KR20160030069A - Cation-polymerizable composition - Google Patents

Abstract

The cationic polymerizable composition of the present invention is a cationically polymerizable composition comprising (1) a cationic polymerizable organic material, which contains an aromatic epoxy compound (1A) as a main component and further contains at least one of an aliphatic epoxy compound (1B) or an alicyclic epoxy compound , And (2) an energy ray-sensitive cationic polymerization initiator. It is preferable that at least one polyfunctional epoxy compound is contained as the aliphatic epoxy compound (1B) or the alicyclic epoxy compound (1C).

Description

CATION-POLYMERIZABLE COMPOSITION [0002]

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

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

For example, the following Patent Documents 1 to 3 disclose various photocurable adhesives.

Japanese Patent Application Laid-Open No. 2011-236389 Japanese Unexamined Patent Application Publication No. 2012-149262 International Publication No. 2008/111584

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

Disclosure of the Invention The present invention has been made based on the above finding. It is an object of the present invention to provide a curable composition comprising (1) an aromatic epoxy compound (1A) as a main component as a cationic polymerizable organic material, And (2) an energy ray sensitive (positive) cationic polymerization initiator. The present invention also provides a cationic polymerizable composition comprising a cationic polymerizable organic material mixture containing a cationic polymerizable organic material and an energy ray sensitive cationic polymerization initiator.

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

The cationic polymerizable composition of the present invention is particularly useful as an adhesive agent because of its excellent curability, adhesiveness and water resistance.

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

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

The aromatic epoxy compound (1A) refers to an epoxy compound containing an aromatic ring, and specific examples of the aromatic epoxy compound include monovalent phenol having at least one aromatic ring such as phenol, cresol, butylphenol, Mono / polyglycidyl ether compounds such as bisphenol A, bisphenol F, or compounds in which an alkylene oxide is further added thereto, such as glycidyl ether or epoxy novolac resins; Glycidyl ether which is an aromatic compound having two or more phenolic hydroxyl groups such as resorcinol, hydroquinone and catechol; Mono / polyglycidyl ether compounds which are aromatic compounds having two or more alcoholic hydroxyl groups such as benzene dimethanol, benzene diethanol and benzene dibutanol; Glycidyl esters which are polybasic acid aromatic compounds having two or more carboxylic acids such as phthalic acid, terephthalic acid and trimellitic acid, glycidyl esters such as benzoic acid, toluic acid and naphthoic acid, glycidyl esters such as benzoic acid, styrene oxide or divinylbenzene, Cargo, and the like.

Among them, glycidyl ether as a phenol, glycidyl ether as an aromatic compound having two or more alcoholic hydroxyl groups, glycidyl ether as a polyhydric phenol, glycidyl ester as a benzoic acid, glycidyl as a polybasic acid, It is preferable to contain at least one member selected from the group of epoxides which are diesters, styrene oxides or divinylbenzenes from the viewpoint of low viscosity of the composition.

The aromatic epoxy compound preferably has an epoxy equivalent of 80 to 500 because it is excellent in curability.

Examples of the aromatic epoxy compound (1A) include commercially available products such as Denacol EX-121, Denacol EX-141, Denacol EX-142, Denacol EX-145, Denacol EX- Oncote EX-1020, Oncote EX-1040, Oncote EX-1050, Oncoat EX-1020, , Oncoat EX-1051, Oncoat EX-1010, Oncoat EX-1011, Oncoat 1012 (manufactured by Nagase ChemteX Corporation); Ogrosol PG-100, Oggol EG-200, Oggol EG-210, Oggol EG-250 (manufactured by Osaka Gas Chemical Co., Ltd.); HP4032, HP4032D, HP4700 (manufactured by DIC); ESN-475V (manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd.); Epikote YX8800 (manufactured by Mitsubishi Kagaku Co., Ltd.); Mapffe G-0105SA, Mapffe G-0130SP (similar to Nicht); Epiclon N-665, Epiclon HP-7200 (manufactured by DIC); EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, XD-1000, NC-3000, EPPN-501H, EPPN-501HY, EPPN-502H, NC-7000L (manufactured by Nippon Kayaku); Adeka glycylol ED-501, adekaglycylol ED-502, adekaglycylol ED-509, adekaglycylol ED-529, ADEKA RESIN EP-4100, ADEKA RESIN EP-4901 (manufactured by ADEKA); TECHMORE VG-3101L, EPOX-MKR710 and EPOX-MKR151 (manufactured by PRINTEC).

As the aromatic epoxy compound (1A), it is preferable that at least one polyfunctional epoxy compound is contained in view of curability and adhesiveness. The cationic polymerizable composition of the present invention preferably contains 25 to 70 parts by mass of the polyfunctional aromatic epoxy compound (1A) per 100 parts by mass of the mixture (1) of the cationic polymerizable organic material, and preferably contains 30 to 60 parts by mass .

Here, the amount of (1A) is an amount including one corresponding to (1D).

Specific examples of the alicyclic epoxy compound (1C) include polyglycidyl ether compounds, polyhydric alcohols having at least one alicyclic ring, cyclohexene oxide obtained by epoxidizing cyclohexene or cyclopentane ring-containing compounds with an oxidizing agent And cyclopentene oxide-containing compounds. For example, hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl- Epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4- Epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, bis (3,4- Epoxycyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), propane-2,2-diyl-bis Cyclohexane), 2,2-bis (3,4-epoxycyclohexyl) propane, dicyclopentadienediepoxide, ethylenebis (3,4-epoxycyclohexanecarboxylate), dioctylhexahydrophthalate, Phe Dihydro-acid di-2-ethylhexyl, 1-ethyl-3,4-epoxy-epoxy-cyclohexane, and the like can be 1,2-epoxy-2-epoxy-ethylcyclohexane, α- pinene oxide, limonene dioxide.

As the alicyclic epoxy compound (1C), an epoxy equivalent of 80 to 500 is preferable.

Examples of the alicyclic epoxy compound (1C) include commercially available products such as Celloxide 2021P, Celloxide 2081, Celloxide 2000, and Celloxide 3000 (manufactured by Daicel Chemical Industries, Ltd.).

The aliphatic epoxy compound (1B) refers to an epoxy compound not classified as the aromatic epoxy compound (1A) or the alicyclic epoxy compound (1C). Specific examples of the aliphatic epoxy compound include glycidyl ethers such as aliphatic alcohols Polyglycidyl ether compounds such as aliphatic polyhydric alcohols or alkylene oxide adducts thereof, polyglycidyl esters such as aliphatic long chain polybasic acids, and the like can be used. Polyfunctional epoxy compounds. Representative compounds include allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, C12-13 mixed alkyl glycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexane Diol diglycidyl ether, triglycidyl ether of glycerin, triglycidyl ether of trimethylol propane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, Glycidyl ether, which is a polyhydric alcohol such as diglycidyl ether of polypropylene glycol, and polyether polyol obtained by adding at least one alkylene oxide to an aliphatic polyhydric alcohol such as propylene glycol, trimethylol propane, glycerin and the like And diglycidyl esters of aliphatic long-chain dibasic acids. Further, monoglycidyl ether as an aliphatic higher alcohol, glycidyl ester as a higher fatty acid, epoxidized soybean oil, octyl stearate, octyl stearate, epoxylated soybean oil, and epoxylated polybutadiene.

The aliphatic epoxy compound (1B) preferably has an epoxy equivalent of 80 to 500.

Examples of the aliphatic epoxy compound (1B) include commercially available products such as DENARCOL EX-121, DENARCOL EX-171, DENARCOL EX-192, DENARCOL EX-211, Denacol EX-611, Denacol EX-611, Denacol EX-412, Denacol EX-412, Denacol EX-821, Denacol EX-830, Denacol EX-821, Denacol EX-850, Denacol EX-851, Denacol EX-821, Denacol EX-830, Denacol EX-931, Denacol EX-911, Denacol EX-941, Denacol EX-920, Denacol EX-931 (manufactured by Nagase ChemteX Corporation); (For example, Epitolite M-1230, Epolite 40E, Epolite 100E, Epolite 200E, Epolite 400E, Epolite 70P, Epolite 200P, Epolite 400P, Epolite 1500NP, Epolite 1600, Epolight 80MF, Adekaglycylol ED-503G, Adekaglycylol ED-506, Adekaglycylol ED-523T (manufactured by ADEKA), and the like, .

The cationic polymerizable composition of the present invention preferably contains at least one polyfunctional epoxy compound as the aliphatic epoxy compound (1B) or the alicyclic epoxy compound (1C). The cationic polymerizable composition of the present invention comprises (1) the total amount of the polyfunctional aliphatic epoxy compound (1B) and the polyfunctional alicyclic epoxy compound (1C) in an amount of 10 to 65 parts by mass based on 100 parts by mass of the mixture of the cationic polymerizable organic material Part, particularly preferably 20 to 50 parts by mass. The content of the polyfunctional aliphatic epoxy compound (1B) is preferably 10 to 45 parts by mass based on 100 parts by mass of the mixture of (1) the cationic polymerizable organic material, and the content of the polyfunctional alicyclic epoxy compound (1C) It is preferably 0 to 10 parts by mass.

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

Examples of the high molecular weight compound (1D) having an epoxy group and having a weight average molecular weight of 1,000 to 1,000,000 include a polymer obtained by radical polymerization, and a polymer obtained by homopolymerizing an ethylenically unsaturated monomer having a cationic polymerizable substituent or a cationically polymerizable substituent Is preferably copolymerized with an ethylenically unsaturated monomer having no ethylenic unsaturated monomer.

The ethylenically unsaturated monomer constituting the high molecular weight compound (1D) having an epoxy group and having a weight average molecular weight of 1,000 to 1,000,000 is not particularly limited and a known one can be used. For example, as an example of the ethylenically unsaturated monomer having no cationic polymerizable substituent, there may be mentioned a group represented by the following general formula (1), and examples of the ethylenically unsaturated monomer having a cationic polymerizable substituent include the following Include groups in which at least one hydrogen atom in the alkyl group, aryl group or alicyclic hydrocarbon group in the general formula (1) is substituted with an epoxy group, oxetane group or vinyl ether group.

[Chemical Formula 1]

(Wherein R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom, a straight chain, branched chain or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms 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-)

Also, in the case of the above copolymer, the high molecular weight compound (1D) contains 10 to 80 mass% of an ethylenically unsaturated monomer having a structure substituted by a cationic polymerizable substituent such as an epoxy group, oxetane group or vinyl ether group, An ethylenic group or a branched alkyl group having 3 to 7 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alicyclic hydrocarbon group having 6 to 10 carbon atoms in an amount of 20 to 90 mass% %, And the total amount of other ethylenically unsaturated monomers is preferably 100% by mass.

The high molecular weight compound (1D) having an epoxy group and having a weight average molecular weight of 1,000 to 1,000,000 is preferably a weight average molecular weight of 5,000 to 100,000, more preferably 7,000 to 700,000.

Examples of the vinyl ether compound or the oxetane compound (1E) include ethylene glycol divinyl ether, triethylene glycol divinyl ether, n-dodecyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl 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, Vinyl ether compounds such as vinyl ether, diethylene glycol monovinyl ether, 1,4-butanediol divinyl ether, and 1,6-cyclohexanedimethanol divinyl ether; Bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 1,2-bis [3- (3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) Ethyl-3-oxetanylmethyl) ether, triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis Ethyl-3 - [(phenoxymethyl) oxetane, 3-ethyl-3- (hexyl Ethyl-3- (hydroxymethyl) oxetane, 3-ethyl-3- (chloromethyl) oxetane and the like Oxetane compounds of the following formula (1). 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 the oxetane compound (1E) may be either a monofunctional or polyfunctional vinyl ether compound, or a vinyl ether compound having one or two vinyl ether groups or an oxetane compound having one or two oxetane groups It is preferable to use a cetane compound.

As the vinyl ether compound or oxetane compound (1E), a commercially available product containing a cationic polymerizable monomer as a main component can be used. Examples thereof include 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl Ether (manufactured by Maruzen Sekiyu Kagaku Co., Ltd.); OXT-221, OXT-221, EXOH, POX, OXA, OXT-101, OXT-211 and OXT-212 (manufactured by Toagosei Co., Ltd.), Eteracol OXBP and OXTP have.

(1D) having a weight average molecular weight of 1,000 to 1,000,000 and an epoxy group, wherein the aromatic epoxy compound (1A), the alicyclic epoxy compound (1C), the aliphatic epoxy compound (1B) , The vinyl ether compound or the oxetane compound (1E) is used in an amount of 25 to 70 parts by mass, particularly 30 to 60 parts by mass, relative to 100 parts by mass of the mixture of the cationic polymerizable organic material (1) 0 to 45 parts by mass, particularly 0 to 30 parts by mass of the epoxy compound (1C), 0 to 45 parts by mass, particularly 10 to 40 parts by mass, particularly 10 to 40 parts by mass of the aliphatic epoxy compound (1B) 0 to 30 parts by mass, particularly 0 to 25 parts by mass of the vinyl ether compound or the oxetane compound (1E), and 0 to 50 parts by mass, particularly 0 to 15 parts by mass of the alicyclic epoxy compound (1C) The sum of the compound (1B) is not 0, and the aromatic epoxy compound (1A) is the main component To use the lock is preferred.

Here, the amounts of (1B) and (1C) are amounts excluding those of (1D) above, and the amount of (1A) is an amount including those corresponding to (1D).

Herein, the main component refers to a compound in which the total amount of the epoxy compound of the same kind is the largest when several types of epoxy compounds are mixed. When the cationic polymerizable organic compound mixture contains a cationic polymerizable organic material other than the epoxy compound, The total amount of the kinds having the largest total amount is more than the total amount of the cationic polymerizable organic substances other than the epoxy compound. The total amount of each type of epoxy compound referred to here includes those corresponding to (1D).

The energy ray-sensitive cationic polymerization initiator (2) used in the present invention may be any compound capable of releasing a substance that initiates cationic polymerization by energy ray irradiation. Preferably, the energy ray- Is an onium salt that releases an acid, or a derivative thereof. Representative examples of related compounds include,

[A] ^{r +} [B] ^r- (wherein A represents a cationic species, B represents an anionic species, and r represents a valence number).

Here, the cation [A] ^{r +} is preferably onium, and its structure is, for example,

[(R ¹ ) _a Q] ^{r +}

.

Also, R ¹ is an organic group having 1 to 60 carbon atoms and may contain several atoms other than carbon atoms. and a is an integer of 1 to 5. The a R ^{1 s} may be independently the same or different. And at least one of them is 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, In addition, when the Q atomic value in the cation [A] ^{r +} is q, r = aq should be satisfied (N = N is treated as 0).

The anion [B] ^r- is preferably a halide complex, and its structure is, for example,

[LX _b ] ^r-

.

In this case, L is a metal or a metalloid which is a central atom of the halide complex, and B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, Mn, and Co. X is a halogen atom. B is an integer of 3 to 7. When the valence of L in the anion [B] ^r- is p, r = bp must be established.

Anion [LX _b] Specific examples of the ^r- in the formula is a tetrakis (penta-fluorophenyl) borate, tetra (3,5-difluoro-4-methoxyphenyl) borate, tetrafluoro borate (BF ₄₎ ^- , Hexafluorophosphate (PF ₆ ) ^- , hexafluoroantimonate (SbF ₆ ) ^- , hexafluoroarsenate (AsF ₆ ) ^- , and hexachloroantimonate (SbCl ₆ ) ^- .

The anion [B] ^r- is represented by the following general formula,

[LX _b-1 (OH)] ^r-

May be preferably used. L, X, and b are as defined above. Other anions that can be used include perchlorate ion (ClO _{4 )} ^- , trifluoromethyl sulfite ion (CF ₃ SO ₃ ) ^- , fluorosulfonate ion (FSO ₃ ) ^- , toluylsulfonate anion, trinitrobenzenesulfonate anion, nonafluorobutanesulfonate, hexadecafluorooctanesulfonate, tetraarylborate, tetrakis (pentafluorophenyl) borate, and the like can be given.

Among the onium salts, in the present invention, it is particularly effective to use the following aromatic onium salts (a) to (c). Of these, one type may be used alone, or two or more types may be used in combination.

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

(B) a compound selected from the group consisting of diphenyl iodonium hexafluoroantimonate, di (4-methylphenyl) iodonium hexafluorophosphate, di (4-tert- butylphenyl) iodonium hexafluorophosphate, tolylumyl iodonium tetrakis (pentafluorophenyl ) Diaryl iodonium salts such as borate

(C) Sulfonium cations represented by the following Group I or Group II: sulfonium cations such as hexafluoroantimony ion, hexafluorophosphate ion, tetrakis (pentafluorophenyl)

<Group I>

<Group II>

Other preferred examples include (η ⁵ -2,4-cyclopentadien-1-yl) [(1,2,3,4,5,6-η) - (1-methylethyl) benzene] (Acetylacetonato) aluminum, tris (ethyl acetonatoacetato) aluminum, tris (salicylaldehyde) aluminum and the like and a silanol derivative such as triphenylsilanol in the presence of an iron- Mixtures, and the like.

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

The ratio of the (2) energy ray-sensitive cationic polymerization initiator to the cationic polymerizable organic substance mixture (1) is not particularly limited and may be generally used within a range that does not impair the object of the present invention , For example, (1) 0.001 to 10 parts by mass, preferably 0.1 to 5 parts by mass of (2) the energy ray-sensitive cationic polymerization initiator per 100 parts by mass of the mixture of the cationic polymerizable organic material. If it is too small, the curing tends to be insufficient, while if it is too much, there is a case that adverse effects are exerted on various physical properties such as the water absorption of the cured product and the cured product strength.

The cationic polymerizable composition of the present invention may optionally contain a silane coupling agent.

Examples of the silane coupling agent include dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyl Alkenyl functional alkoxysilanes such as vinyl trichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, and allyltrimethoxysilane, alkoxy functional alkoxysilanes such as trimethoxysilane, 3-methacryloxypropyl tri Methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 2-methacryloxypropyltrimethoxysilane, Epoxyfunctional alkoxysilanes such as glycidoxypropyltrimethoxysilane,? -Glycidoxypropylmethyldiethoxysilane and? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-β (aminoethyl ) -γ-aminopropyltri Amino functional alkoxysilanes such as methoxysilane,? -Aminopropyltriethoxysilane and N-phenyl-? -Aminopropyltrimethoxysilane, mercapto functional alkoxysilanes such as? -Mercaptopropyltrimethoxysilane , Titanium alkoxides such as titanium tetraisopropoxide and titanium tetra n-butoxide, titanium chelates such as titanium dioctyloxybis (octylene glycolate) and titanium diisopropoxybis (ethylacetoacetate), zirconium tetra Zirconium chelates such as acetylacetonate and zirconium tributoxymonoacetylacetonate; zirconium acylates such as zirconium tributoxymonostearate; and isocyanate silanes such as methyltriisocyanate silane.

The amount of the silane coupling agent to be used is not particularly limited, but is usually in the range of 1 to 20 parts by mass based on 100 parts by mass of the total amount of the solid matters in the cationic polymerizable composition.

The cationic polymerizable composition of the present invention may optionally contain a thermal polymerization initiator.

A thermal polymerization initiator is a compound capable of generating a cationic species or a Lewis acid upon heating, such as a salt of a sulfonium salt, a thiophenium salt, a thioranium salt, a benzylammonium salt, a pyridinium salt, a hydrazinium salt or the like; Polyalkylpolyamines such as diethylenetriamine, triethylenetriamine, and tetraethylenepentamine; Alicyclic polyamines such as 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane and isophoronediamine; aromatic polyamines such as m-xylylenediamine, diaminodiphenylmethane and diaminodiphenylsulfone; The polyamines and glycidyl ethers such as phenyl glycidyl ether, butyl glycidyl ether, bisphenol A-diglycidyl ether, and bisphenol F-diglycidyl ether, or glycidyl esters of carboxylic acid A polyepoxy addition modified product prepared by reacting various epoxy resins such as a polyether polyol, An amide modification product prepared by reacting the above organic polyamines with carboxylic acids such as phthalic acid, isophthalic acid and dimeric acid by a conventional method; Aldehydes such as polyamines and formaldehyde, and phenols having at least one aldehyde-reactive position in the nuclei such as phenol, cresol, xylenol, tert-butylphenol, resorcin and the like by a conventional method Mannich decarburant; There may be mentioned polyvalent carboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecane diacid, Aliphatic dicarboxylic acids such as 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, Aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and naphthalene dicarboxylic acid, alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, trimellitic acid, Tetracarboxylic acids such as pyromellitic acid and the like); Dicyandiamide, imidazoles, carboxylic acid esters, sulfonic acid esters, amine imides, and the like.

As the thermal polymerization initiator, a commercially available product may be used. For example, ADEKA OPTON CP77, ADEKA OPTON CP66 (ADEKA), CI-2639, CI-2624 (manufactured by Nippon Soda Co., Ltd.) Sun Aid SI-80L, and Sun Aid SI-100L (manufactured by San-Shin Kagaku Kogyo Co., Ltd.).

The amount of the thermal polymerization initiator to be used is not particularly limited, but is usually in the range of 0.001 to 10 parts by mass based on 100 parts by mass of the total amount of the solid matter in the cationic polymerizable composition. When the thermal polymerization initiator is used, When curing, it is preferable to heat at 130 to 180 ° C for 20 minutes to 1 hour.

The properties of the cured product may be improved by using a thermoplastic organic polymer (except for the high molecular weight compound (1D) having an epoxy group and having a weight average molecular weight of 1,000 to 1,000,000) as necessary in the cationic polymerizable composition of the present invention. Examples of the thermoplastic organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene- (meth) acrylic acid copolymer, Methacrylate copolymer, glycidyl (meth) acrylate-polymethyl (meth) acrylate copolymer, polyvinyl butyral, cellulose ester, polyacrylamide, and saturated polyester.

The cationic polymerizable composition of the present invention is not particularly limited and a solvent capable of dissolving or dispersing the components (1) and (2) commonly used can be used. Examples thereof include methyl ethyl ketone, methyl amyl ketone, Ketones such as diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; Ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, propylene glycol monomethyl ether and dipropylene glycol dimethyl ether; Esters such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and texanol; Cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Alcohol solvents such as methanol, ethanol, iso or n-propanol, iso or n-butanol, and amyl alcohol; Propylene glycol monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethoxyethyl propionate, etc. Ether-based solvent; BTX type solvents such as benzene, toluyl, and xylene; Aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; Terpene hydrocarbon oils such as terbinaf oil, D-limonene, and pinene; Paraffin solvents such as Mineral Spirit, Swazor # 310 (Kosomo Matsuyama Sekiyu Co., Ltd.), Solvesso # 100 (Exxon Chemical Co., Ltd.); Halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichlorethylene, methylene chloride, and 1,2-dichloroethane; Halogenated aromatic hydrocarbon solvents such as chlorobenzene; Propylene carbonate, carbitol-based solvent, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N, N-dimethylformamide, N, N-dimethylacetamide, Seed, water and the like. These solvents may be used as one or more mixed solvents.

The total amount of the components other than (1) the cationic polymerizable organic substance mixture and (2) the energy ray-sensitive cationic polymerization initiator in the cationic polymerizable composition of the present invention will depend on the use and the like of the present invention, (1) 20 parts by mass or less, particularly preferably 10 parts by mass or less, based on 100 parts by mass of the mixture of cationic polymerizable organic materials.

The cationic polymerizable composition of the present invention preferably has a water content of 5 mass% or less, more preferably 3 mass% or less, from the viewpoints of curability, adhesiveness, and liquid storage stability. If the water content is excessively high, it is not preferable because clouding or components may be precipitated. The water content was measured by the method described in the following Examples.

The cationic polymerizable composition of the present invention preferably has a viscosity of 200 mPa · s or less, more preferably 10 to 150 mPa · s, from the viewpoint of coatability. This viscosity is a viscosity at 25 캜, which is measured by the method described in the following Examples.

The cationic 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, immersion and the like. Further, it may be once transferred onto a support gas such as a film or the like, and then transferred onto another support gas.

The material of the supporting base is not particularly limited and those which are usually used can be used. Examples thereof include inorganic materials such as glass; Cellulose esters such as diacetylcellulose, triacetylcellulose (TAC), propionylcellulose, butyrylcellulose, acetylpropionylcellulose, and nitrocellulose; Polyamide; Polyimide; Polyurethane; Epoxy resin; Polycarbonate; Polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4'-dicarboxylate, polybutyl Polyesters such as rheneterephthalate; polystyrene; Polyolefins such as polyethylene, polypropylene and polymethylpentene; Vinyl compounds such as polyvinyl acetate, polyvinyl chloride, and polyfluorovinyl; Acrylic resins such as polymethyl methacrylate and polyacrylic acid ester; Polycarbonate; Polysulfone; Polyethersulfone; Polyether ketones; Polyetherimide; And polymer materials such as polyoxyethylene, norbornene resin and cycloolefin polymer (COP).

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

As long as it does not impair the effect of the present invention, it is possible to use other monomers, other energy ray-sensitive polymerization initiators, inorganic fillers, organic fillers, colorants such as pigments and dyes, photosensitizers, defoamers, thickeners, , Various additives such as a flame retardant, a thickener, a diluent, a plasticizer, a stabilizer, a polymerization inhibitor, an ultraviolet absorber, an antioxidant, an antistatic agent, a flow regulator and an adhesion promoter.

The cationic polymerizable composition of the present invention is cured by irradiation with an active energy ray. Examples of the active energy ray include ultraviolet rays, electron rays, X rays, radiation, high frequency waves, 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 cationic polymerizable composition of the present invention include optical materials typified by glasses, image pickup lenses, paints, coating agents, lining agents, inks, resists, liquid resists, adhesives, printing plates, insulating varnishes, Laminates, printed circuit boards, semiconductor devices, LED packages, liquid crystal injection openings, organic EL devices, optical devices, electrical insulating devices, electronic components, separators, etc., putty ), Glass fiber impregnants, fillers, passivation films for semiconductors and solar cells, interlayer insulating films, protective films, prism lens sheets used for backlights of liquid crystal displays, projection televisions, A lens portion of a lens sheet such as a sheet or a lenticular lens sheet, or an optical lens such as a microlens such as a backlight using such a sheet, an optical element, an optical connector, optical fatigue, There may be mentioned, for example, as a base material that can be applied as a coating may be a metal, wood, rubber, plastic, glass, ceramic products and the like.

Example

Hereinafter, the present invention will be described in more detail by way of examples and the like, but the present invention is not limited to these examples.

Hereinafter, the cationic polymerizable composition of the present invention and the cured product obtained by curing the cationic polymerizable composition will be specifically described by Examples, Evaluation Examples and Comparative Examples. In Examples and Comparative Examples, "part" means "mass part" and "%" means mass%.

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

The components shown in [Table 1] to [Table 3] below were sufficiently mixed to obtain Practical Compositions 1 to 30 and Comparative Compositions 1 and 2, respectively.

(1B), (1B-1) to (1B-4), (1C-1) to (1C-3), 1D-1) to (1D-2) and (1E-1) to (1E-4).

The epoxy equivalents thereof are shown in Table 1 to Table 5.

Compound 1A-1: Resorcinol diglycidyl ether

Compound 1A-2: Diglycidyl o-phthalate

Compound 1A-3: Divinylbenzene oxide

Compound 1A-4: Phenyl glycidyl ether

Compound 1A-5: Styrene oxide

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

Compound 1A-7: Adeka Resin EP-4901L

Compound 1A-8: Adeka Resin EP-4000L

Compound 1A-9: TECHMORE VG-3101L

Compound 1A-10: Adekaglycylol ED-509S (manufactured by ADEKA)

Compound 1A-11: Adekaglycylol ED-501 (manufactured by ADEKA)

Compound 1A-12: Adekaglycylol ED-529 (manufactured by ADEKA)

Compound 1B-1: neopentyl glycol diglycidyl ether

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

Compound 1B-3: 2-ethylhexyl glycidyl ether

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

Compound 1C-1: Celloxide 2021P (alicyclic epoxy; manufactured by Daicel Chemical Industries, Ltd.)

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

Compound 1C-3: Celloxide 3000 (alicyclic epoxy; manufactured by Daicel Chemical Industries, Ltd.)

Compound 1D-1: Copolymer of GMA / MMA = 3/7 (Mw: 8000)

Compound 1D-2: Copolymer of GMA / MMA = 3/7 (Mw: 15000)

Compound 1E-1: Aronoxetane OXT-101 (Toagosei Co., Ltd.)

Compound 1E-2: Aronoxetane OXT-211 (Toagosei Co., Ltd.)

Compound 1E-3: Hydroxybutyl vinyl ether

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

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

Compound 2-1: CPI-100P (manufactured by SANAPRO)

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

The following evaluations were carried out on the composition obtained in Examples 1 to 30 and the comparative compositions obtained in Comparative Examples 1 and 2. The results are shown in [Table 1] to [Table 5].

(Viscosity)

Viscosities of 1 to 30 of the obtained practical compositions and 1 to 2 of the comparative compositions were measured at 25 캜 using an E-type viscometer. The results are shown in [Table 1] to [Table 5].

(Hardenability)

Each of the obtained practical compositions 1 to 30 and comparative compositions 1 to 2 was coated on a PET film with a thickness of 3 to 6 占 퐉 using a bar coater and irradiated with an energy of 1000 mJ / . After 5 minutes of irradiation, it was evaluated that the coated surface became tack-free.?, 15 minutes later,?, And 15 minutes later. The results are shown in [Table 1] to [Table 5].

(Hot water test)

Each of the obtained Practical Compositions 1 to 30 and Comparative Compositions 1 to 2 was applied to a TAC (triacetylcellulose) film, followed by bonding to a COP (cycloolefin polymer) film using a laminator, And irradiated with energy of 1000 mJ / cm &lt; 2 &gt; using an external light lamp and adhered to obtain a test piece. After 48 hours, the specimen was cut into 2 cm x 4 cm, immersed in hot water at 60 ° C, and the progress was observed. The condition of the test piece after 12 and 24 hours was observed and it was evaluated that when no change was observed in comparison with that before the start, the peeling of the end surface was observed. The peeling of the film was peeled off completely . The results are shown in [Table 1] to [Table 5].

(Adhesive property)

Each of the obtained Practical Compositions 1 to 30 and Comparative Compositions 1 to 2 was applied to a COP (cycloolefin polymer) film subjected to one corona discharge treatment, and then the film was subjected to corona discharge treatment using a laminator And further irradiated with energy of 1000 mJ / cm &lt; 2 &gt; using an electrodeless ultraviolet lamp, and a test piece was obtained. The test pieces thus obtained were subjected to a 90-degree peeling test to evaluate whether the strength was 2.0 N / cm or more,?, 1.0 to 2.0 N / cm and? And 1.0 N / cm or less, respectively. The results are shown in [Table 1] to [Table 5].

(Water content)

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

From [Table 1] to [Table 5], it is clear that the cationic polymerizable composition of the present invention is excellent in curability, water resistance at room temperature and adhesiveness.

Claims (9)

(1) A cationic polymerizable organic material mixture comprising a cationic polymerizable organic substance as a main component and an aromatic epoxy compound (1A) and at least one of an aliphatic epoxy compound (1B) or an alicyclic epoxy compound , And (2) an energy ray sensitive (positive) cationic polymerization initiator. The method according to claim 1,
Wherein the aliphatic epoxy compound (1B) or the alicyclic epoxy compound (1C) contains at least one polyfunctional epoxy compound. 3. The method according to claim 1 or 2,
Examples of the aromatic epoxy compound (1A) include glycidyl ether as a phenol, glycidyl ether compound as an aromatic compound having two or more alcoholic hydroxyl groups, glycidyl ether compound as a polyhydric phenol, glycidyl Wherein the cationic polymerizable composition contains at least one member selected from the group consisting of esters, glycidyl esters of polybasic acids, and epoxides of styrene oxide or divinylbenzene. 4. The method according to any one of claims 1 to 3,
The cationic polymerizable composition according to claim 1, wherein the aromatic epoxy compound (1A) contains at least one polyfunctional epoxy compound. 5. The method according to any one of claims 1 to 4,
Wherein the epoxy equivalent of the aromatic epoxy compound (1A) is 80 to 500. 6. The method according to any one of claims 1 to 5,
(1) A cationic polymerizable composition comprising at least one of a high molecular weight compound (1D) having a weight average molecular weight of 1,000 to 1,000,000 and an epoxy group, a vinyl ether compound or an oxetane compound (1E) as a cationic polymerizable organic material. 7. The method according to any one of claims 1 to 6,
(2) The energy ray-sensitive cationic polymerization initiator is represented by [A] ^{r +} [B] ^r- (wherein A represents a cationic species, B represents an anionic species, and r represents a valence) A cationic polymerizable composition which is a salt of a cation and an anion. 8. The method according to any one of claims 1 to 7,
And the water content is 5 mass% or less. An adhesive comprising the cationic polymerizable composition according to any one of claims 1 to 8.