KR20170133312A - Composition - Google Patents

Abstract

As the cationic polymerizable organic substance mixture (1), an aromatic epoxy compound (1-1); Alicyclic epoxy compounds (1-2A) or aliphatic epoxy compounds (1-2B); And a polyfunctional aliphatic oxetane compound (1-3), wherein the aromatic epoxy compound (1-1) is a main component. Examples of the aromatic epoxy compound (1-1) include glycidyl ethers of phenols, glycidyl ether compounds of aromatic compounds having two or more alcoholic hydroxyl groups, glycidyl ether compounds of polyhydric phenols, glycidyl esters of benzoic acids , Glycidyl esters of polybasic acids, and epoxides of styrene oxide or divinylbenzene.

Description

Composition {COMPOSITION}

The present invention relates to a composition and an adhesive comprising the composition.

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

For example, the following Patent Documents 1 to 4 disclose various optical (light) curable adhesives.

Japanese Laid-Open Patent Publication No. 2011-236389 Japanese Laid-Open Patent Publication No. 2012-149262 International Publication No. 2008/111584 International Publication No. 2015/005211

It is an object of the present invention to provide a composition excellent in hardenability, adhesiveness and heat resistance.

The present invention has been made based on the above finding, and as the cationic polymerizable organic substance mixture (1), aromatic epoxy compound (1-1); Alicyclic epoxy compounds (1-2A) or aliphatic epoxy compounds (1-2B); And a polyfunctional aliphatic oxetane compound (1-3), wherein the aromatic epoxy compound (1-1) is a main component.

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

The composition of the present invention is particularly useful as an adhesive since it has excellent curability and adhesiveness.

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

In the cationic polymerizable organic substance mixture (1) used in the present invention, the cationic polymerizable organic substance constituting the mixture is a cationic polymerizable organic substance which causes a polymerizing or crosslinking reaction by the cationic polymerization initiator activated by light irradiation / RTI > In the composition of the present invention, as the cationic polymerizable organic material, an aromatic epoxy compound (1-1); Alicyclic epoxy compounds (1-2A) and / or aliphatic epoxy compounds (1-2B); And a polyfunctional aliphatic oxetane compound (1-3) are used.

The aromatic epoxy compound (1-1) 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, Glycidyl ether compounds of glycidyl ether compounds of the alkylene oxide adducts such as bisphenol A, bisphenol F, or compounds in which alkylene oxide is also added thereto, or epoxy novolac resins; Glycidyl ethers of aromatic compounds having two or more phenolic hydroxyl groups such as resorcinol, hydroquinone, and catechol; Glycidyl ether compounds of aromatic compounds having two or more alcoholic hydroxyl groups such as benzene dimethanol, benzene diethanol and benzene dibutanol; Glycidyl esters of polybasic acid aromatic compounds having two or more carboxylic acids such as phthalic acid, terephthalic acid and trimellitic acid, glycidyl esters of benzoic acids such as benzoic acid, tolylic acid and naphthoic acid, styreneses such as styrene oxide or divinylbenzene And an epoxy compound.

Among them, glycidyl ethers of phenols, glycidyl ether compounds of aromatic compounds having two or more alcoholic hydroxyl groups, glycidyl ether compounds of polyhydric phenols, glycidyl ethers of glycidyl ethers, It is preferable that the composition contains at least one member selected from the group of epoxides of epoxides of styrene, sebacate, glycidyl esters of polybasic acids, styrene oxide or divinylbenzene because the Tg of the composition is high.

As the aromatic epoxy compound (1-1), an epoxy equivalent of 80 to 500 is preferable because of excellent curability.

Examples of the aromatic epoxy compound (1-1) include commercially available products such as Denacol EX-121, Denacol EX-141, Denacol EX-142, Denacol EX-145, Denacol EX-146 Oncot EX-1020, Oncot EX-1040, Oncot EX-1040, Oncot EX-720, Oncot EX- Coat EX-1050, Oncoat EX-1051, Oncoat EX-1010, Oncoat EX-1011, Oncoat 1012 (manufactured by Nagase Chemtech Co., Ltd.); 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 Chemical Corporation); 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 glycyrrhizol ED-501, adekaglycylol ED-509, adekaglycylol ED-529, adecarezin EP-4000, adekarezin EP-4005, Resin EP-4901 (manufactured by ADEKA); TECHMORE VG-3101L (manufactured by PRINTECH CORPORATION).

The aromatic epoxy compound (1-1) preferably contains at least one polyfunctional epoxy compound from the viewpoint of curability and adhesiveness. The composition of the present invention preferably contains 30 to 70 parts by mass of the polyfunctional aromatic epoxy compound (1-1) in 100 parts by mass of the cationically polymerizable organic substance mixture (1), more preferably 35 to 60 parts by mass Is more preferable.

Specific examples of the alicyclic epoxy compound (1-2A) include polyglycidyl ether compounds of polyhydric alcohols having at least one alicyclic ring or cyclohexene or cyclopentane ring-containing compounds obtained by epoxidizing a cyclohexene or cyclopentane ring- Hexene oxide 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, dicyclopentadiene diepoxide, ethylenebis (3,4-epoxycyclohexanecarboxylate), dioctylhexahydrophthalate, Epoxy 2-ethylhexyl dihydroxyphthalate, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane,? -Pinene oxide and limonene dioxide .

As the alicyclic epoxy compound (1-2A), an epoxy equivalent of 80 to 500 is preferable.

As the alicyclic epoxy compound (1-2A), a commercially available product can be used. Examples of the alicyclic epoxy compound (1-2A) include Celloxide 2021P, Celloxide 2081, Celloxide 2000, and Celloxide 3000 (manufactured by Daicel Chemical Industries, Ltd.).

The aliphatic epoxy compound (1-2B) refers to an epoxy compound not classified as the aromatic epoxy compound (1-1) or the alicyclic epoxy compound (1-2A). Specific examples of the aliphatic epoxy compound include aliphatic alcohol A glycidyl ether compound of an aliphatic long chain polybasic acid, a glycidyl ether compound of an aliphatic polybasic acid, a glycidyl ether compound of an aliphatic polybasic acid, a glycidyl ether compound of an aliphatic polybasic acid, And the like. Representative compounds include alkyl 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, neopentyl glycol diglycidyl ether , Glycidyl ethers of polyhydric alcohols such as diglycidyl ether of polyethylene glycol and diglycidyl ether of polypropylene glycol and aliphatic polyhydric alcohols such as propylene glycol, trimethylol propane and glycerin, Polyglycidyl ether compounds of polyether polyols obtained by adding alkylene oxide, and diglycidyl esters of aliphatic long chain dibasic acids. Also, monoglycidyl ethers of aliphatic higher alcohols, glycidyl esters of higher fatty acids, epoxidized soybean oil, octyl stearate, butyl stearate, epoxidized soybean oil, epoxidized polybutadiene and the like can be given.

The aliphatic epoxy compound (1-2B) preferably has an epoxy equivalent of 80 to 500.

Examples of the aliphatic epoxy compound (1-2B) include commercially available products such as Denacol EX-121, Denacol EX-171, Denacol EX-192, Denacol EX-211, Denacol EX-212 Denacol EX-411, Denacol EX-411, Denacol EX-412, Denacol EX-511, Denacol EX-611, Denacol EX-821, Denacol EX-821, Denacol EX-821, Denacol EX-850, Denacol EX-821, Denacol EX-821, Denacol EX-930, Denacol EX-930, Denacol EX-930, Denacol EX-830, Denacol EX-832, Denacol EX-841, Denacol EX-861, Denacol EX-911, Denacol EX-941, Denacol EX- product); 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 ( Adekaglycylol ED-503G, Adekaglycylol ED-506, Adekaglycylol ED-523T (manufactured by ADEKA), and the like, .

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

The polyfunctional aliphatic oxetane compound (1-3) is suitably used for obtaining a high Tg, and the polyfunctional aliphatic oxetane compound (1-3) includes 3,7-bis (3-oxetanyl) -5 (3-ethyl-3-oxetanylmethoxy) methyl] benzene, 1,2-bis [ (3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis Tetradecylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, and the like.

As the polyfunctional aliphatic oxetane compound (1-3), a commercially available product containing a cationic polymerizable monomer as a main component may be used. Examples of the polyfunctional aliphatic oxetane compound (1-3) include AARON oxetane OXT-221, AARON oxetane OXT-121 product); Etanacol OXBP, etanacol OXTP, ethanolek OXIPA (manufactured by UBE CORPORATION), and the like.

In the cationic polymerizable organic substance mixture (1), the aromatic epoxy compound (1-1), the alicyclic epoxy compound (1-2A), the aliphatic epoxy compound (1-2B) and the polyfunctional aliphatic oxetane compound (1- 3) is used in an amount of 35 to 80 parts by mass of the aromatic epoxy compound (1-1), 0 to 45 parts by mass of the alicyclic epoxy compound (1-2A) 0 to 45 parts by weight of an aliphatic epoxy compound (1-2B) and 5 to 40 parts by weight of a polyfunctional aliphatic oxetane compound (1-3), wherein the alicyclic epoxy compound (1-2A) and the aliphatic epoxy compound (1-2B) Is not 0, and the aromatic epoxy compound (1-1) is used as a main component.

Here, the main component is a mixture of several kinds of cationic polymerizable organic materials, which means that the total mass of the same kind of compound is the largest. For example, the composition of Example 4 to be described later contains 45 parts by mass of an aromatic epoxy compound (1-1-1), 5 parts by mass of an alicyclic epoxy compound (1-2A-1) , 30 parts by mass of the epoxy compound (1-2B-2) and 20 parts by mass of the polyfunctional aliphatic oxetane compound (1-3-1). In this case, the aromatic epoxy compound having the largest content in the composition is the main component of the composition. In Example 4, instead of 45 parts by mass of the aromatic epoxy compound (1-1-1), 25 parts by mass of the aromatic epoxy compound (1-1-1) and 20 parts by mass of the aromatic epoxy compound (1-1-2) 20 Mass part, the total content of 1-1-1 and 1-1-2, which are the same kind of aromatic epoxy compounds, is the largest in the composition, so that the content of the aromatic epoxy compound in the composition It becomes the main ingredient.

In the cationic polymerizable organic substance mixture (1), as the cationic polymerizable organic substance constituting the mixture, a vinyl ether compound, a high molecular weight substance having a cationic polymerizable group, or the like may also be used.

The composition of the present invention may further contain a cationic polymerization initiator (2).

The cationic polymerization initiator (2) used in the present invention is not particularly limited as long as it is a compound capable of generating an acid upon irradiation with energy rays. Preferably, onium salt which releases Lewis acid Or a derivative thereof. Representative of such compounds are compounds of the general formula < RTI ID = 0.0 >

p [A] ^{q +} s [B] ^t- (wherein A represents a cationic species, B represents an anionic species, q and t each independently represent 1 or 2, p and s represent a charge neutral ) ^-

And a salt of an anion.

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

_{^{[(R 10) a Q]}} q +

.

Here, R < ¹⁰ > is an organic group having 1 to 60 carbon atoms which may contain several atoms other than carbon atoms. a is an integer between 1 and 5. a > R < ¹⁰ > may each independently be the same or different. It is also preferred that at least one 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, Further, when the valence of Q in the cation [A] ^{q +} is t, it is necessary that q = at is satisfied (note that N = N is treated as 0).

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

[LX _b ] ^t-

.

In addition, L is a metal or a metalloid, which is a central atom of a 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 from 3 to 7. Further, when the valence of L in the anion [B] ^t- is p, it is necessary that the relationship r = bp is established.

Specific examples of the anion [LX _b ] ^t- of the above general formula include tetrakis (pentafluorophenyl) borate, tetra (3,5-difluoro-4-methoxyphenyl) borate, tetrafluoroborate ₄₎ ^- or the like ^-, phosphate (PF ₆₎ ^hexafluoro-, antimonate hexafluorophosphate (SbF ₆₎ ^-, it is Senate hexafluorophosphate (AsF ^_6), hexachloro antimonate (SbCl ₆₎ .

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

[LX _{b - 1} (OH)] ^{t -}

Can also 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 ) ^- , toluenesulfonate anion, trinitrobenzenesulfonate anion , Camphorsulfonate, nonafluorobutanesulfonate, hexadecafluorooctanesulfonate, 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). 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) Diphenyliodonium hexafluoroantimonate, di (4-methylphenyl) iodonium hexafluorophosphate, di (4-tert-butylphenyl) iodonium hexafluorophosphate, trilumyl iodonium tetrakis Diaryl iodonium salts such as pentafluorophenylborate

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

Further, as another preferable example, (侶⁵ -2,4-cyclopentadien-1-yl) [(1,2,3,4,5,6-η) - (1- (Acetylacetonato) aluminum, tris (ethylacetonatoacetato) aluminum, tris (salicylaldehydato) aluminum, etc., and triphenylsilanol 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 viewpoint of practical use and photosensitivity.

The ratio of the cationic polymerization initiator (2) to the cationic polymerizable organic substance mixture (1) is not particularly limited and may be used in a range of a normal and a normal use ratio within the range not hindering the object of the present invention. , 0.5 to 20 parts by mass, preferably 1.0 to 10 parts by mass, of the cationic polymerization initiator (2) may be used per 100 parts by mass of the cationic polymerizable organic substance mixture (1). If the amount is too small, the curing tends to be insufficient, while if it is too large, adverse effects may be exerted on the physical properties such as the water absorption rate and the cured product strength of the cured product.

In the composition of the present invention, a silane coupling agent may be used if necessary.

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, and 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-aminopropyl 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 matter in the composition.

In the composition of the present invention, a thermal polymerization initiator may be used if necessary.

The thermal polymerization initiator is a compound which generates a cationic species or a Lewis acid by heating, and includes salts of sulfonium salts, thiophenium salts, thioronium salts, benzylammonium, pyridinium salts and hydrazinium salts; 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 Polyepoxy addition-modified products prepared by reacting various epoxy resins such as polyether polyols, polyether polyols, polyether polyols, An amidated modified product prepared by reacting the above organic polyamines with carboxylic acids such as phthalic acid, isophthalic acid and dimeric acid by a conventional method; A method of reacting phenols having at least one aldehyde reactive site in the nuclei such as aldehydes such as polyamines and formaldehyde and phenol, cresol, xylenol, tert -butylphenol and resorcinol by a conventional method, Denatures; It is possible to use polycarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 2-methylsuccinic acid, Aliphatic dicarboxylic acids such as methyl adipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, hydrogenated dimer acid and dimer acid; , Aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and naphthalene dicarboxylic acid, alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, and trimeric acid, trimesic acid, and trimer of castor fatty 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, commercially available products may be used. Examples of the thermal polymerization initiator include Adekaoptone CP77, Adekaoptone CP66 (ADEKA), CI-2639, CI-2624 (Nippon Soda Co.) , Sun Aid SI-80L, Sun Aid SI-100L (manufactured by San-Shin Kagaku Kogyo Co., Ltd.), and the like.

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 composition. When the thermal polymerization initiator is used, It is preferable to heat at 130 to 180 ° C for 20 minutes to 1 hour.

The composition of the present invention may also improve the properties of the cured product by using a thermoplastic organic polymer, if necessary. 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.

In the composition of the present invention, a solvent capable of dissolving or dispersing the components (1) and (2) can be used without particular limitation, and examples thereof include methyl ethyl ketone, methyl amyl ketone, diethyl ketone, Ketones such as 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-based 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, toluene and xylene; Aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; Terpene-based hydrocarbon oils such as terphenyl 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, N-methylpyrrolidone, dimethylsulfoxide , And water. These solvents may be used alone or in combination of two or more.

The composition of the present invention preferably has a moisture content of 5% or less, more preferably 3% or less, from the viewpoints of curability, adhesiveness, and liquid storage stability. If the water content is excessively high, it may be cloudy or the components may be precipitated.

The composition of the present invention is applied on a supporting base by a known means such as a roll coater, a curtain coater, various printing, immersion or the like. In addition, the film may be once transferred onto a supporting substrate such as a film, and then transferred onto another supporting substrate.

The material of the support base is not particularly limited and can be used usually, and 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 alcohol (PVA), polyvinyl chloride, and polyvinyl fluoride; Acrylic resins such as polymethyl methacrylate and polyacrylic acid ester; 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, laser treatment and the like.

As long as the effect of the present invention is not impaired, the coloring agent such as other monomers, other energy ray-sensitive polymerization initiators, inorganic fillers, organic fillers, pigments, dyes, photosensitizers, defoamers, thickeners, surfactants, Various resin additives such as an antioxidant, a flame retardant, a shrink agent, 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 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 examples of the application of the 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, insulating sheets, Devices, LED packages, liquid crystal injection holes, organic EL devices, optical devices, electrical insulation materials, electronic parts, and separator films, molding materials, putties, glass fiber impregnants, fillers, semiconductors, solar cells A prism lens sheet used for a backlight of a liquid crystal display device, a fresnel lens sheet used for a screen of a projection TV or the like, a lenticular lens sheet, or the like An optical element such as a microlens, an optical element, an optical connector, an optical waveguide, an optical shaping mold, or the like using a lens portion of a lens sheet or a backlight using such a sheet For example, metal, wood, rubber, plastic, glass, ceramic products and the like can be cited as examples of the substrate which can be applied as a coating agent.

Since the composition of the present invention is excellent in curability and adhesiveness, it can be used particularly suitably as an adhesive.

Example

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 composition of the present invention and the cured product obtained by curing the composition will be specifically described with reference to Examples, Evaluation Examples and Comparative Examples. In the examples and comparative examples, "parts" means parts by mass.

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

The components shown in [Table 1] to [Table 4] below were sufficiently mixed to obtain Practical Compositions 1 to 24 and Comparative Compositions 1 to 3, respectively.

(1) The cationic polymerizable organic materials include the following compounds (1-1-1) to (1-1-2), (1-2A-1) to (1-2A- 1) to (1-2B-3) and (1-3-1) were used.

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

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

Compound 1-2A-1: Celloxide 2021P (alicyclic epoxy; manufactured by Daicel Chemical Industries, Ltd.)

Compound 1-2A-2: (4R) -1,2-epoxy-4- (2-methyloxiranyl) -1-methylcyclohexanemethyl 3,4-epoxycyclohexanecarboxylate

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

Compound 1-2B-2: Adekaglycylol ED-523T (manufactured by ADEKA)

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

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

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

Compound 2-1: A 50% solution of propylene carbonate in a mixture of the compound represented by the first chemical formula shown below and the compound represented by the second chemical formula shown below

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

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

(Viscosity)

Viscosity of each of the obtained composition 1 to 24 and comparative compositions 1 to 3 was measured with an E-type viscometer at 25 占 폚. The results are shown in [Table 1] to [Table 4].

(Tg)

Each of the obtained Practical Compositions 1 to 24 and Comparative Compositions 1 to 3 was coated on a PET film to a thickness of 30 탆 with a bar coater and irradiated with energy of 3000 mJ / cm 2 using a metal halide lamp. After 24 hours, the adhesive cured product was taken out from the film, and Tg was measured using a viscoelasticity measuring apparatus (DMA 7100) manufactured by Hitachi High-Tech Science Co., Ltd. The results are shown in [Table 1] to [Table 4].

(Hardenability)

Tg specimens were also checked for curability. A state in which the coated surface was tack-free immediately after the irradiation was evaluated as " Good ", " Good " in 5 minutes, and " Good " in 15 minutes. The results are shown in [Table 1] to [Table 4].

(Adhesive property)

Each of the obtained Practical Compositions 1 to 24 and Comparative Compositions 1 to 3 was applied to a TAC (triacetylcellulose) film subjected to one corona discharge treatment, and then the film was subjected to a corona discharge treatment using a laminator Further, the resultant was adhered to one COP (cycloolefin polymer) film, irradiated with energy of 800 mJ / cm < 2 > using a metal halide lamp and adhered to obtain a test piece. A 90-degree peel test of the obtained test piece was carried out. The results are shown in [Table 1] to [Table 4].

From [Table 1] to [Table 4], it is clear that the composition of the present invention is excellent in curability, adhesiveness and heat resistance.

Claims (7)

As the cationic polymerizable organic substance mixture (1), an aromatic epoxy compound (1-1); Alicyclic epoxy compounds (1-2A) or aliphatic epoxy compounds (1-2B); And a polyfunctional aliphatic oxetane compound (1-3), wherein the aromatic epoxy compound (1-1) is a main component. The method according to claim 1,
Wherein the aromatic epoxy compound (1-1) is at least one selected from the group consisting of glycidyl ether of a monohydric phenol, glycidyl ether of an aromatic compound having two or more alcoholic hydroxyl groups, glycidyl ether of a polyhydric phenol, A glycidyl ester of a polybasic acid type, an epoxidized product of styrene oxide or divinylbenzene, and the like. 3. The method according to claim 1 or 2,
Wherein the aromatic epoxy compound (1-1) contains at least one polyfunctional epoxy compound. 4. The method according to any one of claims 1 to 3,
Wherein the epoxy equivalent of the aromatic epoxy compound (1-1) is 80-500. 5. The method according to any one of claims 1 to 4,
Wherein the cationic polymerization initiator (2) is contained in an amount of 0.5 to 20 parts by mass based on 100 parts by mass of the cationic polymerizable organic substance mixture (1). 6. The method according to any one of claims 1 to 5,
The cationic polymerization initiator ^{(2), p [A] q + ·} s [B] t- ( wherein, A represents a cationic species, B represents an anion species, q and t independently are 1 or 2, respectively , And p and s represent a coefficient for keeping the charge neutral). An adhesive comprising the composition according to any one of claims 1 to 6.