TWI732891B - Curable composition, method of manufacturing hardened material, and hardened material - Google Patents

Abstract

The present invention is to provide a curable composition with excellent adhesion of the cured product, a method for producing the cured product, and the cured product.

The present invention is a curable composition containing 100 parts by mass of cationic polymerizable component (A), 1-10 parts by mass of cationic polymerization initiator (B), and cationic polymerizable component (A) It is a polymer of aromatic epoxy compound (A1), aliphatic epoxy propyl compound (A2), propylene oxide compound (A3), and cationically polymerizable substituent with a weight average molecular weight of 1,000 to 30,000 ( A4) As an essential component, the aromatic epoxy compound (A1) is the main component of the cationically polymerizable component (A), and contains a polyfunctional aromatic epoxy compound and a monofunctional aromatic epoxy compound.

Description

Curable composition, manufacturing method of cured product, and cured product

The present invention relates to a curable composition, a method of manufacturing a cured product, and a cured product thereof, and more specifically, a curable composition having excellent adhesion of a cured product, a method of manufacturing a cured product, and a cured product thereof.

The curable composition is used in the fields of paints, coatings, various coating agents, adhesives, and optical components. There are various reports on the improvement of such a curable composition.

For example, Patent Documents 1 to 4 propose various photocurable adhesives. Specifically, Patent Document 1 proposes a photo-curing adhesive, which combines polyvinyl alcohol-based polarizers and various protective films with the same photo-curing adhesive, which can be easily and strongly adhered, and does not substantially contain Organic solvents have low viscosity and excellent film coating properties. In addition, Patent Document 2 proposes a light-curing epoxy resin adhesive that does not require irradiation with very strong illuminance and does not require heating after light irradiation. In addition, Patent Document 3 proposes a photocurable adhesive that has excellent storage stability, can suppress discoloration of the adhesive itself and the object to be adhered during curing, has a high curing speed, and can provide good adhesiveness. In addition, Patent Document 4 proposes a cationic polymerizable composition that is excellent in curability, adhesiveness, and water resistance, and is superior to adhesive applications.

Prior art literature Patent literature

Patent Document 1: Japanese Patent Application Publication No. 2011-236389

Patent Document 2: JP 2012-149262 A

Patent Document 3: International Publication No. 2008/111584

Patent Document 4: International Publication No. 2015/005211

However, even with the adhesives proposed in Patent Documents 1 to 4, the adhesiveness of the cured product is not necessarily satisfied, and the current situation requires further investigations regarding the adhesiveness of the cured product.

Here, the object of the present invention is to provide a curable composition with excellent adhesion of the cured product, a method for producing the cured product, and the cured product.

The inventors of the present invention conducted intensive studies on the above-mentioned problems to be solved, and found that as long as a curable composition having a specific composition can solve the above-mentioned problems, the present invention was further completed.

That is, the curable composition of the present invention is characterized by containing 100 parts by mass of the cationic polymerizable component (A) and 1-10 parts by mass of the cationic polymerization initiator (B). The aforementioned cationic polymerizable component (A) is an aromatic epoxy compound (A1), an aliphatic epoxy propyl compound (A2), a propylene oxide compound (A3), and a weight average molecular weight of 1,000 to 30,000 with cationically polymerizable substituents The polymer (A4) is an essential component, and the aromatic epoxy compound (A1) is the main component of the cationically polymerizable component (A), and contains a polyfunctional aromatic epoxy compound and a monofunctional aromatic epoxy compound.

In the curable composition of the present invention, it is preferable to further contain an alicyclic epoxy compound (A5) as the cationically polymerizable component (A). In addition, in the curable composition of the present invention, the aforementioned propylene oxide compound (A3) is preferably a polyfunctional propylene oxide compound.

The production method of the cured product of the present invention is characterized by irradiating the curable composition of the present invention with active energy rays or heating.

The cured product of the present invention is the cured product of the curable composition of the present invention.

According to the present invention, it is possible to provide a curable composition having excellent adhesion of the cured product, a method for manufacturing the cured product, and the cured product. The curable composition of the present invention is useful for adhesives, especially adhesives for polarizing plates.

The form used to implement the invention

Hereinafter, the curable composition of the present invention will be described in detail.

The curable composition of the present invention is polymerized or crosslinked by a cationic polymerization initiator activated by energy ray irradiation or heating, and contains 100 parts by mass of the cationic polymerizable component (A), and cationic The polymerization initiator (B) is 1 to 10 parts by mass. In the curable composition of the present invention, the cationic polymerizable component (A) is a combination of an aromatic epoxy compound (A1), an aliphatic epoxy propyl compound (A2), a propylene oxide compound (A3), and a The polymer (A4) of the weight average molecular weight of the cationically polymerizable substituent is 1,000 to 30,000 as an essential component, and the aromatic epoxy compound (A1) is the main component of the cationically polymerizable component (A). In addition, an alicyclic epoxy compound (A5), a vinyl ether compound (A6), etc. may also be contained. Here, the main component means a mixture of a plurality of cationically polymerizable components, and the total of the same type of cationically polymerizable components is the largest.

The aromatic epoxy compound (A1) means an epoxy compound containing an aromatic ring, and the curable composition of the present invention contains both a polyfunctional aromatic epoxy compound and a monofunctional aromatic epoxy compound.

As monofunctional aromatic epoxy compounds, there are phenol compounds such as phenol, cresol, and butylphenol or monoglycidyl ether of alkylene oxide adducts; resorcinol, hydroquinone, and Monoglycidyl etherate of aromatic compounds with two or more phenolic hydroxyl groups such as tea phenol; aromatic compounds with two or more alcoholic hydroxyl groups such as phenyldimethanol, phenyldiethanol, and phenyldibutanol Compound monoglycidyl etherate; phthalic acid, terephthalic acid, trimellitic acid and other polybasic acid aromatic compounds with more than 2 carboxylic acid monoglycidyl esters; benzoic acid epoxy Monoepoxide of propyl ester, styrene oxide or divinylbenzene, etc.

Examples of polyfunctional aromatic epoxy compounds include polyglycidyl etherate of polyphenols having at least one aromatic ring, such as bisphenol A and bisphenol F, or their alkylene oxide adducts; epoxy Phenolic resin; polyglycidyl etherate of aromatic compounds with more than two phenolic hydroxyl groups such as resorcinol, hydroquinone, catechol, etc.; phenyl dimethanol or phenyl diethanol, phenyl dibutyl Polyglycidyl etherate of aromatic compounds with two or more alcoholic hydroxyl groups such as alcohols; polybasic acid aromatics with two or more carboxylic acids such as phthalic acid, terephthalic acid, trimellitic acid, etc. Polyglycidyl ester of compound; Diepoxide of divinylbenzene, etc.

The ratio of the polyfunctional aromatic epoxy compound to the monofunctional aromatic epoxy compound is relative to 100 parts by mass of the polyfunctional aromatic epoxy compound, and the monofunctional aromatic epoxy compound is 20-50 parts by mass, especially 30-40 parts by mass. The part by mass is preferable from the viewpoints of low viscosity, coatability, and reactivity.

As the aromatic epoxy compound (A1), commercially available products can be used, for example, Denacor EX-146, Denacor EX-147, Denacor EX-201, Denacor EX-203, Denacor EX-711, Denacor EX-721, On Court EX-1020, On Court EX-1030, On Court EX-1040, On Court EX-1050, On Court EX-1051, On Court EX-1010, On Court EX-1011, On Court 1012 (Nagase ChemteX (shares) Company system); Ogsol PG-100, Ogsol EG-200, Ogsol EG-210, Ogsol EG-250 (manufactured by Osaka Gas Chemical Co., Ltd.); HP4032, HP4032D, HP4700 (manufactured by DIC Co., Ltd.); ESN- 475V (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.); Epikote YX8800 (manufactured by Mitsubishi Chemical Co., Ltd.); Marproof G-0105SA, Marproof G-0130SP (manufactured by NOF Corporation); Epiclon N-665, Epiclon HP-7200 (made by DIC Corporation); EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, XD-1000, NC-3000, EPPN-501H, EPPN-501HY, EPPN-502H, NC -7000L (manufactured by Nippon Kayaku Co., Ltd.); Adeka Glycyrrole ED-509s, Adeka Glycyrrole ED-501, Adeka Resin EP-4000, Adeka Resin EP-4005, Adeka Resin EP-4100, Adeka Resin EP-4901 (( (Stock) ADEKA Corporation); TECHMORE VG-3101L ((Stock) Printech Corporation), etc. As the above-mentioned aromatic epoxy compound (A1), it is preferable to be polyfunctional because it is excellent in curability.

Relative to 100 parts by mass of the cationically polymerizable component (A), the aromatic epoxy compound (A1) is 20 to 80 parts by mass, especially 30 to 50 parts by mass. Due to the increase in viscosity, coatability, reactivity and curability, So better. In addition, as described above, the main component means a mixture of a plurality of cationically polymerizable components, and the total of the same type of cationically polymerizable components is the largest.

The aliphatic glycidyl compound (A2) means an epoxy compound that is not classified as the aforementioned aromatic epoxy compound (A1) or the later-mentioned alicyclic epoxy compound (A5), as an aliphatic glycidyl compound ( Specific examples of A2) include monofunctional epoxy compounds such as glycidyl etherate of aliphatic alcohols, glycidyl esters of alkyl carboxylic acids, or aliphatic polyols or their alkylene oxides. Polyfunctional epoxy compounds such as polyglycidyl etherate and polyglycidyl ester of aliphatic long-chain polybasic acid. 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-Hexanediol Diglycidyl Ether, Neopentyl Glycol Diglycidyl Ether, Triglycidyl Ether of Glycerol, Trihydroxy Triglycidyl ether of methyl propane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dineopentyl erythritol, diglycidyl ether of polyethylene glycol, and two of polypropylene glycol Glycidyl ether of polyhydric alcohols such as glycidyl ether, or aliphatic polyhydric alcohols such as propylene glycol, trimethylolpropane, glycerol, etc., by adding one or more alkylene oxides Polyglycidyl etherate of ether polyol, diglycidyl ester of aliphatic long-chain dibasic acid. Furthermore, there are monoglycidyl ethers of aliphatic higher alcohols or glycidyl esters of higher fatty acids, epoxidized soybean oil, octyl epoxy stearate, butyl epoxy stearate, epoxidized soybean oil, Epoxidized polybutadiene and so on.

As the aliphatic glycidyl compound (A2), it is the glycidyl etherate of aliphatic alcohol or the polyglycidyl etherate of aliphatic polyol or its alkylene oxide adduct due to viscosity and coating properties And the reactivity will be improved, so it is better.

As the aliphatic glycidyl compound (A2), commercially available products can be used, for example, Denacor EX-121, Denacor EX-171, Denacor EX-192, Denacor EX-211, Denacor EX-212, Denacor EX-313 , Denacor EX-314, Denacor EX-321, Denacor EX-411, Denacor EX-421, Denacor EX-512, Denacor EX-521, Denacor EX-611, Denacor EX-612, Denacor EX-614, Denacor EX-622 , Denacor EX-810, Denacor EX-811, Denacor EX-850, Denacor EX-851, Denacor EX-821, Denacor EX-830, Denacor EX-832, Denacor EX-841, Denacor EX-861, Denacor EX-911 , Denacor EX-941, Denacor EX-920, Denacor EX-931 (manufactured by Nagase ChemteX Co., Ltd.); Epolight M-1230, Epolight 40E, Epolight 100E, Epolight 200E, Epolight 400E, Epolight 70P, Epolight 200P, Epolight 400P , Epolight 1500NP, Epolight 1600, Epolight 80MF, Epolight 100MF (manufactured by Kyoeisha Chemical Co., Ltd.), Adeka Glycyrrole ED-503, Adeka Glycyrrole ED-503G, Adeka Glycyrrole ED-506, Adeka Glycyrrole ED-523T, Adeka Resin EP-4088S, Adeka Resin EP-4080E (made by ADEKA Corporation), etc.

Relative to 100 parts by mass of the cationic curable component (A), the aliphatic epoxypropyl compound (A2) is 1 to 70 parts by mass, especially 10 to 30 parts by mass. The viscosity, coating properties and reactivity will increase, so it is more good.

The propylene oxide compound (A3) contains two or more propylene oxide groups contained in the same molecule, a multifunctional propylene oxide compound contained in the same molecule, and one propylene oxide group contained in the same molecule, either one functional propylene oxide compound . As the propylene oxide compound (A3), 3,7-bis(3-epoxypropylene)-5-oxa-nonanone, 1,4-bis[(3-ethyl-3-epoxy Propylmethoxy)methyl]benzene, 1,2-bis[(3-ethyl-3-glycidylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl -3-glycidyl methoxy) methyl) propane, ethylene glycol bis(3-ethyl-3-glycidyl methyl) ether, triethylene glycol bis(3-ethyl-3- Glycidyl methyl) ether, tetraethylene glycol bis(3-ethyl-3-glycidyl methyl) ether, 1,4-bis(3-ethyl-3-glycidyl methoxy) Multifunctional propylene oxide compounds such as 1,6-bis(3-ethyl-3-glycidylmethoxy)hexane, 3-ethyl-3-((phenoxy) Methyl) propylene oxide, 3-ethyl-3-(hexyloxymethyl) propylene oxide, 3-ethyl-3-(2-ethylhexyloxymethyl) propylene oxide, 3-ethyl Monofunctional propylene oxide compounds such as 3-(hydroxymethyl)propylene oxide and 3-ethyl-3-(chloromethyl)propylene oxide. These can be used singly or in combination of two or more, and the polyfunctional propylene oxide compound is preferred because of the high curability and adhesion of the cured product.

As the propylene oxide compound (A3), commercially available products can be used, and for example, Aaron Oxetane OXT-121, OXT-221, EXOH, POX, OXA, OXT-101, OXT-211, OXT-212 (Toagosei Co., Ltd. ) Company system), Ethanacol OXBP, OXTP (Ube Industries Co., Ltd. system), etc.

The propylene oxide compound (A3) is 1 to 70 parts by mass, especially 10 to 40 parts by mass, relative to 100 parts by mass of the cationic curable component (A), because the viscosity, coatability, and reactivity are improved, so it is preferable.

A polymer (A4) with a weight average molecular weight of 1,000 to 30,000 (hereinafter also referred to as "polymer (A4)") having a cationically polymerizable substituent, as long as the side chain has a cationically polymerizable substituent, and the backbone of the main chain It is not particularly limited, but it is preferable to monopolymerize or copolymerize the compound having an ethylenically unsaturated bond. The cationically polymerizable substituent means an epoxy group or a propylene oxide group.

As the polymer (A4), there are exemplified those obtained by monopolymerizing monomers represented by the following general formula (I), those obtained by copolymerizing plural monomers represented by the following general formula (I), and those having the following general formula (I). (II) The monomer represented by the monomer is polymerized alone, the plural monomer represented by the following general formula (I) is copolymerized, and the monomer represented by the following general formula (I) is combined with the following general formula (II) ) Copolymerization of the monomers.

Here, in the formula, X is an alkyl group with 1 to 7 carbon atoms, an alkoxy group with 1 to 7 carbon atoms, an aryl group with 6 to 12 carbon atoms, an aryloxy group with 6 to 12 carbon atoms, or The alicyclic hydrocarbon group having 6 to 10 carbon atoms, or the hydrogen atom in these groups is substituted with one or more groups selected from the group consisting of epoxy groups and propylene oxide groups.

In the formula, R ¹ represents a hydrogen atom, a methyl group or a halogen atom, X'is an alkyl group with 1 to 7 carbon atoms, an aryl group with 6 to 12 carbon atoms or an alicyclic hydrocarbon group with 6 to 10 carbon atoms, Or the hydrogen atoms in these groups are substituted with one or more groups selected from the group consisting of epoxy groups and propylene oxide groups.

Examples of the alkyl group having 1 to 7 carbon atoms represented by X in the formula (I) include methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl , Iso-butyl, pentyl, iso-pentyl, tert-pentyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 4-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl Base, iso-heptyl, tert-heptyl, etc. Among these, an alkyl group with 1 to 4 carbon atoms, or an alkyl group with 1 to 4 carbon atoms partially substituted by one or more groups selected from the group consisting of epoxy and propylene oxide groups, From the viewpoint of hardening properties, it is preferable.

As the alkoxy group having 1 to 7 carbon atoms represented by X in the formula (I), methoxy, ethoxy, propoxy, iso-propoxy, butoxy, sec-butoxy, tert-butoxy, iso-butoxy, pentoxy, iso-pentoxy, tert-pentoxy, hexyloxy, 2-hexyloxy, 3-hexyloxy, cyclohexyloxy, 4 -Methylcyclohexyloxy, heptyloxy, 2-heptyloxy, 3-heptyloxy, iso-heptyloxy, tert-heptyloxy, etc. Among these, an alkyl group with 1 to 4 carbon atoms, or an alkoxy group with 1 to 4 carbon atoms partially substituted by one or more groups selected from the group consisting of epoxy and propylene oxide groups From the viewpoint of hardening properties, it is preferable.

Examples of the aryl group having 6 to 12 carbon atoms represented by X in the formula (I) include a phenyl group, a methylphenyl group, and a naphthyl group.

Examples of the aryloxy group having 6 to 12 carbon atoms represented by X in the formula (I) include a phenoxy group, a methylphenoxy group, and a naphthoxy group.

As the alicyclic hydrocarbon group with 6 to 10 carbon atoms represented by X in the formula (I), there are cyclohexyl, methylcyclohexyl, norbornyl, dicyclopentyl, bicyclooctyl, trimethylbicyclo Heptyl, tricyclooctyl, tricyclodecyl, cyclic octyl, cyclic bicyclopentyl, adamantyl, isobornyl, etc.

In the formula (I), when a part of X is substituted with an epoxy group or a propylene oxide group, examples of the monomer represented by the formula (I) include monomers represented by the following formulas (1) to (3).

In the formula, R ² represents a hydrogen atom or an alkyl group with 1 to 6 carbon atoms, and m is an integer of 1 to 6.

In the formula, R ³ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n is an integer of 1 to 6.

In the formula, R ⁴ represents a hydrogen atom or an alkyl group with 1 to 6 carbon atoms, and s is an integer of 1 to 6.

In the formula (II), ^{examples of the halogen atom represented by R 1} include fluorine, chlorine, bromine, and iodine.

In the formula (II), when a part of X'is substituted with an epoxy group or a propylene oxide group, examples of the monomer represented by the formula (II) include those represented by the following formulas (4) to (6).

In the formula, R ¹ is the same as the above formula (II), R ⁵ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and t is an integer of 1 to 6.

In the formula, R ¹ is the same as the above formula (II), R ⁶ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and q is an integer of 1 to 6.

In the formula, R ¹ is the same as the above formula (II), R ⁷ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and y is an integer of 1 to 6.

In the polymer (A4), the ratio of the monomers constituting the polymer is used. The above X is the number of carbon atoms of 1-7 substituted by one or more groups selected from the group consisting of epoxy groups and propylene oxide groups When the alkyl group, the aryl group with 6 to 12 carbon atoms, or the alicyclic hydrocarbon group with 6 to 10 carbon atoms, the monomer represented by (I) or (II) above is relative to the monomer constituting the polymer The total amount is 100% by mass, and it is used as 10-100% by mass. Since the adhesion improves, it is preferable.

As a monomer constituting the polymer (A4), an ethylenically unsaturated compound having a hydroxyl group or a carboxyl group can be used in combination with the monomer represented by (I) or (II), and the adhesion is improved, which is preferable.

The amount of the polymer (A4) is 1-20 parts by mass, especially 3-10 parts by mass, relative to 100 parts by mass of the cationic curable component (A), since viscosity, coatability, and reactivity are improved, so it is preferable.

The alicyclic epoxy compound (A5) means one that directly bonds an oxirane ring to a saturated ring without interposing a bonding group. As a specific example of the alicyclic epoxy compound, there are Polyglycidyl etherate of a polyhydric alcohol with one alicyclic ring or cyclohexene or cyclopentene ring-containing compound obtained by epoxidizing cyclohexene oxide or cyclopentene oxide-containing compound with an oxidizing agent. For example, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1- Methyl hexane carboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexane carboxylate, 3,4-epoxy-3 -Methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexane carboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5 -Methylcyclohexane carboxylate, bis(3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexane carboxylate, ethylene bis (3,4-epoxycyclohexane), propane-2,2-diyl-bis(3,4-epoxycyclohexane), 2,2-bis(3,4-epoxycyclohexyl)propane , Diepoxydicyclopentadiene, ethylene bis(3,4-epoxycyclohexane carboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethyl epoxyhexahydrophthalate Base hexyl ester, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, α-pinene oxide, limonene dioxide, etc. As an alicyclic epoxy compound, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate or 3,4-epoxy-1-methylcyclohexyl-3,4- Epoxy-1-methylhexane carboxylate is preferable from the viewpoint of improving adhesion.

As an alicyclic epoxy compound (A5), a commercially available product can be used, for example, Celloxide 2021P, Celloxide 2081, Celloxide 2000, Celloxide 3000 (made by Daicel Corporation) etc. are mentioned.

Relative to 100 parts by mass of the cationic curable component (A), the above-mentioned alicyclic epoxy compound (A5) is 0-30 parts by mass, especially 0-20 parts by mass. The viscosity, coating properties and reactivity will increase, so it is more good.

As the vinyl ether compound (A6), there are, for example, diethylene glycol monovinyl 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 mono Vinyl ether, ethylene glycol divinyl ether, 1,4-butanediol divinyl ether, 1,6-cyclohexanedimethanol divinyl ether, etc.

The cationic polymerization initiator (B) related to the curable composition of the present invention means a compound that can release a substance that initiates cationic polymerization by energy ray irradiation or heating, any of them may be used, preferably by The irradiation of energy rays releases the double salt of the onium salt of Lewis acid or its derivative. As a representative of related compounds, the following general formula [A] ^r+ [B] ^r-

The cation and anion salts shown.

Here, the cation [A] ^r+ is preferably onium, and its structure can be, for example, the following general formula [(R ⁸ ) _a Q] ^r+

Represented.

Furthermore, here, R ⁸ is an organic group having 1 to 60 carbon atoms and several atoms other than carbon atoms. a is an integer from 1 to 5. A R ⁸ may be independent of each other and may be the same or different. In addition, at least one of them is preferably an organic group as described above having an aromatic ring. Q is an atom or group of atoms selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F, N=N. Moreover, when the valence of Q in the cation [A] ^r+ is set to q, the relationship of r=aq must be satisfied (however, N=N is regarded as the valence of 0).

In addition, the anion [B] ^r- is preferably a halide complex, and its structure can be, for example, the following general formula [LY _b ] ^r-

Represented.

Furthermore, L is the metal or semimetal (Metalloid) of the central atom of the halide complex, which is B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr , Mn, Co, etc. Y is a halogen atom. b is an integer of 3-7. Moreover, when the valence of L in the anion [B] ^r- is set to p, the relationship of r=bp must be satisfied.

As specific examples of the general formula of the anion [LYb] ^r- , four (pentafluorophenyl) borate, tetra(3,5-difluoro-4-methoxyphenyl) borate, tetrafluoroborate Salt (BF ₄ ) ^- , hexafluorophosphonate (PF ₆ ) ^- , hexafluoroantimonate (SbF ₆ ) ^- , hexafluoroarsenate (AsF ₆ ) ^- , hexachloroantimonate (SbCl ₆ ) ^- Wait.

In addition, the anion [B] ^r- can use the following general formula [LY _b-1 (OH)] ^r-

The structure shown is better. L, Y, and b are the same as above. And, as other anions that can be used, perchlorate ion (ClO ₄ ) ^- , trifluoromethyl sulfite ion (CF ₃ SO ₃ ) ^- , fluorosulfonic acid ion (FSO ₃ ) ^- , toluene sulfonic acid ion Anion, trinitrobenzene sulfonic acid anion, camphor sulfonate, nonfluorobutane sulfonate, hexachlorooctane sulfonate, tetraaryl borate, tetrakis (pentafluorophenyl) borate, etc.

In the curable composition of the present invention, among such onium salts, it is particularly effective to use the following aromatic onium salts (A) to (C). Among these, one kind can be used alone, or two or more kinds can be mixed and used.

(A) Phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate, 4-methylphenyldiazonium hexafluorophosphate and other aryl diazonium salts

(B) Diphenyl iodonium hexafluoroantimonate, bis(4-methylphenyl) iodonium hexafluorophosphate, bis(4-tert-butylphenyl) iodonium hexafluorophosphate, tolyl Diaryl phosphonium salts such as cumyl phosphonium (pentafluorophenyl) borate

(C) The sulfonium cation represented by the following group I or group II, hexafluoroantimony ion, hexafluorophosphonate ion, tetrakis (pentafluorophenyl) borate ion, etc.

And, as another preferable one, (η ⁵ -2,4-cyclopentadien-1-yl) [(1,2,3,4,5,6-η)-(1-methyl (Ethyl)benzene]-iron-hexafluorophosphate and other iron-arene complexes, or ginseng (acetylpyruvate) aluminum, ginseng (ethylpyruvate acetate) aluminum, ginseng (salaldehyde methyl ether) aluminum A mixture of aluminum complexes such as triphenylsilanol and silanols such as triphenylsilanol; thiophenium salt, tetrahydrothiophenium salt, phenylbenzylammonium, pyridinium, hydrazine, etc.; diethylenetriamine, triphenylsilanol Polyalkyl polyamines such as ethylene triamine and tetraethylene pentamine; 1,2-diamine cyclohexane, 1,4-diamine-3,6-diethyl cyclohexane, isophorone two Alicyclic polyamines such as amines; aromatic polyamines such as m-xylylene diamine, diamine diphenylmethane, and diamine diphenyl benzene; combining the above polyamines with phenyl glycidyl Glycidyl ether, butyl glycidyl ether, bisphenol A-diglycidyl ether, bisphenol F-diglycidyl ether, etc. or glycidyl esters of carboxylic acid Polyepoxy adduct modified products made by reacting various epoxy resins by conventional methods; combining the above-mentioned organic polyamines with carboxylic acids such as phthalic acid, isophthalic acid, and diacids by conventional methods. Method to make the aminated modified product produced by the reaction; the above-mentioned polyamines, aldehydes such as formaldehyde, and phenol, cresol, xylenol, tertiary butylphenol, resorcinol, etc. have at least the core A Mannich reaction modifier produced by the reaction of phenols in a formaldehyde-reactive place by conventional methods; polycarboxylic acids (oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid) , Pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 2-methylsuccinic acid, 2-methyladipic acid, 3-methyladipic acid, 3-methyl Fats such as pentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, hydrogenated dimer acid, dimer acid, etc. Aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; trimellitic acid , Tricarboxylic acid, tricarboxylic acid, trimer of castor oil fatty acid; tetracarboxylic acid, pyromellitic acid, etc.) anhydride; dicyandiamine, imidazole, carboxylic acid ester, sulfonic acid ester, amine Base imine and so on.

Among these, from the viewpoint of practicality and light sensitivity improvement, it is preferable to use aromatic phosphonium salts, aromatic sulfonium salts, and iron-arene complexes, which are 100% by mass relative to the cationic polymerization initiator (B) It is more preferable to contain at least 0.1% by mass or more of an aromatic sulfonium salt having the following structure.

Here, in the formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a halogen atom, and the number of carbon atoms is 1-10 The alkyl group, the alkoxy group with 1 to 10 carbon atoms or the ester group with 2 to 10 carbon atoms, R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent a hydrogen atom, a halogen atom or a carbon atom number of 1~ An alkyl group of 10, R ²⁵ represents a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbon atoms, or a substituent selected from any one of the following chemical formulas (A) to (C), An ^q- represents a valence of q The anion, p represents the coefficient of making the charge neutral.

Here, in the formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ each independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbon atoms, and one with 1 to 10 carbon atoms An alkoxy group or an ester group with 2 to 10 carbon atoms, R ³⁰ , R ³¹ , R ³² , R ³³ and R ³⁴ each independently represent a hydrogen atom, a halogen atom or an alkyl group with 1 to 10 carbon atoms, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ The hydrogen atoms of the groups represented by, R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ can also pass through halogen atoms, nitro groups, cyano groups, hydroxyl groups, amino groups, carboxyl groups, methacrylic groups, and acrylic groups , Epoxy, vinyl, mercapto, isocyanate, heterocyclic-containing group substitution, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁵ , R ³⁶ , R ³⁷ , R ^38, and R ³⁹ in the group represented by the methylene group may also be -O-, -CO-, -COO-, -OCO-, -S-, -SO ₂ -, -SCO- or -COS- substitution.

In the compound represented by general formula (1), as R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ The halogen atom includes fluorine, chlorine, bromine, iodine and the like.

As R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ represent an alkyl group with 1-10 carbon atoms, There are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, isopentyl, t-pentyl, hexyl, heptyl, Octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl and isodecyl, etc.

As R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ represent alkoxy groups with 1 to 10 carbon atoms. Examples include methoxy, ethoxy, propoxy, and isopropoxy. Oxy, butoxy, s-butoxy, t-butoxy, isobutoxy, pentoxy, isopentoxy, t-pentoxy, hexyloxy, cyclohexyloxy, cyclohexyl Methoxy, tetrahydrofuranyloxy, tetrahydropiperanyloxy, 2-methoxyethyloxy, 3-methoxypropoxy, 4-methoxybutoxy, 2-butoxy Ethoxy, methoxyethoxyethoxy, methoxyethoxyethoxyethoxy, 3-methoxybutoxy, 2-methylthioethoxy, trifluoromethoxy Base and so on.

As R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ represent ester groups with 2 to 10 carbon atoms, including methoxycarbonyl, ethoxycarbonyl, and isopropoxycarbonyl , Phenoxycarbonyl, acetoxy, propoxy, butoxy, chloroacetoxy, dichloroacetoxy, trichloroacetoxy, trifluoroacetoxy, t- Butylcarbonyloxy, methoxyacetoxy, benzyloxy and the like.

The use ratio of the cationic polymerization initiator (B) relative to the cationic polymerizable component (A) is 1 to 10 parts by mass relative to 100 parts by mass of the cationic polymerizable component (A), and the cationic polymerization initiator (B) is 1 to 10 parts by mass, Preferably it is 2-8 mass parts. If it is too small, the hardening is likely to be insufficient. If it is too large, it may adversely affect various physical properties such as the water absorption rate and the strength of the hardened product.

In the curable composition of the present invention, a sensitizer and/or a sensitization aid can be further used as necessary. The sensitizer exhibits maximum absorption at longer wavelengths than the maximum absorption wavelength indicated by the cationic polymerization initiator (B), and is a compound that promotes the polymerization initiation reaction caused by the cationic polymerization initiator (B). In addition, the sensitizer is a compound that further promotes the effect of the sensitizer.

As the sensitizer and the sensitization aid, there are scallion-based compounds, naphthalene-based compounds and the like.

Examples of the onion-based compound include those represented by the following formula (7).

Here, in formula (7), R ⁵⁰ and R ⁵¹ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxyalkyl group having 2 to 12 carbon atoms, and R ⁵² represents a hydrogen atom or carbon Alkyl group with 1 to 6 atoms.

Specific examples of the onion-based compound represented by the formula (7) include the following compounds.

For example, 9,10-dimethoxy onion, 9,10-diethoxy onion, 9,10-dipropoxy onion, 9,10-diisopropoxy onion, 9,10-dibutyl onion Onion, 9,10-dipentyloxy onion, 9,10-dihexoxy onion, 9,10-bis(2-methoxyethoxy) onion, 9,10-bis(2-ethyl Oxyethoxy) shallot, 9,10-bis(2-butoxyethoxy) shallot, 9,10-bis(3-butoxypropoxy) shallot, 2-methyl- or 2- Ethyl-9,10-dimethoxy onion, 2-methyl- or 2-ethyl-9,10-diethoxy onion, 2-methyl- or 2-ethyl-9,10-di Propoxy onions, 2-methyl- or 2-ethyl-9,10-diisopropoxy onions, 2-methyl- or 2-ethyl-9,10-dibutoxy onions, 2- Methyl-or 2-ethyl-9,10-dipentyloxy onion, 2-methyl-or 2-ethyl-9,10-dihexyloxy onion, etc.

Examples of the naphthalene-based compound include those represented by the following formula (8).

Here, in formula (8), R ⁵³ and R ⁵⁴ each independently represent an alkyl group having 1 to 6 carbon atoms.

Specific examples of the naphthalene-based compound represented by the formula (8) include the following compounds.

Examples include 4-methoxy-1-naphthol, 4-ethoxy-1-naphthol, 4-propoxy-1-naphthol, 4-butoxy-1-naphthol, 4-hexyl Oxy-1-naphthol, 1,4-dimethoxynaphthalene, 1-ethoxy-4-methoxynaphthalene, 1,4-diethoxynaphthalene, 1,4-dipropoxynaphthalene , 1,4-Dibutoxynaphthalene, etc.

Relative to the cationic polymerizable component (A), the use ratio of the sensitizer and the sensitization aid is not particularly limited. As long as it does not hinder the purpose of the present invention, it can be used in a conventional general use ratio, for example, relatively Based on 100 parts by weight of the cationically polymerizable component (A), the sensitizer and the sensitizer auxiliary are each 0.1 to 3 parts by mass, which is preferable from the viewpoint of improving the hardenability.

In the curable composition of the present invention, a silane coupling agent can be used as necessary. As the silane coupling agent, for example, dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, and methyltrimethoxysilane can be used. Alkyl functional alkoxysilanes such as methyl silane, methyl triethoxy silane, ethyl trimethoxy silane, ethyl trimethoxy silane, etc., vinyl trichlorosilane, vinyl trimethoxy silane, vinyl Alkenyl functional alkoxysilanes such as triethoxysilane, allyltrimethoxysilane, etc., 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane , 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 2-methacryloxypropyltrimethoxysilane, γ-epoxy Epoxy function of propoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc. Alkoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyl Amino-functional alkoxysilanes such as trimethoxysilane, mercapto-functional alkoxysilanes such as γ-mercaptopropyl trimethoxysilane, titanium alkoxides such as titanium tetraisopropoxide, titanium tetra-n-butoxide, etc. Type, titanium dioctyl oxy bis (octyl glycolate), titanium diisopropoxy bis (ethyl acetyl acetate) and other titanium clamp compounds, zirconium tetraacetyl pyruvate, Zirconium clamp compounds such as zirconium tributoxy monoacetate pyruvate, zirconium acetyl esters such as zirconium tributoxy monostearate, isocyanate silanes such as methyl triisocyanate silane, etc.

The amount of the silane coupling agent used is not particularly limited, and it is generally in the range of 0.01 to 20 parts by mass relative to 100 parts by mass of the total amount of solids in the curable composition.

The curable composition of the present invention can improve the characteristics of the cured product by using a thermoplastic organic polymer as necessary. As the thermoplastic organic polymer, there are, for example, polystyrene, polymethmethacrylate, methacrylate ethyl acrylate copolymer, methacrylate glycidyl methacrylate Copolymer, poly(meth)acrylic acid, styrene-(meth)acrylic acid copolymer, (meth)acrylic acid-methmethacrylate copolymer, glycidyl (meth)acrylate- Polymethyl (meth)acrylate copolymer, polyvinyl butyral, cellulose ester, polyacrylamide, saturated polyester, etc.

The curable composition of the present invention is not particularly limited, and a generally used solvent capable of dissolving or dispersing the above-mentioned (A) and (B) components can be used. Examples of solvents include ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone. Class; Ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, propylene glycol monomethyl ether, dipropylene glycol dimethyl ether, etc. System solvent; methyl acetate, ethyl acetate, -n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, monoisobutyrate, etc. Ester solvents of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc. Celosine solvents; methanol, ethanol, iso- or n-propanol, iso- or n-butanol, pentanol Alcohol solvents such as ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether Ether ester solvents such as acetate, 3-methoxybutyl acetate, and ethoxyethyl propionate; BTX solvents such as benzene, toluene, xylene, etc.; hexane, heptane, octane Aliphatic hydrocarbon solvents such as, cyclohexane; terpene hydrocarbon oils such as turpentine, D-limonene and pinene; mineral spirits, Swazole#310 (manufactured by Cosmo Songshan Petroleum Co., Ltd.), Solvesso#100( Exxon Chemical Corporation) and other paraffin-based solvents; halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, chlorinated methane, 1,2-dichloroethane, etc.; halogenated aromatic hydrocarbons such as chlorobenzene Solvents; acrylic carbonate, carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, water, etc. These solvents can be used as a mixed solvent of one type or two or more types.

Since the curable composition of the present invention has improved curability, adhesion, and liquid storage stability, the water content is preferably 5 parts by mass or less, and more preferably 3 parts by mass or less. If there is too much water, it may become cloudy or may be out of components, so it is not good.

In the curable composition of the present invention, an ultraviolet absorber can be further used as necessary, or it is inert at room temperature and heated by a specific temperature. Light exposure. Acids, etc., will detach the protective group and be activated to exhibit ultraviolet absorbing energy.

Moreover, as long as the effect of the present invention is not impaired, coloring agents such as radical polymerizable monomers, radical polymerization initiators, polyols, inorganic fillers, organic fillers, pigments, dyes, etc., antifoaming agents, and thickening agents can be added as necessary. Among other agents, surfactants, leveling agents, flame retardants, thixotropic agents, thinners, plasticizers, stabilizers, polymerization inhibitors, ultraviolet absorbers, antioxidants, antistatic agents, flow regulators, adhesion promoters, etc. Various resin additives, etc.

The curable composition of the present invention is applied to a supporting substrate by known means such as roll coating, curtain coating, various printing, and dipping. Moreover, once it is applied to a supporting substrate such as a film, it can also be transferred to other supporting substrates, and the method of application is not limited.

There are no particular restrictions on the material of the above-mentioned support matrix, and general users can be used, such as inorganic materials such as glass; diacetyl cellulose, triacetyl cellulose (TAC), propyl cellulose , Butyl cellulose, acetyl propyl cellulose, nitrocellulose and other cellulose esters; Polyamide; Polyimine; Polyurethane; Epoxy resin; Polycarbonate; Polyethylene terephthalate Formate, polyethylene naphthalate, polybutylene terephthalate, poly-1,4-cyclohexane dimethylene terephthalate, polyethylene-1,2-di Polyesters such as phenoxyethane-4,4'-dicarboxylate and polybutylene terephthalate; Polystyrene; Polyolefins such as polyethylene, polypropylene, and polymethylpentene; Vinyl compounds such as polyvinyl acetate, polyvinyl chloride, and polyvinyl fluoride; acrylic resins such as polymethylmethacrylate, polyacrylate, etc.; polycarbonate; Ether ketone; polyether imine; polyoxyethylene, norbornene resin, cyclic olefin polymer (COP) and other polymer materials. Furthermore, surface activation treatments such as corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, and laser treatment may also be performed on the above-mentioned support substrate.

In the method of curing the curable composition of the present invention by irradiation of energy rays, examples of the energy rays include ultraviolet rays, electron rays, X-rays, radiation rays, high frequency, etc., and ultraviolet rays are economically optimal. As the light source of ultraviolet rays, there are ultraviolet lasers, mercury lamps, xenon lasers, metal halide lamps, and the like.

The conditions in the method of hardening the curable composition of the present invention by heating are at 70 to 250°C for 1 to 100 minutes. After pre-bake (PAB; Pre applied bake), it can also be pressurized and then post-bake (PEB; Postexposure bake), or it can be bake at different temperatures in several stages. The heating conditions will vary depending on the types of ingredients and the mixing ratios, but for example, at 70-180°C, it takes 5 to 15 minutes for the oven, and 1 to 5 minutes for the hot plate. After that, in order to harden the coating film, the cured film can be obtained by heat treatment at 180-250°C, preferably 200-250°C, 30-90 minutes in the oven, and 5-30 minutes in the hot plate.

Specific uses of the curable composition of the present invention or its cured product include adhesives, adhesives for polarizing plates, glasses, optical materials represented by lenses for photographing, paints, coating agents, lining agents, paints, Photoresist, liquid photoresist, printing plates, color TVs, PC monitors, mobile information terminals, digital cameras, organic EL, touch panels and other display components, insulating varnishes, insulating sheets, laminates, printing substrates, For semiconductor devices. For LED packaging. For liquid crystal injection port. For organic EL. For optical components. For electrical insulation. For electronic parts. Sealants, molding materials, adhesives, glass fiber impregnation agents, fillers, and semiconductors for separation membranes. Passivation films, interlayer insulating films, protective films for solar cells, etc., lens sheets used in backlights of liquid crystal display devices, Fresnel lens sheets used in screens of projection TVs, etc., lenticular lens sheets, etc. The lens part of the sheet, or the backlight, etc. using such a sheet, the optical lens such as the micro lens, optical element, optical connector, optical waveguide, optical molding injection, etc.

As the display device of the present invention, a primer layer, a reflection prevention layer, a polarizing element layer, a retardation layer, a birefringence layer, a light scattering layer, a hard coating layer, a lubricating layer, and a protective layer can be provided on the transparent support as necessary. For each layer, a film made of the cured product of the present invention can be used for each layer.

Hereinafter, the present invention will be explained in further detail with examples and the like, but the present invention is not limited to these examples.

[Examples 1 to 16, Comparative Examples 1 to 7]

The components were thoroughly mixed in the blending amounts shown in the following [Table 1] to [Table 3] to obtain the curable composition of each of Examples 1 to 16 and the curable composition of Comparative Examples 1 to 7. In addition, the units of Examples and Comparative Examples are parts by mass.

As the cationically polymerizable component (A), the following compounds A1-1 to A1-5, A2-1 to A2-2, A3-1, A4-1, and A5-1 were used.

Compound A1-1: Bisphenol type diglycidyl ether

Compound A1-2: Adeka Glycyrrole ED-509S (monofunctional aromatic epoxy compound manufactured by ADEKA)

Compound A1-3: Adeka Glycyrrole ED-501 (monofunctional aromatic epoxy compound manufactured by ADEKA)

Compound A1-4: o-allyl phenyl glycidyl ether

Compound A1-5: o-phenylphenol glycidyl ether

Compound A2-1: Neopentyl glycol diglycidyl ether

Compound A2-2: 1,4-Butanediol Diglycidyl Ether

Compound A3-1: Aaron Oxetane OXT-221 (manufactured by Toagosei Co., Ltd.)

Compound A4-1: Copolymer of 75 parts by mass of methacrylate and 25 parts by mass of glycidyl methacrylate (weight average molecular weight 7,000)

Compound A5-1: Celloxide 2021P (alicyclic epoxy compound manufactured by Daicel)

Compound A5-2: Limonene Dioxide

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

Compound B-1: Propylene carbonate 50% solution of a mixture of the compound represented by the following formula (9) and the compound represented by the following formula (10)

(Adhesion)

The curable compositions of Examples 1 to 16 and Comparative Examples 1 to 7 obtained above were respectively coated on a piece of PMMA film (Sumitomo Chemical Co., Ltd.: Technology 125S001), and then subjected to corona discharge treatment with the other piece of PMMA film (Sumitomo Chemical Co., Ltd.: Technology 125S001). COP (Cyclic Olefin Polymer, Japan Zeon Co., Ltd.: Product Code Zeonor film 14-060) film is laminated using a laminating machine, using an electrodeless UV lamp, irradiating the equivalent of 1000mJ/cm ² of light through the COP The film is attached to obtain a test piece. A 90-degree peel test of the obtained test piece was performed. As long as it is a curable composition with an adhesion of 1.0 N/cm or more, it can be used as an adhesive for polarizing plates. Preferably, the adhesion is 2.0 N/cm or more, and the adhesion is more preferably 3.0 N/cm. cm above. Record the results obtained in Tables 1 to 3.

(Hardening)

When preparing the above test piece, it was confirmed with the curability. It was evaluated as ++ if the coated surface became tack-free immediately after irradiation, + was evaluated as being non-sticky after 5 minutes, and-was evaluated as remaining sticky after 15 minutes. The curable composition with curability of ++ or + can be used as an adhesive for polarizing plates, and the curable composition with curability of ++ can be used as an adhesive for polarizing plates. The curable composition is particularly good for curing with- The sexual composition cannot be used as an adhesive for polarizing plates. Record the results obtained in Tables 1 to 3.

(Coatability)

The curable compositions of Examples 1 to 16 and Comparative Examples 1 to 7 were respectively coated on one sheet of PMMA film (Sumitomo Chemical Co., Ltd.: Technology 125S001), and then combined with another sheet of COP( Cycloolefin polymer, manufactured by Zeon (Japan): Product No. Zeonor film 14-060) The film is laminated using a laminating machine, using an electrodeless UV lamp, irradiating the equivalent of 1000mJ/cm ² of light through the COP film for bonding , Get the test piece. Observe the appearance of the obtained sample, and set the ones with no unevenness or bubbles as ○, and the ones with unevenness or bubbles as ×. The curable composition whose coatability is ○ can be used as an adhesive for polarizing plates, and the curable composition whose coatability is × cannot be used as an adhesive for polarizing plates.

From [Table 1] to [Table 3], it is clear that the hardened product of the curable composition of the present invention has excellent adhesion.

Claims (7)

A curable composition characterized by containing 100 parts by mass of a cationic polymerizable component (A) and 1-10 parts by mass of a cationic polymerization initiator (B), the aforementioned cationic polymerizable component (A) The aromatic epoxy compound (A1), the aliphatic epoxy propyl compound (A2), and the propylene oxide compound (A3), and a polymer with a weight average molecular weight of 1,000 to 30,000 ( A4) As an essential component, the aromatic epoxy compound (A1) is the main component of the cationically polymerizable component (A), and contains a polyfunctional aromatic epoxy compound and a monofunctional aromatic epoxy compound, which is more than the aforementioned 100 parts by mass of the functional aromatic epoxy compound, and 30 to 50 parts by mass of the aforementioned monofunctional aromatic epoxy compound. The curable composition according to claim 1, which further contains an alicyclic epoxy compound (A5) as the cationically polymerizable component (A). The curable composition according to claim 1, wherein the propylene oxide compound (A3) is a polyfunctional propylene oxide compound. The curable composition according to claim 2, wherein the propylene oxide compound (A3) is a polyfunctional propylene oxide compound. A hardening method of hardening composition, which is characterized by The curable composition of any one of 1 to 4 is irradiated with active energy rays. A method for hardening a hardening composition, which is characterized by heating the hardening composition as in any one of Claims 1 to 4. A hardened product, which is a hardened product of the hardenable composition according to any one of claims 1 to 4.