JP6705623B2 - Cationic polymerizable composition - Google Patents

Description

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 particularly useful as an adhesive.

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

For example, Patent Document 1 below discloses an ultraviolet-curable resin composition containing a polyorganosiloxane having alicyclic epoxy functional groups at both ends, and Patent Document 2 below discloses a silyl group in the molecule. There is disclosed a cationically polymerizable curable composition containing a vinyl ether compound having:

JP, 9-143248, A JP 2004-284221 A

However, the conventional cationically polymerizable composition is not sufficient in terms of compatibility of coating property, curability and adhesiveness.
An object of the present invention is to provide a cationically polymerizable composition having excellent coatability, curability and adhesiveness.

The present invention has been made on the basis of the above findings, and is cationically polymerizable with an alicyclic epoxy compound (1A) and an epoxy compound having a glycidyl group (excluding (1A)) (1B) as an essential component. The above object is achieved by providing a cationically polymerizable composition comprising a monomer mixture (1) and a polymer (2) having a weight average molecular weight of 5,000 to 50,000 and having at least one organosilyl group. It was done.

The present invention also provides an adhesive obtained from the above cationically polymerizable composition.

The cationically polymerizable composition of the present invention has excellent coatability, curability, and adhesiveness, and thus is particularly useful as an adhesive.

Hereinafter, the cationically polymerizable composition of the present invention and the adhesive obtained from the cationically polymerizable composition will be described in detail.

In the cationically polymerizable monomer mixture (1) used in the present invention, the cationically polymerizable monomers constituting the mixture cause a polymerization or a crosslinking reaction by an energy ray-sensitive cationic polymerization initiator activated by light irradiation. A compound, an epoxy compound, an oxetane compound, a cyclic lactone compound, a cyclic acetal compound, a cyclic thioether compound, a spiro orthoester compound, a vinyl ether or the like can be used, and among them, the ease of obtaining a uniform mixture, curability, and adhesiveness, From the viewpoint of adhesion, it is essential to contain an alicyclic epoxy compound (1A) and an epoxy compound having a glycidyl group (however, excluding (1A)) (1B). In addition to this, the oxetane compound (1C) is preferably used.

Examples of the alicyclic epoxy compound (1A) include polyglycidyl ether of polyhydric alcohol having at least one alicyclic ring, cyclohexene oxide, and cyclohexene oxide obtained by epoxidizing a cyclopentene ring-containing compound with an oxidizing agent. Examples include cyclopentene oxide-containing compounds. Specifically, cyclohexene oxide, hydrogenated bisphenol A diglycidyl ether, ethylene bis(3,4-epoxycyclohexanecarboxylate), 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1- Methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3- Methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4- Epoxy) cyclohexane-metadioxane, bis(3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexylcarboxylate, methylenebis(3,4-epoxycyclohexane), propane-2,2-diyl- Bis(3,4-epoxycyclohexane), 2,2-bis(3,4-epoxycyclohexyl)propane, dicyclopentadiene diepoxide, ethylenebis(3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate , Epoxyhexahydrophthalic acid di-2-ethylhexyl, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, α-pinene oxide, limonene dioxide, and the like. From the viewpoint of adhesion, it is preferable to use a bifunctional or higher functional one. These may be used alone or in combination of two or more.

As the alicyclic epoxy compound (1A), a commercially available product containing the alicyclic epoxy compound (1A) as a main component can be used. For example, Celoxide 2021P, Celoxide 2081, Celoxide 2000, Celoxide 3000( Manufactured by Daicel) and the like.

Specific examples of the epoxy compound having a glycidyl group (excluding (1A)) (1B) include, for example, at least a glycidyl ether of an aliphatic alcohol, a glycidyl ester of an alkylcarboxylic acid, and phenol/cresol/butylphenol. Monoglycidyl ether compound of monohydric phenol having one aromatic ring or its alkylene oxide adduct, monoglycidyl ether compound of aromatic compound having two or more phenolic hydroxyl groups such as resorcinol, hydroquinone and catechol A monofunctional epoxy compound, a polyhydric phenol having at least two aromatic rings such as bisphenol A and bisphenol F, or a polyglycidyl etherified product of an alkylene oxide adduct thereof, or glycidyl of a compound obtained by further adding an alkylene oxide thereto. Ether compounds and epoxy novolac resins; polyglycidyl ether compounds of aromatic compounds having two or more phenolic hydroxyl groups such as resorcinol, hydroquinone and catechol; two alcoholic hydroxyl groups such as benzenedimethanol, benzenediethanol and benzenedibutanol Glycidyl ether compound of aromatic compound having the above; polybasic acid aromatic compound glycidyl ester having two or more carboxylic acids such as phthalic acid, terephthalic acid and trimellitic acid; polyglycidyl ester of aliphatic long-chain polybasic acid Polyfunctional epoxy compounds, glycidyl esters of benzoic acid, polyepoxylated products of polyfunctional aliphatic polyhydric alcohols such as diepoxy compounds of divinylbenzene or their alkylene oxide adducts, benzoic acids such as toluic acid and glycidyl esters of naphthoic acid Glycidyl esters; monofunctional aromatic epoxy compounds such as styrene oxides, alkylated styrene oxides, styrene oxides such as epoxidized vinylnaphthalene, and bisphenol A/bisphenol F polyphenols having at least two aromatic rings Or, a polyglycidyl ether compound of an alkylene oxide adduct thereof, or a glycidyl ether compound of a compound obtained by further adding an alkylene oxide thereto or an epoxy novolac resin; an aromatic compound having two or more phenolic hydroxyl groups such as resorcinol, hydroquinone, and catechol Compound polyglycidyl ether compound; benzene dimethanol, benzene diethanol, benzene dibutanol, etc. Glycidyl ether compound of aromatic compound having two or more cholic hydroxyl groups; glycidyl ester of polybasic acid aromatic compound having two or more carboxylic acids such as phthalic acid, terephthalic acid and trimellitic acid; aliphatic long chain polybasic Examples thereof include polyfunctional epoxy compounds such as polyglycidyl esters of acids, glycidyl esters of benzoic acid, and polyfunctional epoxy compounds such as diepoxy compounds of divinylbenzene. Specifically, allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, C12-13 mixed alkyl glycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and triglyceride Glycidyl ethers, trimethylolpropane triglycidyl ethers, sorbitol tetraglycidyl ethers, dipentaerythritol hexaglycidyl ethers, polyethylene glycol diglycidyl ethers, polypropylene glycol diglycidyl ethers and other polyhydric alcohol glycidyl ethers, and propylene glycol. A glycidyl ether of a polyether polyol obtained by adding one or more alkylene oxides to an aliphatic polyhydric alcohol such as trimethylolpropane or glycerin, a diglycidyl ester of an aliphatic long-chain dibasic acid, Examples thereof include monoglycidyl ethers of higher aliphatic alcohols, monoglycidyl ethers of polyether alcohols obtained by adding alkylene oxides to these, and glycidyl esters of higher fatty acids. These may be used alone or in combination of two or more.

As the epoxy compound having a glycidyl group (however, excluding (1A)) (1B), commercially available products can be used, and examples thereof include Denacol EX-121, Denacol EX-171, Denacol EX-192, Denacol EX-211, Denacol EX-212, Denacol EX-313, Denacol EX-314, Denacol EX-321, Denacol EX-411, Denacol EX-421, Denacol EX-512, Denacol EX-521, Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX-622, Denacol EX-810, Denacol EX-811, Denacol EX-850, Denacol EX-851, Denacol EX-821, Denacol EX-830, Denacol EX-832, Denacol EX-841, Denacol EX-861, Denacol EX-911, Denacol EX-941, Denacol EX-920, Denacol EX-931, Denacol EX-145, Denacol EX-146, Denacol EX-147, Denacol EX-201, Denacol EX-711, Denacol EX-721, On-coat EX-1020, On-coat EX-1030, On-coat EX-1040, On-coat EX-1050, On-coat EX-1051, On-coat EX-1010, On-coat EX- 1011 on coat 1012 (manufactured by Nagase Chemtex); Epolite M-1230, Epolite 40E, Epolite 100E, Epolite 200E, Epolite 400E, Epolite 70P, Epolite 200P, Epolite 400P, Epolite 1500NP, Epolite 1600, Epolite 80MF, Epolite 100MF. (Kyoeisha Chemical Co., Ltd.), Oxol PG-100, Oxol EG-200, Oxol EG-210, Oxol EG-250 (Osaka Gas Chemical Co., Ltd.), HP4032, HP4032D, HP4700 (DIC), ESN-475V (Nippon Steel) Sumikin Chemical Co., Ltd.; -4100, Adeka Resin EP-4100G, Adeka Resin EP-4100E, Adeka Resin EP-4100L, Adeka Resin EP -4100TX, ADEKA RESIN EP-4000, ADEKA RESIN EP-4005, ADEKA RESIN EP-4080E, ADEKA RESIN EP-4082HT, ADEKA RESIN EP-4901, ADEKA RESIN EP-4901E, ADEKA GLYSILOL ED-501, ADEKA GLYCYLOL ED-509E, ADEKA GLYCILOL. ED-509S, ADEKA GLYSILOL ED-529 (made by ADEKA), etc. are mentioned.

In the epoxy compound having a glycidyl group (excluding (1A)) (1B), the number of glycidyl groups in the molecule is 1, that is, containing a monofunctional aromatic epoxy compound results in viscosity and It is preferable from the viewpoint of coatability. Specifically, the cationically polymerizable composition of the present invention contains 20 to 100 monofunctional aromatic epoxy compounds in 100 parts by mass of the epoxy compound having the glycidyl group (excluding (1A)) (1B). It is preferably contained in an amount of 30 parts by mass, more preferably 30 to 100 parts by mass, still more preferably 40 to 100 parts by mass.

Examples of the oxetane compound (1C) include 3,7-bis(3-oxetanyl)-5-oxa-nonane, 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, Bifunctional aliphatic oxetane compounds such as 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane 3-ethyl-3-[(phenoxy)methyl]oxetane, 3-ethyl-3-(hexyloxymethyl) Examples include monofunctional oxetane compounds such as oxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(hydroxymethyl)oxetane, 3-ethyl-3-(chloromethyl)oxetane. It is preferable to use a bifunctional aliphatic oxetane compound from the viewpoint of curability and reactivity. These may be used alone or in combination of two or more.

As the oxetane compound (1C), a commercially available product having a cationic polymerizable monomer as a main component can be used, and for example, 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, Ltd.) and the like can be mentioned.

In the cationically polymerizable monomer mixture (1), the mixing ratio of the alicyclic epoxy compound (1A), the epoxy compound having a glycidyl group (however, excluding (1A)) (1B) and the oxetane compound (1C) is , 80 to 80 parts by mass of the alicyclic epoxy compound (1A) in 100 parts by mass of the cationically polymerizable monomer mixture (1), and an epoxy compound having the glycidyl group (however, excluding (1A)) ( 1B) is preferably 20 to 80 parts by mass, and the oxetane compound (1C) is preferably 0 to 30 parts by mass. A more preferred amount of the alicyclic epoxy compound (1A) in 100 parts by mass of the cationically polymerizable monomer mixture (1) is 20 to 60 parts by mass, and a further preferred amount is 25 to 55 parts by mass, and even more. The preferred amount is 30 to 50 parts by mass. A more preferable amount of the epoxy compound having a glycidyl group (excluding (1A)) (1B) in 100 parts by weight of the cationically polymerizable monomer mixture (1) is 20 to 60 parts by weight, and a further preferable amount. Is 25 to 55 parts by mass, and an even more preferable amount is 30 to 50 parts by mass. When the oxetane compound (1C) is contained, the more preferable amount of the oxetane compound (1C) in 100 parts by mass of the cationically polymerizable monomer mixture (1) is 10 to 30 parts by mass, and the further preferable amount is 15 to 25 parts by mass.

The cationically polymerizable composition of the present invention preferably contains the cationically polymerizable monomer mixture (1) in the cationically polymerizable composition in an amount of 70 to 95% by mass, more preferably 75 to 95% by mass. It is particularly preferable to contain 80 to 95% by mass. It is preferable to contain 70% by mass or more from the viewpoint of low viscosity, and it is preferable to contain 95% by mass or less from the viewpoint of adhesion.

Examples of the polymer (2) having at least one organosilyl group having the weight average molecular weight of 5,000 to 50,000 used in the present invention include polycondensation, polyaddition, addition polymerization, ring-opening polymerization, cationic polymerization, anionic polymerization and radical. Polymers obtained by various reactions such as polymerization can be used, and in particular, monomers or copolymers obtained by radical polymerization or ring-opening polymerization are preferable because the synthesis is easy.

As the polymer (2) having at least one organosilyl group and having a weight average molecular weight of 5,000 to 50,000, one having at least one structural unit selected from the following structural units (I) to (III) is used. Is preferable because it is easy to synthesize.

(In the formula, R ¹ , R ² and R ³ are hydrogen atoms, and R ⁴ represents an alkyl group having 1 to 4 carbon atoms.)

(In the formula, R ⁵ and R ⁶ are hydrogen atoms, and R ⁷ and R ⁸ represent an alkyl group having 1 to 4 carbon atoms.)

(In the formula, R ⁹ and R ¹⁰ are hydrogen atoms, R ¹¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹² is an alkoxy group having 1 to 10 carbon atoms. )

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ⁴ in the general formula (I), R ⁷ and R ⁸ in the general formula (II), and R ¹¹ in the general formula (III) include , Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, 2 ethylhexyl and the like.

Examples of the alkoxy group having 1 to 10 carbon atoms represented by R ¹² in the above general formula (III) include methyloxy, ethyloxy, propyloxy, isopropyloxy, butyloxy, isobutyloxy, t-butyloxy, pentyloxy, isopentyl. Oxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy and the like can be mentioned.

The organosilyl group is a group having at least one organic group on silicon, and for example, a group represented by the following formula (a) can be used. The organosilyl group may be at the side chain or at the end of the polymer. When the organosilyl group is not present at the end, the end of the polymer is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 20 carbon atoms, an acryl group or a methacryl group. It is preferable to use one.

(In the formula, X ¹ and X ² are each independently a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted A C1-C20 alkenyl group, a substituted or unsubstituted C1-C20 alkenyloxy group, a substituted or unsubstituted C6-C24 aryl group, a substituted or unsubstituted C6-C24 Represents an aryloxy group, a substituted or unsubstituted acyloxy group, R ¹³ represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted C1-20 alkenyl group, substituted or unsubstituted C1-20 alkenyloxy group, substituted or unsubstituted C6-24 aryl group, substituted or unsubstituted C6-24 Indicates an aryloxy group or a substituted or unsubstituted acyloxy group.)

Examples of the above-mentioned organosilyl group include alkoxysilyl groups such as trimethoxysilyl, triethoxysilyl, dimethoxymethylsilyl, methoxydimethylsilyl and dimethoxyphenylsilyl; trichlorosilyl, methyldichlorosilyl, dimethylchlorosilyl, trimethylsiloxydichlorosilyl and the like. Halogenated silyl group; Acyloxysilyl such as methyldiacetoxysilyl and trimethylsiloxymethylacetoxysilyl; Hydrosilyl group having two or more Si—H bonds in the molecule such as dimethylsilyl and trimethylsiloxymethylsilyl; Examples thereof include alkenyloxysilyl groups such as propenyloxy)silyl and the like.

As the polymer (2) having at least one organosilyl group having a weight average molecular weight of 5,000 to 50,000, a polymer of another monomer, for example, a polymer of another ethylenically unsaturated monomer can be used. , A methyl group not substituted by a cationically polymerizable substituent, a branched alkyl group having 2 to 7 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alicyclic hydrocarbon group having 6 to 10 carbon atoms, or epoxy A polymer of an ethylenically unsaturated monomer substituted with a cationically polymerizable substituent such as a group, an oxetane group or a vinyl ether group can be used.

The weight average molecular weight of the polymer (2) having at least one organosilyl group is preferably 5,000 to 50,000 in terms of polystyrene, and more preferably 7,000 to 40,000.

The proportion of the polymer (2) having at least one organosilyl group having a weight average molecular weight of 5,000 to 50,000 relative to the above cationically polymerizable monomer mixture (1) is not particularly limited and is within a range not impairing the object of the present invention. Although it may be used in a generally normal use ratio, for example, it is preferably 5 to 30 parts by mass, more preferably 10 to 25 parts by mass with respect to 100 parts by mass of the cationically polymerizable monomer mixture (1). preferable.

An energy ray sensitive acid generator (3) can be further used in the cationically polymerizable composition of the present invention. The energy ray-sensitive acid generator (3) may be any compound as long as it can generate an acid by irradiation with energy rays, but from the viewpoint of availability and sensitivity, it is preferably A double salt, which is an onium salt that releases a Lewis acid upon irradiation with energy rays, or a derivative thereof. Specifically, the following general formula,
[A] ^r+ [B] ^r- (wherein A is a cation species, B is an anion species, and r represents the valence of the ion).
Examples thereof include salts of cations and anions.

The cation [A] ^r+ is preferably onium, and the structure thereof is, for example, the following general formula:
[(R ¹ ) _a Q] ^r+
Can be expressed as

Further, R ¹ is an organic group having ¹ to 60 carbon atoms and may contain any number of atoms other than carbon atoms. a is an integer of 1 to 5. a number of R ¹ are each independently, it may be the same or different. Further, at least one is preferably the above-mentioned organic group having an aromatic ring. Q is an atom or atomic group selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F, and N=N. Further, when the valence of Q in the cation [A] ^r+ is q, it is necessary that the relation r=a−q holds (however, N=N is treated as valence 0).

Further, the anion [B] ^{r −} is preferably a halide complex, and the structure thereof is, for example, the following general formula,
[LX _b ] ^r-
Can be expressed as

Further, L is a metal or metalloid that is the central atom of the halide complex, and B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co, etc. X is a halogen atom. b is an integer of 3 to 7. In addition, when the valence of L in the anion [B] ^r − is p, it is necessary that the relation r=bp holds.

Specific examples of the anion [LX _b] ^r- in the formula is tetrakis (pentafluorophenyl) borate, tetra (3,5-difluoro-4-methoxyphenyl) borate, tetrafluoroborate (BF ₄₎ ^-, Hexafluorophosphate (PF ₆ ) ^- , hexafluoroantimonate (SbF ₆ ) ^- , hexafluoroarsenate (AsF ₆ ) ^- , hexachloroantimonate (SbCl ₆ ) ^{- and the} like can be mentioned.

Further, the anion [B] ^r- is represented by the following general formula:
[LX _b-1 (OH)] ^r-
Those having a structure represented by can also be preferably used. L, X and b are the same as above. Other anions that can be used include perchlorate ion (ClO ₄ ) ^-- , trifluoromethyl sulfite ion (CF ₃ SO ₃ ) ^-- , fluorosulfonate ion (FSO ₃ ) ^-- , and toluenesulfonate anion. , Trinitrobenzene sulfonate anion, camphor sulfonate, nonafluorobutane sulfonate, hexadecafluorooctane sulfonate, tetraaryl borate, tetrakis(pentafluorophenyl)borate and the like.

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

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

(B) Diphenyls such as diphenyliodonium hexafluoroantimonate, di(4-methylphenyl)iodonium hexafluorophosphate, di(4-tert-butylphenyl)iodonium hexafluorophosphate, tolylcumyliodonium tetrakis(pentafluorophenyl)borate Iodonium salt

(C) Sulfonium cations represented by the following group I or group II, sulfonium salts such as hexafluoroantimony ion, tetrakis(pentafluorophenyl)borate ion, etc.

Further, as another preferable example, (η ⁵ -2,4-cyclopentadien-1-yl) [(1,2,3,4,5,6-η)-(1-methylethyl)benzene]-iron An iron-arene complex such as hexafluorophosphate, an aluminum complex such as tris(acetylacetonato)aluminum, tris(ethylacetonatoacetato)aluminum, tris(salicylaldehidato)aluminum and silanols such as triphenylsilanol. And the like.

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

The ratio of the energy ray-sensitive acid generator (3) to be used for the cationically polymerizable monomer mixture (1) is not particularly limited, and may be used at a generally normal ratio within the range not impairing the object of the present invention. For example, with respect to 100 parts by mass of the cationically polymerizable monomer mixture (1), the energy ray sensitive acid generator (3) is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass. it can. If the amount is too small, the curing tends to be insufficient, and if the amount is too large, various properties such as the water absorption of the cured product and the strength of the cured product may be adversely affected.

A silane coupling agent (4) can be further used in the cationically polymerizable composition of the present invention. Use of the silane coupling agent (4) is preferable from the viewpoint of low viscosity. Examples of the silane coupling agent (4) include dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltrimethoxysilane. Alkyl-functional alkoxysilanes such as methoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, alkenylfunctional alkoxysilanes such as allyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyl Trimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 2-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldi Epoxy-functional alkoxysilanes such as ethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N -Amino-functional alkoxysilanes such as phenyl-γ-aminopropyltrimethoxysilane, mercapto-functional alkoxysilanes such as γ-mercaptopropyltrimethoxysilane, titanium tetraisopropoxide, titanium alkoxides such as titanium tetranormalbutoxide, titanium Titanium chelates such as dioctyloxybis (octylene glycolate) and titanium diisopropoxybis (ethylacetoacetate), zirconium tetraacetylacetonate, zirconium chelates such as zirconium tributoxymonoacetylacetonate, zirconium trioxide. Zirconium acylates such as butoxymonostearate and isocyanate silanes such as methyltriisocyanatesilane can be used.

The amount of the silane coupling agent (4) used is not particularly limited, but is usually 0 to 40 parts by mass, preferably 1 to 40 parts by mass with respect to 100 parts by mass of the total amount of the cationically polymerizable monomer mixture (1). , More preferably 1 to 30 parts by mass, further preferably 1 to 20 parts by mass.

A thermal polymerization initiator can be used in the cationically polymerizable composition of the present invention, if necessary.
The thermal polymerization initiator is a compound that generates a cationic species or a Lewis acid by heating, and is a salt such as sulfonium salt, thiophenium salt, thioranium salt, benzylammonium, pyridinium salt or hydrazinium salt; diethylenetriamine, triethylenetriamine, tetraethylenepenta Alicyclic polyamines such as 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane and isophoronediamine; m-xylylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone And other aromatic polyamines; various epoxy resins such as polyamines and glycidyl ethers such as phenylglycidyl ether, butylglycidyl ether, bisphenol A-diglycidyl ether, bisphenol F-diglycidyl ether or carboxylic acid glycidyl esters And a polyepoxy addition modified product produced by reacting with and by a conventional method; amidation produced by reacting the organic polyamines with carboxylic acids such as phthalic acid, isophthalic acid and dimer acid by a conventional method Modified product; produced by reacting the polyamines with aldehydes such as formaldehyde and phenols having at least one aldehyde-reactive site in the nucleus such as phenol, cresol, xylenol, tert-butylphenol and resorcin by a conventional method. Mannich modified products: polyvalent carboxylic acids (oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 2-methylsuccinic acid, 2- Methyladipic acid, 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, hydrogenated dimer acid, dimer acid, etc. Aliphatic dicarboxylic acids; phthalic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid and other aromatic dicarboxylic acids; cyclohexanedicarboxylic acid and other alicyclic dicarboxylic acids; trimeric acid, trimesic acid, castor oil fatty acid trimer, etc. Tricarboxylic acids; tetracarboxylic acids such as pyromellitic acid) acid anhydrides; dicyandiamide, imidazoles, carboxylic acid esters, sulfonic acid esters, amine imides, and the like.

A commercial item can also be used as said thermal-polymerization initiator, for example, Adeka Opton CP77, Adeka Opton CP66 (made by ADEKA), CI-2639, CI-2624 (made by Nippon Soda Co., Ltd.), Sun-Aid SI-60L, Sun-Aid SI. -80L, San-Aid SI-100L (manufactured by Sanshin Chemical Industry Co., Ltd.) and the like can be mentioned.

The amount of the thermal polymerization initiator used is not particularly limited, but is usually in the range of 0.001 to 10 parts by mass with respect to 100 parts by mass of the total amount of the cationically polymerizable monomer mixture (1). When an agent is used, it is preferable to heat the cationically polymerizable composition of the present invention at 130 to 180° C. for 20 minutes to 1 hour.

If necessary, a thermoplastic organic polymer may be used in the cationically polymerizable composition of the present invention to improve the properties of the cured product. Examples of the thermoplastic organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly(meth)acrylic acid, styrene-(meth)acrylic acid copolymer, (meth)acrylic acid- Examples thereof include methyl methacrylate copolymer, glycidyl (meth)acrylate-polymethyl (meth)acrylate copolymer, polyvinyl butyral, cellulose ester, polyacrylamide, and saturated polyester.

For the cationically polymerizable composition of the present invention, a solvent that is not particularly limited and can dissolve or disperse each of the above-mentioned components (1) and (2) can be used. For example, methyl ethyl ketone, methyl amyl ketone, Ketones such as diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, propylene glycol monomethyl ether, Ether-based solvents such as dipropylene glycol dimethyl ether; ester-based solvents such as methyl acetate, ethyl acetate, acetic acid-n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, texanol; ethylene glycol monomethyl Cellosolve solvents such as ether and ethylene glycol monoethyl ether; alcohol solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, amyl alcohol; ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, Propylene glycol-1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ether ester solvents such as ethoxyethyl propionate; BTX solvents such as benzene, toluene, xylene, etc. Hexane, heptane, octane, cyclohexane, and other aliphatic hydrocarbon solvents; terpine oil, D-limonene, pine, and other terpene hydrocarbon oils; mineral spirits, Swazol #310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso # Paraffinic solvents such as 100 (Exxon Chemical Co., Ltd.); halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, 1,2-dichloroethane; halogenated aromatic hydrocarbons such as chlorobenzene. System solvents: propylene carbonate, carbitol system solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, water, etc. These solvents can be used as one kind or as a mixed solvent of two or more kinds.

The cationically polymerizable composition of the present invention preferably has a water content of 0.01 to 3.0% by mass, and 0.03 to 2.0% by mass from the viewpoint of curability, adhesiveness, and liquid storage stability. Is more preferable. Too much water is not preferred because it may cause clouding or precipitation of components.

The cationically polymerizable composition of the present invention preferably has a viscosity of 400 mPa·s or less when measured at 25° C., particularly 1 to 400 mPa·s because of excellent curability and coatability. The viscosity can be measured by the method described in Examples below.

The cationically polymerizable composition of the present invention is applied onto a supporting substrate by a known means such as a roll coater, a curtain coater, various printing and dipping. In addition, it is possible to apply it once to a supporting substrate such as a film and then transfer it to another supporting substrate, and the application method thereof is not limited.

The material for the supporting substrate is not particularly limited and may be a commonly used one. For example, inorganic materials such as glass; diacetyl cellulose, triacetyl cellulose (TAC), propionyl cellulose, butyryl cellulose, acetyl propionyl. Cellulose, cellulose ester such as nitrocellulose; polyamide; polyimide; polyurethane; epoxy resin; polycarbonate; polyethylene terephthalate (PET), polyethylene naphthalate, polybutylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2. -Polyphenols such as diphenoxyethane-4,4'-dicarboxylate and polybutylene terephthalate; polystyrene; polyolefins such as polyethylene, polypropylene and polymethylpentene; polyvinyl alcohol, polyvinyl acetate, polyvinyl chloride, polyvinyl fluoride, etc. Vinyl compounds; acrylic resins such as polymethylmethacrylate and polyacrylic acid ester; polycarbonate; polysulfone; polyethersulfone; polyetherketone; polyetherimide; polyoxyethylene, norbornene resin, cycloolefin polymer (COP) and other polymers Materials are listed.
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 and laser treatment.

Further, unless impairing the effects of the present invention, with respect to the cationically polymerizable composition, other monomers, other energy ray sensitive polymerization initiators, inorganic fillers, organic fillers, pigments, colorants such as dyes, if necessary, Photosensitizer, defoaming agent, thickener, surfactant, leveling agent, flame retardant, thixotropic agent, diluent, plasticizer, stabilizer, polymerization inhibitor, ultraviolet absorber, antioxidant, static Various resin additives such as an antistatic agent, a flow control agent and an adhesion promoter can be added.

In the cationically polymerizable composition of the present invention, the alicyclic epoxy compound (1A), the epoxy compound having a glycidyl group (however, excluding (1A)) (1B), the oxetane compound (1C), the weight average molecular weight. Containing 5,000 to 50,000 other components (excluding solvent) other than the polymer (2) having at least one organosilyl group, the energy ray sensitive acid generator (3) and the silane coupling agent (4). The amount is preferably 10% by mass or less and more preferably 5% by mass or less in the cationically polymerizable composition.

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

Specific applications of the cationically polymerizable composition of the present invention include glasses, optical materials typified by imaging lenses, paints, coating agents, lining agents, inks, resists, liquid resists, adhesives, printing plates, and insulating materials. Varnishes, insulating sheets, laminated plates, printed boards, sealants for semiconductor devices, LED packages, liquid crystal injection ports, organic EL, optical elements, electrical insulation, electronic parts, separation films, etc. Material, putty, glass fiber impregnating agent, sealing agent, passivation film for semiconductors and solar cells, interlayer insulating film, protective film, prism lens sheet used for backlight of liquid crystal display device, screen for projection TV, etc. Lens parts of lens sheets such as Fresnel lens sheets and lenticular lens sheets used for, or backlights using such sheets, optical lenses such as microlenses, optical elements, optical connectors, optical waveguides, optical shaping Examples thereof include casting agents, and examples of the base material applicable as a coating agent include metal, wood, rubber, plastic, glass, and ceramic products.

Next, the adhesive obtained from the cationically polymerizable composition of the present invention will be described.
The adhesive of the present invention has the cationically polymerizable composition of the present invention. For example, the adhesive of the present invention is prepared by uniformly mixing the cationically polymerizable composition of the present invention and applied to a supporting substrate for use. Alternatively, when it is used for an optical film, a support substrate provided with each layer such as an undercoat layer, an antireflection layer, a hard coat layer, a lubricating layer, a protective layer, and a liquid crystal layer as necessary is used, and selected from each layer. An adhesive layer can be provided between any two adjacent two of the above, and the adhesive layer can be obtained by applying the cationically polymerizable composition of the present invention. The thickness of the adhesive layer is preferably 2 to 400 μm. After application, the active energy ray is irradiated to cure.

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

Hereinafter, the cationically polymerizable composition of the present invention and a cured product obtained by curing the cationically polymerizable composition will be specifically described with reference to Examples, Evaluation Examples and Comparative Examples. In Examples and Comparative Examples, “part” means “part by mass”. Further,% of water content means% by mass.

[Examples 1 to 7, Comparative Examples 1 to 4]
The components were thoroughly mixed in the formulations shown in [Table 1] below to obtain Working Compositions 1 to 7 and Comparative Compositions 1 to 4, respectively. [Table 1] below shows the amount of water in the working compositions 1 to 7 and the comparative compositions 1 to 4.

The following compounds (1A-1), (1B-1 to 3) and (1C-1) were used as the cationically polymerizable monomer.
Compound 1A-1: Celoxide 2021P (alicyclic epoxy compound manufactured by Daicel)
Compound 1B-1: ADEKA GLYSILOL ED-501 (Glycidyl epoxy compound manufactured by ADEKA)
Compound 1B-2: 1,4 butanediol diglycidyl ether Compound 1B-3: Adeka Resin EP-4100L (bisphenol A type epoxy resin manufactured by ADEKA)
Compound 1C-1: Aron oxetane OXT-221 (Oxetane compound manufactured by Toagosei Co., Ltd.)

The following compounds (2-1) to (2-3) were used as the polymer (2) having a weight average molecular weight of 5,000 to 50,000 and having at least one organosilyl group.
Compound 2-1: Kaneka Cyryl SAT350 (MS polymer manufactured by Kaneka: weight average molecular weight 14000)
Compound 2-2: Kaneka Cyryl SAT010 (MS polymer manufactured by Kaneka: weight average molecular weight 6000)
Compound 2-3: Kaneka XMAP OR110S (TA polymer manufactured by Kaneka: weight average molecular weight 18,000)

The following compound (3-1) was used as the energy ray-sensitive acid generator (3).
Compound 3-1: Compound represented by [Chemical Formula 7]

The following compound (4-1) was used as the silane coupling agent (4).
Compound 4-1: β-(3,4 epoxycyclohexyl)ethyltrimethoxysilane

[Evaluation Examples 1 to 7, Comparative Evaluation Examples 1 to 4]
The following evaluations were performed on the example compositions 1 to 7 obtained in the above examples 1 to 7 and the comparative compositions 1 to 4 obtained in the comparative examples 1 to 4. The results are shown in [Table 1] above.
(Liquid state) What was uniformly mixed was evaluated as ◯, and what was separated was evaluated as x, and visually evaluated.
(Coatability) Each of the obtained Example Composition and Comparative Composition was applied onto a PET film having a thickness of 40 μm, and the state when the PET film was pasted with another 40 μm-thick PET film using a laminator was confirmed. A film having no air bubbles between them and having no wrinkles or irregularities was evaluated as ◯, and a film having air bubbles between the films or having wrinkles or irregularities in the film was evaluated as x.
(Curable)
The film used in the coatability test was irradiated with energy of 1000 mJ/cm ² using an electrodeless ultraviolet light lamp. Two minutes after the irradiation, the two films were peeled off, and the case where the coated surfaces of both films were tack-free was evaluated as ◯, and the one where the tack remained was evaluated as x.
(viscosity)
The viscosity of each of the obtained practical compositions 1 to 7 and comparative compositions 1 to 4 was measured with an E-type viscometer at 25°C.
(Adhesive strength)
Each of the obtained practical compositions 1 to 7 and comparative compositions 1 to 4 was applied to one piece of corona discharge-treated TAC (triacetyl cellulose) film, and then the film was corona-coated using a laminator. Another COP (cycloolefin polymer) film that had been subjected to a discharge treatment was attached to it, and irradiated with energy of 1000 mJ/cm ² using an electrodeless ultraviolet light lamp to adhere it to obtain a test piece. A 90-degree peel test was performed on the obtained test piece (N/2 cm).

From Table 1, it is clear that the cationically polymerizable composition of the present invention is excellent in coatability, curability and adhesiveness.

Claims (10)

A cationically polymerizable monomer mixture (1) containing an alicyclic epoxy compound (1A) and an epoxy compound having a glycidyl group (excluding (1A)) (1B) as an essential component, and a weight average molecular weight of 5,000 to 50,000, Contains a polymer (2) having at least one organosilyl group,
5 to 30 parts by mass of the polymer (2) having at least one organosilyl group and having a weight average molecular weight of 5,000 to 50,000 per 100 parts by mass of the cationically polymerizable monomer mixture (1), and the above cationic polymerization The amount of the alicyclic epoxy compound (1A) is 20 to 80 parts by mass in 100 parts by mass of the polymerizable monomer mixture (1) , and the epoxy compound having the glycidyl group (excluding (1A)) (1B). ) Is 80 parts by mass or less, and 20 parts by mass or more of a monofunctional aromatic epoxy compound having a glycidyl group is contained in 100 parts by mass of the cationically polymerizable monomer mixture (1), and the glycidyl group is further added. An epoxy compound (however, (1A) is excluded.) (1B) The amount of the said monofunctional aromatic epoxy compound is 100 mass parts or less in 100 mass parts, The cationically polymerizable composition characterized by the above-mentioned. The cationically polymerizable composition according to claim 1 , wherein the polymer (2) having at least one organosilyl group having a weight average molecular weight of 5,000 to 50,000 has the following structural unit (I).
(In the formula, R ¹ , R ² and R ³ are hydrogen atoms, and R ⁴ represents an alkyl group having 1 to 4 carbon atoms.) The cationically polymerizable composition according to claim 1 , wherein the polymer (2) having at least one organosilyl group and having a weight average molecular weight of 5,000 to 50,000 has the following structural unit (II).

(In the formula, R ⁵ and R ⁶ are hydrogen atoms, and R ⁷ and R ⁸ represent an alkyl group having 1 to 4 carbon atoms.) The cationically polymerizable composition according to claim 1 , wherein the polymer (2) having at least one organosilyl group and having a weight average molecular weight of 5,000 to 50,000 has the following structural unit (III).

(In the formula, R ⁹ and R ¹⁰ are hydrogen atoms, R ¹¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹² is an alkoxy group having 1 to 10 carbon atoms. ) The cationically polymerizable monomer mixture (1) 100 parts by weight, further, the oxetane compound (1C) cationically polymerizable composition according to any one of claims 1 to 4, characterized in that it contains 10 to 30 parts by weight .. The cationically polymerizable monomer mixture (1) with respect to 100 parts by weight, further, any one of the claims 1-5, characterized in that it comprises an energy beam-sensitive acid generator (3) 0.1 to 20 parts by weight The cationically polymerizable composition according to the item. The energy ray-sensitive acid generator (3) has the following general formula [A] ^r+ [B] ^r- (wherein A is a cation species, B is an anion species, and r is a valence of an ion). Indicates)
Cationically polymerizable composition according to any one of claims 1-6 in a cation and a salt of the anion represented. Per 100 parts by mass of the cationically polymerizable monomer mixture (1), further, to any one of claims 1-7, characterized in that it contains a silane coupling agent (4) 1 to 40 parts by weight The cationically polymerizable composition described. The cationically polymerizable composition according to any one of claims 1 to 9 , which contains 0.01 to 3% by mass of water. Bonding agent characterized by resulting from the cationically polymerizable composition according to any one of claims 1-9.