymer having a cationically polymerizable group may be used as the cationically polymerizable organic substance constituting the mixture.

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 means 1 or 2, p and s represent the coefficient of keeping the charge 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.

(2) The ratio of use of the cationic polymerization initiator to the above-mentioned (1) cationically polymerizable organic substance mixture is not particularly limited, and is substantially within the scope of the object of the present invention. In general, it may be used in a ratio of, for example, 100 parts by mass of the (1) cationically polymerizable organic substance mixture, and may be (2) cationic polymerization initiator 0.5 to 20 parts by mass, preferably 1.0 to 10 mass. Share. When the amount is too small, the curing 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.

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. Amidoxime modification; the above polyamines and aldehydes such as formaldehyde and phenol, cresol, xylenol, t-butylphenol, and resorcinol have at least one hydroformylation reactivity on the nucleus by a conventional method. a Mannich modification produced by reacting a phenol at a site; a polycarboxylic acid (oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid,癸Acid, dodecanedioic acid, 2-methylsuccinic acid, 2-methyladipate, 3-methyladipate, 3-methylglutaric acid, 2-methyloctanedioic acid, 3,8 - aliphatic dicarboxylic acids such as dimethyl sebacic acid, 3,7-dimethyl sebacic acid, hydrogenated dimer acid, dimer acid; phthalic acid, terephthalic acid, isophthalic acid, naphthalene An aromatic dicarboxylic acid such as a dicarboxylic acid; an alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid; a tricarboxylic acid such as a trimer of trimellitic acid, trimesic acid or castor oil; and pyromellitic acid; An acid anhydride such as tetracarboxylic acid; dicyandiamide, imidazole, carboxylate, sulfonate, amine imine 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, Preferably, the composition of the present invention is cured at 130 to 180 Heat at °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 dissolve or disperse the components of the above (1) and (2) can be used without particular limitation, and examples thereof include methyl ethyl ketone, methyl amyl ketone, and diethyl ether. Ketones such as ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone; diethyl ether, 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.

In the composition of the present invention, the moisture content is preferably 5% or less, and more preferably 3% or less from the viewpoint of curability, adhesion, and liquid storage stability. If there is too much water, it will be cloudy or analyzed, so it is not good.

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 acetate, polyvinyl alcohol (PVA), Vinyl compounds such as polyvinyl chloride and polyvinyl fluoride; acrylic resins such as polymethyl methacrylate and polyacrylate; polyfluorene; polyether oxime; polyether ketone; polyether oximine; polyoxyethylene 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.

Moreover, as long as the effect of the present invention is not impaired, other monomers, other energy ray-sensitive polymerization initiators, inorganic fillers, organic fillers, pigments, dyes and the like, colorants, photosensitizers, defoamers, and tackifiers may be added as needed. Agent, surfactant, leveling agent, flame retardant, thixotropic agent, diluent, plasticizer, stabilizer, polymerization inhibitor, ultraviolet absorber, antioxidant, antistatic agent, flow regulator, and subsequent accelerator Various resin additives and the like.

The composition of the present invention is hardened by irradiation of an active energy ray as an active energy The measuring line includes ultraviolet rays, electron beams, X-rays, radiation, high frequencies, etc., and ultraviolet rays are economically optimal. 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.

The composition of the present invention is particularly suitable as an adhesive because it is excellent in curability and adhesion.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited to the 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. Further, in the examples and comparative examples, the parts mean parts by mass.

[Examples 1 to 24, Comparative Examples 1 to 3]

According to the compounding composition shown in the following [Table 1] to [Table 4], the components are thoroughly mixed and obtained. Compositions 1 to 24 and comparative compositions 1 to 3 were each carried out.

As the (1) cationically polymerizable organic substance, the following compounds (1-1-1) to (1-1-2), (1-2A-1) to (1-2A-2), (1-2B) are used. -1)~(1-2B-3) and (1-3-1).

Compound 1-1-1: Adeka Resin EP-4100L (bisphenol A epoxy resin: manufactured by ADEKA Corporation)

Compound 1-1-2: Adeka Resin EP-4901L (bisphenol A epoxy resin: manufactured by ADEKA Corporation)

Compound 1-2A-1: Celloxide 2021P (alicyclic epoxy resin; manufactured by Daicel Corporation)

Compound 1-2A-2: (4R)-1,2-epoxy-4-(2-methyloxiranyl)-1-methylcyclohexanemethyl 3,4-epoxycyclohexane Carboxylic ester

Compound 1-2B-1: 1,4-butanediol diglycidyl ether

Compound 1-2B-2: Adeka Glycirol ED-523T (made by ADEKA)

Compound 1-2B-3: 1,6-hexanediol diglycidyl ether

Compound 1-3-1: ARON OXETANE OXT-221 (manufactured by Toagosei Co., Ltd.)

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

Compound 2-1: a propylene carbonate 50% solution of a compound represented by [Chemical Formula 3] and a compound represented by [Chemical Formula 4]

[Chemical 4]

[Evaluation Examples 1 to 24, Comparative Evaluation Examples 1 to 3]

The comparative compositions obtained in the above Examples 1 to 24 and the comparative compositions obtained in Comparative Examples 1 to 3 were subjected to the following evaluations. The results are shown in the above [Table 1] to [Table 4].

(viscosity)

For each of the obtained compositions 1 to 24 and the comparative compositions 1 to 3, the viscosity was measured at 25 ° C using an E-type viscometer. The results are shown in [Table 1] to [Table 4].

(Tg)

Each of the obtained compositions 1 to 24 and the comparative compositions 1 to 3 was applied to a PET film by a bar coater at a thickness of 30 μm, and an energy of 3000 mJ/cm ^{2 was} irradiated with a metal halide lamp. . 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].

(hardenability)

When the test piece of Tg was produced, the hardenability was also confirmed. Those who did not adhere to the coated surface immediately after the irradiation were evaluated as ◎, those who did not adhere after 5 minutes were evaluated as ○, and those who remained after 15 minutes were evaluated as ×. The results are shown in [Table 1] to [Table 4].

(adhesive)

Each of the obtained compositions 1 to 24 and 1 to 3 of the comparative composition was applied to a TAC (triethyl fluorene cellulose) film subjected to corona discharge treatment, and then the film was laminated using a laminator. The film was bonded to another COP (cycloolefin polymer) film subjected to corona discharge treatment, and irradiated with a metal halide lamp at an energy of 800 mJ/cm ² to obtain a test piece. A 90 degree peel test of the obtained test piece was performed. 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 curability, adhesion, and heat resistance.

Claims (7)

A composition comprising an aromatic epoxy compound (1-1), an alicyclic epoxy compound (1-2A) or an aliphatic epoxy compound (1) as the cationically polymerizable organic substance mixture (1) -2B) and a polyfunctional aliphatic oxetane compound (1-3), and the aromatic epoxy compound (1-1) is a main component. The composition of claim 1, wherein the aromatic epoxy compound (1-1) contains a glycidyl ether selected from the group consisting of monophenols, a glycidyl ether compound having an aromatic compound having two or more alcoholic hydroxyl groups, and a polyphenol. At least one of a glycidyl ether compound, a glycidyl benzoate, a glycidyl ester of a polybasic acid, a styrene oxide or an epoxide of divinylbenzene. The composition of claim 1, wherein the aromatic epoxy compound (1-1) contains at least one polyfunctional epoxy compound. The composition of claim 1, wherein the aromatic epoxy compound (1-1) has an epoxy group equivalent of from 80 to 500. The composition of claim 1 which contains 0.5 to 20 parts by mass of the cationic polymerization initiator (2) based on 100 parts by mass of the cationically polymerizable organic substance mixture (1). The composition of claim 1, wherein the cationic polymerization initiator (2) is p[A] ^q+ ‧s[B] ^t- (wherein A represents a cationic species, B represents an anionic species, and q and t are each independently The ground represents 1 or 2, and p and s represent a salt of a cation and an anion represented by a coefficient that maintains a neutral charge. An adhesive comprising the composition of claim 1.