JP6932744B2 - Liquid resin composition for active ray-curable adhesive - Google Patents

Description

The present invention relates to a color-developing liquid resin composition used as an adhesive. Specifically, it is hardly colored before use, and after being adhered, it is cured by irradiation with active rays, and the dye precursor develops a color to form a colored adhesive portion. The present invention relates to a liquid resin composition capable of full-color coloring and having a high curing rate.

Active ray-curable adhesives that are cured by irradiating them with light such as laser light or ultraviolet rays are more energy efficient than heat-curable adhesives, so they are used in the fields of electricity, automobiles, precision machinery, etc. It is used in a wide range of fields, and in recent years, it has been used as a material for adhering a plurality of optical films such as a polarizing film to a liquid crystal cell used in a display device such as a liquid crystal television, a notebook computer, and a smartphone.
Normally, when a heat-curable adhesive is used to bond an optical film, the optical film made of a polymer film such as polyvinyl alcohol is prone to deformation such as heat shrinkage, and as a result, the bonded portion is cracked or peeled off. , There is a drawback that it causes light leakage. Further, in a display device using an LED as a light source, since the brightness of the LED light source is high, light leakage tends to be conspicuous.

Japanese Unexamined Patent Publication No. 2007-84727

In a display device using an LED light source, in order to prevent light leakage, a method of using a liquid resin composition containing a colorant to bond and then curing is conceivable, but since the resin composition itself is colored. There is a drawback that the light does not easily reach the curable resin or the polymerization initiator during curing and it takes a long time to cure.
The present invention has a high curing rate, is capable of coloring each desired color and full color, has excellent light storage resistance, and is used for adhesion between an adherend such as a liquid crystal cell and an optical film such as a polarizing film. It is an object of the present invention to provide a liquid resin composition for an active ray-curable adhesive according to a novel coloring system and composition capable of reducing light leakage.

As a result of various studies, the present inventors have found that the above-mentioned problems can be achieved by a liquid resin composition for an active ray-curable adhesive containing the following components, and have completed the present invention.
That is, the present invention
(I) A liquid resin composition for an active ray-curable adhesive containing the following components (A), (B) and (C) as essential components.
(A) Active ray-polymerizable organic compound (B) Compound that generates acid by irradiation with active rays (C) Acid-coloring dye precursor (ii) The (A) active ray-polymerizable organic compound is as follows (A-1). ) And / or (A-2), the liquid resin composition for an active ray-curable adhesive according to (i).
(A-1) Radical-polymerizable organic compound (A-2) Cationic-polymerizable organic compound (iii) The radical-polymerizable organic compound of (A-1) is an organic compound having at least one unsaturated double bond. , (Ii) Liquid resin composition for active ray-curable adhesive.
(Iv) A liquid resin composition for an active ray-curable adhesive according to any one of (i) to (iii), further containing (D) a radical photopolymerization initiator.
(V) The liquid resin composition for an active ray-curable adhesive according to any one of (ii) to (iv), wherein the cationically polymerizable organic compound of (A-2) is an organic compound having two or more epoxy groups. ..
(Vi) The liquid resin composition for an active ray-curable adhesive according to any one of (i) to (v), wherein the compound that generates an acid by irradiation with the active ray of (B) is a cationic photopolymerization initiator.
(Vii) The (C) acid chromogenic dye precursor is a fluorene compound, a phthalide compound, an azaphthalide compound, a fluorenspirophthalide compound system, a triphenylmethane compound, a diphenylmethane compound, a thiazine compound, or a lactam compound. The liquid resin composition for an active ray-curable adhesive according to any one of (i) to (vi), which is at least one color former selected from a compound and a diketone compound.
(Viii) A liquid resin composition for an active ray-curable adhesive according to any one of (i) to (vii), which exhibits curability and color development using visible light as an active ray.
(Ix) A liquid resin composition for an active ray-curable adhesive according to any one of (i) to (viii), further containing (E) an ultraviolet absorber.
Regarding.

The liquid resin composition for an active ray-curable adhesive of the present invention is hardly colored before use, is rapidly cured by irradiation with active rays after adhesion, and is colored to a desired color by irradiation with active rays. The bonded portion can be colored. For this reason, when an adherend such as a liquid crystal cell is adhered to an optical film such as a polarizing film, or when used as a sealant for a polarizing film, the bonded portion is colored black to reduce light leakage. Can be done
Further, since the liquid resin composition for an active ray-curable adhesive of the present invention is hardly colored before use, the active rays easily reach the inside of the resin composition and the curing rate is high.
Further, in the embodiment in which visible light, particularly blue LED light, is used as the curing active ray and the ultraviolet absorber is contained in the resin composition, the device for the light source can be set simply and inexpensively, and the adhesive portion can be set. Especially excellent in light storage resistance.

The liquid resin composition for an active ray-curable adhesive of the present invention contains the following components (A), (B) and (C) as essential components.
(A) Active ray-polymerizable organic compound (B) Compound that generates acid by irradiation with active ray (C) Acid-coloring dye precursor

Hereinafter, each component will be described in detail.
[(A) Active ray-polymerizable organic compound]
The active ray-polymerizable organic compound is an organic compound having a group in the molecule that is polymerized by irradiation with active rays, and is classified into (A-1) radically polymerizable organic compound and (A-2) cationically polymerizable organic according to the type of polymerization. It can be distinguished from compounds.
When the active ray-polymerizable organic compound is (A-1) a radically polymerizable organic compound, the liquid resin composition for an active ray-curable adhesive of the present invention simultaneously contains (D) a radical photopolymerization initiator. Things are preferable. However, (A-1) and (A-2) and (A-2) are obtained by using (A-1) a radically polymerizable organic compound and (A-2) a cationically polymerizable organic compound in combination, and (B) a compound that generates an acid by irradiation with active rays. ) Is copolymerizable, the content of the radical photopolymerization initiator (D) may be low or may not be contained.
For example, (A-1) contains a group having an active hydrogen such as a hydroxyl group and a compound having an ethylenically unsaturated bond at the same time, and (A-2) contains a compound having two or more epoxy groups. If (B) can be copolymerized with a compound that generates an acid by irradiation with active rays, the content of (D) radical photopolymerization initiator may be low or may not be contained.

[(A-1) Radical Polymerizable Organic Compound]
The radically polymerizable organic compound is a radically polymerizable compound that polymerizes or undergoes a cross-linking reaction by irradiation with active rays, and is preferably a compound having at least one unsaturated double bond in one molecule. Examples of these compounds include acrylate compounds, methacrylate compounds, allyl urethane compounds, unsaturated polyester compounds, polythiol compounds and the like.
Compounds having one unsaturated double bond in one molecule include linear or branched alkyl (meth) acrylates, alicyclic-containing (meth) acrylates, heterocyclic-containing (meth) acrylates, styrene, vinylcyclohexene, and the like. Examples thereof include isobutylene and butadiene, but (meth) acrylates are preferable.
Examples of the linear or branched alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, isobutyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and isostearyl (meth) acrylate. , T-butyl (meth) acrylate and the like.
Examples of the alicyclic-containing (meth) acrylate include cyclohexyl (meth) acrylate, 4-t-cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and dicyclopentanyl (meth) acrylate.
Examples of the heterocyclic-containing (meth) acrylate include tetrahydrofurfuryl (meth) acrylate, 4- (meth) acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, and 4- (meth) acryloyloxymethyl. -2-cyclohexyl-1,3-dioxolane, adamantyl (meth) acrylate] and the like.

Examples of compounds having one unsaturated double bond in one molecule that can be preferably used include acrylamide, (meth) acryloylmorpholine, 7-amino-3,7-dimethyloctyl (meth) acrylate, and isobutoxymethyl (meth). Meta) acrylamide, isobornyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethyldiethylene glycol (meth) acrylate, t-octyl (meth) acrylamide, diacetone (meth) acrylamide, dimethyl Aminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, lauryl (meth) acrylate, dicyclopentadiene (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, N, N -Dimethyl (meth) acrylamide Tetrachlorophenyl (meth) acrylate, 2-tetrachlorophenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, tetrabromophenyl (meth) acrylate, 2-tetrabromophenoxyethyl (meth) acrylate , 2-Trichlorophenoxyethyl (meth) acrylate, tribromophenyl (meth) acrylate, 2-tribromophenoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, vinyl caprolactam , N-vinylpyrrolidone, phenoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, pentachlorophenyl (meth) acrylate, pentabromophenyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate , Bornyl (meth) acrylate, methyltriethylene diglycol (meth) acrylate and the like can be exemplified.

Among these compounds having one unsaturated double bond in one molecule, isobornyl (meth) acrylate, lauryl (meth) acrylate, and phenoxyethyl (meth) acrylate are particularly preferable. Commercially available products of these compounds include, for example, Aronix M-101, M-102, M-111, M-113, M-117, M-152, TO-1210 (all manufactured by Toagosei Co., Ltd.), KAYARAD. TC-110S, R-564, R-128H (above, Nippon Kayaku Co., Ltd.), Biscort 192, Viscort 220, Viscort 2311HP, Viscort 2000, Viscort 2100, Viscort 2150, Viscort 8F, Viscort 17F (above, Osaka Organic) (Made by Chemical Industry Co., Ltd.) and the like.
Further, in order to adjust the flexibility of the resin composition, it is preferable to contain a compound having a hydroxyl group and one unsaturated double bond as a copolymerization component with a compound having two or more epoxy groups.
Examples of the compound having a hydroxyl group and having one unsaturated double bond include a hydroxyl group-containing (meth) acrylate having 5 to 15 carbon atoms, a hydroxyl group-containing (meth) acrylate having a number average molecular weight of 200 to 2,000, and a hydroxyl group-containing compound (meth). Meta) Acrylamide derivatives and the like are preferable.
Examples of the hydroxyl group-containing (meth) acrylate having 5 to 15 carbon atoms include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. The hydroxyl group-containing (meth) acrylate having a number average molecular weight of 200 to 2,000 includes, for example, polyethylene glycol mono (meth) acrylate, methoxypolyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and methoxypolypropylene glycol mono (meth). Examples thereof include meta) acrylate and mono (meth) acrylate of polyethylene glycol-polypropylene glycol block polymer. Examples of the hydroxyl group-containing (meth) acrylamide derivative include N-hydroxyethyl (meth) acrylamide, N-hydroxypropyl (meth) acrylamide, and N-hydroxybutyl (meth) acrylamide.
The content of the compound having a hydroxyl group and one unsaturated double bond varies depending on the composition of the other active ray-polymerizable organic compound.

The compound having two or more unsaturated double bonds in one molecule is preferably a compound having two or more (meth) acrylic groups in one molecule. Examples thereof include epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, and (meth) acrylic acid ester of alcohols.
The epoxy (meth) acrylate is an acrylate obtained by reacting, for example, an aromatic epoxy resin, an alicyclic epoxy resin, an aliphatic epoxy resin, or the like with (meth) acrylic acid. Among these epoxy (meth) acrylates, a particularly preferable one is a (meth) acrylate of an aromatic epoxy resin, which is a polyhydric phenol having at least one aromatic nucleus or a polyglycidyl ether of an alkylene oxide adduct thereof. It is a (meth) acrylate obtained by reacting with (meth) acrylic acid. For example, (meth) acrylate, epoxy novolac resin and (meth) obtained by reacting glycidyl ether obtained by reacting bisphenol A or an alkylene oxide adduct thereof with epichlorohydrin with (meth) acrylic acid. Examples thereof include (meth) acrylate obtained by reacting acrylic acid.

Preferred urethane (meth) acrylates are (meth) acrylates obtained by reacting one or more types of hydroxyl group-containing polyesters and hydroxyl group-containing polyethers with hydroxyl group-containing (meth) acrylic acid esters and isocyanates, and hydroxyl groups. A (meth) acrylate obtained by reacting a contained (meth) acrylic acid ester with isocyanates.
The hydroxyl group-containing polyester used here is preferably a hydroxyl group-containing polyester obtained by reacting one or more fatty acid polyhydric alcohols with one or more polybasic acids, and is aliphatic. Examples of polyhydric alcohols include 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, neopentyl glycol, polyethylene glycol, polypropylene glycol, trimethylolpropane, and glycerin. Examples thereof include pentaerythritol and dipentaerythritol. Examples of the polybasic acid include adipic acid, terephthalic acid, phthalic anhydride, and trimellitic acid.

Preferred as the hydroxyl group-containing polyether is a hydroxyl group-containing polyether obtained by adding one or more kinds of alkylene oxides to the aliphatic polyhydric alcohol, and the aliphatic polyhydric alcohol is the above-mentioned compound. The same as the above can be exemplified. Examples of the alkylene oxide include ethylene oxide and propylene oxide.
A preferred hydroxyl group-containing (meth) acrylic acid ester is a hydroxyl group-containing (meth) acrylic acid ester obtained by an esterification reaction between an aliphatic polyhydric alcohol and (meth) acrylic acid, and the aliphatic polyhydric alcohol is preferred. , The same as the above-mentioned compound can be exemplified.
Among such hydroxyl group-containing (meth) acrylic acids, the hydroxyl group-containing (meth) acrylic acid ester obtained by the esterification reaction between the aliphatic dihydric alcohol and (meth) acrylic acid is particularly preferable, and for example, 2-hydroxylethyl (meth) ethyl (meth). ) Acrylic can be mentioned.
As the isocyanates, compounds having at least one isocyanate group in the molecule are desirable, and divalent isocyanate compounds such as tolylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate are particularly preferable.

A preferred polyester (meth) acrylate is a polyester (meth) acrylate obtained by reacting a hydroxyl group-containing polyester with (meth) acrylic acid. The hydroxyl group-containing polyester used here is preferably obtained by an esterification reaction between one or more aliphatic polyhydric alcohols and one or more monobasic acids, polybasic acids, and phenols. Examples of the obtained hydroxyl group-containing polyester as the aliphatic polyhydric alcohol include the same compounds as those described above. Examples of the monobasic acid include formic acid, acetic acid, butylcarboxylic acid, benzoic acid and the like. Examples of the polybasic acid include adipic acid, terephthalic acid, phthalic anhydride, and trimellitic acid. Examples of phenols include phenol, p-nonylphenol, bisphenol A and the like.

A preferred polyether (meth) acrylate is a polyether (meth) acrylate obtained by reacting a hydroxyl group-containing polyether with (meth) acrylic acid. The hydroxyl group-containing polyether used here is preferably a hydroxyl group-containing polyether obtained by adding one or more alkylene oxides to an aliphatic polyhydric alcohol, and the aliphatic polyhydric alcohol is a preferred one. , Similar to the above-mentioned compounds can be exemplified. Examples of the alkylene oxide include ethylene oxide and propylene oxide.

Preferable (meth) acrylic acid esters of alcohols are obtained by reacting an aromatic or aliphatic alcohol having at least one hydroxyl group in the molecule and an alkylene oxide adduct thereof with (meth) acrylic acid (meth). ) Acrylate, for example 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, isoamyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate. , Isooctyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobonyl (meth) acrylate, benzyl (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate , 1,6-hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di ( Examples thereof include meta) acrylate, trimethylolpropanthry (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and ε-caprolactone-modified dipentaerythritol hexa (meth) acrylate.

Examples of compounds having two or more unsaturated double bonds in one molecule that can be preferably used include ethylene glycol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, triethylene glycol diacrylate, and tetraethylene glycol. Di (meth) acrylate, tricyclodecanediyl dimethylene di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide (hereinafter referred to as "EO") modified trimethylolpropane tri (meth) acrylate, propylene oxide (hereinafter "" PO ".) Modified trimethylolpropane Tri (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, bi-terminal (meth) acrylic acid adduct of bisphenol A diglycidyl ether, 1 , 4-Butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, polyester di (meth) acrylate, polyethylene glycol di ( Meta) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate ) Acrylate, ditrimethylolpropane tetra (meth) acrylate, EO-modified bisphenol A di (meth) acrylate, PO-modified bisphenol A di (meth) acrylate, EO-modified hydrogenated bisphenol A di (meth) acrylate, PO-modified hydrogenated bisphenol A Examples thereof include di (meth) acrylate, EO-modified bisphenol F di (meth) acrylate, and (meth) acrylate of phenol novolac polyglycidyl ether.
Of these (meth) acrylates, poly (meth) acrylates of polyhydric alcohols are particularly preferable.

Commercially available products of compounds having two or more unsaturated double bonds in one molecule include, for example, SA1002 (all manufactured by Mitsubishi Chemical Co., Ltd.), biscoat 195, biscoat 230, biscoat 260, biscoat 215, biscoat 310. , Viscoat 214HP, Viscoat 295, Viscoat 300, Viscoat 360, Viscoat GPT, Viscoat 400, Viscoat 700, Viscoat 540, Viscort 3000, Viscoat 3700 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Kayarad R-526, HDDA, NPGDA, TPGDA, MANDA, R-551, R-712, R-604, R-684, PET-30, GPO-303, TMPTA, THE-330, DPHA, DPHA-2H, DPHA-2C, DPHA-2I, D-310, D-330, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DN-0075, DN-2475, T-1420, T-2020, T-2040, TPA-320, TPA- 330, RP-1040, RP-2040, R-011, R-300, R-205 (all manufactured by Nippon Kayaku Co., Ltd.), Aronix M-210, M-220, M-233, M-240, M-305, M-309, M-310, M-400, M-6200, M-6400 (all manufactured by Toa Synthetic Co., Ltd.), Light Acrylate BP-4EA, BP-4PA, BP-2EA, BP- 2PA, DCP-A (above, manufactured by Kyoeisha Chemical Co., Ltd.), New Frontier BPE-4, BR-42M, GX-8345 (above, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), ASF-400 (above, New Japan) Tetsugaku Co., Ltd.), Lipoxy SP-1506, SP-1507, SP-1509, VR-77, SP-4010, SP-4060 (all manufactured by Showa Polymer Co., Ltd.), NK ester A-BPE- 4 (above, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) and the like can be mentioned.

In the liquid resin composition for an active ray-curable adhesive of the present invention, in order to increase the physical and chemical strength of the bonded portion during photocuring and after curing, the radically polymerizable organic compound is 1 in 1 molecule. A compound having an unsaturated double bond and a compound having two or more unsaturated double bonds in one molecule can be combined in combination of two or more, or one unsaturated double bond in one molecule. It is preferable to combine at least one kind of the compound having at least one kind and at least one kind of compound having two or more unsaturated double bonds in one molecule. It is also preferable to further combine compounds having three or more unsaturated double bonds in one molecule. Examples of the compound having three or more unsaturated double bonds in one molecule include a tri (meth) acrylate compound, a tetra (meth) acrylate compound, a penta (meth) acrylate compound, and a hexa (meth) acrylate compound. , Specifically, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate. Acrylate is preferred.
When the liquid resin composition for an active ray-curable adhesive of the present invention contains a radically polymerizable organic compound, the curing rate of the bonded portion becomes faster.

[(A-2) Cationic Polymerizable Organic Compound]
The cationically polymerizable organic compound is a cationically polymerizable compound that polymerizes or undergoes a cross-linking reaction by irradiation with active rays in the presence of a cationic photopolymerizable initiator, preferably an epoxy compound, an oxetane compound, an oxolane compound, a cyclic acetal compound, or the like. Examples thereof include a cyclic lactone compound, a thiirane compound, a thietan compound, a spirooltoester compound which is a reaction product of an epoxy compound and a lactone compound, and a vinyl ether compound.

Examples of the epoxy compound include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, and epoxy novolac. Resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexanecarboxylate, 2- (3,3) 4-Epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meth-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate , 3,4-Epoxy-6-methylcyclohexyl-3', 4'-epoxy-6'-methylcyclohexanecarboxylate, ε-caprolactone modified 3,4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexanecarboxylate , Trimethylcaprolactone modified 3,4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexanecarboxylate, β-methyl-δ-valerolactone modified 3,4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexanecarboxylate , Methylenebis (3,4-epoxycyclohexane), di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylenebis (3,4-epoxycyclohexanecarboxylate), dioctyl epoxycyclohexahydrophthalate, epoxycyclohexyl Di-2-ethylhexyl sahydrophthalate, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, Glycerin triglycidyl ethers, polypropylene glycol diglycidyl ethers; polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin. Kind Diglycidyl esters of aliphatic long-chain dibasic acids; Monoglycidyl ethers of aliphatic higher alcohols; Monoglycidyl ethers of polyether alcohols obtained by adding phenol, cresol, butylphenol or alkylene oxide; Esters; epoxidized soybean oil; butyl epoxide stearate; octyl epoxide stearate; epoxidized linseed oil; epoxidized polybutadiene and the like can be exemplified.

Examples of the oxetane compound include trimethylene oxide, 3,3-dimethyloxetane, 3,3-dikuclomethyloxetane, 3-ethyl-3-phenoxymethyloxetane, and bis (3-ethyl-3-methyloxy) butane. It can be exemplified.
Examples of the oxolane compound include tetrahydrofuran, 2,3-dimethyltetrahydrofuran and the like.
Examples of the cyclic acetal compound include trioxane, 1,3-dioxolane, 1,3,6-trioxanecyclooctane and the like.
Examples of the cyclic lactone compound include β-propiolactone and ε-caprolactone.

Examples of the thiirane compound include ethylene sulfide, 1,2-propylene sulfide, and thioepichlorohydrin.
Examples of the thietane compound include 3,3-dimethylthietane.
Examples of the vinyl ether compound include ethylene glycol divinyl ether, triethylene glycol divinyl ether, trimethylolpropane trivinyl ether, and oxygen-containing alicyclic divinyl ether.
Examples of the ethylenically unsaturated compound include vinylcyclohexane, isobutylene, and polybutadiene.
Among these cationically polymerizable organic compounds, 3,4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, ε-caprolactone-modified 3,4-epoxycyclohexyl Methyl-3', 4'-epoxycyclohexanecarboxylate, trimethylcaprolactone modified 3,4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexanecarboxylate, β-methyl-δ-valerolactone modified 3,4-epoxycyclohexyl Methyl-3', 4'-epoxycyclohexanecarboxylate, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, 1,4-butanediol diglycidyl ether , 1,6-Hexanediol diglycidyl ether, trimethylpropan triglycidyl ether, glycerin triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, oxygen-containing alicyclic divinyl ether and the like are preferable.
More preferably, it has two or more alicyclic epoxy groups in one molecule such as 3,4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexanecarboxylate, and bis (3,4-epoxycyclohexylmethyl) adipate. It is a compound.
In addition, oxygen-containing alicyclic divinyl ethers can be copolymerized with epoxy compounds, radically polymerizable organic compounds (meth) acrylate compounds, etc. to provide heat resistance, toughness, adhesion, and flexibility to the bonded portion. Can be granted.
In the liquid resin composition for an active ray-curable adhesive of the present invention, it is also preferable to use two or more of the above-mentioned cationically polymerizable organic compounds in combination.

Commercially available products of cationically polymerizable organic compounds that can be preferably used include UVR-6100, UVR-6105, UVR-6110, UVR-6128, UVR-6200, UVR-6216 (all manufactured by Union Carbide), celoxide 2021, and the like. Selokiside 2021P, Selokiside 2081, Selokiside 2083, Selokiside 2085, Epolide GT-300, Epolide GT-301, Epolide GT-302, Epolide GT-400, Epolide 401, Epolide 403, ONB-DVE, OXT-DVE, ISB-DVE ( As mentioned above, manufactured by Daicel Chemical Industry Co., Ltd., KRM-2100, KRM-2110, KRM-2199, KRM-2400, KRM-2410, KRM-2408, KRM-2490, KRM-2200, KRM-2720, KRM-2750. (Asahi Denka Kogyo Co., Ltd.), Rapi-cureDVE-3, CHVE, PEPC (above, ISP) Epicoat 828, Epicoat 812, Epicoat 1031, Epicoat 872, Epicoat CT508 (Above, Japan Epoxy Resin Co., Ltd.) ), XDO (above, manufactured by Toa Synthetic Co., Ltd.), VECOMER 2010, 2020, 4010, 4020 (above, manufactured by Allied Signal Co., Ltd.) and the like.
The above-mentioned compounds having an epoxy group may have a slightly high viscosity for use as a liquid resin composition for an active ray-curable adhesive. In such a case, the viscosity can be lowered by blending a liquid ethylenically unsaturated compound. In particular, a liquid ethylenically unsaturated compound having a small molecular weight has a large effect of lowering the viscosity. It is also effective to add liquid plasticizers within a range that does not affect other properties such as curability in order to reduce the viscosity.

[(B) Compound that generates acid by irradiation with active rays]
As the compound that generates an acid by irradiation with active rays, a cationic photopolymerization initiator can be used.
As a particularly preferable example of the cationic photopolymerization initiator, an onium salt having a structure represented by the following general formula (1) can be mentioned.

[R ¹ _a R ² _b R ³ _c R ⁴ _d W] ^{+ p} [MX _{p + q} ] ^−q (1)

[In the formula (1), the cation is an onium ion, W is S, Se, Te, P, As, Sb, Bi, O, I, Br, Cl or −N = N, and R ¹ , R ² , R ³ and R ⁴ are the same or different organic groups, respectively, a, b, c and d are integers 0 to 3 respectively, and (a + b + c + d) is equal to the valence of W.

M is the metal or metalloid that constitutes the central atom of the halide complex [MXp + q], X is the halogen atom, q is the net charge of the halide complex ion, and p is the valence of M. ] Can be mentioned as an onium salt having a structure represented by.
M is preferably B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co.
X is preferably F, Cl, Br, I.
Specific examples of the anion [MXp + q] include tetrafluoroborate (BF4-), hexafluorophosphate (PF6-), hexafluoroantimonate (SbF6-), hexafluoroarsenate (AsF6-), and hexachloroantimonate (SbCl6-). ) And so on.
Further, in the structure represented by the general formula (1), an onium salt having an anion represented by the general formula [MXp (OH) −] can be used instead of the anion [MXp + q].
Furthermore, instead of the anion [MXp + q], perchlorate ion (ClO4-), trifluoromethanesulphonate ion (CF3SO3-), fluorosulphonate ion (FSO3-), toluene sulphonate ion, trinitrobenzene sulphonate anion, tri Onium salts with other anions, such as nitrotoluene sulfone anion, can also be used.

The onium salt represented by the general formula (1) releases Lewis acid by irradiation with active rays.
An aromatic onium salt is particularly effective as a cationic photopolymerization initiator as a compound that generates an acid by irradiation with active rays. Among them, the aromatic halonium salts described in JP-A-50-151996, JP-A-50-158680, etc., JP-A-50-151997, JP-A-52-30899, JP-A. VIA group aromatic onium salt described in JP-A-56-55420, JP-A-55-125105, etc., VA group aromatic onium salt described in JP-A-50-158698, JP-A-56-8428. No. 56-149402, JP-57-192429, etc., oxosulfoxonium salt, Aromatic diazonium salt, JP-A-49-17040, etc. The thiovirylium salt described in No. 4,139,655 is preferable. In addition, iron / allen complex, aluminum complex / photodegradable silicon compound-based initiator and the like can also be mentioned.

Particularly preferred cationic photopolymerization initiators are triarylsulfonium salts, diaryliodonium salts, aryldiazonium salts having BF4-, PF6-, ASF6-, SBF6- and the like as counterions, and triphenylsulfonium hexafluorophosphate. p-thiophenoxyphenyldiphenylsulfonium hexafluorophosphate, triphenylsulfonium tetrafluoroborate, 4-morpholino-2,5-dimethoxyphenyldiazonium fluoroborate, diphenyliodonium salt or ditriliodonium salt whose counterion is BF4-, Examples thereof include phenyldiazonium tetrafluoroborate, trildiazonium tetrafluoroborate, trildiazonium hexafluorophosphate, and bis (4-t-butylphenyl) iodonium hexafluorophosphate.

Commercially available cationic photopolymerization initiators that can be suitably used as compounds that generate acid by irradiation with active rays include UVI-6950, UVI-6970, UVI-6974, and UVI-6990 (all manufactured by Union Carbide). , Adecaca Putomer SP-150, SP-151, SP-170, SP-172 (above, manufactured by Asahi Denka Kogyo Co., Ltd.), UVacure 261 (above, manufactured by Ciba Specialty Chemicals Co., Ltd.), CI-2481, CI -2624, CI-2339, CI-2064 (above, manufactured by Nippon Soda Co., Ltd.), CD-1010, CD-1011, CD-1012 (above, manufactured by Sartmer), DTS-102, DTS-103, NAT- 103, NDS-103, TPS-103, MDS-103, MPI-103, BBI-103 (above, manufactured by Midori Kagaku Co., Ltd.), PCI-061T, PCI-062T, PCI-020T, PCI-022T (above, Examples thereof include Nippon Kayaku Co., Ltd.), CPI-110A (all manufactured by Sun Appro Co., Ltd.), and t-BuDPI (manufactured by Tokyo Kasei Kogyo Co., Ltd.).
Of these, UVI-6970, UVI-6974, ADEKA OPTMER SP-170, SP-172, CD-1012, MPI-103, CPI-110A, and t-BuDPI are included in the resin composition. It is particularly preferable because it can exhibit high photocuring sensitivity. The above-mentioned cationic photopolymerization initiator can be used alone or in combination of two or more.

[(C) Acid Coloring Dye Precursor]
A color former (leuco dye) can be used as the acid chromogenic dye precursor.
The color former is an organic compound that is usually colorless but develops various colors by acid, and is widely used as a heat-sensitive recording material, a pressure-sensitive recording material, a heat-discoloring material, and the like.
The color former that can be used as an acid-developing dye precursor in the liquid resin composition for an active ray-curable adhesive of the present invention is not particularly limited, and is fluorene-based, phthalide-based, azaphthalide-based, fluorenespirophthalide-based, and triphenyl. Examples thereof include methane-based, diphenylmethane-based, thiazine-based, lactam-based, and diketone-based.
In particular, fluorene-based, phthalide-based, azaphthalide-based, fluorene spirophthalide-based, triphenylmethane-based compounds, lactam-based, and diketone-based compounds are preferable.

Color formers that develop a blue color include 3,3-bis (4-dimethylaminophenyl) -6-dimethylaminophthalide, N-benzoyl leucomethylene blue, 3- (4-diethylamino-2-ethoxyphenyl) -3. -(1-Ethyl-2-methylindol-3-yl) phthalide, 3- (4-diethylamino-2-methylphenyl) -3- (4-dimethylaminophenyl) -6-dimethylaminophthalide, 3-( 4-Diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide, 3- (4- (N-ethyl-N-phenylamino) -2-ethoxy Phenyl) -3- (1-ethyl-2-methylindole-3-yl) -4-azaphthalide, 3- (4-diethylamino-2-methylphenyl) -3- (1-ethyl-2-methylindole-3) -Il) phthalide, 3- (1-ethyl-2-methylindol-3-yl) -3- (2-n-hexyloxy-4-diethylaminophenyl) -4-azaphthalide, 3- (4-diethylamino-2) −ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4,7-diazaphthalide, 3-diphenylamino-6-diphenylaminofluorane and the like can be mentioned.

Colorformers that develop a green color include 2-anilino-6- (N-ethyl-Nn-hexylamino) fluorane, 2-dibenzylamino-6-diethylaminofluorane, and 3,3-bis (4-bis). Diethylamino-2-ethoxyphenyl) -4-azaphthalide, 2- (N-phenyl-N-methylamino) -6- (N-ethyl-N-p-tolylamino) fluorane, 2-chloro-3-methyl-6- [P- (p-anilinoanilino) anilino] fluorane, 3- (4-diethylaminophenyl) -3- (2,2-bis (1-ethyl-2-methylindol-3-yl) -1-ethenyl) phthalide, Examples thereof include 3,6-bis (dimethylamino) fluorene-9-spiro-3'-(6'-dimethylamino) phthalide.

Color formers that develop a red color include 3,6-bis (diethylamino) fluoran-γ-anilinolactam, 3,6-bis (diethylamino) fluoran-γ- (p-nitro) anilinolactam, and 3,6. -Bis (diethylamino) fluorane-γ- (o-chloro) anilinolactam, 2-bromo-6-diethylaminofluorane, 6-diethylaminofluorane, 3-methyl-6-diethylaminofluorane, 2-methyl-6- Diethylaminofluorane, 2-chloro-6-diethylaminofluorane, 1,2-benzo-6-diethylaminofluorane, 1,2-benzo-6-di-n-butylaminofluorane, 1,3-dimethyl-6 -Diethylaminofluorane, 2-chloro-3-methyl-6-diethylaminofluorane, 2-methyl-6- (N-ethyl-N-p-tolylamino) fluorane, 2-chloro-3-methyl-6- (N) -Ethyl-N-isobutylamino) fluorane, 1,2-benzo-6- (N-ethyl-N-isoamylamino) fluorane, 3,3-bis (1-butyl-2-methylindol-3-yl) phthalide , 3,3-Bis (1-octyl-2-methylindol-3-yl) phthalide, 7- (N-ethyl-N-isoamylamino) -3-methyl-1-phenylspiro [(1,4-dihydro) Chromeno [2,3-c] pyrazole) -4,3'-phthalide], 7- (N-ethyl-Nn-hexylamino) -3-methyl-1-phenylspiro [(1,4-dihydro) Chromeno [2,3-c] pyrazole) -4,3'-phthalide] and the like can be mentioned.

Color formers that develop a yellow color include 3,6-dimethoxyfluorine, 3,6-di-n-butoxyfluorane, 2-chlor-6-cyclohexylaminofluorine, and 2,6-bis [4-di]. -N-Butylaminobenzoyl] pyridine (diketone compound), 2,6-bis [4- [N-methyl-N-cyclohexyl] aminobenzoyl] pyridine (diketone compound), 2,6-diphenyl-4- ( 4-Dimethylaminophenyl) -pyridine, 2,2-bis (4- (2- (4-diethylaminophenyl) quinazolyl) oxyphenyl) propane, N, N-dimethyl-4- [2- (2-octyloxyphenyl) ) -6-Phenyl-4-pyridinyl] -benzeneamine, N, N-dimethyl-4- [2- (2-butoxyphenyl) -6-phenyl-4-pyridinyl] -benzeneamine, 4-chloro-N- (4- (N- (4-methylbenzyl) -N-methylamino) benzylidene) aniline, 1- (2-quinolyl) -2- (3-methoxy-4-dodecyloxyphenyl) ethene, 1- (4- (4-) Examples thereof include n-dodecyloxy-3-methoxyphenyl) -2- (2-quinolyl) ethylene.

Examples of color formers that develop a black color include 2-anilino-3-methyl-6-diethylaminofluorane, 2-anilino-3-methyl-6-di-n-butylaminofluorane, and 2- (3-methylanilino). -3-Methyl-6-diethylaminofluorane, 2- (2,4-dimethylanilino) -3-methyl-6-diethylaminofluorane, 2-anilino-3-methyl-6- (N-methyl-N-) Cyclohexylamino) fluorane, 2-anilino-3-methyl-6- (N-ethyl-N-isoamylamino) fluorane, 2- (o-chloroanilino) -6-diethylaminofluorane, 2-anilino-3-chloro-6 -Diethylaminofluorane, 2- (2-carbomethoxy-phenylamino) -6-diethylaminofluorane, 2-anilino-3-methyl-6-dipentylaminofluorane, 2-anilino-3-methyl-6- (N) -Ethyl-N-tetrahydrofurfuryl) aminofluorane, 2-anilino-3-methyl-6-pyrrolidinofluorane and the like can be mentioned.

In addition, as a color former that develops an orange color, 3-chloro-6-cyclohexylaminofluorane, 3-chloro-6-anilinofluorane, etc., as a color former that develops a vermilion color, 2-chloro-6-diethylamino. Colors that develop vermilion such as fluorane, 2-bromo-3-methyl-6- (di-n-butyl) aminofluorane, 2-phenoxy-6- (N-ethyl-N-isoamyl) aminofluorane, etc. Examples of the former include Rhodamine B anilinolactam and the like.
In the liquid resin composition for an active ray-curable adhesive of the present invention, one kind of color former or a color former of the same system color may be mixed and used in one kind of resin composition, or a mixed color may be used. In order to obtain the above, color formers showing different colors may be mixed and used in one kind of resin composition.

[(D) Radical Photopolymerization Initiator]
As described above, when the liquid resin composition for an active ray-curable adhesive of the present invention contains (A-1) a radically polymerizable organic compound, it also contains (D) a radical photopolymerization initiator. Is preferable. However, (A-1) and (A-2) and (A-2) are obtained by using (A-1) a radically polymerizable organic compound and (A-2) a cationically polymerizable organic compound in combination and (B) a compound that generates an acid by irradiation with active rays. ) Is copolymerizable, this is not the case.

The radical photopolymerization initiator is not particularly limited as long as it produces a radically active species by irradiation with active rays in order to increase the molecular weight of the (A-1) radically polymerizable organic compound by radical polymerization.
Preferably, an acetophenone-based compound, a benzophenone-based compound, a benzoin-based compound, a benzyl-based compound, a thioxanthone-based compound, an acylphosphine-based compound, or the like is used.
Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxymethyl-1-phenylpropan-1-one, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, and 2-hydroxy-2-methylpropio. Phenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, p-dimethylaminoacetophenone, p-tert. -Butyldichloroacetophenone, p-tert. -Butyltrichloroacetophenone, 2,2-diethoxyacetophenone, p-azidobenzalacetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, Examples thereof include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1.

Examples of benzophenone compounds include benzophenone, methyl o-benzoyl benzoate, Michler ketone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-dichlorobenzophenone, 4 -Benzoyl-4'-methyldiphenylsulfide, 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone (BTTB) and the like can be mentioned.
Examples of benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, α-methoxybenzoin methyl ether and the like.

Examples of the benzyl compound include benzyl, anisyl, benzylmethyl ketal, benzyl-β-methoxyethyl acetal and the like.
Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-diethylthioxanthone and the like.
Examples of the acylphosphine compound include acylphosphine compounds such as monoacylphosphine oxide, bisacylphosphine oxide, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

In addition, xanthones, fluorenones, benzaldehydes, fluorenes, anthraquinones, naphthalsendiones, triphenylamines, carbazoles, 2,4,6-trimethylbenzoyldiphenylphosphenoxide, bis (cyclopentadienyl) -Bis [2,6-difluoro-3- (pill-1-yl)] Titanium, and a combination of BTTB with xanthones, thioxanthenes, coumarins, ketocoumarins and other pigment sensitizers can be mentioned. ..
In particular, naphthalsendiones such as 5,11-bis (silyloxy) naphthalcene-6,12-dione and the combination of these with anthraquinone-based compounds and anthracene-based compound sensitizers are highly sensitive to blue LED light. Have.
Of these, benzyl dimethyl ketal, 1-hydroxycyclohexylphenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, α-methoxybenzoin methyl ether, 2-benzyl-2-dimethylamino-1- (4-morpholino) Phenyl) -butane-1-one, 5,11-bis (silyloxy) naphthacene-6,12-dione and the like are particularly preferable.
Commercially available names of radical photopolymerization initiators include IRGACURE184, 369, 651, 500, 819, 907, CGI1700, CGI1750, CGI1850, CG24-61, DAROCUR1116, 1173 (all manufactured by Ciba Specialty Chemicals); LUCIRIN TPO ( BASF); Yubekrill P36 (UCB) and the like. These radical photopolymerization initiators can be used alone or in combination of two or more.

[Other additives]
The liquid resin composition for an active ray-curable adhesive of the present invention may contain various additives as other components, if necessary, as long as the object and effect of the present invention are not impaired.
Such additives include polymers or oligomers, (heat) polymerization inhibitors, chain transfer agents, antioxidants, photosensitizers, leveling agents, wettability improvers, surfactants, plasticizers, UV absorbers. , Silane coupling agents, inorganic fillers, pigments, dyes and the like.
Among these, the ultraviolet absorber is very useful especially in the embodiment of curing the liquid resin composition for an active ray-curable adhesive of the present invention using visible light, and will be described separately later as a component (E).
The polymer or oligomer can be added to adjust the viscosity of the liquid resin composition for active ray-curable adhesive of the present invention.

Examples of polymers or oligomers include epoxy resins, polyamides, polyamideimides, polyurethanes, polybutadienes, polychloroprenes, polyethers, polyesters, styrene-butadiene block copolymers, petroleum resins, xylene resins, ketone resins, cellulose resins, fluorine-based Examples thereof include polymers such as oligomers, silicone-based oligomers, and polysulfide-based oligomers, or oligomers.
Examples of the (heat) polymerization inhibitor include phenol compounds [hydroquinone, hydroquinone monomethyl ether, 2,6-di-t-butyl-p-cresol, 2,2-methylene-bis- (4-methyl-6-t-). Butylphenol), 1,1,3-tris- (2-methyl-4-hydroxy-5-t-butylphenyl) butane, etc.], sulfur compounds [dilaurylthiodipropionate, etc.], phosphorus compounds [triphenylphosphite, etc.] Etc.], amine compounds [phenothiazine, etc.] and the like.

Examples of the chain transfer agent include hydrocarbons [compounds of C6 to 24, for example, aromatic hydrocarbons (toluene, xylene, etc.) and unsaturated aliphatic hydrocarbons (1-butene, 1-nonene, etc.)]; halogenated hydrocarbons. (C1-24 compounds such as dichloromethane, carbon tetrachloride); alcohols (C1-24 compounds such as methanol, 1-butanol); thiols (C1-24 compounds such as ethylthiol, 1-octylthiol); ketones (C3-24 compounds, eg acetone, methyl ethyl ketone); aldehydes (C2-18 compounds, eg 2-methyl-2-propylaldehyde, 1-pentylaldehyde); phenols (C6-36 compounds, eg phenol, m- , P- and o-cresol); quinone (compounds of C6-24, eg hydroquinone); amines (compounds of C3-24, eg diethylmethylamine, diphenylamine); and disulfides (compounds of C2-24, eg diethyldisulfide, Di-1-octyl disulfide) and the like.

Examples of the antioxidant include phenol compounds [monocyclic phenol (2,6-di-t-butyl-p-cresol, etc.), bisphenol [2,2'-methylenebis (4-methyl-6-t-butylphenol), etc.) and the like. ], Polycyclic phenol [1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, etc.], etc.], Sulfur compounds (dilauryl 3,3) '-Thiodipropionate, etc.), phosphorus compounds (triphenylphosphite, etc.), amine compounds (octylated diphenylamine, etc.) and the like can be mentioned. Examples of commercially available products of these antioxidants include IRGANOX 1010, 1035, 1076, 1222 (manufactured by Ciba Specialty Chemicals Co., Ltd.), ANTIGENE P, 3C, Sumilizer GA-80, GP (manufactured by Sumitomo Chemical Co., Ltd.) and the like.

Examples of the photosensitizer (polymerization accelerator) include amine compounds such as triethanolamine, methyldiethanolamine, triethylamine, and diethylamine; derivatives of thioxanthone and thioxanthone; anthraquinone, 2- (2-hydroxyethylthio) -9,10. -Anthraquinone derivatives such as anthraquinone, 2- (n-butyloxycarbonylmethylthio) anthraquinone, 2- (3-methylbutylthio) anthraquinone, 2- [2- (diethylaminocarbonylethyl) thio] anthraquinone; anthracene, anthracene derivatives; Perylene, derivatives of perylene; benzophenone; benzoin isopropyl ether; pigments such as coumarins and ketocoumarins; and the like.

Examples of the surfactant include a molecular weight of 264 or more and 5,000 or less, for example, a PEG-type nonionic surfactant [ethylene oxide of nonylphenol (hereinafter abbreviated as EO) 1 to 40 mol additive, EO 1 to 40 mol additive of stearate. Etc.], Polyhydric alcohol type nonionic surfactant (sorbitan palmitate monoester, sorbitan stearate monoester, sorbitan stearate triester, etc.), Fluorine-containing surfactant (perfluoroalkyl EO 1 to 50 mol adduct, par Fluoroalkyl carboxylates, perfluoroalkyl betaines, etc.), modified silicone oils [polyether-modified silicone oils, (meth) acrylate-modified silicone oils, etc.] and the like.

Examples of the inorganic filler include metal powder (aluminum powder, copper powder, etc.), metal oxide (alumina, silica, talc, mica, clay, etc.), metal hydroxide (aluminum hydroxide, etc.), and metal salt (calcium carbonate). , Magnesium hydroxide, magnesium carbonate, zinc oxide, calcium silicate, etc.), Fiber [Inorganic fiber (carbon fiber, glass fiber, asbestos, etc.), Organic fiber (cotton, nylon, acrylic, rayon fiber, etc.)], Microballoon (Glass, silas, phenol resin, etc.), carbons (carbon black, stone ink, coal powder, etc.), metal sulfides (molybdenum disulfide, etc.) and the like can be mentioned.
As the pigments and dyes, various known organic / inorganic pigments and dyes are used. However, in the liquid resin composition for an active ray-curable adhesive of the present invention, it is used for the purpose of toning, and the curing speed is increased by coloring. It is not preferable to contain a large amount so that the amount is greatly reduced.

[(E) UV absorber]
As the ultraviolet absorber, benzotriazole-based, benzophenone-based, triazine derivatives, salicylic acid derivatives, hindered amines and the like are preferable.
Examples of the benzotriazole system include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole, and 2- (2'-hydroxy-). 5'-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'- tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'- Hydroxy-3', 5'-ditert-amylphenyl) benzotriazole, 2- (2'-hydroxy-4'-octylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methacryloxyethylphenyl) -2H-benzotriazol, 2-{(2'-hydroxy-3', 3'', 4'', 5'', 6''-tetrahydrophthalimidemethyl) -5'-methylphenyl} benzotriazole, etc. Can be mentioned.

Examples of the benzophenone system include 2-hydroxybenzophenone, 5-chloro-2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, and 2-hydroxy-. 4-dodecyloxybenzophenone, 2-hydroxy-4-octadesiloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4- Examples thereof include methoxy-5-sulfobenzophenone.

Examples of the triazine derivative include 2- [4-{(2-hydroxy-3-dodecyloxy-propyl) oxy} -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3. 5-Triazine, 2- [4-{(2-Hydroxy-3-tridecyloxy-propyl) oxy} -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5- Triazine, 2- {4- (octyl-2-methylethanoate) oxy-2-hydroxyphenyl-4,6- {bis (2,4-dimethylphenyl)}-1,3,5-triazine [Ciba Specialty] Made by Tea Chemicals, trade name Chinubin 479], Tris [2,4,6-[2- {4- (octyl-2-methylethanoate) oxy-2-hydroxyphenyl}]]] -1,3,5-triazine [Ciba Specialty Chemicals, trade name "Chinubin 777" and the like can be mentioned.

Examples of the salicylic acid derivative include phenylsalicylate, p-tert-butylphenylsalicylate, p-octylphenylsalicylate, p- (1,1,3,3-tetramethylbutyl) phenylsalicylate and the like.
Examples of hindered amines include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, and bis (1). , 2,2,6,6-pentamethyl-4-piperidyl) [{3,5-bis (1,1-dimethylethyl) -4-hydrideiphenyl} methyl] butylmalonate and the like.

Of these, 2- [4-{(2-hydroxy-3-dodecyloxy-propyl) oxy} -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5- Triazine, 2- {4- (octyl-2-methylethanoate) oxy-2-hydroxyphenyl-4,6- {bis (2,4-dimethylphenyl)}-1,3,5-triazine, 2-( 2'-Hydroxy-5'-tert-butylphenyl) benzotriazole is particularly preferred.
In addition to the above, commercially available products of these UV absorbers include, for example, TINUVIN P, 234, 320, 326, 327, 328, 329, 213 (all manufactured by Ciba Specialty Chemicals), Seesorb 102, 103, 501, 202, etc. Examples thereof include, but are not limited to, 712 and 704 (all manufactured by Ciba Inc.).
These UV absorbers can be used alone or in combination of two or more.
In the liquid resin composition for an active ray-curable adhesive of the present invention, in the case of curing using ultraviolet rays as active rays, the ultraviolet absorber affects the curing rate and the cured film thickness, so that it is not often used. Not preferable.
On the other hand, in the mode of curing using visible light, the curing is hardly affected and the durability of the adhesive portion after curing and coloring is improved. Therefore, the liquid resin for the active ray-curable adhesive of the present invention. It is preferable that the composition contains an ultraviolet absorber.

[Liquid resin composition for active ray-curable adhesive]
The liquid resin composition for an active ray-curable adhesive of the present invention requires (A) an active ray-polymerizable organic compound, (B) a compound that generates an acid by irradiation with an active ray, and (C) an acid-coloring dye precursor. Contains as an ingredient.

The contents (% by weight) of the components (A) to (C) in the resin composition are shown below.
The content of the active ray-polymerizable organic compound (A) is 15 to 99%, preferably 20 to 98%, and more preferably 30 to 97% in the resin composition.
In order to preferably adjust the viscosity, curing rate, strength and durability of the bonded portion of the liquid resin composition for an active ray-curable adhesive of the present invention, a plurality of types of compounds are used as the active ray-polymerizable organic compound. Is also preferable. For example, (1) 30 to 80% of a compound having one ethylenically unsaturated group and 20 to 60% of a compound having two or more ethylenically unsaturated groups are used, and (2) an epoxy group in the molecule. 10 to 60% of the compounds having two or more of the compounds, and 50 to 90% of the ethylenically unsaturated compounds having a hydroxyl group and an ethylenically unsaturated bond in the molecule at the same time can be exemplified. Further, it is also preferable to use a plurality of types of compounds having different structures for each of the compound having an ethylenically unsaturated group and the compound having two or more epoxy groups in the molecule.

The content of (B) the compound that generates an acid by irradiation with active rays varies depending on the type of (A) active ray-polymerizable organic compound and (D) whether or not it further contains a radical photopolymerization initiator. Usually, it is 0.1 to 20%, preferably 0.5 to 15%, and more preferably 1 to 10% in the resin composition. When the (A-1) radically polymerizable organic compound is contained in an active ray-polymerizable organic compound in an amount of 50% or more of the active ray-polymerizable organic compound and further contains a radical photopolymerization initiator, 0.1 to 1 It is 15%, preferably 0.5 to 10%, more preferably 1 to 8%.
If the content of the compound that generates acid by irradiation with active rays is less than the lower limit of the above range, the color development concentration of the acid chromogenic dye precursor may not be sufficient, and if it exceeds the upper limit, the curable thickness of the resin composition or It may adversely affect the strength of the bonded part.

The content of the acid chromogenic dye precursor (C) is 0.3 to 15%, preferably 0.5 to 12%, and more preferably 1 to 10% in the resin composition. If the content of the acid-coloring dye precursor is less than the lower limit of the above range, the color-developing concentration may not be sufficient, and if it exceeds the upper limit, the curable thickness of the resin composition and the strength of the adhesive portion may be adversely affected. be. The optimum content of the acid chromogenic dye precursor differs depending on the color tone (absorption wavelength) of the acid chromogenic dye precursor and the wavelength of the active ray used for curing.
Further, the acid chromogenic dye precursor is preferably one having compatibility with the (A) active ray-polymerizable organic compound, but it can also be mixed using a solvent or finely pulverized and used.
Next, each content (% by weight) of the components other than the components (A) to (C) in the resin composition is shown below.

The content of the (D) radical photopolymerization initiator depends on the content of the (A-1) radically polymerizable organic compound in the (A) active ray-polymerizable organic compound, and is usually found in the radically polymerizable organic compound. The content is 0.1 to 10%, preferably 0.3 to 8%. However, even when the radically polymerizable organic compound is not contained, it is preferable to contain a small amount of the radical photopolymerization initiator from the viewpoint of improving the curing rate and the like.

(E) The content of the ultraviolet absorber varies depending on the type (wavelength) of the active ray used for curing. When ultraviolet rays are used as the active rays, it is preferable that the ultraviolet absorber is not contained or the amount is small. When an active ray other than ultraviolet rays, for example, visible light is used, the content thereof is 0.1 to 10%, preferably 0.2 to 5%, and more preferably 0.3% to 3% in the resin composition. .. If the content is less than the lower limit of the above range, the effect is not sufficient, and if it exceeds the upper limit, the heat resistance of the resin composition after curing may decrease.
The adhesive portion of the resin composition containing an appropriate amount of an ultraviolet absorber improves not only the durability of the adhesive portion but also the durability of the colored dye, so that the characteristics of the adhesive portion can be maintained for a long period of time. ..

(A) Polymers or oligomers other than the active ray-polymerizable organic compound are added as necessary in order to adjust the viscosity and the characteristics of the bonded portion of the liquid resin composition for the active ray-curable adhesive of the present invention. The content thereof is 10% or less, preferably 5% or less in the resin composition.
The contents of polymerization inhibitors, chain transfer agents, antioxidants, leveling agents, wettability improvers, surfactants, plasticizers, silane coupling agents, pigments, and dyes are the liquid resin compositions for active ray-curable adhesives. Although it depends on the composition of the product and the purpose of use, it is usually 0.1 to 3%, preferably 0.1 to 2%, respectively, in the resin composition. In addition, the case where each is not contained at all is also included.
The photosensitizer is contained as necessary depending on the type of the polymerization initiator and the type (wavelength) of the active ray used for curing. The content is usually 0.1 to 5%, preferably 0.1 to 3% in the resin composition.

The inorganic filler is used to make the bonded portion opaque or to modify the physical properties, and the content thereof is 20% or less, preferably 15% or less in the resin composition. However, since it affects the color tone of the acid-coloring dye precursor, it is preferable to contain a small amount in order to obtain an adhesive portion having a bright color tone. Moreover, it does not have to be contained at all.
The liquid resin composition for an active ray-curable adhesive of the present invention can be produced by uniformly mixing each of the above-mentioned essential components and optionally contained components using a mixing and stirring device or the like.
In order to assist the mixing and dissolution of each component, an arbitrary amount of an aliphatic solvent, an aromatic solvent, an alcohol solvent, an aqueous solvent or the like may be used as long as the effect of the present invention is not hindered.

Hereinafter, a method for adhering the liquid resin composition for an active ray-curable adhesive and a method for curing and coloring the liquid resin composition of the present invention will be described.
As an bonding method, the base materials are bonded to each other via the liquid resin composition for an active ray-curable adhesive of the present invention. Examples of the base material include a plastic film or a plastic sheet, a glass plate, a copper plate, an aluminum plate, an iron plate and the like. The base materials to be bonded may be the same material or different materials. The coating method on the base material is appropriately selected depending on the viscosity of the liquid resin composition for the active ray-curable adhesive of the present invention and the thickness of the target base material. Examples of the coating method include a reverse coater, a gravure coater (direct, reverse and offset), a bar reverse coater, a roll coater, a die coater, a bar coater, a rod coater and the like. In addition, a method such as a dipping method can be appropriately used for coating.
When used as a sealing agent, a method of sealing with a dispenser can be mentioned.

The active ray used for curing is not particularly limited, and can be appropriately selected from far infrared rays, infrared rays, visible rays, near ultraviolet rays, ultraviolet rays and the like depending on the compound that generates an acid by irradiation with the active ray and the active ray polymerizable organic compound. In particular, near-ultraviolet rays, ultraviolet rays, blue LED light, blue laser light, argon laser light having wavelengths of 488 nm and 514.5 nm, and YAG laser light having a second harmonic of 532 nm are preferable.
When visible light is used as the active ray, it is possible to easily include an ultraviolet absorber in the resin composition as described above, so that there is an advantage that the durability of the bonded portion can be improved. In particular, blue LED light is preferable in that it has a good balance in terms of high active energy and content of an ultraviolet absorber, and that a light source is easily available and can be obtained at low cost.
In the liquid resin composition for an active ray-curable adhesive of the present invention, the acid-coloring dye precursor can also be colored by irradiation with the active ray used for curing the resin composition, and a colored adhesive portion can be obtained. can. Even when the film thickness of the resin composition is thick, the curing of the resin composition is completed before the color development of the acid-coloring dye precursor, and the curing rate and the cured film thickness of the resin composition are affected by the shielding of the active rays by the color development. The decline is unlikely to occur. If necessary, after the curing of the resin composition is completed, the color development of the acid chromogenic dye precursor can be completed by further irradiating with active rays.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. Examples 1-6 and 11-15 are examples according to the embodiment of the present invention, and the others are reference examples.

Example 1
Isobornyl acrylate [radical polymerizable organic compound, trade name light acrylate IB-XA, manufactured by Kyoeisha Chemical Co., Ltd., average number of functional groups 1] 70 parts by weight, tripropylene glycol diacrylate [radical polymerizable organic compound, trade name APG -200, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., average number of functional groups 2] 30 parts by weight, 1-hydroxycyclohexylphenylketone [radical photopolymerization initiator] 2 parts by weight, triarylsulfonium hexafluorophosphate [by activation ray irradiation Compounds that generate acids] 3 parts by weight, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindole-3-yl) -4-azaphthalide [acid-coloring dye precursor] ] 3 parts by weight were sufficiently mixed and stirred using a stirrer to obtain a uniform liquid resin composition. This resin composition was not colored.
This resin composition was uniformly applied on a glass plate of 200 mm × 200 mm to a thickness of about 100 μm using an applicator bar, and another glass plate of 200 mm × 200 mm was laminated thereto. When this was irradiated with ultraviolet rays for 1 minute using a metal halide lamp and the resin composition was cured, an adhesive portion colored in blue was confirmed.

Example 2
In Example 1, as the acid chromogenic dye precursor, 3 parts by weight of 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindole-3-yl) -4-azaphthalide Instead, a resin composition was obtained in the same manner as in Example 1 except that 3 parts by weight of 3,3-bis (1-n-butyl-2-methylind-lu-3-yl) phthalide was used. ..
To this, in the same manner as in Example 1, it was applied on a glass plate, another glass plate was attached onto this, and then it was cured by irradiating it with ultraviolet rays for 1 minute, and a red-colored adhesive portion was confirmed. bottom.

Example 3
In Example 1, as an acid chromogenic dye precursor, 3 parts by weight of 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindole-3-yl) -4-azaphthalide Alternatively, 3- [4- (N-ethyl--N- phenylamino) -2-ethoxyphenyl] -3- (1-ethyl-2-methylindole-3-yl) - 4-a Zafutarido 1.5 weight A resin composition was obtained in the same manner as in Example 1 except that parts and 1.5 parts by weight of 2,6-bis [4-di-n-butylaminobenzoyl] pyridine were used.
To this, in the same manner as in Example 1, it was applied on a glass plate, another glass plate was attached onto this, and then it was cured by irradiating it with ultraviolet rays for 1 minute, and a green-colored adhesive portion was confirmed. bottom.

Example 4
Dicyclopentanyl acrylate [radical polymerizable organic compound, trade name FA-513AS, manufactured by Hitachi Chemical Co., Ltd., average number of functional groups 1] 65 parts by weight, dicyclopentane dimethylol diacrylate [radical polymerizable organic compound, trade name Light acrylate DCP-A, manufactured by Kyoeisha Chemical Co., Ltd., average number of functional groups 2] 10 parts by weight, urethane acrylate oligomer [radical polymerizable organic compound, trade name Photomer 6010, manufactured by Cognis Co., Ltd., average number of functional groups 2] 25 parts by weight , 1,3,5-trimethylbenzoyldiphenylphosphine oxide [radical photopolymerization initiator, trade name Lucillin TPO, manufactured by BASF Co., Ltd.] 2 parts by weight, 4-isopropylphenyl-4'-methylphenyliodonium tetrakispentafluorophenyl Borate [Compound that generates acid by irradiation with active rays, trade name: RHODORSIL PHOTOINITIATOR 2074, manufactured by Rhodia Japan Co., Ltd.] 3 parts by weight, coumarin 6 [photosensitizer, also known as 3- [2-benzothiazolyl] -7- [ Diethylamino] coumarin] 1 part by weight, 2-hydroxy-4-methoxybenzophenone [ultraviolet absorber] 1 part by weight, 2-anilino-3-methyl-6-di-n-butylaminofluorane [acid-coloring dye precursor] ] 3 parts by weight were sufficiently mixed and stirred using a stirrer to obtain a uniform liquid resin composition.
This resin composition was uniformly applied on a glass plate of 200 mm × 200 mm to a thickness of about 100 μm using an applicator bar, and another glass plate of 200 mm × 200 mm was laminated thereto. When this was irradiated with blue LED light (peak wavelength of about 460 nm) for 1 minute and the resin composition was cured, a black-colored adhesive portion was confirmed.

Example 5
In Example 4, as the acid chromogenic dye precursor, 3,3-bis (4-diethylamino-2-ethoxy) instead of 3 parts by weight of 2-anilino-3-methyl-6-di-n-butylaminofluorane. Same as Example 4 except that 3 parts by weight of phenyl) -4-azaphthalide was used and 1 part by weight of 2- (n-butyloxycarbonylmethylthio) anthraquinone was used instead of 1 part by weight of coumarin 6 as a photosensitizer. A resin composition was obtained.
To this, in the same manner as in Example 4, the glass plate was coated, another glass plate was laminated on the glass plate, and then blue LED light was irradiated for 1 minute to cure the bonded portion, which was colored green. It was confirmed.

Example 6
In Example 4, as the acid chromogenic dye precursor, 3 parts by weight of 3-chloro-6-cyclohexylaminofluorane instead of 3 parts by weight of 2-anilino-3-methyl-6-di-n-butylaminofluorane. As a compound that generates an acid by irradiation with active rays, 6 parts by weight of bis (4-t-butylphenyl) iodonium hexafluorophosphate instead of 3 parts by weight of 4-isopropylphenyl-4'-methylphenyliodonium tetrakispentafluorophenylborate. A resin composition was obtained by carrying out the same operation as in Example 4 except that the portion was used.
To this, in the same manner as in Example 4, the glass plate was coated, another glass plate was laminated on the glass plate, and then the adhesive portion was colored orange when it was cured by irradiating it with blue LED light for 1 minute. It was confirmed.

Example 7
3', 4'-Epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate [cationically polymerizable organic compound] 70 parts by weight, 2-hydroxyethyl methacrylate [copolymer for reducing viscosity] 30 parts by weight, bis (4-t-Butylphenyl) Iodonium hexafluorophosphate [Compound that generates acid by irradiation with active rays] 8 parts by weight, 1,2-benzo-6-di-n-butylaminofluorane [Acid chromogenic dye precursor ] 3 parts by weight were sufficiently mixed and stirred using a stirrer to obtain a uniform liquid resin composition. This resin composition was not colored.
This resin composition was uniformly applied on a glass plate of 200 mm × 200 mm to a thickness of about 100 μm using an applicator bar, and another glass plate of 200 mm × 200 mm was laminated thereto. When this was irradiated with ultraviolet rays for 1 minute using a metal halide lamp and the resin composition was cured, an adhesive portion colored in red was confirmed.

Example 8
3', 4'-Epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate [cationically polymerizable organic compound] 70 parts by weight, 2-hydroxyethyl methacrylate [copolymer for reducing viscosity] 30 parts by weight, bis (4-t-Butylphenyl) Iodonium hexafluorophosphate [Compound that generates acid by activation ray irradiation] 8 parts by weight, Kumarin 6 [Photosensitizer] 1 part by weight, 2-Hydroxy-4-methoxybenzophenone [Ultraviolet absorption Agent] 1 part by weight and 3 parts by weight of 3,6-di-n-butoxyfluorane [acid-coloring dye precursor] were sufficiently mixed and stirred using a stirrer to obtain a uniform liquid resin composition. This resin composition was not colored.
This resin composition was uniformly applied on a glass plate of 200 mm × 200 mm to a thickness of about 100 μm using an applicator bar, and another glass plate of 200 mm × 200 mm was laminated thereto. When this was irradiated with blue LED light (peak wavelength of about 460 nm) for 1 minute and the resin composition was cured, a yellow-colored adhesive portion was confirmed.

Example 9
In Example 8, instead of 3 parts by weight of 3,6-di-n-butoxyfluorane as the acid chromogenic dye precursor, 2- (2,4-dimethylanilino) -3-methyl-6-diethylaminoflu A resin composition was obtained in the same manner as in Example 8 except that 3 parts by weight of Oran was used. To this, in the same manner as in Example 8, the glass plate was coated, another glass plate was laminated on the glass plate, and then blue LED light was irradiated for 1 minute to cure the bonded portion. It was confirmed.

Example 10
In Example 8, 3 parts by weight of 2-N, N-dibenzylamino-6-diethylaminofluorane was used as the acid chromogenic dye precursor instead of 3 parts by weight of 3,6-di-n-butoxyfluorane. A resin composition was obtained in the same manner as in Example 8 except that the resin composition was obtained.
To this, in the same manner as in Example 8, the glass plate was coated, another glass plate was laminated on the glass plate, and then blue LED light was irradiated for 1 minute to cure the bonded portion, which was colored green. It was confirmed.

<Evaluation 1>
The curability and durability of the bonded portions of the laminated glass plates prepared in Examples 1 to 10 were confirmed as follows. The results are shown in Table 1 below.
Curability:
The curability was confirmed by sandwiching the laminated glass plates with hands and moving them left and right. The case where it does not move at all is indicated by ○, and the case where it shifts is indicated by ×.
durability:
Using a xenon fade meter (Suntest XLS +, manufactured by Toyo Seiki Co., Ltd.) using a xenon arc lamp, continuous irradiation was performed at 310 W from one of the glass plate surfaces for 72 hours, and the presence or absence of fading was confirmed. ..
The case where no fading is seen is indicated by ⊚, the case where slight fading is observed is indicated by ○, the case where there is moderate fading is indicated by Δ, and the case where fading is clearly observed is indicated by ×.

As shown in Table 1, the liquid resin composition for an active ray-curable adhesive of the present invention had sufficient curability. In addition, the light-storing property was good, and in particular, the adhesive portion containing an ultraviolet absorber and cured by irradiation with blue LED light had a very excellent light-storing property.
Further, the adhesive portion has a vivid color and sufficient strength, and is very suitable as a liquid resin composition for an active ray-curable adhesive that can be colored in full color.

Example 11
Isobornyl acrylate [radical polymerizable organic compound, trade name light acrylate IB-XA, manufactured by Kyoeisha Chemical Co., Ltd., average number of functional groups 1] 70 parts by weight, tripropylene glycol diacrylate [radical polymerizable organic compound, trade name APG -200, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., average number of functional groups 2] 30 parts by weight, 1-hydroxycyclohexylphenylketone [radical photopolymerization initiator] 2 parts by weight, triarylsulfonium hexafluorophosphate [by activation ray irradiation Compounds that generate acids] 3 parts by weight, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindole-3-yl) -4-azaphthalide [acid-coloring dye precursor] ] 3 parts by weight were sufficiently mixed and stirred using a stirrer to obtain a uniform liquid resin composition. This resin composition was not colored.
This resin composition was drawn on a 200 mm × 200 mm glass plate using a dispenser to form a 30 mm × 30 mm square with a thickness of about 1000 μm. When this was irradiated with ultraviolet rays for 1 minute using a metal halide lamp and the resin composition was cured, an adhesive portion colored in blue was confirmed.

Example 12
In Example 11, as the acid chromogenic dye precursor, 3 parts by weight of 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindole-3-yl) -4-azaphthalide. Alternatively, 3- [4- (N-ethyl--N- phenylamino) -2-ethoxyphenyl] -3- (1-ethyl-2-methylindole-3-yl) - 4-a Zafutarido 1.5 weight A resin composition was obtained in the same manner as in Example 11 except that 1.5 parts by weight of 2,6-bis [4-di-n-butylaminobenzoyl] pyridine was used.
When a 30 mm × 30 mm square was drawn on the glass plate in the same manner as in Example 11 and then irradiated with ultraviolet rays for 1 minute to be cured, a green-colored adhesive portion was confirmed.

Example 13
Dicyclopentanyl acrylate [radical polymerizable organic compound, trade name FA-513AS, manufactured by Hitachi Chemical Co., Ltd., average number of functional groups 1] 65 parts by weight, dicyclopentanedimethylol diacrylate [radical polymerizable organic compound, trade name Light acrylate DCP-A, manufactured by Kyoeisha Chemical Co., Ltd., average number of functional groups 2] 10 parts by weight, urethane acrylate oligomer [radical polymerizable organic compound, trade name Photomer6010, manufactured by Cognis Co., Ltd., average number of functional groups 2] 25 parts by weight , 1,3,5-trimethylbenzoyldiphenylphosphine oxide [radical photopolymerization initiator, trade name Lucillin TPO, manufactured by BASF Co., Ltd.] 2 parts by weight, 4-isopropylphenyl-4'-methylphenyliodonium tetrakispentafluorophenyl Borate [Compound that generates acid by irradiation with active rays, trade name: RHODORSIL PHOTOINITIATOR 2074, manufactured by Rhodia Japan Co., Ltd.] 3 parts by weight, coumarin 6 [photosensitizer, also known as 3- [2-benzothiazolyl] -7- [ Diethylamino] coumarin] 1 part by weight, 2-hydroxy-4-methoxybenzophenone [ultraviolet absorber] 1 part by weight, 2-anilino-3-methyl-6-di-n-butylaminofluorane [acid-coloring dye precursor] ] 3 parts by weight were sufficiently mixed and stirred using a stirrer to obtain a uniform liquid resin composition.
This resin composition was drawn on a 200 mm × 200 mm glass plate using a dispenser to form a 30 mm × 30 mm square with a thickness of about 1000 μm. When this was irradiated with blue LED light (peak wavelength of about 460 nm) for 1 minute and the resin composition was cured, a black-colored adhesive portion was confirmed.

Example 14
In Example 13, as the acid chromogenic dye precursor, 3,3-bis (4-diethylamino-2-ethoxy) instead of 3 parts by weight of 2-anilino-3-methyl-6-di-n-butylaminofluorane. Same as in Example 13 except that 3 parts by weight of phenyl) -4-azaphthalide was used and 1 part by weight of 2- (n-butyloxycarbonylmethylthio) anthraquinone was used instead of 1 part by weight of coumarin 6 as a photosensitizer. A resin composition was obtained.
When a 30 mm × 30 mm square was drawn on the glass plate in the same manner as in Example 13 and then irradiated with blue LED light for 1 minute to be cured, a green-colored adhesive portion was confirmed.

Example 15
In Example 13, as the acid chromogenic dye precursor, 3 parts by weight of 3-chloro-6-cyclohexylaminofluorane instead of 3 parts by weight of 2-anilino-3-methyl-6-di-n-butylaminofluorane. As a compound that generates an acid by irradiation with active rays, 6 parts by weight of bis (4-t-butylphenyl) iodonium hexafluorophosphate instead of 3 parts by weight of 4-isopropylphenyl-4'-methylphenyliodonium tetrakispentafluorophenylborate. A resin composition was obtained in the same manner as in Example 13 except that the portion was used.
When a 30 mm × 30 mm square was drawn on the glass plate in the same manner as in Example 13 and then irradiated with blue LED light for 1 minute to be cured, an orange-colored adhesive portion was confirmed.

Example 16
3', 4'-Epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate [cationically polymerizable organic compound] 70 parts by weight, 2-hydroxyethyl methacrylate [copolymer for reducing viscosity] 30 parts by weight, bis (4-t-Butylphenyl) Iodonium hexafluorophosphate [Compound that generates acid by irradiation with active rays] 8 parts by weight, 1,2-benzo-6-di-n-butylaminofluorane [Acid chromogenic dye precursor ] 3 parts by weight were sufficiently mixed and stirred using a stirrer to obtain a uniform liquid resin composition. This resin composition was not colored.
This resin composition was drawn on a 200 mm × 200 mm glass plate using a dispenser to form a 30 mm × 30 mm square with a thickness of about 1000 μm. When this was irradiated with ultraviolet rays for 1 minute using a metal halide lamp and the resin composition was cured, an adhesive portion colored in red was confirmed.

Example 17
3', 4'-Epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate [cationically polymerizable organic compound] 70 parts by weight, 2-hydroxyethyl methacrylate [copolymer for reducing viscosity] 30 parts by weight, bis (4-t-Butylphenyl) Iodonium hexafluorophosphate [Compound that generates acid by activation ray irradiation] 8 parts by weight, Kumarin 6 [Photosensitizer] 1 part by weight, 2-Hydroxy-4-methoxybenzophenone [Ultraviolet absorption Agent] 1 part by weight and 3 parts by weight of 3,6-di-n-butoxyfluorane [acid-coloring dye precursor] were sufficiently mixed and stirred using a stirrer to obtain a uniform liquid resin composition. This resin composition was not colored.
This resin composition was drawn on a 200 mm × 200 mm glass plate using a dispenser to form a 30 mm × 30 mm square with a thickness of about 1000 μm. When this was irradiated with blue LED light (peak wavelength of about 460 nm) for 1 minute and the resin composition was cured, a yellow-colored adhesive portion was confirmed.

<Evaluation 2>
The viscosity of the liquid resin composition prepared in Examples 11 to 17 at 70 ° C. was measured using a viscometer BLII (manufactured by Toki Sangyo Co., Ltd.). The results are shown in Table 2 below.
Furthermore, the cured resin film was touched with a finger to confirm the presence or absence of stickiness. The case where there is no stickiness is indicated by ○, and the case where there is stickiness is indicated by ×.
Further, a liquid crystal was added to the obtained 30 mm × 30 mm square, and it was confirmed whether or not liquid leakage occurred. The case where no liquid leakage was observed was indicated by ◯, and the case where liquid leakage was clearly observed was indicated by ×.
As shown in Table 2, the liquid resin composition for an active ray-curable adhesive of the present invention had sufficient curability. In addition, the adhesive portion does not leak, has vivid colors and sufficient strength, and is very suitable as a liquid resin composition for an active ray-curable adhesive that can be colored in full color.

The liquid resin composition for an active ray-curable adhesive of the present invention had a viscosity suitable for an adhesive and had sufficient curability. In addition, the light-storing property was good, and in particular, the adhesive portion containing an ultraviolet absorber and cured by irradiation with blue LED light had a very excellent light-storing property.
Further, the adhesive portion has a vivid color and sufficient strength, and is very suitable as a liquid resin composition for an active ray-curable adhesive that can be colored in full color.

The liquid resin composition for an active ray-curable adhesive of the present invention can be rapidly cured by irradiation with active rays after adhesion, and can be vividly colored to a desired color by irradiation with active rays to color the bonded portion. can. For this reason, when an adherend such as a liquid crystal cell is adhered to an optical film such as a polarizing film, or when used as a sealing agent for a polarizing film, the bonded portion is colored black to reduce light leakage. It is very suitable as a liquid crystal composition that can be colored in full color with a simple structure.

Claims (4)

A substantially colorless composition containing the following components (A-1), (B), (C) and (D) as essential components, and a liquid resin for an active ray-curable adhesive that develops color by irradiation with active rays. Composition.
(A-1) Radical-polymerizable organic compound having at least one unsaturated double bond (B) Cationic photopolymerization initiator (C) One or more compounds selected from the following acid-coloring dye precursors
3- (4-Diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindole-3-yl) -4-azaphthalide,
3- (4- (N-Ethyl-N-Phenylamino) -2-ethoxyphenyl) -3- (1-Ethyl-2-methylindole-3-yl) -4-azaphthalide,
2-N, N-dibenzylamino-6-diethylaminofluorane,
3,3-Bis (4-diethylamino-2-ethoxyphenyl) -4-azaphthalide,
1,2-benzo-6-di-n-butylaminofluorane,
3,3-bis (1-n-butyl-2-methylindole-3-yl) phthalide,
3,6-di-n-butoxyfluorane,
2,6-bis [4-di-n-butylaminobenzoyl] pyridine,
2-anilino-3-methyl-6-di-n-butylaminofluorane,
2- (2,4-Dimethylanilino) -3-methyl-6-diethylaminofluorane,
3-Chloro-6-cyclohexylaminofluorane (D) radical photopolymerization initiator Further, the liquid resin composition for an active ray-curable adhesive according to claim 1, further comprising a radically polymerizable organic compound having at least two unsaturated double bonds as the radically polymerizable organic compound. The liquid resin composition for an active ray-curable adhesive according to claim 1 or 2 , which exhibits curability and color development using visible light as an active ray. The liquid resin composition for an active ray-curable adhesive according to any one of claims 1 to 3 , further comprising (E) an ultraviolet absorber.