JP2019196493A - Liquid resin composition for active ray-curable adhesive - Google Patents

Abstract

To provide a liquid resin composition for active ray-curable adhesive which has a high curing speed, enables coloring of each color and full color coloring to be desired, is excellent in light resistant preservability, and can reduce leakage of light when being bonded to an adherend such as a liquid crystal cell, a polarizing film, and the like and being used in a sealant for polarizing film.SOLUTION: A liquid resin composition for active ray-curable adhesive contains the following components (A-1), (B), (C) and (D) as essential components: (A-1) a radical polymerizable organic compound having at least one unsaturated double bond; (B) a cationic photopolymerization initiator; (C) an acid color-forming pigment precursor; and (C) a radical photopolymerization initiator.SELECTED DRAWING: None

Description

  The present invention relates to a color developing liquid resin composition used for an adhesive. Specifically, it is hardly colored before use, and is cured by actinic ray irradiation after being bonded, and the dye precursor is colored to form a colored bonded portion. The present invention relates to a liquid resin composition capable of full color coloring and having a high curing speed.

Actinic radiation curable adhesives that are cured by irradiating with light such as laser light or ultraviolet rays are more energy efficient than thermosetting adhesives. It is used in a wide range of fields, and in particular, in recent years, it is used as a material for bonding a plurality of optical films such as a polarizing film and a liquid crystal cell used in a display device such as a liquid crystal television, a notebook computer, and a smartphone.
Usually, when a thermosetting adhesive is used to bond an optical film, an optical film made of a polymer film such as polyvinyl alcohol is likely to be deformed such as heat shrinkage, and as a result, the bonded portion is cracked or peeled off. , Has the disadvantage of causing light leakage. Furthermore, in a display device using an LED as a light source, light leakage tends to be prominent because the luminance of the LED light source is high.

JP 2007-84727 A

In a display device using an LED light source, in order to prevent light leakage, a method of curing after bonding using a liquid resin composition containing a colorant can be considered, but the resin composition itself is colored. , There is a drawback that it takes time to cure because it is difficult for light to reach the curable resin or the polymerization initiator during curing.
The present invention has a high curing speed, enables each desired color and full color coloring, is excellent in light-resistant storage stability, and when 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 actinic radiation curable adhesive having 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 problems can be achieved by a liquid resin composition for an actinic radiation curable adhesive containing the following components, and completed the present invention.
That is, the present invention
(I) A liquid resin composition for an actinic radiation curable adhesive containing the following components (A), (B) and (C) as essential components.
(A) Actinic ray-polymerizable organic compound (B) Compound that generates an acid upon irradiation with actinic rays (C) Acid-color-forming dye precursor (ii) The (A) actinic-ray-polymerizable organic compound is the following (A-1 And / or (A-2), the liquid resin composition for active ray curable adhesives of (i).
(A-1) Radical polymerizable organic compound (A-2) Cationic polymerizable organic compound (iii) The radical polymerizable organic compound (A-1) is an organic compound having at least one unsaturated double bond. (Ii) Liquid resin composition for active ray curable adhesives.
(Iv) The liquid resin composition for active ray curable adhesives according to any one of (i) to (iii), further comprising (D) a radical photopolymerization initiator.
(V) The liquid resin composition for an actinic radiation curable adhesive according to any one of (ii) to (iv), wherein the cationically polymerizable organic compound (A-2) is an organic compound having two or more epoxy groups. .
(Vi) The liquid resin composition for an actinic radiation curable adhesive according to any one of (i) to (v), wherein the compound that generates acid upon irradiation with actinic radiation in (B) is a cationic photopolymerization initiator.
(Vii) The (C) acid color-forming dye precursor is a fluorane compound, a phthalide compound, an azaphthalide compound, a fluorene spirophthalide compound system, a triphenylmethane compound, a diphenylmethane compound, a thiazine compound, or a lactam compound. The liquid resin composition for active ray curable adhesives according to any one of (i) to (vi), which is at least one color former selected from a compound and a diketone compound.
(Viii) The liquid resin composition for active ray curable adhesives according to any one of (i) to (vii), which exhibits curing / coloring properties using visible light as an active ray.
(Ix) The liquid resin composition for an actinic radiation curable adhesive according to any one of (i) to (viii), further comprising (E) an ultraviolet absorber.
About.

The liquid resin composition for an actinic radiation curable adhesive of the present invention is almost uncolored before use, is quickly cured by actinic radiation after adhesion, and develops a desired color by this actinic radiation. Thus, the bonded portion can be colored. For this reason, when it is used for adherends such as liquid crystal cells and optical films such as polarizing films, or when used as a sealing agent for polarizing films, the leakage of light is reduced by coloring the adhesion portion black. Can
Moreover, since the liquid resin composition for active ray curable adhesives of the present invention is not substantially colored before use, the active ray easily reaches the inside of the resin composition, and the curing rate is fast.
Further, in an embodiment in which visible light, particularly blue LED light is used as the active ray for curing and the ultraviolet light absorber is contained in the resin composition, the apparatus for the light source can be set simply and inexpensively, Excellent light-resistant storage stability.

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

Hereinafter, each component will be described in detail.
[(A) Active-line polymerizable organic compound]
An actinically polymerizable organic compound is an organic compound having a group that polymerizes in the molecule upon irradiation with actinic radiation. From the polymerization type, (A-1) a radically polymerizable organic compound and (A-2) a cationically polymerizable organic A distinction can be made between compounds.
When the active ray polymerizable organic compound is (A-1) a radical 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) radical polymerizable organic compound and (A-2) cationic polymerizable organic compound are used in combination, and (B) (A-1) and (A-2) are generated by a compound that generates an acid upon irradiation with actinic rays. ) Can be copolymerized, the content of the (D) radical photopolymerization initiator is small 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, When (B) is copolymerizable with a compound that generates an acid upon irradiation with actinic radiation, the content of (D) radical photopolymerization initiator may be small or may not be contained.

[(A-1) Radical polymerizable organic compound]
The radical-polymerizable organic compound is a radical-polymerizable compound that is polymerized or cross-linked by irradiation with actinic radiation, 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, and polythiol compounds.
As a compound having one unsaturated double bond in one molecule, linear or branched alkyl (meth) acrylate, alicyclic ring-containing (meth) acrylate, heterocyclic ring-containing (meth) acrylate, styrene, vinylcyclohexene, Examples include isobutylene and butadiene, with (meth) acrylates being preferred.
Examples of linear or branched alkyl (meth) acrylates 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 ring-containing (meth) acrylate include cyclohexyl (meth) acrylate, 4-t-cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and the like.
Examples of the heterocycle-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.

  As a compound having one unsaturated double bond per molecule that can be suitably used, for example, acrylamide, (meth) acryloylmorpholine, 7-amino-3,7-dimethyloctyl (meth) acrylate, isobutoxymethyl ( (Meth) 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, vinylcaprolactam, N-vinylpyrrolidone, phenoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, Examples include n-chlorophenyl (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. be able to.

Of these compounds having one unsaturated double bond in one molecule, isobornyl (meth) acrylate, lauryl (meth) acrylate, and phenoxyethyl (meth) acrylate are particularly preferable. Examples of commercially available products of these compounds include Aronix M-101, M-102, M-111, M-113, M-117, M-152, TO-1210 (above, manufactured by Toagosei Co., Ltd.), KAYARAD. TC-110S, R-564, R-128H (above, Nippon Kayaku Co., Ltd.), Biscote 192, Biscote 220, Biscote 2311HP, Biscote 2000, Biscote 2100, Biscote 2150, Biscote 8F, Biscote 17F (above, Osaka Organic) Chemical Industry Co., Ltd.).
Moreover, in order to adjust the softness | flexibility of a resin composition, it is preferable to contain the compound which has one unsaturated double bond which has a hydroxyl group as a copolymerization component with the compound which has 2 or more of 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 ( A meta) acrylamide derivative 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, 4-hydroxybutyl (meth) acrylate, and the like. Examples of the hydroxyl group-containing (meth) acrylate having a number average molecular weight of 200 to 2,000 include polyethylene glycol mono (meth) acrylate, methoxypolyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxypolypropylene glycol mono ( And a mono (meth) acrylate of a polyethylene glycol-polypropylene glycol block polymer. Examples of the hydroxyl group-containing (meth) acrylamide derivative include N-hydroxyethyl (meth) acrylamide, N-hydroxypropyl (meth) acrylamide, N-hydroxybutyl (meth) acrylamide and the like.
The content of the compound having a hydroxyl group and having one unsaturated double bond varies depending on the composition of the other active-line polymerizable organic compound.

The compound having two or more unsaturated double bonds in one molecule is preferably a compound having two or more (meth) acryl groups in one molecule. Examples thereof include epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, and (meth) acrylic acid esters 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, and (meth) acrylic acid. Among these epoxy (meth) acrylates, a particularly preferred one is a (meth) acrylate of an aromatic epoxy resin, and a polyglycidyl ether of a polyhydric phenol having at least one aromatic nucleus or an alkylene oxide adduct thereof, It is (meth) acrylate obtained by making it react with (meth) acrylic acid. For example, (meth) acrylate, epoxy novolac resin and (meth) obtained by reacting glycidyl ether obtained by reaction of bisphenol A or its alkylene oxide adduct and epichlorohydrin with (meth) acrylic acid. Examples thereof include (meth) acrylate obtained by reacting acrylic acid.

Preferred as the urethane (meth) acrylate is a (meth) acrylate obtained by reacting a hydroxyl group-containing (meth) acrylic acid ester and an isocyanate with one or two or more hydroxyl group-containing polyesters or hydroxyl group-containing polyethers, or a hydroxyl group. And (meth) acrylates obtained by reacting the containing (meth) acrylic acid ester with isocyanates.
Preferred as the hydroxyl group-containing polyester used here is a hydroxyl group-containing polyester obtained by reaction of one or more fatty acid polyhydric alcohols with one or more polybasic acids, and is aliphatic. Examples of the polyhydric alcohol include 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, neopentyl glycol, polyethylene glycol, polypropylene glycol, trimethylolpropane, glycerin, Examples 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 alkylene oxides to an aliphatic polyhydric alcohol, and the aliphatic polyhydric alcohol includes the compounds described above. The same thing can be illustrated. Examples of the alkylene oxide include ethylene oxide and propylene oxide.
What is preferable as a hydroxyl group-containing (meth) acrylic acid ester is a hydroxyl group-containing (meth) acrylic acid ester obtained by esterification reaction of an aliphatic polyhydric alcohol and (meth) acrylic acid, The same compounds as those described above can be exemplified.
Among such hydroxyl group-containing (meth) acrylic acids, a hydroxyl group-containing (meth) acrylic acid ester obtained by an esterification reaction between an aliphatic dihydric alcohol and (meth) acrylic acid is particularly preferred. ) Acrylates.
As the isocyanate, a compound having at least one isocyanate group in the molecule is desirable, and divalent isocyanate compounds such as tolylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate are particularly preferable.

  The polyester (meth) acrylate is preferably a polyester (meth) acrylate obtained by reacting a hydroxyl group-containing polyester with (meth) acrylic acid. Preferred as the hydroxyl group-containing polyester used here is an esterification reaction of one or more aliphatic polyhydric alcohols with one or more monobasic acids, polybasic acids, and phenols. In the obtained hydroxyl group-containing polyester, examples of the aliphatic polyhydric alcohol include the same compounds as those described above. Examples of monobasic acids include formic acid, acetic acid, butyl carboxylic 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 preferable polyether (meth) acrylate is a polyether (meth) acrylate obtained by reacting a hydroxyl group-containing polyether with (meth) acrylic acid. What is preferable as the hydroxyl group-containing polyether used here is a hydroxyl group-containing polyether obtained by adding one or more alkylene oxides to an aliphatic polyhydric alcohol, The same compounds as those described above 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 (meta) ) 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, isobornyl (meth) acrylate, benzyl (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate 1,6-hex Didiol (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 (meth) acrylate, Trimethylolpropane Examples include tri (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 that can be suitably used include, for example, ethylene glycol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, triethylene glycol diacrylate, and tetraethylene glycol. Di (meth) acrylate, tricyclodecanediyldimethylene di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide (hereinafter referred to as “EO”) modified trimethylolpropane tri (meth) acrylate, propylene oxide (hereinafter referred to as “ PO ”) modified trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, bisphenol A diglycidyl a (Meth) acrylic acid adducts at both terminals of 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 (meth) 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, 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 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 preferred.

  Examples of commercially available compounds having two or more unsaturated double bonds in one molecule include SA1002 (above, manufactured by Mitsubishi Chemical Corporation), biscoat 195, biscoat 230, biscoat 260, biscoat 215, and biscoat 310. Biscoat 214HP, biscoat 295, biscoat 300, biscoat 360, biscoat GPT, biscoat 400, biscoat 700, biscoat 540, biscoat 3000, biscoat 3700 (manufactured by Osaka Organic Chemical Co., Ltd.), Kayrad 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- 10, 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 (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 (manufactured by Toagosei Co., Ltd.), light acrylate BP-4EA, BP-4PA, BP-2EA, BP-2PA, DCP-A (manufactured by Kyoeisha Chemical Co., Ltd.), New Frontier BPE-4, BR-42M, GX-8345 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), ASF-400 As described above, manufactured by Nippon Steel Chemical Co., Ltd.), lipoxy SP-1506, SP-1507, SP-1509, VR-77, SP-4010, SP-4060 (above, Showa Polymer Co., Ltd.), NK ester A-BPE-4 (above, Shin-Nakamura Chemical Co., Ltd.) etc. can be mentioned.

In the liquid resin composition for an actinic radiation curable adhesive of the present invention, at the time of photocuring, in order to increase the physical and chemical strength of the bonded portion after curing, the radical polymerizable organic compound is 1 per molecule. A compound having one unsaturated double bond and a compound having two or more unsaturated double bonds in one molecule may be combined in two or more, or one unsaturated double bond in one molecule may be combined. It is preferable to compose a combination of at least one compound having at least one compound having at least one compound having two or more unsaturated double bonds in one molecule. In addition, it is also preferable to further combine the compounds having three or more unsaturated double bonds in one molecule. Examples of the compound having 3 or more unsaturated double bonds in one molecule include tri (meth) acrylate compounds, tetra (meth) acrylate compounds, penta (meth) acrylate compounds, hexa (meth) acrylate compounds, and the like. Specifically, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tetra (meth) Acrylate is preferred.
In the liquid resin composition for actinic radiation curable adhesive of the present invention, when a radical polymerizable organic compound is contained, 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 is polymerized or crosslinked by irradiation with actinic radiation in the presence of a cationic photopolymerizable initiator, preferably an epoxy compound, an oxetane compound, an oxolane compound, a cyclic acetal compound, A cyclic lactone compound, a thiirane compound, a thietane compound, a spiro orthoester compound that is a reaction product of an epoxy compound and a lactone compound, a vinyl ether compound, and the like can be given.

  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 4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) Dipetate, 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, ethyl Bis (3,4-epoxycyclohexanecarboxylate), epoxycyclohexahydrophthalate dioctyl, epoxycyclohexahydrophthalic acid di-2-ethylhexyl, 1,4-butanediol diglycidyl ether, 1,6-hexanediol di Glycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, glycerin triglycidyl ether, polypropylene glycol diglycidyl ethers; aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin Polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides; Diglycidyl esters of aliphatic long-chain dibasic acids; monoglycidyl ethers of higher aliphatic alcohols; monoglycidyl ethers of polyether alcohols obtained by adding phenol, cresol, butylphenol or alkylene oxide; glycidyl esters of higher fatty acids Epoxidized soybean oil; butyl epoxy stearate; octyl epoxy stearate; epoxidized linseed oil; epoxidized polybutadiene and the like.

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

Examples of thiirane compounds include ethylene sulfide, 1,2-propylene sulfide, thioepichlorohydrin, and the like.
An example of the thietane compound is 3,3-dimethylthietane.
Examples of vinyl ether compounds include ethylene glycol divinyl ether, triethylene glycol divinyl ether, trimethylolpropane trivinyl ether, oxygen-containing alicyclic divinyl ether, and the like.
Examples of the ethylenically unsaturated compound include vinylcyclohexane, isobutylene, polybutadiene and the like.
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-epoxycyclohexyl methyl-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 Glycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, oxygen-containing fat Ring 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, bis (3,4-epoxycyclohexylmethyl) adipate. A compound.
In addition, oxygen-containing alicyclic divinyl ethers are copolymerized with epoxy compounds and (meth) acrylate compounds, which are radically polymerizable organic compounds, to provide heat resistance, fastness, adhesion, and flexibility at the joints. Can be granted.
In the liquid resin composition for active ray curable adhesives of the present invention, it is also preferable to use a combination of two or more of the above cationic polymerizable organic compounds.

Examples of commercially available cationically polymerizable organic compounds that can be suitably used include UVR-6100, UVR-6105, UVR-6110, UVR-6128, UVR-6200, UVR-6216 (manufactured by Union Carbide), Celoxide 2021, Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, Epolide GT-300, Epolide GT-301, Epolide GT-302, Epolide GT-400, Epolide 401, Epolide 403, ONB-DVE, OXT-DVE, ISB-DVE ( As described above, manufactured by Daicel Chemical Industries, Ltd.), KRM-2100, KRM-2110, KRM-2199, KRM-2400, KRM-2410, KRM-2408, KRM-2490, KRM-2200 KRM-2720, KRM-2750 (manufactured by Asahi Denka Kogyo Co., Ltd.), Rapi-cureDVE-3, CHVE, PEPC (manufactured by ISP) Epicoat 828, Epicoat 812, Epicoat 1031, Epicoat 872, Epicoat CT508 ( As mentioned above, Japan Epoxy Resin Co., Ltd.), XDO (above, manufactured by Toagosei Co., Ltd.), VECOMER 2010, 2020, 4010, 4020 (above, manufactured by Allied Signal Co., Ltd.) can be exemplified.
In addition, the above-mentioned compounds having an epoxy group may have a slightly high viscosity when used as a liquid resin composition for an actinic radiation 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 reducing the viscosity. It is also effective to reduce the viscosity by adding liquid plasticizers within a range that does not affect other properties such as curability.

[(B) Compound that generates acid upon irradiation with actinic radiation]
A cationic photopolymerization initiator can be used as the compound that generates an acid upon irradiation with actinic radiation.
Examples of particularly preferred cationic photopolymerization initiators include onium salts having a structure represented by the following general formula (1).

_{^{[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, a, b, c and d are each an integer of 0 to 3, and (a + b + c + d) is equal to the valence of W.

M is a metal or metalloid constituting the central atom of the halide complex [MXp + q], X is a halogen atom, q is the net charge of the halide complex ion, and p is the valence of M. An onium salt having a structure represented by the formula:
M is preferably B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, or Co.
X is preferably F, Cl, Br, or I.
Specific examples of the anion [MXp + q] include tetrafluoroborate (BF4-), hexafluorophosphate (PF6-), hexafluoroantimonate (SbF6-), hexafluoroarsenate (AsF6-), hexachloroantimonate (SbCl6-). ) And the like.
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].
Further, in place of the anion [MXp + q], perchlorate ion (ClO4-), trifluoromethanesulfonate ion (CF3SO3-), fluorosulfonate ion (FSO3-), toluenesulfonate ion, trinitrobenzenesulfonate anion, Onium salts with other anions such as nitrotoluene sulfonate anions can also be used.

The onium salt represented by the general formula (1) releases a Lewis acid by actinic ray irradiation.
An onium salt particularly effective as a cationic photopolymerization initiator as a compound that generates an acid upon irradiation with actinic rays is an aromatic onium salt. Of these, aromatic halonium salts described in JP-A-50-151996, JP-A-50-158680, etc., JP-A-50-151997, JP-A-52-30899, JP Group VIA aromatic onium salts described in JP-A-56-55420, JP-A-55-125105, etc., Group VA aromatic onium salts described in JP-A-50-158698, etc., JP-A-56-8428 Oxosulfoxonium salts described in JP-A Nos. 56-149402 and 57-192429, aromatic diazonium salts described in JP-A-49-17040, and the like. The thiobililium salts described in US Pat. No. 4,139,655 are preferred. Moreover, an iron / allene complex, an aluminum complex / photolytic 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-, etc. as counterions, and triphenylsulfonium hexafluorophosphate, p-thiophenoxyphenyl diphenylsulfonium hexafluorophosphate, triphenylsulfonium tetrafluoroborate, 4-morpholino-2,5-dimethoxyphenyldiazonium fluoroborate, diphenyliodonium salt or ditolyliodonium salt whose counter ion is BF4−, Phenyldiazonium tetrafluoroborate, tolyldiazonium tetrafluoroborate, tolyldiazonium hexafluorophosphate, bis (4-t-butylphenyl) io Such as de hexafluorophosphate and the like.

Examples of commercially available cationic photopolymerization initiators that can be suitably used as a compound that generates an acid upon irradiation with actinic radiation include UVI-6950, UVI-6970, UVI-6974, and UVI-6990 (manufactured by Union Carbide). , Adekaoptomer SP-150, SP-151, SP-170, SP-172 (above, manufactured by Asahi Denka Kogyo Co., Ltd.), Irgacure 261 (above, manufactured by Ciba Specialty Chemicals Co., Ltd.), CI-2481, CI -2624, CI-2639, CI-2064 (above, Nippon Soda Co., Ltd.), CD-1010, CD-1011, CD-1012 (above, Sartomer), DTS-102, DTS-103, NAT- 103, NDS-103, TPS-103, MDS-103, MPI-103, BBI-103 (above (Midori Chemical Co., Ltd.), PCI-061T, PCI-062T, PCI-020T, PCI-022T (above, Nippon Kayaku Co., Ltd.), CPI-110A (above, San Apro Co., Ltd.), t- Examples thereof include BuDPI (manufactured by Tokyo Chemical Industry Co., Ltd.).
Among these, UVI-6970, UVI-6974, Adekaoptomer SP-170, SP-172, CD-1012, MPI-103, CPI-110A, and t-BuDPI are resin compositions containing these. It is particularly preferable because high photocuring sensitivity can be expressed. Said cationic photoinitiator can be used individually by 1 type or in combination of 2 or more types.

[(C) Acid coloring dye precursor]
A color former (leuco dye) can be used as the acid coloring dye precursor.
A color former is an organic compound that is usually colorless but develops various colors with an acid, and is widely used in heat-sensitive recording materials, pressure-sensitive recording materials, thermochromic materials, and the like.
The color former that can be used as the acid color-forming dye precursor in the liquid resin composition for actinic radiation curable adhesive of the present invention is not particularly limited, and is a fluorane-based, phthalide-based, azaphthalide-based, fluorene spirophthalide-based, triphenyl. Examples include methane, diphenylmethane, thiazine, lactam, and diketone.
In particular, fluoran, phthalide, azaphthalide, fluorene spirophthalide, triphenylmethane compound, lactam, and diketone are preferable.

As color formers that develop blue color, 3,3-bis (4-dimethylaminophenyl) -6-dimethylaminophthalide, N-benzoylleucomethylene 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-methylindol-3-yl) -4-azaphthalide, 3- (4-diethylamino-2-methylphenol) ) -3- (1-ethyl-2-methylindol-3-yl) 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 etc. can be mentioned.

  Examples of color formers that develop a green color include 2-anilino-6- (N-ethyl-Nn-hexylamino) fluorane, 2-dibenzylamino-6-diethylaminofluorane, 3,3-bis (4- Diethylamino-2-ethoxyphenyl) -4-azaphthalide, 2- (N-phenyl-N-methylamino) -6- (N-ethyl-Np-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 include 3,6-bis (dimethylamino) fluorene-9-spiro-3 ′-(6′-dimethylamino) phthalide.

  Color formers that develop red color include 3,6-bis (diethylamino) fluorane-γ-anilinolactam, 3,6-bis (diethylamino) fluorane-γ- (p-nitro) anilinolactam, 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-Np-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-dihydrochromeno [2,3-c] pyrazole) -4,3'-phthalide], 7- ( N-ethyl-Nn-hexylamino) -3-methyl-1-phenylspiro [(1,4-dihydrochromeno [2,3-c] pyrazole) -4,3′-phthalide] and the like. Can do.

  Examples of color formers that develop a yellow color include 3,6-dimethoxyfluorane, 3,6-di-n-butoxyfluorane, 2-chloro-6-cyclohexylaminofluorane, 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] -benzenamine, 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-n-dodecyloxy-3-methoxyphenyl) -2- (2-quinolyl) ethylene and the like.

  Examples of color formers that develop black color include 2-anilino-3-methyl-6-diethylaminofluorane, 2-anilino-3-methyl-6-di-n-butylaminofluorane, 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- -Methyl-6-dipentylaminofluorane, 2-anilino-3-methyl-6- (N-ethyl-N-tetrahydrofurfuryl) aminofluorane, 2-anilino-3-methyl-6-pyrrolidinofluorane, etc. Can be mentioned.

In addition, as a color former that develops orange, 3-chloro-6-cyclohexylaminofluorane, 3-chloro-6-anilinofluorane, etc. As a color former that develops vermilion, 2-chloro-6-diethylamino 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.
In the liquid resin composition for an actinic radiation curable adhesive of the present invention, one type of color former or a color former of the same color may be mixed and used in one type of resin composition. In order to obtain a color former, a color former exhibiting different colors may be mixed in one kind of resin composition.

[(D) radical photopolymerization initiator]
As described above, in the liquid resin composition for an actinic radiation curable adhesive of the present invention, when it contains (A-1) a radical polymerizable organic compound, it simultaneously contains (D) a radical photopolymerization initiator. Is preferred. However, (A-1) radically polymerizable organic compound and (A-2) cation polymerizable organic compound are used in combination, and (B) (A-1) and (A-2) are generated by a compound that generates an acid upon irradiation with active rays. This is not the case when) is copolymerizable.

The radical photopolymerization initiator is not particularly limited as long as it generates radical active species by irradiation with active rays in order to increase the molecular weight of the (A-1) radical polymerizable organic compound by radical polymerization.
Preferably, acetophenone compounds, benzophenone compounds, benzoin compounds, benzyl compounds, thioxanthone compounds, acylphosphine compounds, and the like are used.
Examples of acetophenone compounds include diethoxyacetophenone, 2-hydroxymethyl-1-phenylpropan-1-one, 4′-isopropyl-2-hydroxy-2-methylpropiophenone, 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-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 and the like.

Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-dichlorobenzophenone, 4 -Benzoyl-4'-methyldiphenyl sulfide, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone (BTTB) and the like.
Examples of the benzoin compound 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, and 2,4-diethylthioxanthone.
Examples of the acylphosphine compound include acylphosphine compounds such as monoacylphosphine oxide, bisacylphosphine oxide, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

Others, xanthones, fluorenones, benzaldehydes, fluorenes, anthraquinones, naphthacenediones, triphenylamines, carbazoles, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (cyclopentadienyl) -Bis [2,6-difluoro-3- (py-1-yl)] titanium, and combinations of BTTB and xanthenes, thioxanthenes, coumarins, ketocoumarins and other dye sensitizers .
In particular, naphthacenediones such as 5,11-bis (silyloxy) naphthacene-6,12-dione, and combinations of these with sensitizers of anthraquinone compounds and anthracene compounds have high sensitivity to blue LED light. Have
Among these, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, α-methoxybenzoin methyl ether, 2-benzyl-2-dimethylamino-1- (4-morpholino Particularly preferred are phenyl) -butan-1-one, 5,11-bis (silyloxy) naphthacene-6,12-dione, and the like.
Commercially available product names of radical photopolymerization initiators include IRGACURE 184, 369, 651, 500, 819, 907, CGI 1700, CGI 1750, CGI 1850, CG 24-61, DAROCUR 1116, 1173 (above, manufactured by Ciba Specialty Chemicals); LUCIRIN TPO ( BASF); Ubekrill P36 (UCB) and the like. These radical photopolymerization initiators can be used singly or in combination of two or more.

[Other additives]
The liquid resin composition for actinic radiation curable adhesive of the present invention may contain various additives as other components as necessary within the range not impairing the object and effects of the present invention.
Such additives include polymers or oligomers, (thermal) 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, an ultraviolet absorber is very useful especially in the aspect which hardens the liquid resin composition for active ray curable adhesives of this invention using visible light, and it demonstrates separately by the postscript as a component (E) below.
The polymer or oligomer can be added to adjust the viscosity or the like 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 polymers. Examples thereof include polymers such as oligomers, silicone oligomers, and polysulfide oligomers, and oligomers.
Examples of (thermal) polymerization inhibitors 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 [dilauryl thiodipropionate, etc.], phosphorus compounds [triphenyl phosphite Etc.], amine compounds [phenothiazine etc.] and the like.

  Examples of chain transfer agents include hydrocarbons [C6-24 compounds such as 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 such as acetone, methyl ethyl ketone); aldehydes (C2-18 compounds such as 2-methyl-2-propylaldehyde, 1-pentylaldehyde); phenols (C6-36 compounds such as phenol, m- , P- and o-cresol); quinones (C6-24 compounds such as hydrides) Quinone); amine (compound of C3～24, such as diethyl methyl amine, diphenylamine); Compound of and disulfides (C2～24, such as diethyl disulfide, 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. ], Polycyclic phenol [1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene etc.], etc.], sulfur compound (dilauryl 3,3 '-Thiodipropionate etc.), phosphorus compounds (triphenyl phosphite etc.), amine compounds (octylated diphenylamine etc.) and the like. Examples of commercially available products of these antioxidants include IRGANOX 1010, 1035, 1076, 1222 (manufactured by Ciba Specialty Chemicals), 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; thioxanthone, thioxanthone derivatives; 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 and anthracene derivatives; Perylene, derivatives of perylene; benzophenone; benzoin isopropyl ether; pigments such as coumarins and ketocoumarins;

  Examples of the surfactant include a molecular weight of 264 or more and 5,000 or less, for example, a PEG type nonionic surfactant [nonylphenol ethylene oxide (hereinafter abbreviated as EO) 1 to 40 mol adduct, stearic acid EO 1 to 40 mol adduct Etc.], polyhydric alcohol type nonionic surfactant (sorbitan palmitic acid monoester, sorbitan stearic acid monoester, sorbitan stearic acid triester, etc.), fluorine-containing surfactant (perfluoroalkyl EO 1-50 mol adduct, per Fluoroalkylcarboxylate, perfluoroalkylbetaine, etc.), modified silicone oils [polyether-modified silicone oil, (meth) acrylate-modified silicone oil, 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.), metal salt (calcium carbonate, etc.) , 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.), etc.], microballoon (Glass, shirasu, phenol resin, etc.), carbons (carbon black, graphite, coal powder, etc.), metal sulfides (molybdenum disulfide, etc.) and the like.
As the pigment and dye, various known organic / inorganic pigments and dyes are used. In the liquid resin composition for actinic radiation 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 as it greatly decreases.

[(E) UV absorber]
As the ultraviolet absorber, benzotriazole, benzophenone, triazine derivatives, salicylic acid derivatives, hindered amines and the like are preferable.
Examples of the benzotriazole series include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-tert-butylphenyl) benzotriazole, 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′-ditert-butylphenyl) -5-chlorobenzotriazole, 2- (2′- Hydroxy-3 ′, 5′-ditert-amylphenyl) benzotriazole, 2- (2′-hydroxy-4′-octylphenyl) benzotriazol 2- (2′-hydroxy-5′-methacryloxyethylphenyl) -2H-benzotriazole, 2-{(2′-hydroxy-3 ′, 3 ″, 4 ″, 5 ″, 6 ′ And '-tetrahydrophthalimidomethyl) -5'-methylphenyl} benzotriazole.

  Examples of the benzophenone series include 2-hydroxybenzophenone, 5-chloro-2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy- 4-dodecyloxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2-hydroxy-4- And methoxy-5-sulfobenzophenone.

  Examples of triazine derivatives 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 Special Manufactured by Tea Chemicals, trade name Tinuvin 479], tris [2,4,6- [2- {4- (octyl-2-methylethanoate) oxy-2-hydroxyphenyl}]]- 1,3,5-triazine [manufactured by Ciba Specialty Chemicals, trade name “Tinubin 777] and the like.

Examples of the salicylic acid derivative include phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate, p- (1,1,3,3-tetramethylbutyl) phenyl salicylate, 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-hydroxyphenyl} methyl] butyl malonate.

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.
As commercially available products of these ultraviolet absorbers, in addition to those described above, for example, TINUVIN P, 234, 320, 326, 327, 328, 329, 213 (above, manufactured by Ciba Specialty Chemicals), Seesorb 102, 103, 501, 202, 712 and 704 (manufactured by Sipro Kasei Co., Ltd.) and the like, but are not limited thereto.
These ultraviolet absorbers can be used singly or in combination of two or more.
In the liquid resin composition for actinic radiation curable adhesive of the present invention, in the case of curing using ultraviolet rays as the actinic radiation, ultraviolet absorbers are often used because they affect the curing speed and the cured film thickness. It is not preferable.
On the other hand, in the mode of curing using visible light, it hardly affects the curing and improves the durability of the bonded part after curing and color development. Therefore, the liquid resin for active ray curable adhesive of the present invention The composition preferably contains an ultraviolet absorber.

[Liquid resin composition for actinic radiation curable adhesive]
The liquid resin composition for an actinic radiation curable adhesive of the present invention comprises (A) an actinic radiation polymerizable organic compound, (B) a compound that generates an acid upon irradiation with actinic radiation, and (C) an acid coloring dye precursor. Contains as a component.

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

(B) The content of the compound that generates an acid upon irradiation with actinic radiation varies depending on (A) the type of actinic radiation polymerizable organic compound and (D) whether or not it further contains a radical photopolymerization initiator, Usually, it is 0.1 to 20% in the resin composition, preferably 0.5 to 15%, more preferably 1 to 10%. When containing 50% or more of the actinically polymerizable organic compound (A-1) as the actinically polymerizable organic compound and further containing a radical photopolymerization initiator, 15%, preferably 0.5 to 10%, more preferably 1 to 8%.
If the content of the compound that generates an acid upon irradiation with actinic radiation is less than the lower limit of the above range, the color density of the acid color-forming dye precursor may not be sufficient, and if it exceeds the upper limit, the curable thickness of the resin composition The strength of the bonded part may be adversely affected.

(C) Content of an acid coloring pigment | dye precursor is 0.3-15% in a resin composition, Preferably it is 0.5-12%, More preferably, it is 1-10%. If the content of the acid coloring dye precursor is less than the lower limit of the above range, the coloring density may not be sufficient, and if the upper limit is exceeded, the curable thickness of the resin composition and the strength of the bonded portion may be adversely affected. is there. The optimal content of the acid color-forming dye precursor varies depending on the color tone (absorption wavelength) and the wavelength of the active ray used for curing.
The acid color-forming dye precursor is preferably compatible with the (A) actinic ray-polymerizable organic compound, but can be mixed using a solvent or finely pulverized for use.
Next, each content (% by weight) of components other than the components (A) to (C) in the resin composition is shown below.

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

(E) Content of a ultraviolet absorber changes with kinds (wavelength) of the actinic radiation used for hardening. When ultraviolet rays are used as the actinic radiation, it is preferable that no ultraviolet absorber is contained or the amount thereof is small. When using actinic rays other than ultraviolet rays, for example, visible light, the content thereof is 0.1 to 10% in the resin composition, preferably 0.2 to 5%, more preferably 0.3% to 3%. . When the content is less than the lower limit of the above range, the effect is not sufficient, and when the content exceeds the upper limit, the heat resistance after curing of the resin composition may be lowered.
The adhesive part of the resin composition containing an appropriate amount of UV absorber improves not only the durability of the adhesive part but also the durability of the colored pigment, so that the characteristics of the adhesive part can be maintained for a long period of time. .

(A) A polymer or oligomer other than the actinic radiation polymerizable organic compound is added as necessary in order to adjust the viscosity of the liquid resin composition for actinic radiation curable adhesive of the present invention and the properties of the adhesion part. The content thereof is 10% or less, preferably 5% or less in the resin composition.
Polymerization inhibitor, chain transfer agent, antioxidant, leveling agent, wettability improver, surfactant, plasticizer, silane coupling agent, pigment, dye content is liquid resin composition for actinic radiation curable adhesive Although it varies depending on the composition of the product and the purpose of use, it is usually 0.1 to 3%, preferably 0.1 to 2% in the resin composition. Moreover, the case where it does not contain at all is also included.
A photosensitizer is contained as required depending on the type of polymerization initiator and the type (wavelength) of active rays used for curing. Content is 0.1 to 5% normally in a resin composition, Preferably it is 0.1 to 3%.

The inorganic filler is used for opacifying the adhesion part or modifying physical properties, and its content is 20% or less, preferably 15% or less in the resin composition. However, since it affects the color tone of the acid color-forming dye precursor, it is preferably contained in a small amount in order to obtain an adhesive part having a vivid color tone. Further, it may not be contained at all.
The liquid resin composition for an actinic radiation curable adhesive of the present invention can be produced by uniformly mixing the above-described essential components and components that are optionally contained 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 effects of the present invention are not hindered.

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

The actinic radiation used for the 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 according to the compound that generates an acid upon irradiation with actinic rays and the active ray polymerizable organic compound. In particular, near ultraviolet rays, ultraviolet rays, blue LED light, blue laser light, argon laser light with wavelengths of 488 nm and 514.5 nm, YAG laser light with 532 nm as the second harmonic, and the like are preferable.
In the case of using visible light as the actinic ray, as described above, the resin composition can be easily incorporated with the ultraviolet absorber, so that there is an advantage that the durability of the bonded portion can be increased. In particular, blue LED light is preferable in that it has a good balance in terms of high active energy and contains an ultraviolet absorber, and that a light source can be obtained easily and inexpensively.
In the liquid resin composition for actinic radiation curable adhesive of the present invention, the color development of the acid color-forming dye precursor is also achieved by irradiation of actinic radiation used for curing the resin composition, and a colored adhesive part can be obtained. it can. Even when the film thickness of the resin composition is large, the curing of the resin composition is completed prior to the color development of the acid color-forming dye precursor, and the curing rate and the cured film thickness of the resin composition are blocked by shielding the active ray by color development. There is little reduction. If necessary, after the curing of the resin composition is completed, the active color can be further irradiated to complete the color development of the acid color-forming dye precursor.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these 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 Co., Ltd., average functional group number 2] 30 parts by weight, 1-hydroxycyclohexyl phenyl ketone [radical photopolymerization initiator] 2 parts by weight, triarylsulfonium hexafluorophosphate [by actinic radiation irradiation Compound generating acid] 3 parts by weight, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-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 to a thickness of about 100 μm on a 200 mm × 200 mm glass plate using an applicator bar, and another 200 mm × 200 mm glass plate was laminated thereon. When the resin composition was cured by irradiating the resin composition with ultraviolet rays for 1 minute using a metal halide lamp, an adhesive portion colored in blue was confirmed.

Example 2
In Example 1, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide (3 parts by weight) was used as the acid color-forming dye precursor. 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-methylindo-lu-3-yl) phthalide was used. .
This was coated on a glass plate in the same manner as in Example 1, and another glass plate was laminated thereon, followed by curing by irradiation with ultraviolet rays for 1 minute. did.

Example 3
In Example 1, 3 parts by weight of 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide was used as the acid color-forming dye precursor. Instead, 3- [4- (N-ethyl-N-phenylamino) -2-ethoxyphenyl] -3- (1-ethyl-2-methylindol-3-yl) -4,7-diazaphthalide 1.5 A resin composition was obtained in the same manner as in Example 1 except that 1 part by weight and 1.5 parts by weight of 2,6-bis [4-di-n-butylaminobenzoyl] pyridine were used.
This was coated on a glass plate in the same manner as in Example 1, and another glass plate was laminated on it, and then cured by irradiating with ultraviolet rays for 1 minute. did.

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 functional group number 2] 10 parts by weight, urethane acrylate oligomer [radical polymerizable organic compound, product name Photomer 6010, manufactured by Cognis Co., Ltd., average functional group number 2] 25 parts by weight 1,3,5-trimethylbenzoyldiphenylphosphine oxide [radical photopolymerization initiator, trade name Lucillin TPO, manufactured by BASF Corp.] 2 parts by weight, 4-isopropylphenyl-4′-methylphenyliodonium tetrakispentafluorophenyl Borate [by irradiation with actinic radiation Product, product name: RHODORSIL PHOTOINITIATOR 2074, manufactured by Rhodia Japan Ltd.] 3 parts by weight, Coumarin 6 [photosensitizer, also known as 3- [2-benzothiazolyl] -7- [diethylamino] coumarin] 1 part by weight , 1 part by weight of 2-hydroxy-4-methoxybenzophenone [ultraviolet absorber], 3 parts by weight of 2-anilino-3-methyl-6-di-n-butylaminofluorane [acid coloring dye precursor] are stirred. The mixture was sufficiently mixed and stirred using a machine to obtain a uniform liquid resin composition.
This resin composition was uniformly applied to a thickness of about 100 μm on a 200 mm × 200 mm glass plate using an applicator bar, and another 200 mm × 200 mm glass plate was laminated thereon. This was irradiated with blue LED light (peak wavelength of about 460 nm) for 1 minute to cure the resin composition, and as a result, an adhesive portion colored black was confirmed.

Example 5
In Example 4, 3,3-bis (4-diethylamino-2-ethoxy) was used instead of 3 parts by weight of 2-anilino-3-methyl-6-di-n-butylaminofluorane as the acid color-forming dye precursor. Example 3 except that 3 parts by weight of phenyl) -4-azaphthalide and 1 part by weight of 2- (n-butyloxycarbonylmethylthio) anthraquinone instead of 1 part by weight of coumarin 6 were used as a photosensitizer. To obtain a resin composition.
In the same manner as in Example 4, after applying onto a glass plate and pasting another glass plate on it, the blue LED light was irradiated for 1 minute to cure, and an adhesive portion colored green It was confirmed.

Example 6
In Example 4, 3 parts by weight of 3-chloro-6-cyclohexylaminofluorane instead of 3 parts by weight of 2-anilino-3-methyl-6-di-n-butylaminofluorane was used as the acid color-forming dye precursor. As a compound that generates an acid upon irradiation with actinic radiation, 6 parts by weight of bis (4-tert-butylphenyl) iodonium hexafluorophosphate instead of 3 parts by weight of 4-isopropylphenyl-4′-methylphenyliodonium tetrakispentafluorophenylborate A resin composition was obtained by operating in the same manner as in Example 4 except that the parts were used.
In the same manner as in Example 4, after coating on a glass plate and pasting another glass plate on it, the blue LED light was irradiated for 1 minute to cure, and an adhesive portion colored orange It was confirmed.

Example 7
3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate [cationic polymerizable organic compound] 70 parts by weight, 2-hydroxyethyl methacrylate [viscosity reducing copolymer] 30 parts by weight, bis (4-t-Butylphenyl) iodonium hexafluorophosphate [compound that generates acid upon irradiation with actinic radiation] 8 parts by weight, 1,2-benzo-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 not colored.
This resin composition was uniformly applied to a thickness of about 100 μm on a 200 mm × 200 mm glass plate using an applicator bar, and another 200 mm × 200 mm glass plate was laminated thereon. When this was irradiated with ultraviolet rays for 1 minute using a metal halide lamp to cure the resin composition, an adhesive portion colored red was confirmed.

Example 8
3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate [cationic polymerizable organic compound] 70 parts by weight, 2-hydroxyethyl methacrylate [viscosity reducing copolymer] 30 parts by weight, bis (4-t-butylphenyl) iodonium hexafluorophosphate [compound that generates acid upon irradiation with active rays] 8 parts by weight, coumarin 6 [photosensitizer] 1 part by weight, 2-hydroxy-4-methoxybenzophenone [ultraviolet absorption Agent] 1 part by weight, 3,6-di-n-butoxyfluorane [acid coloring dye precursor] 3 parts by weight was 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 to a thickness of about 100 μm on a 200 mm × 200 mm glass plate using an applicator bar, and another 200 mm × 200 mm glass plate was laminated thereon. This was irradiated with blue LED light (peak wavelength of about 460 nm) for 1 minute to cure the resin composition, and an adhesive portion colored yellow was confirmed.

Example 9
In Example 8, instead of 3 parts by weight of 3,6-di-n-butoxyfluorane as an acid color-forming dye precursor, 2- (2,4-dimethylanilino) -3-methyl-6-diethylaminofluor A resin composition was obtained in the same manner as in Example 8 except that 3 parts by weight of oran was used. This was coated on a glass plate in the same manner as in Example 8, and another glass plate was laminated thereon, and then cured by irradiating with blue LED light for 1 minute. It was confirmed.

Example 10
In Example 8, 3 parts by weight of 2-N, N-dibenzylamino-6-diethylaminofluorane was used in place of 3 parts by weight of 3,6-di-n-butoxyfluorane as the acid color-forming dye precursor. The resin composition was obtained by operating in the same manner as in Example 8 except that.
This was coated on a glass plate in the same manner as in Example 8, and after another glass plate was laminated thereon, it was cured by irradiation with blue LED light for 1 minute. It was confirmed.

<Evaluation 1>
About the adhesion part of the laminated glass plate produced in Examples 1-10, sclerosis | hardenability and durability were confirmed as follows. The results are shown in Table 1 below.
Curability:
The cured glass plate was sandwiched by hand and moved left and right to confirm curability. The case where it did not move at all was indicated by ○, and the case where it shifted was indicated by ×.
durability:
Using a xenon fade meter (Suntest XLS +, manufactured by Toyo Seiki Co., Ltd.) using a xenon arc lamp, irradiation was continued for 72 hours from either glass plate surface at 310 W, and the presence or absence of fading was confirmed. .
The case where no fading was observed was indicated by ◎, the case where slight fading was observed, ○, the case where there was a moderate fading, and the case where apparently fading was indicated by ×.

As shown in Table 1, the liquid resin composition for an actinic radiation curable adhesive of the present invention had sufficient curability. Moreover, the light-resistant storage stability was good, and especially the adhesion part which contained the ultraviolet absorber and was hardened | cured by blue LED light irradiation was very excellent in light-resistant storage stability.
Furthermore, the bonding portion has a clear color and sufficient strength, and is very suitable as a liquid resin composition for an active ray curable adhesive capable of full color coloring.

Example 11
Isobornyl acrylate [radical polymerizable organic compound, trade name Light acrylate IB-XA, manufactured by Kyoeisha Chemical Co., Ltd., average functional group number 1] 70 parts by weight, tripropylene glycol diacrylate [radical polymerizable organic compound, trade name APG -200, manufactured by Shin-Nakamura Chemical Co., Ltd., average functional group number 2] 30 parts by weight, 1-hydroxycyclohexyl phenyl ketone [radical photopolymerization initiator] 2 parts by weight, triarylsulfonium hexafluorophosphate [by actinic radiation irradiation Compound generating acid] 3 parts by weight, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-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 with a thickness of about 1000 μm and a 30 mm × 30 mm square using a dispenser. This was irradiated with ultraviolet rays for 1 minute using a metal halide lamp to cure the resin composition. As a result, an adhesive portion colored blue was confirmed.

Example 12
In Example 11, 3 parts by weight of 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide was used as the acid color-forming dye precursor. Instead, 3- [4- (N-ethyl-N-phenylamino) -2-ethoxyphenyl] -3- (1-ethyl-2-methylindol-3-yl) -4,7-diazaphthalide 1.5 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.
In the same manner as in Example 11, after drawing a square of 30 mm × 30 mm on a glass plate and curing by irradiating with ultraviolet rays for 1 minute, an adhesion portion colored green 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, dicyclopentane dimethylol diacrylate [radical polymerizable organic compound, trade name Light acrylate DCP-A, manufactured by Kyoeisha Chemical Co., Ltd., average functional group number 2] 10 parts by weight, urethane acrylate oligomer [radical polymerizable organic compound, product name Photomer 6010, manufactured by Cognis Co., Ltd., average functional group number 2] 25 parts by weight 1,3,5-trimethylbenzoyldiphenylphosphine oxide [radical photopolymerization initiator, trade name Lucillin TPO, manufactured by BASF Corp.] 2 parts by weight, 4-isopropylphenyl-4′-methylphenyliodonium tetrakispentafluorophenyl Borate [by irradiation with actinic radiation Product, product name: RHODORSIL PHOTOINITIATOR 2074, manufactured by Rhodia Japan Ltd.] 3 parts by weight, Coumarin 6 [photosensitizer, also known as 3- [2-benzothiazolyl] -7- [diethylamino] coumarin] 1 part by weight , 1 part by weight of 2-hydroxy-4-methoxybenzophenone [ultraviolet absorber], 3 parts by weight of 2-anilino-3-methyl-6-di-n-butylaminofluorane [acid coloring dye precursor] are stirred. The mixture was sufficiently mixed and stirred using a machine to obtain a uniform liquid resin composition.
This resin composition was drawn on a 200 mm × 200 mm glass plate with a thickness of about 1000 μm and a 30 mm × 30 mm square using a dispenser. This was irradiated with blue LED light (peak wavelength of about 460 nm) for 1 minute to cure the resin composition, and as a result, an adhesive portion colored black was confirmed.

Example 14
In Example 13, instead of 3 parts by weight of 2-anilino-3-methyl-6-di-n-butylaminofluorane as an acid color-forming dye precursor, 3,3-bis (4-diethylamino-2-ethoxy Example 3 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. To obtain a resin composition.
In the same manner as in Example 13, after a 30 mm × 30 mm square was drawn on the glass plate, it was cured by irradiating with blue LED light for 1 minute, and an adhesion portion colored green was confirmed.

Example 15
In Example 13, 3 parts by weight of 3-chloro-6-cyclohexylaminofluorane was used instead of 3 parts by weight of 2-anilino-3-methyl-6-di-n-butylaminofluorane as the acid color-forming dye precursor. As a compound that generates an acid upon irradiation with actinic radiation, 6 parts by weight of bis (4-tert-butylphenyl) iodonium hexafluorophosphate instead of 3 parts by weight of 4-isopropylphenyl-4′-methylphenyliodonium tetrakispentafluorophenylborate A resin composition was obtained by operating in the same manner as in Example 13 except that the parts were used.
In the same manner as in Example 13, after a 30 mm × 30 mm square was drawn on the glass plate, it was cured by irradiating with blue LED light for 1 minute. As a result, an adhesive portion colored orange was confirmed.

Example 16
3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate [cationic polymerizable organic compound] 70 parts by weight, 2-hydroxyethyl methacrylate [viscosity reducing copolymer] 30 parts by weight, bis (4-t-Butylphenyl) iodonium hexafluorophosphate [compound that generates acid upon irradiation with actinic radiation] 8 parts by weight, 1,2-benzo-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 not colored.
This resin composition was drawn on a 200 mm × 200 mm glass plate with a thickness of about 1000 μm and a 30 mm × 30 mm square using a dispenser. When this was irradiated with ultraviolet rays for 1 minute using a metal halide lamp to cure the resin composition, an adhesive portion colored red was confirmed.

Example 17
3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate [cationic polymerizable organic compound] 70 parts by weight, 2-hydroxyethyl methacrylate [copolymer for viscosity reduction] 30 parts by weight, bis (4-t-butylphenyl) iodonium hexafluorophosphate [compound that generates an acid upon irradiation with active rays] 8 parts by weight, coumarin 6 [photosensitizer] 1 part by weight, 2-hydroxy-4-methoxybenzophenone [ultraviolet absorption Agent] 1 part by weight, 3,6-di-n-butoxyfluorane [acid coloring dye precursor] 3 parts by weight was 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 with a thickness of about 1000 μm and a 30 mm × 30 mm square using a dispenser. This was irradiated with blue LED light (peak wavelength of about 460 nm) for 1 minute to cure the resin composition, and an adhesive portion colored yellow was confirmed.

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

The liquid resin composition for active ray curable adhesives of the present invention had a viscosity suitable for adhesives and had sufficient curability. Moreover, the light-resistant storage stability was good, and especially the adhesion part which contained the ultraviolet absorber and was hardened | cured by blue LED light irradiation was very excellent in light-resistant storage stability.
Furthermore, the bonding portion has a clear color and sufficient strength, and is very suitable as a liquid resin composition for an active ray curable adhesive capable of full color coloring.

  The liquid resin composition for an actinic radiation curable adhesive of the present invention can be rapidly cured by irradiation with actinic radiation after bonding, and can also be vividly colored in a desired color by this actinic radiation to color an adhesive part. it can. For this reason, when it is used for adherends such as liquid crystal cells and optical films such as polarizing films, or when used as a sealing agent for polarizing films, the leakage of light is reduced by coloring the adhesion portion black. Therefore, it is very suitable as a liquid resin composition capable of full color coloring with a simple structure.

Claims (5)

A liquid resin composition for an actinic radiation curable adhesive, comprising the following components (A-1), (B), (C) and (D) as essential components.
(A-1) Radical polymerizable organic compound having at least one unsaturated double bond (B) Cationic photopolymerization initiator (C) Acid coloring dye precursor (D) Radical photopolymerization initiator The liquid resin composition for an actinic radiation curable adhesive according to claim 1, further comprising a radical polymerizable organic compound having at least two unsaturated double bonds as the radical polymerizable organic compound. The (C) acid coloring dye precursor is a fluorane compound, a phthalide compound, an azaphthalide compound, a fluorene spirophthalide compound, a triphenylmethane compound, a diphenylmethane compound, a thiazine compound, a lactam compound, or a diketone. The liquid resin composition for an actinic radiation curable adhesive according to claim 1 or 2, which is at least one color former selected from a series compound. The liquid resin composition for an actinic radiation curable adhesive according to any one of claims 1 to 3, which exhibits curing / coloring properties using visible light as an actinic radiation. Furthermore, (E) Liquid resin composition for active ray curable adhesives in any one of Claims 1-4 containing a ultraviolet absorber.