TWI650369B - Cationic polymerizable composition - Google Patents

Abstract

The cationically polymerizable composition of the present invention contains (1) a cationically polymerizable organic substance mixture, and (2) an energy ray-sensitive cationic polymerization initiator, wherein the (1) cationically polymerizable organic substance mixture contains an aromatic epoxy compound ( At least one of the aliphatic epoxy compound (1B) or the alicyclic epoxy compound (1C) is a cationically polymerizable organic substance, and the aromatic epoxy compound (1A) is used as a main component. It is preferred to contain at least one polyfunctional epoxy compound as the above aliphatic epoxy compound (1B) or alicyclic epoxy compound (1C).

Description

Cationic polymerizable composition

The present invention relates to a cationically polymerizable composition and a cured product obtained by irradiating the cationically polymerizable composition with an active energy ray. The cationically polymerizable composition is especially useful as an adhesive.

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 3 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

An object of the present invention is to provide a cationically polymerizable composition which is excellent in curability, adhesion and water resistance.

The present invention has been made in view of the above findings, and provides the above object by providing a cationically polymerizable composition characterized by containing (1) a cationically polymerizable organic substance mixture, and (2) energy. Line-sensitive cationic polymerization initiation The (1) cationically polymerizable organic substance mixture contains at least one of an aromatic epoxy compound (1A), an aliphatic epoxy compound (1B) or an alicyclic epoxy compound (1C) as a cationically polymerizable organic compound. The substance contains the aromatic epoxy compound (1A) as a main component.

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

Since the cationically polymerizable composition of the present invention is excellent in curability, adhesion, and water resistance, it is particularly useful as an adhesive.

Hereinafter, the cationically polymerizable composition of the present invention and an adhesive containing the cationically polymerizable composition 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 polymerized or caused by an energy ray-sensitive cationic polymerization initiator activated by light irradiation. The compound of the crosslinking reaction is preferably an epoxy compound. As the epoxy compound, an aromatic epoxy compound (1A), an alicyclic epoxy compound (1C), an aliphatic epoxy compound (1B), and a high molecular weight having an epoxy group having a weight average molecular weight of 1,000 to 1,000,000 can be used. Body (1D). Further, as the cationically polymerizable organic substance, a vinyl ether compound or an oxetane compound (1E) can also be used.

The above-mentioned aromatic epoxy compound (1C) 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 butylphenol. a mono/polyglycidyl etherate of a monohydric phenol or an alkylene oxide adduct thereof, such as bisphenol A, bisphenol F, or a glycidyl etherate of a compound obtained by further adding an alkylene oxide or An epoxy novolac resin; a glycidyl ether of an aromatic compound having two or more phenolic hydroxyl groups such as resorcin or hydroquinone or catechol; benzene Mono/polyglycidyl etherate of an aromatic compound having two or more alcoholic hydroxyl groups such as dimethanol, phenylenediethanol or phenylbutanol; two of phthalic acid, terephthalic acid and trimellitic acid A glycidyl ester of a polycarboxylic acid aromatic compound of the above carboxylic acid, a glycidyl ester of benzoic acid such as benzoic acid or toluic acid or naphthoic acid, or an epoxide of styrene oxide or divinylbenzene.

Among them, from the viewpoint of low viscosity of the composition, glycidyl ether containing a glycidyl ether selected from phenols, an aromatic compound having two or more alcoholic hydroxyl groups, and glycidol of a polyhydric phenol are preferable. At least one of an etherified group, a glycidyl ester of benzoic acid, a glycidyl ester of a polybasic acid, a styrene oxide or an epoxide of divinylbenzene.

As the aromatic epoxy compound, an epoxy equivalent of 80 to 500 is preferred because it has excellent curability.

A commercially available product can be used as the aromatic epoxy compound (1A), and examples thereof include Denacol EX-121, 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, Oncoat1012 (manufactured by Changchun Chemical Co., Ltd.); Ogsol PG-100, Ogsol EG-200, Ogsol EG-210, Ogsol EG-250 (manufactured by Osaka Gas Chemical Co., Ltd.); HP4032, HP4032D, HP4700 (DIC Corporation) Manufactured; 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 (Japan Pharmaceutical Co., Ltd.) Manufacturing); ADEKA GLYCIROL ED-501, ADEKA GLYCIROL ED- 502, ADEKA GLYCIROL ED-509, ADEKA GLYCIROL ED-529, ADEKA RESIN EP-4000, ADEKA RESIN EP-4005, ADEKA RESIN EP-4100, ADEKA RESIN EP-4901 (made by ADEKA); TECHMORE VG-3101L, EPOX- MKR710, EPOX-MKR151 (manufactured by Printec), and the like.

From the viewpoint of hardenability and adhesion, it is preferred to contain at least one polyfunctional epoxy compound as the above aromatic epoxy compound (1A). The cationically polymerizable composition of the present invention preferably contains 25 to 70 parts by mass of the polyfunctional aromatic epoxy compound (1A), more preferably 30%, based on 100 parts by mass of the (1) cationically polymerizable organic substance mixture. ~60 parts by mass.

Here, the amount of the above (1A) includes the amount corresponding to (1D).

Specific examples of the alicyclic epoxy compound (1C) include a polyglycidyl ether compound or a cyclohexene or cyclopentene ring compound having a polyol having at least one alicyclic ring by using an oxidizing agent. A compound containing cyclohexene oxide or cyclopentene oxide obtained by epoxidation. For example, hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexane methyl ester of 3,4-epoxycyclohexanecarboxylic acid, 3,4-epoxy-1-methylhexanecarboxylic acid 3,4-epoxy-1-methylcyclohexyl ester, 6-methyl-3,4-epoxycyclohexanecarboxylic acid 6-methyl-3,4-epoxycyclohexylmethyl ester, 3,4 3-epoxy-3-methylcyclohexanecarboxylic acid 3,4-epoxy-3-methylcyclohexylmethyl ester, 3,4-epoxy-5-methylcyclohexanecarboxylic acid 3,4-ring Oxy-5-methylcyclohexylmethyl ester, bis(3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexanecarboxylate, methylene Bis(3,4-epoxycyclohexane), propane-2,2-diylbis(3,4-epoxycyclohexane), 2,2-bis(3,4-epoxycyclohexyl)propane , dicyclopentadiene diepoxide, ethyl bis(3,4-epoxycyclohexanecarboxylate), dioctyl hexahydrophthalate, epoxy hexahydrophthalic acid Bis(2-ethylhexyl)ester, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, oxidized α-pinene, Limonium dioxide and the like.

As the alicyclic epoxy compound (1C), those having an epoxy equivalent of from 80 to 500 are preferred.

As the alicyclic epoxy compound (1C), a commercially available product can be used, and examples thereof include, for example: Celloxide 2021P, Celloxide 2081, Celloxide 2000, Celloxide 3000 (manufactured by Daicel), and the like.

The above-mentioned aliphatic epoxy compound (1B) is an epoxy compound which is not classified into the above aromatic epoxy compound (1A) or alicyclic epoxy compound (1C), and is a specific example of the aliphatic epoxy compound. Examples thereof 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 a polyglycidyl ether compound of an aliphatic polyol or an alkylene oxide adduct thereof, and an aliphatic long chain. A polyfunctional epoxy compound such as a polybasic acid polyglycidyl ester. 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, poly a glycidyl ether of a polyhydric alcohol such as diglycidyl ether of ethylene glycol or diglycidyl ether of polypropylene glycol, or one or two kinds of aliphatic polyols such as propylene glycol, trimethylolpropane or glycerin The polyglycidyl ether compound of the polyether polyol obtained from the above alkylene oxide, and the 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 an epoxy equivalent of from 80 to 500.

A commercially available product can be used as the aliphatic epoxy compound (1B), and examples thereof include Denacol EX-121, 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 Chemical Co., Ltd.); 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 (made by ADEKA).

Further, the cationically polymerizable composition of the present invention preferably contains at least one polyfunctional epoxy compound as the above aliphatic epoxy compound (1B) or alicyclic epoxy compound (1C). The cationically polymerizable composition of the present invention is a total amount of the polyfunctional aliphatic epoxy compound (1B) and the polyfunctional alicyclic epoxy compound (1C) based on 100 parts by mass of the (1) cationically polymerizable organic substance mixture. It is preferably 10 to 65 parts by mass, particularly preferably 20 to 50 parts by mass. In addition, the content of the polyfunctional aliphatic epoxy compound (1B) is preferably 10 to 45 parts by mass, based on 100 parts by mass of the (1) cationically polymerizable organic substance mixture, and a polyfunctional alicyclic epoxy compound (1C) The content of the compound is preferably from 0 to 10 parts by mass.

Here, the amounts of the above (1B) and (1C) include the amount corresponding to (1D).

The high molecular weight body (1D) having a weight average molecular weight of 1,000 to 1,000,000 having an epoxy group may, for example, be a polymer obtained by radical polymerization, preferably an ethylenically unsaturated group having a cationically polymerizable substituent. A polymer obtained by polymerizing a monomer or a polymer obtained by copolymerizing an ethylenically unsaturated monomer having no cationically polymerizable substituent.

The ethylenically unsaturated monomer constituting the high molecular weight body (1D) having a weight average molecular weight of 1,000 to 1,000,000 having an epoxy group is not particularly limited, and a known one can be used. For example, as an example of the ethylenically unsaturated monomer which does not have a cationically polymerizable substituent, the group represented by the following general formula (1) can be mentioned as a group having a cationically polymerizable substituent. Examples of the ethylenically unsaturated monomer include one or two or more hydrogen atoms of the alkyl group, the aryl group or the alicyclic hydrocarbon group in the following formula (1) via an epoxy group or an oxetane group. A group formed by substituting a vinyl group or a vinyl ether group.

R ¹ R ¹² =R ¹³ R ¹⁴ (1)

(wherein R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, and a carbon atom number of 6 to 12; An alicyclic hydrocarbon group having 6 to 10 carbon atoms, wherein the methylene group in the group may be substituted with -CO-, -O- or -COO-)

Further, in the case of the above copolymer, the high molecular weight body (1D) preferably contains an ethylenic unsaturation having a structure substituted with a cationically polymerizable substituent such as an epoxy group, an oxetanyl group or a vinyl ether group. 10 to 80% by mass of the monomer, and a branched alkyl group substituted with a methyl group, an ethyl group or a carbon number of 3 to 7 and an aryl group having 6 to 12 carbon atoms and a carbon number which are not substituted with a cationically polymerizable substituent 6 to 90% by mass of the alicyclic hydrocarbon group-substituted ethylenically unsaturated monomer of 6 to 10, and other ethylenically unsaturated monomers which are 100% by mass in total.

The high molecular weight body (1D) having an epoxy group having a weight average molecular weight of 1,000 to 1,000,000 is preferably a weight average molecular weight of 5,000 to 100,000, more preferably 7,000 to 70,000.

Examples of the vinyl ether compound or the oxetane compound (1E) include ethylene glycol divinyl ether, triethylene glycol divinyl ether, n-dodecyl vinyl ether, cyclohexyl vinyl ether, and 2-B. Hexyl vinyl ether, 2-chloroethyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, triethylene glycol vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 1, 6-cyclohexanedimethanol monovinyl ether, 1,4-butanediol monovinyl ether, diethylene glycol monovinyl ether, 1,4-butanediol divinyl ether, 1,6-cyclohexane Ethylene etherification such as methanol divinyl ether 3,7-bis(3-oxetanyl)-5-oxa-decane, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl] Benzene, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy) Methyl]propane, ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, tetraethylene glycol Bis(3-ethyl-3-oxetanylmethyl)ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl 3-oxetanylmethoxy)hexane, 3-ethyl-3-[(phenoxy)methyl]oxetane, 3-ethyl-3-(hexyloxymethyl)oxy Heterocyclobutane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(hydroxymethyl)oxetane, 3-B An oxetane compound such as a -3-(chloromethyl)oxetane or the like. The vinyl ether compound is preferably a molecular weight of 58 to 500, and preferably has a molecular weight of 70 to 300. The oxetane compound is preferably one having a molecular weight of from 100 to 1,000, more preferably from 110 to 500. Further, as the vinyl ether compound or the oxetane compound (1E), any of a monofunctional group and a polyfunctional group may be used, and a vinyl ether compound having one or two vinyl ether groups is preferably used or One or two oxetanyl oxetane compounds.

As the vinyl ether compound or the oxetane compound (1E), a commercially available product containing a cationically polymerizable monomer as a main component can be used, and examples thereof include 2-hydroxyethyl vinyl ether and diethylene glycol monoethylene. Ether, 4-hydroxybutyl vinyl ether (manufactured by Maruzen Petrochemical Co., Ltd.); ARON OXETANE OXT-121, OXT-221, EXOH, POX, OXA, OXT-101, OXT-211, OXT-212 (manufactured by Toagosei Co., Ltd.) ); Etanacol OXBP, OXTP (manufactured by Ube Industries Co., Ltd.), etc.

In the above (1) cationically polymerizable organic substance mixture, the aromatic epoxy compound (1A), the alicyclic epoxy compound (1C), the aliphatic epoxy compound (1B), and the weight average molecular weight of the epoxy group are 1000. The use ratio of the high molecular weight body (1D), the vinyl ether compound or the oxetane compound (1E) of ~1000000 is 100 parts by mass relative to the (1) cationically polymerizable organic substance mixture, and the aromatic epoxy compound (1A) is 25~70 parts by mass, especially good The amount of the alicyclic epoxy compound (1C) is 0 to 45 parts by mass, particularly preferably 0 to 30 parts by mass, and the aliphatic epoxy compound (1B) is 0 to 45 parts by mass, particularly preferably 30 to 60 parts by mass. 10 to 40 parts by mass, the high molecular weight body (1D) having an epoxy group having a weight average molecular weight of 1,000 to 1,000,000 is 0 to 50 parts by mass, particularly preferably 0 to 15 parts by mass, a vinyl ether compound or an oxetane compound. (1E) is 0 to 30 parts by mass, particularly preferably 0 to 25 parts by mass, and the sum of the alicyclic epoxy compound (1C) and the aliphatic epoxy compound (1B) is not 0, preferably an aromatic ring. The oxygen compound (1A) is used as a main component.

Here, the amounts of (1B) and (1C) are removed by the amount corresponding to the above (1D), and the amount of (1A) is the amount corresponding to (1D).

Here, the term "main component" refers to a case where a plurality of epoxy compounds are mixed, and the total amount of epoxy compounds of the same type is the largest, and when the cationically polymerizable organic substance mixture contains a cationically polymerizable organic substance other than an epoxy compound, The total amount of the total amount of the epoxy compounds is more than the total amount of the cationically polymerizable organic substances other than the epoxy compound. The total amount of the various types of epoxy compounds herein includes those equivalent to (1D).

The above (2) energy ray-sensitive cationic polymerization initiator used in the present invention may be any compound as long as it is a compound capable of releasing a substance which initiates cationic polymerization by irradiation with an energy ray, and is preferably irradiated by an energy ray. And a double salt of a cerium salt or a derivative thereof which releases a Lewis acid. As a representative of the compound, the following formula

[A] ^r+ [B] ^r- (wherein, A represents a cationic species, B represents an anionic species, and r represents a valence) a salt of a cation and an anion.

Here, the cation [A] ^{r+ is} preferably a cerium ion, and its structure can be, for example, the following general formula [(R ¹ ) _a Q] ^r+

Said.

Further, R ¹ herein is an organic group having 1 to 60 carbon atoms and may contain a plurality of atoms other than carbon atoms. a is an integer from 1 to 5. Each of R ^{1 's} may independently be the same or different. Further, it is preferred that at least one of the organic groups as described above has an aromatic ring. Q is an atom or an atom group selected from the 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] ^r+ is q, the relationship of r = aq must be established (where N = N is regarded as the valence of 0).

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

Said.

Further, here, L is a metal or a semimetal of 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 valence of L in the anion [B] ^r- is p, the relationship of r = bp must be established.

Specific examples of the anion [LX _b ] ^r- of the above formula include tetrakis(pentafluorophenyl)borate ion and tetrakis(3,5-difluoro-4-methoxyphenyl)borate ion. , tetrafluoroborate ion (BF ₄ ) ^- , hexafluorophosphate ion (PF ₆ ) ^- , hexafluoroantimonate ion (SbF ₆ ) ^- , hexafluoroarsenate ion (AsF ₆ ) ^- , hexachloroantimonate ion (SbCl ₆₎ ^- and so on.

Further, the anion [B] ^r- can also use the following general formula [LX _b-1 (OH)] ^r-

The structure represented. 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 ) ^- , toluene Acid anion, trinitrobenzenesulfonate anion, camphorsulfonate ion, decachlorobutanesulfonate ion, cetylchlorooctanesulfonate ion, tetraarylborate ion, tetrakis(pentafluorophenyl)borate ion Wait.

In the present invention, among the above-mentioned onium salts, it is particularly effective to use the following aromatic salts of (A) to (C). Among these, one type may be used alone or two or more types may be used in combination.

(A) phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate, Aryl diazonium salt such as 4-methylphenyldiazonium hexafluorophosphate

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

(C) a phosphonium salt of a phosphonium cation represented by the following Group I or Group II, and a hexafluoroantimonium ion, a hexafluorophosphate ion, a tetrakis(pentafluorophenyl)borate ion or the like

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 aluminum such as tris(acetonitrile)aluminum, tris(ethylacetonateacetate)aluminum or tris(salicylic acid)aluminum a mixture of a substance and a decyl alcohol such as triphenyl stanol.

Among these, from the viewpoints of practical use and light sensitivity, an aromatic sulfonium salt, an aromatic sulfonium salt, and an iron-aromatic hydrocarbon complex are preferably used.

(2) The use ratio of the energy ray-sensitive cationic polymerization initiator to the above (1) cationically polymerizable organic substance mixture is not particularly limited, and is used in a substantially normal use ratio within a range not inhibiting the object of the present invention. For example, (2) energy ray-sensitive cationic polymerization can be carried out with respect to 100 parts by mass of the (1) cationically polymerizable organic substance mixture. The initiator is set to be 0.001 to 10 parts by mass, preferably 0.1 to 5 parts by mass. If it is too small, it is easy to be hardened, and if it is too much, it may have a bad influence on various physical properties, such as a water absorption rate of a hardened material, and hardened material intensity.

A decane coupling agent may optionally be used in the cationically polymerizable composition of the present invention.

As the decane coupling agent, for example, dimethyl dimethoxy decane, dimethyl diethoxy decane, methyl ethyl dimethoxy decane, methyl ethyl diethoxy decane, methyl trimethoxy can be used. 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 - anthranyl 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), titanium diisopropoxide bis(acetic acid ethyl acetate), zirconium tetraacetate pyruvate, tributoxy A zirconium chelate compound such as acetonitrile zirconium acetonate, a zirconium hydride such as tributoxyzirconium 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 cationically polymerizable composition.

A thermal polymerization initiator may optionally be used in the cationically polymerizable composition of the present invention.

The term "thermal polymerization initiator" means a compound which generates a cationic species or a Lewis acid by heating, and examples thereof include a phosphonium salt, a thiobenzoic acid salt, a thiolane salt, a benzyl ammonium salt, a pyridinium salt, 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 reacting the above organic polyamines with a carboxylic acid such as phthalic acid, isophthalic acid or dimer acid by a usual method. The imidization modified product produced by using the above-mentioned polyamines and aldehydes such as formaldehyde and at least one aldehyde on the nucleus such as phenol, cresol, xylenol, t-butylphenol or resorcinol 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, Diacid, azelaic acid, dodecanedioic acid, 2-methylsuccinic acid, 2-methyladipate, 3-methyladipate, 3-methylglutaric acid, 2-methyloctane An aliphatic dicarboxylic acid such as acid, 3,8-dimethylsebacic acid, 3,7-dimethylsebacic acid, hydrogenated dimer acid or dimer acid; phthalic acid, terephthalic acid, and An aromatic dicarboxylic acid such as phthalic acid or naphthalene dicarboxylic acid; an alicyclic dicarboxylic acid such as cyclohexane dicarboxylic acid; a tricarboxylic acid such as a trimer of trimellitic acid, trimesic acid or castor oil fatty acid; An acid anhydride such as a tetracarboxylic acid such as pyromellitic acid; dicyandiamide, an imidazole, a carboxylic acid ester, a sulfonate, an amine imine or the like.

Commercially available products can be used as the above-mentioned thermal polymerization initiator, and examples thereof include: Adekaopton CP77, Adekaopton CP66 (manufactured by Adeka Corporation), CI-2639, CI-2624 (manufactured by Japan 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 content in the cationically polymerizable composition, and the thermal polymerization initiator is used. In the case of curing the cationically polymerizable composition of the present invention, it is preferably heated at 130 to 180 ° C for 20 minutes to 1 hour.

The cationically polymerizable composition of the present invention can also be used to improve the properties of the cured product by using a thermoplastic organic polymer (excluding a high molecular weight body (1D) having an epoxy group having a weight average molecular weight of 1,000 to 1,000,000). Examples of the thermoplastic organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate 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 decylamine , saturated polyester, etc.

In the cationically polymerizable composition of the present invention, a solvent which can be used for dissolving or dispersing the components (1) and (2) which are generally used can be used without particular limitation, and examples thereof include methyl ethyl ketone and methyl pentyl group. Ketones such as ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone; 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 Solvents; alcoholic solvents such as methanol, ethanol, isopropanol or n-propanol, isobutanol or n-butanol, 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 Petroleum (share)), Solvesso # 100 (Exxon Chemical (share)) and other paraffinic solvents; carbon tetrachloride, chloroform, trichloroethylene, dichloromethane, 1,2-dichloroethane, etc. Aliphatic hydrocarbon solvent; halogenated aromatic hydrocarbon solvent such as chlorobenzene; propylene carbonate, carbitol solvent, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N,N-dimethyl The guanamine, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl hydrazine, water, and the like may be used alone or in combination of two or more.

The total amount of the components other than the (1) cationically polymerizable organic substance mixture and (2) the energy ray-sensitive cationic polymerization initiator in the cationically polymerizable composition of the present invention depends on the use of the present invention and the like. In view of further improving the effect of the present invention, it is preferably 20 parts by mass or less, and particularly preferably 10 parts by mass or less, based on 100 parts by mass of the (1) cationically polymerizable organic substance mixture.

The cationically polymerizable composition of the present invention has a water content of preferably 5% by mass or less, and more preferably 3% by mass 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 moisture content was measured by the method described in the following examples.

The cationically polymerizable composition of the present invention preferably has a viscosity of 200 mPa from the viewpoint of coatability. s is below, and further preferably 10 to 150 mPa. s. The viscosity was measured at 25 ° C and measured by the method described in the following examples.

The cationically polymerizable composition of the present invention is applied to a support substrate by a known mechanism such as a roll coater, a curtain coater, various printing, and 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 above-mentioned support base can be used without any particular limitation, and examples thereof include inorganic materials such as glass; diacetyl cellulose, triethyl cellulose (TAC), propylene cellulose, and butyl cellulose. Cellulose esters such as cellulose, nitrocellulose, etc.; polyamine; polyimine; polyurethane; epoxy resin; polycarbonate; polyethylene terephthalate , polyethylene naphthalate, polybutylene terephthalate, 1,4-cyclohexane dimethyl 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 chloride, polyfluorinated Ethylene, etc. Alkenyl compound; acrylic resin such as polymethyl methacrylate or polyacrylate; polycarbonate; polyfluorene; polyether oxime; polyether ketone; polyether phthalimide; polyoxyethylene, norbornene resin, ring A polymer material such as an olefin 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 may be added as needed, and the photosensitizer, defoaming agent, Tackifiers, surfactants, leveling agents, flame retardants, thixotropic agents, diluents, plasticizers, stabilizers, polymerization inhibitors, UV absorbers, antioxidants, antistatic agents, flow regulators, followed by Various resin additives such as accelerators.

The cationically polymerizable 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, etc., and it is most economical. Ultraviolet light. Examples of the light source of the ultraviolet light include an ultraviolet laser, a mercury lamp, a xenon laser, and a metal halide lamp.

Specific examples of the use of the cationically polymerizable composition of the present invention include optical materials represented by glasses and imaging lenses, paints, coating agents, lining agents, inks, resists, liquid resists, and adhesives. , printing plate, insulating varnish, insulating sheet, laminated board, printed circuit board, semiconductor device / LED package / liquid crystal injection port / organic EL / optical element / electrical insulation / electronic parts / separation film, etc. A sealant, a molding material, a putty, a glass fiber impregnating agent, a caulk, a passivation film for a semiconductor/solar battery, an interlayer insulating film, a protective film, and a prismatic lens sheet used for backlighting of a liquid crystal display device a lens portion such as a Fresnel lens sheet or a lenticular lens sheet used for a screen such as a projection television, or a backlight such as a backlight using such a sheet, an optical lens such as a microlens, an optical element, an optical connector, or an optical waveguide As a substrate which can be used as a coating agent, for example, metal, wood, rubber, plastic, glass, etc. Glass, ceramics, etc.

Example

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 cationically polymerizable composition of the present invention and the cured product obtained by curing the cationically polymerizable composition will be more specifically described by way of examples, evaluation examples and comparative examples. In the examples and comparative examples, the parts mean parts by mass, and % means mass%.

[Examples 1 to 30, Comparative Examples 1 to 2]

Each component was sufficiently mixed by the formulation shown in the following [Table 1] to [Table 3], and each of the compositions 1 to 30 and the comparative compositions 1 to 2 were obtained.

(1) The following compounds (1A-1) to (1A-12), (1B-1) to (1B-4), (1C-1) to (1C-3), (the following compounds) are used as the cationically polymerizable organic substance. 1D-1)~(1D-2) and (1E-1)~(1E-4). The epoxy equivalents of these are shown together in [Table 1] to [Table 5].

Compound 1A-1: Resorcinol diglycidyl ether

Compound 1A-2: diglycidyl phthalate

Compound 1A-3: Divinylbenzene oxide

Compound 1A-4: Phenyl glycidyl ether

Compound 1A-5: styrene oxide

Compound 1A-6: EP-4100L (bisphenol A epoxy resin: manufactured by ADEKA Corporation)

Compound 1A-7: ADEKA RESIN EP-4901L

Compound 1A-8: ADEKA RESIN EP-4000L

Compound 1A-9: TECHMORE VG-3101L

Compound 1A-10: ADEKA GLYCIROL ED-509S (made by ADEKA)

Compound 1A-11: ADEKA GLYCIROL ED-501 (made by ADEKA)

Compound 1A-12: ADEKA GLYCIROL ED-529 (made by ADEKA)

Compound 1B-1: Neopentyl glycol diglycidyl ether

Compound 1B-2: Triglycidyl tris(2-hydroxyethyl)isocyanurate

Compound 1B-3: 2-ethylhexyl glycidyl ether

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

Compound 1C-1: Celloxide 2021P (aliphatic epoxy resin: manufactured by Daicel Co., Ltd.)

Compound 1C-2: Methyl 3,4-epoxycyclohexanecarboxylate

Compound 1C-3: Celloxide 3000 (aliphatic epoxy resin: manufactured by Daicel)

Compound 1D-1: GMA/MMA (glycidyl methacrylate/methyl methacrylate) = 3/7 copolymer (Mw: 8000)

Compound 1D-2: GMA/MMA (glycidyl methacrylate/methyl methacrylate) = 3/7 copolymer (Mw: 15000)

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

Compound 1E-2: ARON OXETANE OXT-211 (manufactured by Toagosei Co., Ltd.)

Compound 1E-3: Hydroxybutyl vinyl ether

Compound 1E-4: 1,4-butanediol divinyl ether

(2) Energy ray-sensitive cationic polymerization initiator The following compound (2-1) was used.

Compound 2-1: CPI-100P (manufactured by San-Apro Co., Ltd.)

[Evaluation Examples 1 to 30, Comparative Evaluation Examples 1 to 2]

The following compositions obtained in the above Examples 1 to 30 and Comparative Compositions obtained in Comparative Examples 1 and 2 were subjected to the following evaluations. The results are shown in the above [Table 1] to [Table 5].

(viscosity)

Each of the obtained Compositions 1 to 30 and Comparative Compositions 1 to 2 was measured for viscosity at 25 ° C using an E-type viscometer. The results are shown in [Table 1] to [Table 5].

(hardenability)

Each of the obtained Compositions 1 to 30 and Comparative Compositions 1 to 2 was applied to a PET film by a bar coater to a thickness of 3 to 6 μm, and an electrodeless ultraviolet lamp was used to irradiate 1000 mJ/cm. ² energy. After the irradiation for 5 minutes, the coated surface was evaluated as non-adhesive, and it was evaluated as ◎, and after 15 minutes, the non-adhesive was evaluated as ○, and after 15 minutes, the residual viscosity was evaluated as ×. The results are shown in the above [Table 1] to [Table 5].

(heat resistant water test)

After applying each of the obtained Compositions 1 to 30 and Comparative Compositions 1 to 2 onto a TAC (triethyl fluorene cellulose) film, a COP (cycloolefin polymer) film was bonded thereto using a laminator. From the COP film side, an electrodeless ultraviolet lamp was used to irradiate an energy of 1000 mJ/cm ² to be followed, thereby obtaining a test piece. After 48 hours, a test piece of 2 cm × 4 cm was cut out, immersed in warm water of 60 ° C and observed. After 12 hours, the state of the test piece was observed, and the change was evaluated as ○ before the start, and the detachment was evaluated as Δ at the end face, and the peeling of the film was evaluated as being completely peeled off and evaluated as ×. The results are shown in the above [Table 1] to [Table 5].

(adhesive)

Each of the obtained Compositions 1 to 30 and Comparative Compositions 1 to 2 was applied onto a COP (cycloolefin polymer) 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 an electrodeless ultraviolet lamp was irradiated thereto to irradiate an energy of 1000 mJ/cm ² to obtain a test piece. The 90-degree peeling test of the obtained test piece was carried out, and the strength of 2.0 N/cm or more was evaluated as ◎, the strength of 1.0-2.0 N/cm was evaluated as ○, and the strength of 1.0 N/cm or less was evaluated as ×. The results are shown in [Table 1] to [Table 5].

(water content)

The moisture content was measured by the Karl's method for each of the obtained compositions 1 to 30 and comparative compositions 1 to 2. The results are shown in the above [Table 1] to [Table 5].

It is clear from [Table 1] to [Table 5] that the cationically polymerizable composition of the present invention is excellent in curability, temperature resistance, and adhesion.

Claims (9)

A cationically polymerizable composition comprising (1) a cationically polymerizable organic substance mixture, and (2) an energy ray-sensitive cationic polymerization initiator, wherein (1) cationic polymerization in a cationically polymerizable organic substance mixture The organic substance contains an aromatic epoxy compound (1A) as a main component, and further contains at least one of an aliphatic epoxy compound (1B) or an alicyclic epoxy compound (1C), relative to (1) a cationically polymerizable organic compound. 100 parts by mass of the substance mixture, the amount of the aromatic epoxy compound (1A) is 25 to 70 parts by mass, and the amount of the alicyclic epoxy compound (1C) is 0 to 45 parts by mass, and the aliphatic epoxy compound (1B) is used. The amount is 0 to 45 parts by mass. The cationically polymerizable composition according to claim 1, which contains at least one polyfunctional epoxy compound as the above aliphatic epoxy compound (1B) or alicyclic epoxy compound (1C). The cationically polymerizable composition according to claim 1, which comprises a glycidyl ether selected from the group consisting of phenols, a glycidyl ether compound of an aromatic compound having two or more alcoholic hydroxyl groups, a glycidyl ether compound of a polyhydric phenol, and a benzoic acid. At least one of a group of glycidyl esters, glycidyl esters of polybasic acids, styrene oxides or epoxides of divinylbenzene is used as the aromatic epoxy compound (1A). The cationically polymerizable composition according to claim 1, which contains at least one polyfunctional epoxy compound as the above aromatic epoxy compound (1A). The cationically polymerizable composition according to claim 1, wherein the aromatic epoxy compound (1A) has an epoxy equivalent of from 80 to 500. The cationically polymerizable composition according to any one of claims 1 to 5, which further comprises a high molecular weight (1D), vinyl ether compound or oxetane compound having an epoxy group having a weight average molecular weight of 1,000 to 1,000,000 ( At least one of 1E) is (1) a cationically polymerizable organic substance. The cationically polymerizable composition of claim 1, wherein (2) the energy ray-sensitive cationic polymerization initiator is [A] ^r+ [B] ^r- (wherein A represents a cationic species, B represents an anionic species, and r represents The cation and anion salt represented by the valence. The cationically polymerizable composition of claim 1, which has a water content of 5% by mass or less. An adhesive comprising the cationically polymerizable composition according to any one of claims 1 to 8.