JP6789014B2 - Light-moisture-curable resin composition, adhesive for electronic components, and adhesive for display elements - Google Patents

Description

The present invention relates to a photomoisture-curable resin composition having excellent adhesiveness, weather resistance, and flexibility of a cured product. The present invention also relates to an adhesive for electronic components and an adhesive for display elements using the light-moisture-curable resin composition.

In recent years, liquid crystal display elements, organic EL display elements, and the like have been widely used as display elements having features such as thinness, light weight, and low power consumption. In these display elements, a photocurable resin composition is usually used for sealing a liquid crystal and a light emitting layer, adhering a substrate, an optical film, a protective film, and various members.
By the way, in the present age when mobile devices with various display elements such as mobile phones and portable game machines are widely used, miniaturization of display elements is the most sought after issue, and as a method of miniaturization, the image display unit is narrowed. It is being made into a frame (hereinafter, also referred to as a narrow frame design). However, in the narrow frame design, the photocurable resin composition may be applied to a portion where light does not reach sufficiently, and as a result, the photocurable resin composition applied to a portion where light does not reach is cured. There was a problem that it became insufficient. Therefore, a photothermosetting resin composition is used as a resin composition that can be sufficiently cured even when it is applied to a portion where light does not reach, and both photocuring and thermosetting are used in combination, but at a high temperature. There was a risk that heating would adversely affect the elements and the like.

Further, in recent years, electronic components such as semiconductor chips are required to be highly integrated and miniaturized. For example, a plurality of thin semiconductor chips may be joined via an adhesive layer to form a laminate of semiconductor chips. It is done. Such a laminate of semiconductor chips may be, for example, a method of applying an adhesive on one semiconductor chip, laminating the other semiconductor chip via the adhesive, and then curing the adhesive, or a constant method. It is manufactured by a method of filling an adhesive between semiconductor chips held at intervals of the above and then curing the adhesive.
As an adhesive used for adhering such electronic parts, for example, Patent Document 1 discloses a thermosetting adhesive containing an epoxy compound having a number average molecular weight of 600 to 1000. However, thermosetting adhesives as disclosed in Patent Document 1 are not suitable for bonding electronic components that may be damaged by heat.

As a method for curing a resin composition without heating at a high temperature, Patent Document 2 describes light containing a urethane prepolymer having at least one isocyanate group and at least one (meth) acryloyl group in the molecule. A method of using a moisture-curable resin composition in combination with photocuring and moisture curing is disclosed. However, when a light-moisture-curable resin composition as disclosed in Patent Document 2 is used, the adhesiveness when an adherend such as a substrate is adhered, and the reliability in a high-temperature environment or a high-temperature and high-humidity environment. (Especially creep resistance) and weather resistance may be insufficient. Further, in the conventional photo-moisture-curable resin composition, it is difficult to use the cured product in an application requiring flexibility.

Japanese Unexamined Patent Publication No. 2000-178342 Japanese Unexamined Patent Publication No. 2008-274131

An object of the present invention is to provide a photomoisture-curable resin composition having excellent adhesiveness, weather resistance, and flexibility of a cured product. Another object of the present invention is to provide an adhesive for electronic components and an adhesive for display elements using the light-moisture-curable resin composition.

The present invention is a photo-moisture-curable resin containing a radical-polymerizable compound, a moisture-curable urethane resin, a modified silicone resin having two or more hydrolyzable silyl groups in one molecule, and a photoradical polymerization initiator. It is a composition.
The present invention will be described in detail below.

The present inventors have photo-moisture curing containing a radically polymerizable compound, a moisture-curable urethane resin, a modified silicone resin having two or more hydrolyzable silyl groups in one molecule, and a photoradical polymerization initiator. We have found that the mold resin composition is excellent in adhesiveness, weather resistance, and flexibility of the cured product, and have completed the present invention.

The photomoisture-curable resin composition of the present invention contains a radically polymerizable compound.
The radically polymerizable compound may be any radically polymerizable compound having photopolymerizability, and is not particularly limited as long as it is a compound having a radically reactive functional group in the molecule, but is unsaturated as a radically reactive functional group. A compound having a heavy bond is preferable, and a compound having a (meth) acryloyl group (hereinafter, also referred to as “(meth) acrylic compound”) is particularly preferable from the viewpoint of reactivity.
In the present specification, the above-mentioned "(meth) acryloyl" means acryloyl or methacryloyl, and the above-mentioned "(meth) acrylic" means acrylic or methacrylic.

The (meth) acrylic compound is, for example, a (meth) acrylic acid ester compound obtained by reacting (meth) acrylic acid with a compound having a hydroxyl group, or a (meth) acrylic acid by reacting an epoxy compound. Examples thereof include the obtained epoxy (meth) acrylate and urethane (meth) acrylate obtained by reacting an isocyanate compound with a (meth) acrylic acid derivative having a hydroxyl group.
In addition, in this specification, the said "(meth) acrylate" means acrylate or methacrylate. Further, all the isocyanate groups of the isocyanate compound which is the raw material of the urethane (meth) acrylate are used for forming the urethane bond, and the urethane (meth) acrylate does not have a residual isocyanate group.

Among the above (meth) acrylic acid ester compounds, monofunctional ones include, for example, phthalimide acrylates such as N-acryloyloxyethyl hexahydrophthalimide, various imide (meth) acrylates, methyl (meth) acrylates, and ethyl (meth). Acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) Acrylate, isononyl (meth) acrylate, isodecil (meth) acrylate, lauryl (meth) acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) ) Acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-methoxyethyl ( Meta) acrylate, 2-ethoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, methoxyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethylcarbitol (meth) acrylate, tetrahydrofurfuryl (meth) Meta) acrylate, 2-phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3- Tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinic acid, 2 -(Meta) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl-2-hydroxypropylphthalate, glycidyl (meth) acrylate, 2- (meth) acryloyloxyethyl phosphate and the like can be mentioned.

Among the above (meth) acrylic acid ester compounds, bifunctional ones include, for example, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexane. Dioldi (meth) acrylate, 1,9-nonane dioldi (meth) acrylate, 1,10-decanediol di (meth) acrylate, 2-n-butyl-2-ethyl-1,3-propanedioldi (meth) ) Acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) ) Acrylate, Polypropylene glycol di (meth) acrylate, ethylene oxide-added bisphenol A di (meth) acrylate, propylene oxide-added bisphenol A di (meth) acrylate, ethylene oxide-added bisphenol F di (meth) acrylate, dimethylol dicyclopentadienyldi (Meta) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide-modified isocyanurate di (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, carbonatediol di (meth) acrylate, Examples thereof include polyether diol di (meth) acrylate, polyester diol di (meth) acrylate, polycaprolactone diol di (meth) acrylate, and polybutadiene diol di (meth) acrylate.

Among the above (meth) acrylic acid ester compounds, those having trifunctionality or higher include, for example, trimetyl propanetri (meth) acrylate, ethylene oxide-added trimethyl propanetri (meth) acrylate, and propylene oxide-added trimethyl propanetri (meth) acrylate. Meta) acrylate, caprolactone-modified trimethylol propantri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene oxide-added isocyanuric acid tri (meth) acrylate, glycerin tri (meth) acrylate, propylene oxide-added glycerin tri (meth) acrylate, Examples thereof include tris (meth) acryloyloxyethyl phosphate, ditrimethylolpropantetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.

Examples of the epoxy (meth) acrylate include those obtained by reacting an epoxy compound and (meth) acrylic acid in the presence of a basic catalyst according to a conventional method.

Examples of the epoxy compound used as a raw material for synthesizing the epoxy (meth) acrylate include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and 2,2'-diallyl bisphenol A type epoxy resin. , Hydrogenated bisphenol type epoxy resin, propylene oxide added bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, sulfide type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol Novolac type epoxy resin, orthocresol novolac type epoxy resin, dicyclopentadiene novolac type epoxy resin, biphenyl novolac type epoxy resin, naphthalenephenol novolac type epoxy resin, glycidylamine type epoxy resin, alkyl polyol type epoxy resin, rubber modified epoxy resin , Epoxy ester compounds and the like.

Examples of commercially available bisphenol A type epoxy resins include jER828EL, jER1001, jER1004 (all manufactured by Mitsubishi Chemical Corporation), Epicron 850-S (manufactured by DIC Corporation), and the like.
Examples of commercially available bisphenol F-type epoxy resins include jER806 and jER4004 (both manufactured by Mitsubishi Chemical Corporation).
Examples of commercially available bisphenol S-type epoxy resins include Epicron EXA1514 (manufactured by DIC Corporation).
Among the above 2,2'-diallyl bisphenol A type epoxy resins, commercially available ones include, for example, RE-810NM (manufactured by Nippon Kayaku Co., Ltd.).
Examples of commercially available hydrogenated bisphenol type epoxy resins include Epicron EXA7015 (manufactured by DIC Corporation).
Examples of commercially available propylene oxide-added bisphenol A type epoxy resins include EP-4000S (manufactured by ADEKA Corporation) and the like.
Examples of commercially available resorcinol type epoxy resins include EX-201 (manufactured by Nagase ChemteX Corporation) and the like.
Examples of commercially available biphenyl type epoxy resins include jER YX-4000H (manufactured by Mitsubishi Chemical Corporation) and the like.
Examples of commercially available sulfide-type epoxy resins include YSLV-50TE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
Examples of commercially available diphenyl ether type epoxy resins include YSLV-80DE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) and the like.
Examples of commercially available dicyclopentadiene type epoxy resins include EP-4088S (manufactured by ADEKA Corporation) and the like.
Examples of commercially available naphthalene-type epoxy resins include Epicron HP4032 and Epicron EXA-4700 (both manufactured by DIC Corporation).
Examples of commercially available phenol novolac type epoxy resins include Epicron N-770 (manufactured by DIC Corporation).
Examples of commercially available orthocresol novolac type epoxy resins include Epicron N-670-EXP-S (manufactured by DIC Corporation).
Examples of commercially available dicyclopentadiene novolac type epoxy resins include Epicron HP7200 (manufactured by DIC Corporation).
Examples of commercially available biphenyl novolac type epoxy resins include NC-3000P (manufactured by Nippon Kayaku Co., Ltd.) and the like.
Examples of commercially available naphthalene phenol novolac type epoxy resins include ESN-165S (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
Examples of commercially available glycidylamine type epoxy resins include jER630 (manufactured by Mitsubishi Chemical Corporation), Epicron 430 (manufactured by DIC Corporation), TETRAD-X (manufactured by Mitsubishi Gas Chemical Corporation), and the like.
Commercially available alkyl polyol type epoxy resins include, for example, ZX-1542 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Epicron 726 (manufactured by DIC Corporation), Epolite 80MFA (manufactured by Kyoei Co., Ltd.), and Denacol EX-611. (Manufactured by Nagase ChemteX Corporation) and the like.
Examples of commercially available rubber-modified epoxy resins include YR-450, YR-207 (all manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Epolide PB (manufactured by Daicel Co., Ltd.), and the like.
Examples of commercially available glycidyl ester compounds include Denacol EX-147 (manufactured by Nagase ChemteX Corporation) and the like.
Other commercially available epoxy compounds include, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Corporation), jER1031 and jER1032 (all of which are manufactured by Asahi Kasei Corporation). Mitsubishi Chemical Corporation), EXA-7120 (DIC Corporation), TEPIC (Nissan Chemical Industries, Ltd.) and the like.

Among the above epoxy (meth) acrylates, commercially available ones include, for example, EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3702, EBECRYL3702, EBECRYL3702, EBECRYL3702, EBECRYL370 ), EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (all manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), Epoxy Ester M-600A, Epoxy Ester 40EM, Epoxy Ester 70PA, Epoxy ester 200PA, Epoxy ester 80MFA, Epoxy ester 3002M, Epoxy ester 3002A, Epoxy ester 1600A, Epoxy ester 3000M, Epoxy ester 3000A, Epoxy ester 200EA, Epoxy ester 400EA (all manufactured by Kyoeisha Chemical Co., Ltd.), Denacol acrylate DA-141 , Denacol acrylate DA-314, Denacol acrylate DA-911 (all manufactured by Nagase ChemteX Corporation) and the like.

The urethane (meth) acrylate can be obtained, for example, by reacting an isocyanate compound with a (meth) acrylic acid derivative having a hydroxyl group in the presence of a catalytic amount of a tin compound.

Examples of the isocyanate compound used as a raw material for the urethane (meth) acrylate include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and diphenylmethane-4,4. '-Diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalenediocyanate, norbornan diisocyanate, trizine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanate) Examples thereof include phenyl) thiophosphate, tetramethylxylylene diisocyanate, and 1,6,11-undecantry isocyanate.

The isocyanate compound is obtained by reacting a polyol such as ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, or polycaprolactone diol with an excess of isocyanate compound. Isocyanate compounds with extended chains can also be used.

Examples of the (meth) acrylic acid derivative having a hydroxyl group, which is a raw material of the urethane (meth) acrylate, include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, and 1,4-butane. Mono (meth) acrylate of dihydric alcohol such as diol and polyethylene glycol, mono (meth) acrylate or di (meth) acrylate of trihydric alcohol such as trimethylol ethane, trimetyl propane and glycerin, bisphenol A type epoxy ( Examples thereof include epoxy (meth) acrylate such as meta) acrylate.

Commercially available urethane (meth) acrylates include, for example, M-1100, M-1200, M-1210, M-1600 (all manufactured by Toa Synthetic Co., Ltd.), EBECRYL230, EBECRYL270, EBECRYL4858, EBECRYL8402, EBECRYL8411, EBECRYL8412, EBECRYL8413, EBECRYL8804, EBECRYL8803, EBECRYL8807, EBECRYL9260, EBECRYL1290, EBECRYL5129, EBECRYL4842, EBECRYL210, EBECRYL4827, EBECRYL6700, EBECRYL220, EBECRYL2220, KRM7735, KRM-8295 (all manufactured by Daicel-Orunekusu Co., Ltd.), Art resin UN-9000H , Art Resin UN-9000A, Art Resin UN-7100, Art Resin UN-1255, Art Resin UN-330, Art Resin UN-3320HB, Art Resin UN-1200TPK, Art Resin SH-500B (all manufactured by Negami Kogyo Co., Ltd.) , U-2HA, U-2PHA, U-3HA, U-4HA, U-6H, U-6LPA, U-6HA, U-10H, U-15HA, U-122A, U-122P, U-108, U -108A, U-324A, U-340A, U-340P, U-1084A, U-2061BA, UA-340P, UA-4100, UA-4000, UA-4200, UA-4400, UA-5201P, UA-7100 , UA-7200, UA-W2A (all manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), AI-600, AH-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA-306T (Both are manufactured by Kyoeisha Chemical Co., Ltd.) and the like.

In addition, other radically polymerizable compounds other than those described above can also be used as appropriate.
Examples of the other radically polymerizable compounds include N, N-dimethyl (meth) acrylamide, N- (meth) acryloylmorpholine, N-hydroxyethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, and N. -Isopropyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide and other (meth) acrylamide compounds, styrene, α-methylstyrene, N-vinyl-2-pyrrolidone, N-vinyl-ε-caprolactam and the like Examples include vinyl compounds.

The radically polymerizable compound preferably contains a monofunctional radically polymerizable compound and a polyfunctional radically polymerizable compound from the viewpoint of adjusting curability and the like. By containing the monofunctional radical polymerizable compound and the polyfunctional radical polymerizable compound, the obtained photomoisture-curable resin composition becomes more excellent in curability and tackiness. Among them, it is preferable to use urethane (meth) acrylate as the polyfunctional radically polymerizable compound in combination with the monofunctional radically polymerizable compound. Further, the polyfunctional radical polymerizable compound is preferably bifunctional or trifunctional, and more preferably bifunctional.

When the radical-polymerizable compound contains the monofunctional radical-polymerizable compound and the polyfunctional radical-polymerizable compound, the content of the polyfunctional radical-polymerizable compound is the monofunctional radical-polymerizable compound and the polyfunctional radical-polymerizable compound. The preferable lower limit is 2 parts by weight and the preferable upper limit is 45 parts by weight with respect to 100 parts by weight in total with the functional radical polymerizable compound. When the content of the polyfunctional radical polymerizable compound is in this range, the obtained photomoisture-curable resin composition is more excellent in curability and tackiness. The more preferable lower limit of the content of the polyfunctional radical polymerizable compound is 5 parts by weight, and the more preferable upper limit is 35 parts by weight.

Regarding the content of the radically polymerizable compound, a preferable lower limit is 10 parts by weight and a preferable upper limit is 80 parts by weight with respect to a total of 100 parts by weight of the radically polymerizable compound, the moisture-curable urethane resin and the modified silicone resin. Is. When the content of the radically polymerizable compound is in this range, the obtained photomoisture-curable resin composition is photocurable while maintaining excellent moisture curability, weather resistance, and flexibility of the cured product. Will be better. The more preferable lower limit of the content of the radically polymerizable compound is 20 parts by weight, and the more preferable upper limit is 70 parts by weight.

The photomoisture-curable resin composition of the present invention contains a moisture-curable urethane resin. In the moisture-curable urethane resin, the isocyanate group in the molecule reacts with the moisture in the air or the adherend to cure.

The moisture-curable urethane resin may have only one isocyanate group in one molecule, or may have two or more isocyanate groups. Of these, it is preferable to have isocyanate groups at both ends of the main chain of the molecule.
The moisture-curable urethane resin can be obtained by reacting a polyol compound having two or more hydroxyl groups in one molecule with a polyisocyanate compound having two or more isocyanate groups in one molecule.

The reaction between the polyol compound and the polyisocyanate compound is usually performed by the molar ratio of the hydroxyl group (OH) in the polyol compound to the isocyanate group (NCO) in the polyisocyanate compound [NCO] / [OH] = 2.0 to 2. It is done in the range of .5.

As the polyol compound, known polyol compounds usually used for producing polyurethane can be used, and examples thereof include polyester polyols, polyether polyols, polyalkylene polyols, and polycarbonate polyols. These polyol compounds may be used alone or in combination of two or more.

Examples of the polyester polyol include a polyester polyol obtained by reacting a polyvalent carboxylic acid with a polyol, a poly-ε-caprolactone polyol obtained by ring-opening polymerization of ε-caprolactone, and the like.

Examples of the polyvalent carboxylic acid used as a raw material for the polyester polyol include terephthalic acid, isophthalic acid, 1,5-naphthalic acid, 2,6-naphthalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, and suberic acid. Examples thereof include acids, adipic acid, suberic acid, decamethylenedicarboxylic acid and dodecamethylenedicarboxylic acid.

Examples of the polyol used as a raw material of the polyester polyol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, and 1,6-hexane. Examples thereof include diol, diethylene glycol and cyclohexanediol.

Examples of the polyether polyol include ring-opening polymers of ethylene glycol, propylene glycol and tetrahydrofuran, ring-opening polymers of 3-methyl tetrahydrofuran, and random copolymers or block copolymers of these or derivatives thereof, bisphenols. Examples thereof include type polyoxyalkylene modified products.

The bisphenol-type polyoxyalkylene modified product is a polyether polyol obtained by adding an alkylene oxide (for example, ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, etc.) to the active hydrogen moiety of the bisphenol type molecular skeleton. It may be a random copolymer or a block copolymer. The bisphenol-type polyoxyalkylene modified product preferably has one or more alkylene oxides added to both ends of the bisphenol-type molecular skeleton. The bisphenol type is not particularly limited, and examples thereof include A type, F type, and S type, and bisphenol A type is preferable.

Examples of the polyalkylene polyol include a polybutadiene polyol, a hydrogenated polybutadiene polyol, and a hydrogenated polyisoprene polyol.

Examples of the polycarbonate polyol include polyhexamethylene carbonate polyol and polycyclohexanedimethylene carbonate polyol.

Examples of the polyisocyanate compound include diphenylmethane diisocyanate, liquid modified products of diphenylmethane diisocyanate, polypeptide MDI, tolylene diisocyanate, naphthalene-1,5-diisocyanate and the like. Of these, diphenylmethane diisocyanate and its liquid modified product are preferable from the viewpoints of low vapor pressure, low toxicity, and ease of handling. The polyisocyanate compound may be used alone or in combination of two or more.

Further, the moisture-curable urethane resin is preferably obtained by using a polyol compound having a structure represented by the following formula (1). By using a polyol compound having a structure represented by the following formula (1), a composition having excellent adhesiveness and a cured product having flexibility and good elongation can be obtained, and compatibility with the above radically polymerizable compound. Will be excellent.
Of these, those using a polyether polyol composed of a ring-opening polymerization compound of propylene glycol or a tetrahydrofuran (THF) compound or a ring-opening polymerization compound of a tetrahydrofuran compound having a substituent such as a methyl group are preferable.

In the formula (1), R represents hydrogen, a methyl group, or an ethyl group, n is an integer of 1 to 10, L is an integer of 0 to 5, and m is an integer of 1 to 500. n is preferably 1 to 5, L is preferably 0 to 4, and m is preferably 50 to 200.
The case where L is 0 means the case where the carbon bonded to R is directly bonded to oxygen.

Further, the moisture-curable urethane resin may have a radically polymerizable functional group.
As the radically polymerizable functional group that the moisture-curable urethane resin may have, a group having an unsaturated double bond is preferable, and a (meth) acryloyl group is more preferable from the viewpoint of reactivity.
The moisture-curable urethane resin having a radical-polymerizable functional group is not included in the radical-polymerizable compound and is treated as a moisture-curable urethane resin.

The weight average molecular weight of the moisture-curable urethane resin is not particularly limited, but the preferable lower limit is 800 and the preferable upper limit is 10,000. When the weight average molecular weight of the moisture-curable urethane resin is in this range, the obtained light-moisture-curable resin composition does not have an excessively high crosslink density at the time of curing and becomes more flexible, and has better coatability. It will be excellent. The more preferable lower limit of the weight average molecular weight of the moisture-curable urethane resin is 2000, the more preferable upper limit is 8000, the further preferable lower limit is 2500, and the further preferable upper limit is 6000.
In the present specification, the weight average molecular weight is a value obtained by measuring by gel permeation chromatography (GPC) and converting into polystyrene. Examples of the column for measuring the weight average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko KK) and the like. Further, examples of the solvent used in GPC include tetrahydrofuran and the like.

Regarding the content of the moisture-curable urethane resin, the preferable lower limit is 20 parts by weight and the preferable upper limit is 90 parts by weight with respect to a total of 100 parts by weight of the radically polymerizable compound, the moisture-curable urethane resin and the modified silicone resin. It is a department. When the content of the moisture-curable urethane resin is in this range, the obtained photomoisture-curable resin composition is moisture-curable while maintaining excellent photocurability, weather resistance, and flexibility of the cured product. It becomes better in sex. The more preferable lower limit of the content of the moisture-curable urethane resin is 30 parts by weight, and the more preferable upper limit is 75 parts by weight.

The photomoisture-curable resin composition of the present invention contains a modified silicone resin having two or more hydrolyzable silyl groups in one molecule.
By containing the above-mentioned modified silicone resin, the light-moisture-curable resin composition of the present invention has excellent weather resistance and flexibility of the cured product.
In addition, "two or more" of the above "having two or more hydrolyzable silyl groups in one molecule" means an average value. Further, the modified silicone resin having a radically polymerizable functional group is not included in the radically polymerizable compound and is treated as a modified silicone resin.

Examples of the hydrolyzable silyl group include an alkoxysilyl group, a halosilyl group, an alkenyloxysilyl group, an acyloxysilyl group, and an aminosilyl group. Of these, an alkoxysilyl group is preferable.

Examples of the alkoxysilyl group include a trimethoxysilyl group, a triethoxysilyl group, a dimethoxymethylsilyl group, a dimethoxyethylsilyl group, a diethoxymethylsilyl group, a diethoxyethylsilyl group, a methoxydimethylsilyl group, and a methoxydiethylsilyl group. , Ethoxydimethylsilyl group, ethoxydiethylsilyl group and the like.

The modified silicone resin preferably has a hydrolyzable silyl group at the end of the main chain of the molecule, and more preferably has a hydrolyzable silyl group at both ends of the main chain of the molecule.

The modified silicone resin preferably has at least one skeleton selected from a polyalkylene glycol skeleton, a poly (meth) acrylic skeleton, a polyalkylene skeleton, a polysiloxane skeleton, and a polyurethane skeleton in the main chain, and is stored. From the viewpoint of stability, quick-curing property, and mechanical strength of the cured product, it is preferable to have a polyalkylene glycol skeleton and / or a poly (meth) acrylic skeleton in the main chain.

Examples of the polyalkylene glycol skeleton include a polyethylene glycol skeleton and a polypropylene glycol skeleton.

Examples of the poly (meth) acrylic skeleton include a poly (meth) acrylic acid skeleton, a poly (meth) methyl acrylate skeleton, and a poly (meth) ethyl acrylate skeleton.

Specifically, the modified silicone resin has the following formula (2-) between the structural unit represented by the following formula (2-1) and the structural unit represented by the following formula (2-2). A compound having a structural unit represented by 3) and / or a structural unit represented by the following formula (2-4) is preferably used.

In formula (2-1), R ¹ and R ² are independently alkyl groups having 1 to 10 carbon atoms, p is an integer of 1 to 3, and * is a bond position.
In formula (2-2), R ³ and R ⁴ are independently alkyl groups having 1 to 10 carbon atoms, q is an integer of 1 to 3, and * is a bond position.
In the formula (2-3), R ⁵ is an alkylene group having 1 to 14 carbon atoms, and * is a bond position.
In formula (2-4), R ⁶ is a hydrogen or methyl group, R ⁷ is an alkyl group having 1 to 10 carbon atoms, and * is a bond position.

The preferable lower limit of the number average molecular weight of the modified silicone resin is 2000, and the preferable upper limit is 100,000. When the number average molecular weight of the modified silicone resin is in this range, the phase with the radically polymerizable compound and the moisture-curable urethane resin is not deteriorated without deteriorating the coatability of the obtained photomoisture-curable resin composition. It becomes more soluble. The more preferable lower limit of the number average molecular weight of the modified silicone resin is 3000, and the more preferable upper limit is 50,000.
In the present specification, the number average molecular weight is a value obtained by measuring by gel permeation chromatography (GPC) and converting into polystyrene. Examples of the column for measuring the number average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko KK) and the like.

The content of the modified silicone resin is such that the preferable lower limit is 1 part by weight and the preferable upper limit is 20 parts by weight with respect to 100 parts by weight of the total of the radical polymerizable compound, the moisture-curable urethane resin and the modified silicone resin. is there. When the content of the modified silicone resin is in this range, the obtained photomoisture-curable resin composition is excellent in weather resistance and flexibility of the cured product while maintaining excellent photocurability and moisture curability. It becomes. The more preferable lower limit of the content of the modified silicone resin is 2 parts by weight, and the more preferable upper limit is 18 parts by weight.

The photomoisture-curable resin composition of the present invention contains a photoradical polymerization initiator.
Examples of the photoradical polymerization initiator include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanosen compounds, oxime ester compounds, benzoin ether compounds, thioxanthone and the like.

Commercially available photoradical polymerization initiators include, for example, IRGACURE184, IRGACURE369, IRGACURE379, IRGACURE651, IRGACURE784, IRGACURE819, IRGACURE907, IRGACURE2959, IRGACURE OXE01, and Lucillin TPO. , Benzoin ethyl ether, benzoin isopropyl ether (all manufactured by Tokyo Chemical Industry Co., Ltd.) and the like.

The content of the photoradical polymerization initiator is preferably 0.01 part by weight and a preferable upper limit is 10 parts by weight with respect to 100 parts by weight of the radically polymerizable compound. When the content of the photoradical polymerization initiator is in this range, the obtained photomoisture-curable resin composition is more excellent in photocurability and storage stability. The more preferable lower limit of the content of the photoradical polymerization initiator is 0.1 parts by weight, and the more preferable upper limit is 5 parts by weight.

The photomoisture-curable resin composition of the present invention may contain a filler from the viewpoint of adjusting the coatability and shape retention of the obtained photomoisture-curable resin composition. In the above-mentioned filler, the preferable lower limit of the primary particle size is 1 nm, and the preferable upper limit is 50 nm. If the primary particle size of the filler is less than 1 nm, the obtained photomoisture-curable resin composition may be inferior in coatability. If the primary particle size of the filler exceeds 50 nm, the obtained photomoisture-curable resin composition may be inferior in shape retention after application. The more preferable lower limit of the primary particle size of the filler is 5 nm, the more preferable upper limit is 30 nm, the further preferable lower limit is 10 nm, and the further preferable upper limit is 20 nm. The primary particle size of the filler can be measured by using NICOMP 380ZLS (manufactured by PARTICLE SIZING SYSTEMS) to disperse the filler in a solvent (water, organic solvent, etc.).
Further, the filler may be present as secondary particles (a collection of a plurality of primary particles) in the photomoisture-curable resin composition of the present invention, and a preferable lower limit of the particle size of such secondary particles. Is 5 nm, the preferred upper limit is 500 nm, the more preferred lower limit is 10 nm, and the more preferred upper limit is 100 nm. The particle size of the secondary particles of the filler can be measured by observing the photomoisture-curable resin composition of the present invention or a cured product thereof using a transmission electron microscope (TEM).

Examples of the filler include silica, talc, titanium oxide, zinc oxide and the like. Of these, silica is preferable because the obtained light-moisture-curable resin composition has excellent UV light transmission. These fillers may be used alone or in combination of two or more.

The filler preferably has a hydrophobic surface treatment. By the above hydrophobic surface treatment, the obtained photomoisture-curable resin composition becomes more excellent in shape retention after application.
Examples of the hydrophobic surface treatment include a silylation treatment, an alkylation treatment, and an epoxidation treatment. Among them, the silylation treatment is preferable, and the trimethylsilylation treatment is more preferable because the effect of improving the shape retention is excellent.

Examples of the method for treating the hydrophobic surface of the filler include a method of treating the surface of the filler with a surface treatment agent such as a silane coupling agent.
Specifically, for example, the above-mentioned trimethylsilylated silica can be obtained by, for example, synthesizing silica by a method such as a sol-gel method and spraying hexamethyldisilazane with the silica flowing, or an organic solvent such as alcohol or toluene. It can be produced by adding silica to the inside, further adding hexamethyldisilazane and water, and then evaporating and drying the water and an organic solvent with an evaporator or the like.

The content of the filler is preferably 1 part by weight and a preferable upper limit of 20 parts by weight in 100 parts by weight of the entire photomoisture-curable resin composition of the present invention. If the content of the filler is less than 1 part by weight, the obtained photomoisture-curable resin composition may be inferior in shape retention after coating. If the content of the filler exceeds 20 parts by weight, the obtained light-moisture-curable resin composition may be inferior in coatability. The more preferable lower limit of the content of the filler is 2 parts by weight, the more preferable upper limit is 15 parts by weight, the further preferable lower limit is 3 parts by weight, the further preferable upper limit is 10 parts by weight, and the particularly preferable lower limit is 4 parts by weight. ..

The light-moisture-curable resin composition of the present invention may contain a light-shielding agent. By containing the above-mentioned light-shielding agent, the light-moisture-curable resin composition of the present invention has excellent light-shielding properties and can prevent light leakage from the display element.
In the present specification, the above-mentioned "light-shielding agent" means a material having an ability to hardly transmit light in the visible light region.

Examples of the light-shielding agent include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, resin-coated carbon black and the like. Further, the light-shielding agent does not have to be black, and as long as it is a material having an ability to hardly transmit light in the visible light region, materials listed as fillers such as silica, talc, and titanium oxide are also mentioned above. Included in the light-shielding agent. Of these, titanium black is preferable.

The titanium black is a substance having a higher transmittance in the vicinity of the ultraviolet region, particularly in light having a wavelength of 370 to 450 nm, as compared with the average transmittance for light having a wavelength of 300 to 800 nm. That is, the titanium black has the property of imparting light-shielding properties to the light-moisture-curable resin composition of the present invention by sufficiently blocking light having a wavelength in the visible light region, while transmitting light having a wavelength near the ultraviolet region. It is a light-shielding agent having. Therefore, by using a photoradical polymerization initiator that can initiate the reaction with light having a wavelength (370 to 450 nm) at which the transmittance of titanium black is high, the light of the photomoisture-curable resin composition of the present invention can be used. The curability can be further increased. On the other hand, as the light-shielding agent contained in the light-moisture-curable resin composition of the present invention, a substance having high insulating properties is preferable, and titanium black is also preferable as the light-shielding agent having high insulating properties.
The titanium black has an optical density (OD value) of preferably 3 or more, and more preferably 4 or more. Further, the titanium black preferably has a blackness (L value) of 9 or more, and more preferably 11 or more. The higher the light-shielding property of the titanium black, the better, and the OD value of the titanium black has no particular preferable upper limit, but is usually 5 or less.

The above titanium black exerts a sufficient effect even if it is not surface-treated, but the surface is treated with an organic component such as a coupling agent, silicon oxide, titanium oxide, germanium oxide, aluminum oxide, or oxidation. Surface-treated titanium black, such as those coated with an inorganic component such as zirconium or magnesium oxide, can also be used. Among them, those treated with an organic component are preferable in that the insulating property can be further improved.
Further, the display element manufactured by using the light-moisture-curable resin composition of the present invention is excellent because the light-moisture-curable resin composition has sufficient light-shielding properties and therefore has high contrast without light leakage. It will have the image display quality.

The preferable lower limit of the specific surface area of the titanium black is 5 m ² / g, the preferable upper limit is 40 m ² / g, the more preferable lower limit is 10 m ² / g, and the more preferable upper limit is 25 m ² / g.
Moreover, the preferable lower limit of the sheet resistance of the titanium black, when mixed with the resin (70% formulation), 10 ⁹ Ω / □ and a more preferred lower limit is 10 ¹¹ Ω / □.

Examples of commercially available titanium blacks include 12S, 13M, 13M-C, 13RN (all manufactured by Mitsubishi Materials Co., Ltd.), Tilak D (manufactured by Ako Kasei Co., Ltd.), and the like.

In the photomoisture-curable resin composition of the present invention, the primary particle size of the light-shielding agent is appropriately selected depending on the application, such as the distance between the substrates of the display element or less, but the preferable lower limit is 30 nm and the preferable upper limit is 500 nm. Is. If the primary particle size of the light-shielding agent is less than 30 nm, the viscosity and thixotropy of the obtained light-moisture-curable resin composition may be significantly increased, resulting in poor workability. If the primary particle size of the light-shielding agent exceeds 500 nm, the dispersibility of the light-shielding agent in the obtained light-moisture-curable resin composition may decrease, and the light-shielding property may decrease. The more preferable lower limit of the primary particle diameter of the light shielding agent is 50 nm, and the more preferable upper limit is 200 nm. The particle size of the light-shielding agent can be measured by using NICOMP 380ZLS (manufactured by PARTICLE SIZING SYSTEMS) and dispersing the light-shielding agent in a solvent (water, organic solvent, etc.).

The content of the light-shielding agent in the entire light-moisture-curable resin composition of the present invention is not particularly limited, but the preferable lower limit is 0.05% by weight and the preferable upper limit is 10% by weight. If the content of the light-shielding agent is less than 0.05% by weight, sufficient light-shielding properties may not be obtained. If the content of the light-shielding agent exceeds 10% by weight, the adhesiveness of the obtained light-moisture-curable resin composition to a substrate or the like, the strength after curing may decrease, or the drawability may decrease. The more preferable lower limit of the content of the light-shielding agent is 0.1% by weight, the more preferable upper limit is 2% by weight, and the further preferable upper limit is 1% by weight.

The photomoisture-curable resin composition of the present invention may further contain additives such as a colorant, an ionic liquid, a solvent, metal-containing particles, and a reactive diluent, if necessary.

As a method for producing the photomoisture-curable resin composition of the present invention, for example, a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, or a three-roll is used to obtain a radically polymerizable compound. Examples thereof include a method of mixing a moisture-curable urethane resin, a modified silicone resin, a photoradical polymerization initiator, and an additive added as needed.

The light-moisture-curable resin composition of the present invention preferably contains 100 ppm or less of water. When the water content exceeds 100 ppm, the moisture-curable urethane resin easily reacts with the moisture during storage, and the light-moisture-curable resin composition becomes inferior in storage stability. The water content is more preferably 80 ppm or less.
The water content can be measured by a Karl Fischer titer measuring device.

In the photomoisture-curable resin composition of the present invention, the preferable lower limit of the viscosity measured at 25 ° C. and 1 rpm using a cone plate type viscometer is 50 Pa · s, and the preferable upper limit is 1000 Pa · s. When the above viscosity is in this range, the workability when the light-moisture-curable resin composition is applied to an adherend such as a substrate when used as an adhesive for electronic parts or an adhesive for display elements is improved. Become. The more preferable lower limit of the viscosity is 80 Pa · s, the more preferable upper limit is 500 Pa · s, and the further preferable upper limit is 400 Pa · s.
If the viscosity of the photomoisture-curable resin composition of the present invention is too high, the coatability can be improved by heating at the time of coating.

The preferred lower limit of the thixotropic index of the photomoisture-curable resin composition of the present invention is 1.3, and the preferred upper limit is 5.0. When the thixotropic index is in this range, the workability when the photomoisture-curable resin composition is applied to an adherend such as a substrate when used as an adhesive for electronic parts or an adhesive for display elements is excellent. It becomes a thing. The more preferable lower limit of the thixotropic index is 1.5, and the more preferable upper limit is 4.0.
In the present specification, the above-mentioned thixotropic index is a viscosity measured under the condition of 25 ° C. and 1 rpm using a cone plate type viscometer, and measured under the condition of 25 ° C. and 10 rpm using a cone plate type viscometer. It means the value divided by the viscosity.

The light-moisture-curable resin composition of the present invention preferably has an optical density (OD value) of 1 or more for a cured product having a thickness of 1 mm after curing. When the OD value is 1 or more, the light-shielding property is excellent, light leakage can be prevented when used in a display element, and high contrast can be obtained. The OD value is more preferably 1.5 or more.
The higher the OD value is, the better. However, if too much light-shielding agent is added in order to increase the OD value, workability is deteriorated due to thickening, so that the balance with the amount of the light-shielding agent is balanced. The preferable upper limit of the OD value of the cured product is 4.
The OD value of the light-moisture-curable resin composition after curing can be measured using an optical densitometer.

Examples of the adherend that can be adhered using the photomoisture-curable resin composition of the present invention include various adherends such as metal, glass, and plastic.
Examples of the shape of the adherend include a film shape, a sheet shape, a plate shape, a panel shape, a tray shape, a rod (rod shape) shape, a box shape, a housing shape, and the like.

Examples of the metal include steel, stainless steel, aluminum, copper, nickel, chromium or an alloy thereof.
Examples of the glass include alkaline glass, non-alkali glass, quartz glass and the like.
Examples of the plastic include polyolefin resins such as high-density polyethylene, ultra-high molecular weight polyethylene, isotactic polypropylene, syndiotactic polypropylene, and ethylene-propylene copolymer resin, nylon 6 (N6), nylon 66 (N66), and the like. Nylon 46 (N46), Nylon 11 (N11), Nylon 12 (N12), Nylon 610 (N610), Nylon 612 (N612), Nylon 6/66 copolymer (N6 / 66), Nylon 6/66/610 Polyamide resin such as polymer (N6 / 66/610), nylon MXD6 (MXD6), nylon 6T, nylon 6 / 6T copolymer, nylon 66 / PP copolymer, nylon 66 / PPS copolymer, polybutylene Telephthalate (PBT), polyethylene terephthalate (PET), polyethylene isophthalate (PEI), PET / PEI copolymer, polyarylate (PAR), polybutylene naphthalate (PBN), liquid crystal polyester, polyoxyalkylene diimide diic acid / poly Aromatic polyester resins such as butylene terephthalate copolymer, polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile / styrene copolymer (AS), methacrylonitrile / styrene copolymer, methacrylonitrile / styrene / butadiene Polynitrile-based resin such as copolymer, polycarbonate, polymethacrylate-based resin such as polymethylmethacrylate (PMMA), polyethyl methacrylate, ethylene / vinyl acetate copolymer (EVA), polyvinyl alcohol (PVA), vinyl alcohol / Examples thereof include polyvinyl-based resins such as ethylene copolymer (EVOH), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), vinyl chloride / vinylidene chloride copolymer, and vinylidene chloride / methyl acrylate copolymer.

Further, examples of the adherend include a composite material having a metal plating layer on the surface, and examples of the base material for plating the composite material include the above-mentioned metal, glass, plastic and the like.
Further, as the adherend, a material in which a passivation film is formed by passivating a metal surface can be mentioned, and examples of the passivation treatment include heat treatment and anodic oxidation treatment. .. In particular, in the case of an aluminum alloy or the like whose international aluminum alloy name is in the 6000 series, the adhesiveness can be improved by performing an alumite sulfate treatment or an alumite phosphate treatment as the immobilization treatment.

Examples of the method of adhering the adherend using the photo-moisture-curable resin composition of the present invention include a step of applying the photo-moisture-curable resin composition of the present invention to the first member and the above-mentioned first. A step of irradiating the light-moisture-curable resin composition of the present invention applied to a member with light to cure the radically polymerizable compound in the photo-moisture-curable resin composition of the present invention (first curing step), and the above. A step of laminating the first member and the second member via the light-moisture-curable resin composition after the first curing step (bonding step), and after the laminating step, the light-moisture curing of the present invention. Examples thereof include a method including a step of adhering the first member and the second member by moisture curing of the moisture-curable urethane resin in the mold resin composition (second curing step), and the above-mentioned bonding. It is preferable to include a step of irradiating light after the step. By including the step of irradiating light after the bonding step, the adhesiveness (initial adhesiveness) immediately after the bonding with the adherend can be improved. When the first member and / or the second member is a material that transmits light, it is preferable to irradiate the light through the first member and / or the second member that transmits light. When the first member and / or the second member is made of a material that does not easily transmit light, the first member and the second member are interposed via the light-moisture-curable resin composition. It is preferable to irradiate the side surface of the bonded structure, that is, the portion where the light-moisture-curable resin composition is exposed with light.

The photomoisture-curable resin composition of the present invention can be particularly preferably used as an adhesive for electronic parts and an adhesive for display elements. An adhesive for electronic components made of the light-moisture-curable resin composition of the present invention and an adhesive for a display element made of the light-moisture-curable resin composition of the present invention are also one of the present inventions, respectively.

According to the present invention, it is possible to provide a light-moisture-curable resin composition having excellent adhesiveness, weather resistance, and flexibility of a cured product. Further, according to the present invention, it is possible to provide an adhesive for electronic parts and an adhesive for display elements using the light-moisture-curable resin composition.

(A) is a schematic view showing the case where the adhesiveness evaluation sample is viewed from above, and (b) is a schematic view showing the case where the adhesiveness evaluation sample is viewed from the side.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

(Synthesis Example 1 (Production of Moisture Curable Urethane Resin A))
100 parts by weight of polytetramethylene ether glycol (manufactured by Mitsubishi Chemical Corporation, "PTMG-2000") and 0.01 parts by weight of dibutyltin dilaurate as a polyol compound were placed in a 500 mL separable flask and placed under vacuum (20 mmHg). Below), stirred at 100 ° C. for 30 minutes and mixed. After that, the pressure was adjusted to normal, and 26.5 parts by weight of diphenylmethane diisocyanate (“Pure MDI” manufactured by Nisso Shoji Co., Ltd.) was added as a polyisocyanate compound, and the mixture was stirred at 80 ° C. for 3 hours to react, and the moisture-curable urethane resin A (weight An average molecular weight of 2700) was obtained.

(Synthesis Example 2 (Production of Moisture Curable Urethane Resin B))
As a polyol compound, 100 parts by weight of polypropylene glycol (manufactured by Asahi Glass Co., Ltd., "EXCENOL 2020") and 0.01 parts by weight of dibutyltin dilaurate are placed in a 500 mL separable flask, and placed under vacuum (20 mmHg or less) at 100 ° C. Was stirred for 30 minutes and mixed. After that, the pressure was adjusted to normal pressure, and 26.5 parts by weight of diphenylmethane diisocyanate (“Pure MDI” manufactured by Nisso Shoji Co., Ltd.) was added as a polyisocyanate compound, and the mixture was stirred at 80 ° C. for 3 hours to react, and the moisture-curable urethane resin B (weight) An average molecular weight of 2900) was obtained.

(Synthesis Example 3 (Production of Moisture Curable Urethane Resin C))
In a reaction vessel containing 100 parts by weight of the moisture-curable urethane resin A obtained in the same manner as in Synthesis Example 1, 9.8 parts by weight of 3-mercaptopropyltrimethoxysilane (manufactured by Shinetsu Chemical Industry Co., Ltd., "KBM-803"). Was added, and the mixture was stirred and mixed at 80 ° C. for 1 hour to obtain a moisture-curable urethane resin C (weight average molecular weight 3100) having an isocyanate group and a trimethoxysilyl group at the molecular terminals.

(Examples 1 to 7, Comparative Examples 1 to 4)
According to the compounding ratios shown in Table 1, each material is stirred with a planetary stirrer (Sinky, "Awatori Rentaro"), and then uniformly mixed with three ceramic rolls in Example 1. ~ 7, light moisture-curable resin compositions of Comparative Examples 1 to 4 were obtained.
In Table 1, "KANEKA XMAP SA100S" is a modified silicone resin having dimethoxymethylsilyl groups at both ends of the molecule and a polyacrylic skeleton in the main chain, and "Kaneka MS Polymer S943" is the molecule. It is a modified silicone resin having dimethoxymethylsilyl groups at both ends and a polypropylene glycol skeleton and a polyacrylic skeleton in the main chain. "Cyril MA440" has dimethoxymethylsilyl groups at both ends of the molecule and the main chain. It is a modified silicone resin having a polypropylene glycol skeleton and a polyacrylic skeleton.

<Evaluation>
The following evaluations were carried out for each light-moisture-curable resin composition obtained in Examples and Comparative Examples. The results are shown in Table 1.

(Adhesiveness)
Each light-moisture-curable resin composition obtained in Examples and Comparative Examples was applied onto an aluminum substrate with a width of about 2 mm using a dispensing device. Next, the photo-moisture-curable resin composition was photo-cured by irradiating it with ultraviolet rays at 3000 mJ / cm ² using a UV-LED (wavelength 365 nm), and then another aluminum substrate was overlaid and a 20 g weight was placed. , It was allowed to stand overnight to be cured by moisture to obtain a sample for adhesiveness evaluation.
FIG. 1 is a schematic view showing a case where the adhesiveness evaluation sample is viewed from above (FIG. 1 (a)) and a schematic view showing a case where the adhesiveness evaluation sample is viewed from the side (FIG. 1 (b)). showed that.
The prepared adhesiveness evaluation sample is pulled at a speed of 5 mm / sec in the shearing direction using a tensile tester (manufactured by Shimadzu Corporation, "Ez-Grapf"), and the strength (adhesive strength) when the aluminum substrates are peeled off. ) Was measured and the adhesiveness was evaluated.

(Creep resistance)
A high-temperature reliability evaluation sample was prepared in the same manner as the adhesiveness evaluation sample in the above "(adhesiveness)" evaluation. The obtained high-temperature reliability evaluation sample was hung perpendicular to the ground, placed in an oven at 100 ° C. with a 100 g weight hung on one end of an aluminum substrate, and allowed to stand for 72 hours. "○" if the aluminum substrates were not peeled off after 72 hours of standing, "△" if the aluminum substrates were peeled off after 12 hours or more and less than 72 hours after standing, and less than 12 hours after standing. The creep resistance of the light-moisture-curable resin composition was evaluated as "x" when the aluminum substrates were peeled off from each other.

(Moisture and heat resistance)
A high-temperature reliability evaluation sample was prepared in the same manner as the adhesiveness evaluation sample in the above "(adhesiveness)" evaluation. The obtained high-temperature reliability evaluation sample was hung perpendicular to the ground, placed in an oven at 50 ° C. and 60% RH with a weight of 100 g hung on one end of an aluminum substrate, and allowed to stand for 72 hours. "○" if the aluminum substrates were not peeled off after 72 hours of standing, "△" if the aluminum substrates were peeled off after 12 hours or more and less than 72 hours after standing, and less than 12 hours after standing. , The case where the aluminum substrates were peeled off was regarded as "x", and the moisture and heat resistance of the light moisture curable resin composition was evaluated.

(Flexibility)
By irradiating 3000 mJ / cm ^{2 of} ultraviolet rays using a UV-LED (wavelength 365 nm), each photo-moisture-curable resin composition obtained in Examples and Comparative Examples is photocured and then left overnight. It was cured by moisture. A test piece obtained by punching the obtained cured product into a dumbbell shape (No. 6 specified by "JIS K 6251") is used with a tensile tester (manufactured by Shimadzu Corporation, "EZ-Graph"). It was pulled at a speed of 10 mm / min, and the force when it was stretched by 50% was determined as the elastic modulus, and the flexibility was evaluated.

(Weatherability)
Each light-moisture-curable resin composition obtained in Examples and Comparative Examples was applied onto an aluminum substrate with a width of about 2 mm using a dispensing device. Next, the photo-moisture-curable resin composition was photo-cured by irradiating it with ultraviolet rays at 3000 mJ / cm ² using a UV-LED (wavelength 365 nm), and then glass substrates were placed on top of each other, and a 20 g weight was placed. It was cured by moisture by leaving it to stand at night to obtain a sample A for weather resistance evaluation.
In addition, a carbon arc type sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd., "S300") is set to a discharge voltage of 50 V and a discharge current of 60 A, and is used for weather resistance evaluation under the conditions of a tank temperature of 25 ° C. and a relative humidity of 50%. The surface of the glass substrate of sample A was irradiated for 100 hours to obtain sample B for weather resistance evaluation.
The prepared samples A and B for weather resistance evaluation are pulled at a speed of 5 mm / sec in the shearing direction using a tensile tester (manufactured by Shimadzu Corporation, "Ez-Graph"), and the strength when the substrates are peeled off (" Adhesive strength) was measured and the adhesive strength was evaluated.
Further, the rate of decrease in adhesive force of sample B for weather resistance evaluation with respect to the adhesive force of sample A for weather resistance evaluation is calculated as the rate of decrease in adhesive force, and the case where the rate of decrease in adhesive force is less than 20% is marked with "○". The weather resistance of the light-moisture-curable resin composition is evaluated as "Δ" when the adhesive strength reduction rate is 20% or more and less than 60%, and as "x" when the adhesive strength reduction rate is 60% or more. did.

According to the present invention, it is possible to provide a light-moisture-curable resin composition having excellent adhesiveness, weather resistance, and flexibility of a cured product. Further, according to the present invention, it is possible to provide an adhesive for electronic parts and an adhesive for display elements using the light-moisture-curable resin composition.

1 Aluminum substrate 2 Light and moisture curable resin composition

Claims (4)

A radical polymerizable compound, and a moisture-curable urethane resin, a modified silicone resin having at least two hydrolyzable silyl groups in a molecule (except when having a vinyl group), and contains a photo-radical polymerization initiator ,
The modified silicone resin is a photomoisture-curable resin composition characterized by having a hydrolyzable silyl group at the end of the main chain of the molecule . The light humidity according to claim 1 , wherein the content of the modified silicone resin is 1 to 20 parts by weight based on 100 parts by weight of the total of the radically polymerizable compound, the moisture-curable urethane resin, and the modified silicone resin. Curable resin composition. An adhesive for electronic components, which comprises the light-moisture-curable resin composition according to claim 1 or 2 . An adhesive for a display element, which comprises the light-moisture-curable resin composition according to claim 1 or 2 .