JP6400005B2 - 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 active energy rays. The cationically polymerizable composition is particularly useful for adhesives.

  Cationic polymerizable compositions are used in the fields of inks, paints, various coating agents, adhesives, optical members and the like.

  For example, Patent Literature 1 below discloses various photocurable adhesives.

International Publication No. 2008/111484

  An object of the present invention is to provide a curable composition having high curability and adhesiveness, low viscosity and excellent coatability, and having high water resistance after curing.

  The present invention has been made on the basis of the above findings, and (1) contains at least one of an aliphatic epoxy compound (1A) or an alicyclic epoxy compound (1B) as a cationically polymerizable organic substance, As the epoxy compound (1A) or the alicyclic epoxy compound (1B), it contains a cationically polymerizable organic substance mixture containing at least one monofunctional epoxy compound, and (2) an energy ray-sensitive cationic polymerization initiator. The above object is achieved by providing a cationically polymerizable composition.

  Moreover, this invention contains at least 1 type of an aliphatic epoxy compound (1A) or an alicyclic epoxy compound (1B) as a cationically polymerizable organic substance, and contains an aromatic epoxy compound (1C). A cationically polymerizable organic substance mixture containing at least one monofunctional epoxy compound as the aliphatic epoxy compound (1A), alicyclic epoxy compound (1B) or aromatic epoxy compound (1C), and (2) energy rays The object is achieved by providing a cationically polymerizable composition characterized by containing a sensitive cationic polymerization initiator.

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

  The cationic polymerizable composition of the present invention is particularly useful as an adhesive because it is excellent in curability, adhesiveness, coating property, water resistance after curing, and has a high elastic modulus.

  Hereinafter, the cationic polymerizable composition of the present invention and the adhesive comprising the cationic polymerizable composition will be described in detail.

  In the (1) cationic polymerizable organic substance mixture used in the present invention, the cationic polymerizable organic substance constituting the mixture is polymerized or crosslinked by an energy ray sensitive cationic polymerization initiator activated by light irradiation. An epoxy compound is preferable. As the epoxy compound, an aliphatic epoxy compound (1A) or an alicyclic epoxy compound (1B) is used, and further, an aromatic epoxy compound (1C), a high molecular weight polymer having an epoxy group and a weight average molecular weight of 1,000 to 1,000,000 ( 1D) can be used. In addition, as the cationically polymerizable organic substance, a vinyl ether compound or an oxetane compound (1E) can be used.

Specific examples of the alicyclic epoxy compound (1B) are obtained by epoxidizing a polyglycidyl ether of a polyhydric alcohol having at least one alicyclic ring or a cyclohexene or cyclopentene ring-containing compound with an oxidizing agent. Examples include cyclohexene oxide and cyclopentene oxide-containing compounds. For example, cyclohexene oxide, hydrogenated bisphenol A diglycidyl ether, ethylene bis (3,4-epoxycyclohexanecarboxylate), 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxy Rate, 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, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl Carboxylate, 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, di-2-ethylhexyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2- Examples thereof include epoxy-2-epoxyethylcyclohexane, α-pinene oxide, limonene dioxide and the like.
As said alicyclic epoxy compound (1B), the thing whose epoxy equivalent is 80-500 or a viscosity is 2000 mPa * s or less is preferable from a viewpoint of sclerosis | hardenability and low viscosity of a composition. The viscosity is a viscosity at 25 ° C., and is measured by the method described in Examples described later.

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

Specific examples of the aliphatic epoxy compound (1A) include monofunctional epoxy compounds such as glycidyl ethers of aliphatic alcohols and glycidyl esters of alkylcarboxylic acids, polyglycidyls of aliphatic polyhydric alcohols or alkylene oxide adducts thereof. Examples thereof include polyfunctional epoxy compounds such as etherified products and polyglycidyl esters of aliphatic long-chain polybasic acids. As representative compounds, 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, glycerin Triglycidyl ether, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, glycidyl ether of polyhydric alcohol such as diglycidyl ether of polypropylene glycol, and propylene One or more alkyles in aliphatic polyhydric alcohols such as glycol, trimethylolpropane and glycerin And polyglycidyl etherified products of polyether polyols obtained by adding oxides, and diglycidyl esters of aliphatic long-chain dibasic acids. Furthermore, monoglycidyl ethers of higher aliphatic alcohols and polyether alcohol monoglycidyl ethers obtained by adding alkylene oxides to these, glycidyl esters of higher fatty acids, epoxidized soybean oil, octyl epoxy stearate, butyl epoxy stearate Epoxidized soybean oil, epoxidized polybutadiene and the like.
As said aliphatic epoxy compound (1A), what is epoxy equivalent 80-500 or a viscosity is 2000 mPa * s or less is preferable from a viewpoint of sclerosis | hardenability and low viscosity of a composition. This viscosity is a viscosity at 25 ° C., and is measured by the method described in Examples described later.

  As the aliphatic epoxy compound (1A), commercially available products can be used. For example, 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, Denaco EX-861, Denacol EX-911, Denacol EX-941, Denacol EX-920, Denacol EX-931 (manufactured by Nagase ChemteX Corporation); Epolite M-1230, Epolite 40E, Epolite 100E, Epolite 200E, Epolite 400E, Epolite 70P , Epolite 200P, Epolite 400P, Epolite 1500NP, Epolite 1600, Epolite 80MF, Epolite 100MF (manufactured by Kyoeisha Chemical Co., Ltd.), Adeka Glycilol ED-503, Adeka Glycilol ED-503G, Adeka Glycilol ED-506, Adeka Glycilol ED -523T (made by ADEKA) etc. are mentioned.

The aromatic epoxy compound (1C) refers to an epoxy compound containing an aromatic ring, and specific examples of the aromatic epoxy compound include monovalent phenols having at least one aromatic ring such as phenol, cresol, and butylphenol. Alternatively, mono / polyglycidyl etherified products of the alkylene oxide adducts such as bisphenol A, bisphenol F, or glycidyl etherified products of compounds obtained by further adding alkylene oxide to these and epoxy novolac resins; two such as resorcinol, hydroquinone and catechol Mono / polyglycidyl etherified products of aromatic compounds having the above phenolic hydroxyl groups; aromatic compounds having two or more alcoholic hydroxyl groups such as benzenedimethanol, benzenediethanol, and benzenedibutanol Glycidyl ester of polybasic acid aromatic compound having two or more carboxylic acids such as phthalic acid, terephthalic acid, trimellitic acid; benzoic acid such as glycidyl ester of benzoic acid or glycidyl ester of toluic acid or naphthoic acid Examples thereof include glycidyl esters of acids; styrene oxides such as styrene oxide, alkylated styrene oxide, epoxidized vinylnaphthalene, and diepoxylated divinylbenzene.
Among these, the aromatic epoxy compound (1C) contains at least one selected from the group of glycidyl ethers of phenols, glycidyl esters of benzoic acid or styrene oxides from the viewpoint of reducing the viscosity of the composition. preferable.
As the aromatic epoxy compound, those having an epoxy equivalent of 80 to 500 or a viscosity of 2000 mPa · s or less are preferable because of excellent curability and low viscosity of the composition. This viscosity is a viscosity at 25 ° C., and is measured by the method described in Examples described later.

  As the aromatic epoxy compound (1C), commercially available products can be used. For example, Denacol EX-121, 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, Oncoat 1012 (manufactured by Nagase ChemteX); Ogsol PG-100, Ogsol EG-200, Ogsol EG-210, Ogsol EG-250 (Osaka Gas Chemical); HP4032, HP4032D, HP4700 (made by DIC); ESN -4 5V (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.); 152, 154, 157S70, YX8800 (manufactured by Mitsubishi Chemical Corporation); Adeka Resin EP-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, Adekaglycilol ED-501, Adekaglycilol ED-509E, Adekaglycilol ED-509S, Adeka Glycilol ED-529 (made by ADEKA), TECHMORE VG3101L, EPOX-MKR710, EPOX-MKR151 (made by Printec), etc. Is mentioned.

The cationically polymerizable composition of the present invention contains at least one monofunctional epoxy compound as the above-mentioned aliphatic epoxy compound (1A), alicyclic epoxy compound (1B) or aromatic epoxy compound (1C). Furthermore, the cationically polymerizable composition of the present invention contains at least one monofunctional epoxy compound as the aliphatic epoxy compound (1A) or the alicyclic epoxy compound (1B), or contains the aromatic epoxy compound (1C). It is essential to contain. When the cationically polymerizable composition of the present invention contains a monofunctional epoxy compound as the aliphatic epoxy compound (1A) or the alicyclic epoxy compound (1B), the content of this monofunctional epoxy compound is determined based on the epoxy compound used. For example, the total amount of the monofunctional aliphatic epoxy compound (1A) and the monofunctional alicyclic epoxy compound (1B) is (1) a cation polymerizable organic substance mixture 100, although it varies depending on the type and use of the composition. It is preferable that it is 5-60 mass parts with respect to a mass part, especially 10-50 mass parts. Moreover, it is preferable that content of monofunctional aliphatic epoxy compound (1A) is 0-30 mass parts with respect to 100 mass parts of (1) cation polymerizable organic substance mixture, and monofunctional alicyclic epoxy compound The content of (1B) is preferably 0 to 40 parts by mass. Moreover, it is preferable that content of a monofunctional aliphatic epoxy compound (1A) is 25-100 mass parts with respect to 100 mass parts of aliphatic epoxy compounds (1A), and 100 mass parts of alicyclic epoxy compounds (1B). On the other hand, the content of the monofunctional alicyclic epoxy compound (1B) is preferably 5 to 100 parts by mass.
Here, the amounts of (1A) and (1B) are amounts including those corresponding to (1D).

When the cationic polymerizable composition of the present invention contains the aromatic epoxy compound (1C), it is preferable that the aromatic epoxy compound (1C) contains at least one monofunctional epoxy compound for water resistance and adhesiveness. It is preferable from the viewpoint. When the monofunctional epoxy compound is contained as the aromatic epoxy compound (1C), the content of the monofunctional aromatic epoxy compound is, for example, 0 to 70 parts per 100 parts by mass of (1) the cationic polymerizable organic substance mixture. It is preferable that it is a mass part, especially 10-60 mass parts. Moreover, it is preferable that content of a monofunctional aromatic epoxy compound (1C) is 5-100 mass parts with respect to 100 mass parts of aromatic epoxy compounds (1C).
In the aromatic epoxy compound (1C), the content of the monofunctional aromatic epoxy compound (1C) is preferably larger than the content of the polyfunctional aromatic epoxy compound (1C) from the viewpoint of reducing the viscosity of the composition.
Here, the amount of (1C) includes the amount corresponding to (1D).

  Examples of the polymer (1D) having a weight average molecular weight of 1,000 to 1,000,000 having the epoxy group include a polymer obtained by radical polymerization, and homopolymerizing one kind of ethylenically unsaturated monomer having a cationic polymerizable substituent. Preferred is a polymer copolymerized with an ethylenically unsaturated monomer that does not have a polymer or a cationically polymerizable substituent.

  As an ethylenically unsaturated monomer which comprises the said high molecular weight body (1D) of the weight average molecular weight 1000-1 million which has the said epoxy group, it does not restrict | limit but a well-known thing can be used. For example, an example of an ethylenically unsaturated monomer having no cationically polymerizable substituent includes a group represented by the following general formula (1), and an ethylenically unsaturated group having a cationically polymerizable substituent. As an example of the monomer, one or more hydrogen atoms in the alkyl group, aryl group or alicyclic hydrocarbon group in the following general formula (1) are substituted with an epoxy group, an oxetane group or a vinyl ether group. Groups.

（式中、Ｒ^１１、Ｒ^１２、Ｒ^１３及びＲ^１４はそれぞれ独立に、水素原子、炭素原子数１〜１０の直鎖状、分岐鎖状若しくは環状のアルキル基、炭素原子数６〜１２のアリール基又は炭素原子数６〜１０の脂環式炭化水素基であり、これらの基中のメチレン基は−ＣＯ−、−Ｏ−又は−ＣＯＯ−で置換されていてもよい）

(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, or 6 to 12 carbon atoms. An aryl group or an alicyclic hydrocarbon group having 6 to 10 carbon atoms, and the methylene group in these groups may be substituted with -CO-, -O- or -COO-)

  In the case of the above copolymer, the high molecular weight (1D) comprises 10 to 10 ethylenically unsaturated monomers having a structure substituted with a cationic polymerizable substituent such as an epoxy group, an oxetane group or a vinyl ether group. A methyl group, ethyl group or branched alkyl group having 3 to 7 carbon atoms, aryl group having 6 to 12 carbon atoms, 6 to 10 carbon atoms, which is contained by 80% by mass and not substituted with a cationic polymerizable substituent It is preferable to contain 20 to 90% by mass of the ethylenically unsaturated monomer substituted with an alicyclic hydrocarbon group and to be 100% by mass in total with other ethylenically unsaturated monomers.

  The high molecular weight product (1D) having a weight average molecular weight of 1,000 to 1,000,000 having the epoxy group preferably has 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 oxetane compound (1E) include ethylene glycol divinyl ether, triethylene glycol divinyl ether, n-dodecyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl 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 -Vinyl etherification such as cyclohexanedimethanol divinyl ether 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, 1,6-bis (3 -Ethyl-3-oxetanylmethoxy) hexane, 3-ethyl-3-[(phenoxy) methyl] oxetane 3-ethyl-3- (hexyloxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (hydroxymethyl) oxetane, 3-ethyl-3- (chloromethyl) ) Oxetane compounds such as oxetane. The vinyl ether compound preferably has a molecular weight of 58 to 500, more preferably 70 to 300. The oxetane compound preferably has a molecular weight of 100 to 1000, more preferably 110 to 500. The vinyl ether compound or oxetane compound (1E) may be monofunctional or polyfunctional, but has one or two vinyl ether groups or oxetane groups having one or two vinyl ether groups. It is preferable to use an oxetane compound.

  As the vinyl ether compound or oxetane compound (1E), a commercially available product mainly composed of a cationic polymerizable monomer can be used. For example, 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether (Maruzen) Aron Oxetane OXT-121, OXT-221, EXOH, POX, OXA, OXT-101, OXT-211, OXT-212 (manufactured by Toagosei Co., Ltd.), Etanacol OXBP, OXTP (Ube Industries, Ltd.) Etc.

In the above (1) cation polymerizable organic substance mixture, the use ratio of the alicyclic epoxy compound (1B), aliphatic epoxy compound (1A), aromatic epoxy compound (1C), etc. is as follows: (1) cation polymerizable organic It is preferable that the alicyclic epoxy compound (1B) is 1 to 60 parts by mass and the aliphatic epoxy compound (1A) is 0 to 70 parts by mass with respect to 100 parts by mass of the substance mixture. (1) Cationic polymerization 1 to 50 parts by mass, particularly 5 to 50 parts by mass of the alicyclic epoxy compound (1B), 0 to 50 parts by mass of the aliphatic epoxy compound (1A), 100 parts by mass of the aromatic organic compound mixture, and the aromatic epoxy compound (1C) 20 to 80 parts by mass, particularly 30 to 70 parts by mass, high molecular weight polymer having an epoxy group and a weight average molecular weight of 1000 to 1000000 (1D) 0 to 50 parts by mass, particularly 0 to 2 Parts by weight, a vinyl ether compound or oxetane compound (1E) 0 to 30 parts by weight, in particular 0 to 20 parts by mass, the aromatic epoxy compound (1C) is that the main component further preferable.
However, the amounts of (1A) and (1B) above are amounts excluding those corresponding to (1D) above, and the amount of (1C) is an amount including those corresponding to (1D).
Here, the main component means the one having the largest total amount of the same kind of epoxy compound when several kinds of epoxy compounds are mixed, and the cationic polymerizable organic substance mixture is a cationic polymerizable organic other than the epoxy compound. When a substance is included, the total amount of the type having the largest total amount among several types of epoxy compounds is assumed to be larger than the total amount of cationically polymerizable organic materials other than the epoxy compound. Here, the total amount of each type of epoxy compound includes those corresponding to (1D).

  In the above (1) cation polymerizable organic substance mixture, the proportion of the monofunctional epoxy compound is 20 to 80 parts by mass with respect to 100 parts by mass of (1) cation polymerizable organic substance mixture. It is preferable from the viewpoint of lowering the viscosity.

The (2) energy ray-sensitive cationic polymerization initiator used in the present invention may be any compound that can release a substance that initiates cationic polymerization by irradiation with energy rays, but is preferably Is a double salt that is an onium salt that releases a Lewis acid upon irradiation with energy rays, or a derivative thereof. Representative examples of such compounds include the following general formula:
[A] ^{r +} [B] ^r-
(In the formula, A represents a cationic species, B represents an anionic species, and r represents a valence.)
And cation and anion salts represented by the formula:

Here, 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, here, 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. The a R ^{1 s} are independent and may be the same or different. Further, at least one is preferably an organic group as described above having an aromatic ring. Q is an atom or atomic group selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F, and N = N. Further, when the valence of Q in the cation [A] ^{r +} is q, the relationship r = a−q needs to be satisfied (however, N = N is treated as a valence of 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, here, L is a metal or metalloid which is a central atom of a halide complex, and 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 of 3-7. Further, when the valence of L in the anion [B] ^r− is p, it is necessary that the relationship r = b−p holds.

Specific examples of the anion [LX _b ] ^{r− in} the above general formula include tetrakis (pentafluorophenyl) borate, tetra (3,5-difluoro-4-methoxyphenyl) borate, tetrafluoroborate (BF ₄ ) ⁻ , Examples include hexafluorophosphate (PF ₆ ) ⁻ , hexafluoroantimonate (SbF ₆ ) ⁻ , hexafluoroarsenate (AsF ₆ ) ⁻ , hexachloroantimonate (SbCl ₆ ) ^{− and the} like.

Further, the anion [B] ^r− is represented by the following general formula:
[LX _b-1 (OH)] ^r-
The thing of the structure represented by can also be used preferably. L, X, and b are the same as described 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. , Trinitrobenzenesulfonate anion, camphor sulfonate, nonafluorobutane sulfonate, hexadecafluorooctane sulfonate, tetraarylborate, tetrakis (pentafluorophenyl) borate and the like.

  In the present invention, among these onium salts, it is particularly effective to use the following aromatic onium salts (a) to (c). Among these, one of them can be used alone, or two or more of them can be mixed and used.

  (I) Aryl diazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate, 4-methylphenyldiazonium hexafluorophosphate

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

  (C) a sulfonium cation represented by the following group I or group II and a sulfonium salt such as hexafluoroantimony ion, hexafluorophosphate ion, tetrakis (pentafluorophenyl) borate ion

Other preferable examples include (η ⁵ -2,4-cyclopentadien-1-yl) [(1,2,3,4,5,6-η)-(1-methylethyl) benzene] -iron. -Iron-arene complexes such as hexafluorophosphate, aluminum complexes such as tris (acetylacetonato) aluminum, tris (ethylacetonatoacetato) aluminum, tris (salicylaldehyde) aluminum and silanols such as triphenylsilanol The mixture of these can also be mentioned.

  Among these, from the viewpoint of practical use and photosensitivity, it is preferable to use an aromatic iodonium salt, an aromatic sulfonium salt, or an iron-arene complex.

  The use ratio of the (2) energy ray sensitive cationic polymerization initiator to the above (1) cationic polymerizable organic substance mixture is not particularly limited, and may be used at a generally normal use ratio within a range not impairing the object of the present invention. However, for example, (1) with respect to 100 parts by mass of the cationically polymerizable organic substance mixture, (2) 0.001 to 10 parts by mass, preferably 0.1 to 5 parts by mass of the energy ray sensitive cationic polymerization initiator Can do. If the amount is too small, curing tends to be insufficient, and if the amount is too large, various physical properties such as the water absorption rate and the strength of the cured product may be adversely affected.

In the cationically polymerizable composition of the present invention, a silane coupling agent can be used as necessary.
Examples of the silane coupling agent include dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltrimethoxysilane. Alkyl-functional alkoxysilanes, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane and other alkenyl-functional alkoxysilanes, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxy Silane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 2-methacryloxypropyltrimethoxysilane Epoxy-functional alkoxysilanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-β (aminoethyl) Aminofunctional alkoxysilanes such as γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and mercaptofunctional alkoxysilanes such as γ-mercaptopropyltrimethoxysilane , Titanium alkoxides such as titanium tetraisopropoxide, titanium tetranormal butoxide, titanium chelates such as titanium dioctyloxybis (octylene glycolate), titanium diisopropoxybis (ethyl acetoacetate), di Kou tetra acetylacetonate, zirconium chelates such as zirconium tributoxy monoacetylacetonate, zirconium acylates such as zirconium tributoxy monostearate, an isocyanate silane such as methyl triisocyanate silane.

  Although the usage-amount of the said silane coupling agent is not specifically limited, Usually, it is the range of 1-20 mass parts with respect to 100 mass parts of whole quantity of the solid substance in a cationically polymerizable composition.

In the cationic polymerizable composition of the present invention, a thermal polymerization initiator can be used as necessary.
Thermal polymerization initiator is a compound that generates a cationic species or Lewis acid by heating, such as a salt of sulfonium salt, thiophenium salt, thiolanium salt, benzylammonium, pyridinium salt, hydrazinium salt; diethylenetriamine, triethylenetriamine, tetraethylenepenta Polyalkylpolyamines such as min; alicyclic polyamines such as 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane, isophoronediamine; m-xylylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone Aromatic polyamines such as; such polyamines; phenyl glycidyl ether, butyl glycidyl ether, bisphenol A-diglycidyl ether, bisphenol F-diglycidyl ether, etc. Polyepoxy addition-modified products produced by reacting various kinds of epoxy resins such as glycidyl ethers or glycidyl esters of carboxylic acids in a conventional manner; such organic polyamines as phthalic acid, isophthalic acid, dimer acid, etc. An amidation modified product produced by reacting carboxylic acids with a conventional method; at least one aldehyde reaction in the nucleus of polyamines and aldehydes such as formaldehyde and phenol, cresol, xylenol, tert-butylphenol, resorcin, etc. Mannich-modified products produced by reacting phenols having sex sites by a conventional method; polyvalent carboxylic acids (oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelain Acid, sebacic acid, Decanedioic acid, 2-methylsuccinic acid, 2-methyladipic acid, 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecane Aliphatic dicarboxylic acids such as diacid, hydrogenated dimer acid and dimer acid; aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; trimellitic acid, Tricarboxylic acids such as trimesic acid and trimer of castor oil fatty acid; acid anhydrides of tetracarboxylic acids such as pyromellitic acid); 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-2638, CI-2624 (made by Nippon Soda Co., Ltd.), Sun-Aid SI-60L, Sun-Aid SI -80L, Sun-Aid SI-100L (manufactured by Sanshin Chemical Industry Co., Ltd.) and the like.

  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 solids in the cationic polymerizable composition. When using an initiator, when the cationic polymerizable composition of the present invention is cured, it is preferably heated at 130 to 180 ° C. for 20 minutes to 1 hour.

  In the cationic polymerizable composition of the present invention, a cured product can be obtained by using a thermoplastic organic polymer (excluding a high molecular weight polymer (1D) having a weight average molecular weight of 1,000 to 1,000,000 having an epoxy group) as necessary. It is possible to improve the characteristics. 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 include methyl methacrylate copolymer, glycidyl (meth) acrylate-polymethyl (meth) acrylate copolymer, polyvinyl butyral, cellulose ester, polyacrylamide, and saturated polyester.

  The cationically polymerizable composition of the present invention is not particularly limited, and a solvent that can dissolve or disperse the components (1) and (2) that are usually used 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 solvents such as dipropylene glycol dimethyl ether; ester solvents such as methyl acetate, ethyl acetate, acetic acid-n-propyl, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, texanol; Cellosolve solvents such as lenglycol monomethyl 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 mono Ether ester solvents such as ethyl acetate, propylene glycol-1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethoxyethyl propionate; benzene, toluene, xylene, etc. BTX solvents; aliphatic hydrocarbon solvents such as hexane, heptane, octane, cyclohexane; terpenes such as turpentine oil, D-limonene, and pinene Hydrocarbon oil; paraffinic solvents such as mineral spirit, Swazol # 310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso # 100 (Exxon Chemical Co., Ltd.); carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, 1,2- Halogenated aliphatic hydrocarbon solvents such as dichloroethane; Halogenated aromatic hydrocarbon solvents such as chlorobenzene; Propylene carbonate, carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N, N- Examples thereof include dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, water and the like, and these solvents can be used as one or a mixture of two or more.

  In the cationic polymerizable composition of the present invention, the total amount of optional components other than (1) the cationic polymerizable organic substance mixture and (2) the energy ray sensitive cationic polymerization initiator depends on the use of the present invention, etc. From the viewpoint of further enhancing the effects of the present invention, (1) it is preferably 20 parts by mass or less, particularly 10 parts by mass or less with respect to 100 parts by mass of the 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 viewpoints of curability, adhesiveness, and liquid storage stability. Too much moisture is not preferable because it may cause cloudiness or components may precipitate. The amount of water is measured by the method described in the examples described later.

  The cationic polymerizable composition of the present invention preferably has a viscosity of 200 mPa · s or less, and more preferably 1 to 100 mPa · s, from the viewpoint of coatability. This viscosity is a viscosity at 25 ° C., and is measured by the method described in Examples described later.

  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 types of printing, and immersion. Moreover, after once applying on support bases, such as a film, it can also transfer on another support base | substrate, There is no restriction | limiting in the application method.

The material for the support substrate is not particularly limited and may be any commonly used material, such as inorganic materials such as glass; diacetyl cellulose, triacetyl cellulose (TAC), propionyl cellulose, butyryl cellulose, acetylpropionyl. Cellulose esters such as cellulose and nitrocellulose; Polyamide; Polyimide; Polyurethane; Epoxy resin; Polycarbonate; Polyethylene terephthalate, Polyethylene naphthalate, Polybutylene terephthalate, Poly-1,4-cyclohexanedimethylene terephthalate, Polyethylene-1,2-diphenoxy Polyester such as ethane-4,4′-dicarboxylate, polybutylene terephthalate; polystyrene; polyethylene, polypropylene, polymethylpentene, etc. Polyolefins; Vinyl compounds such as polyvinyl acetate, polyvinyl chloride, and polyvinyl fluoride; Acrylic resins such as polymethyl methacrylate and polyacrylate; Polycarbonate; Polysulfone; Polyethersulfone; Polyetherketone; Polyetherimide; Polymer materials such as oxyethylene, norbornene resin, and cycloolefin polymer (COP) can be used.
Note that 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, laser treatment and the like.

  In addition, as long as the effects of the present invention are not impaired, other monomers, other energy ray-sensitive polymerization initiators, inorganic fillers, organic fillers, pigments, dyes and other colorants, photosensitizers and antifoaming agents as necessary. , Thickener, surfactant, leveling agent, flame retardant, thixotropic agent, diluent, plasticizer, stabilizer, polymerization inhibitor, ultraviolet absorber, antioxidant, antistatic agent, flow regulator, Various resin additives such as an adhesion promoter can be added.

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

  Specific uses of the cationically polymerizable composition of the present invention include glasses, optical materials represented by imaging lenses, paints, coating agents, lining agents, inks, resists, liquid resists, adhesives, printing plates, and insulation. Varnish, insulating sheet, laminate, printed circuit board, sealing agent for molding of semiconductor devices, LED packages, liquid crystal inlets, organic EL, optical elements, electrical insulation, electronic components, separation membranes, etc. Materials, putty, glass fiber impregnating agent, sealant, semiconductor / solar cell passivation film, interlayer insulating film, protective film, prism lens sheet used for backlight of liquid crystal display, screen for projection TV, etc. Lens parts of lens sheets such as Fresnel lens sheets and lenticular lens sheets used in, or back using such sheets And optical lenses such as microlenses, optical elements, optical connectors, optical waveguides, casting agents for optical modeling, etc. Examples of substrates that can be applied as coating agents include metals, wood, rubber, plastics , Glass, ceramic products and the like.

  EXAMPLES Hereinafter, although an Example etc. are given and this invention is demonstrated further in detail, this invention is not limited to these Examples.

  Hereinafter, the cationically polymerizable composition of the present invention and the 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” and “%” means “% by mass”.

[Examples 1-20, Comparative Examples 1-2]
Each component was fully mixed by the mixing | blending shown in the following [Table 1]-[Table 3], and the implementation compositions 1-20 and the comparison compositions 1-2 were obtained, respectively.

(1) As cationically polymerizable organic substances, the following compounds (1A-1) to (1A-4), (1B-1) to (1B-3), (1C-1) to (1C-7), ( 1D-1) to (1D-2) and (1E-1) to (1E-4) were used. These epoxy equivalents and viscosities (mPa · s) are shown together in [Table 1] to [Table 3]. The viscosities described in these tables are measured by the same method as the method for measuring the viscosity of the composition in the following evaluation examples.
Compound 1A-1: 2-ethylhexyl glycidyl ether compound 1A-2: Allyl glycidyl ether compound 1A-3: Neopentyl glycol diglycidyl ether compound 1A-4: Triglycidyl tris (2-hydroxyethyl) isocyanurate compound 1B-1: Celoxide 2021P (alicyclic epoxy; manufactured by Daicel)
Compound 1B-2: Methyl 3,4-epoxycyclohexanecarboxylate compound 1B-3: Celoxide 3000 (alicyclic epoxy: manufactured by Daicel)
Compound 1C-1: Phenyl glycidyl ether compound 1C-2: Styrene oxide compound 1C-3: Glycidyl phthalimide (EX-731: manufactured by Nagase ChemteX Corporation)
Compound 1C-4: Resorcinol diglycidyl ether Compound 1C-5: Adekaglycilol ED-509S (manufactured by ADEKA)
Compound 1C-6: Adekaglycil ED-501 (manufactured by ADEKA)
Compound 1C-7: Adeka Resin EP-4100L (manufactured by ADEKA)
Compound 1D-1: GMA / MMA = 3/7 copolymer (Mw: 8000)
Compound 1D-2: Copolymer of GMA / MMA = 3/7 (Mw: 15000)
Compound 1E-1: Aron oxetane OXT-101 (manufactured by Toagosei Co., Ltd.)
Compound 1E-2: Aron oxetane OXT-221 (manufactured by Toagosei Co., Ltd.)
Compound 1E-3: Hydroxybutyl vinyl ether Compound 1E-4: 1,4-butanediol divinyl ether

(2) The following compound (2-1) was used as an energy ray-sensitive cationic polymerization initiator.
Compound 2-1: CPI-100P (manufactured by San Apro)

[Evaluation Examples 1-20, Comparative Evaluation Examples 1-2]
The following evaluation was performed about the implementation composition obtained by the said Examples 1-20 and the comparison composition obtained by Comparative Examples 1-2. The results are shown in the above [Table 1] to [Table 3].
(viscosity)
Viscosity of each of the obtained practical compositions 1 to 20 and the comparative compositions 1 to 2 was measured with an E-type viscometer at 25 ° C. The results are shown in [Table 1] to [Table 3].
(Curable)
Each of the obtained practical compositions 1 to 20 and comparative compositions 1 to 2 was applied to a thickness of 3 to 6 μm on a PET film with a bar coater, and 1000 mJ / cm ² using an electrodeless ultraviolet lamp. Of energy. Evaluation was made with ◎ indicating that the coated surface was tack-free after 5 minutes of irradiation, ◯ indicating that the surface was tack-free after 15 minutes, and × indicating that the tack remained after 15 minutes. The results are shown in the above [Table 1] to [Table 3].
(Hot water resistance test)
After applying each of the obtained working compositions 1 to 20 and the comparative compositions 1 and 2 to a TAC (triacetyl cellulose) film, the laminator was used to bond the resulting composition to a COP (cycloolefin polymer) film, and the COP film side Then, an electrodeless ultraviolet light lamp was used to irradiate with an energy of 1000 mJ / cm ² and adhere to obtain a test piece. After 48 hours, a test piece was cut out to 2 cm × 4 cm, and was put on 60 ° C. warm water and the progress was observed. Observe the condition of the test piece after 12 and 24 hours, ◯ if there is no change from before the start, △ if there is peeling on the end face, × if the film is peeled off and completely dropped evaluated. The results are shown in the above [Table 1] to [Table 3].
(Adhesiveness)
After apply | coating each of the obtained Example compositions 1-20 and 1-2 of a comparative composition to the COP (cycloolefin polymer) film which performed the corona discharge process, this film was used for the laminator. A test piece was obtained by bonding to another COP (cycloolefin polymer) film that had been subjected to corona discharge treatment, and using an electrodeless ultraviolet lamp to irradiate with 1000 mJ / cm ² of energy. A 90-degree peel test is performed on the obtained test piece. A specimen having a strength of 2.0 N / cm or more is ◎, a specimen having a strength of 1.0 to 2.0 N / cm is ○, and a specimen having a strength of 1.0 N / cm or less Was evaluated as x. The results are shown in the above [Table 1] to [Table 3].
(amount of water)
About each of the obtained Example compositions 1-20 and the comparative compositions 1-2, the moisture content was measured according to the Karl Fischer method. The results are shown in the above [Table 1] to [Table 3].

From [Table 1] to [Table 3], it is clear that the cationically polymerizable composition of the present invention is low in viscosity and excellent in coating property and curability, and is excellent in adhesion and hot water resistance after curing.

Claims (9)

(1) As a cationically polymerizable organic substance, at least one of an aliphatic epoxy compound (1A) or an alicyclic epoxy compound (1B) is contained, and the aliphatic epoxy compound (1A) or alicyclic epoxy compound (1B) As containing at least one monofunctional epoxy compound ,
The content of the alicyclic epoxy compound (1B) is 1 to 60 parts by mass with respect to 100 parts by mass of the (1) cation polymerizable organic substance mixture,
The total amount of the monofunctional aliphatic epoxy compound (1A) and the monofunctional alicyclic epoxy compound (1B) is 30 to 60 parts by mass with respect to 100 parts by mass of the (1) cation polymerizable organic substance mixture. Yes,
The content of the monofunctional aliphatic epoxy compound (1A) is 0 to 30 parts by mass with respect to 100 parts by mass of the (1) cation polymerizable organic substance mixture, and the monofunctional alicyclic epoxy compound ( A cationically polymerizable composition comprising a cationically polymerizable organic substance mixture having a content of 1B) of 0 to 40 parts by mass , and (2) an energy ray-sensitive cationic polymerization initiator. (1) As a cationically polymerizable organic substance, containing at least one of an aliphatic epoxy compound (1A) or an alicyclic epoxy compound (1B), and containing an aromatic epoxy compound (1C), the aliphatic epoxy compound (1A), an alicyclic epoxy compound (1B) or an aromatic epoxy compound (1C), a cationically polymerizable organic substance mixture containing at least one monofunctional epoxy compound, and (2) an energy ray-sensitive cationic polymerization initiator Contains,
The cationic polymerizable organic substance mixture is mainly composed of the aromatic epoxy compound (1C),
Content of alicyclic epoxy compound (1B) is 1-60 mass parts with respect to 100 mass parts of said (1) cation polymerizable organic substance mixture, Cationic polymerizable composition characterized by the above-mentioned. The cationically polymerizable composition according to claim 2 , wherein the aromatic epoxy compound (1C) has an epoxy equivalent of 80 to 500 or a viscosity of 2000 mPa · s or less. The cation according to claim 2 or 3 , wherein the aromatic epoxy compound (1C) contains at least one selected from the group consisting of glycidyl ethers of phenols, glycidyl esters of benzoic acid, and styrene oxides. Polymerizable composition. (1) As the cationically polymerizable organic substances, a high molecular weight having a weight-average molecular weight 1,000 to 1,000,000 having an epoxy group (1D), either one of claims 1-4 comprising at least one of the vinyl ether compound or oxetane compound (1E) The cationically polymerizable composition according to one item. (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 a valence). The cationically polymerizable composition according to any one of claims 1 to 5 , which is a salt of a cation and an anion represented. Water content is 5 mass% or less, The cationically polymerizable composition as described in any one of Claims 1-6 characterized by the above-mentioned. The cationic polymerizable composition according to any one of claims 1 to 7 , wherein the viscosity is 200 mPa · s or less. An adhesive comprising the cationically polymerizable composition according to any one of claims 1 to 8 .