TWI670326B - Light and moisture curing resin composition, adhesive for electronic parts, and adhesive for display elements - Google Patents

Abstract

An object of the present invention is to provide a light and moisture-curable resin composition excellent in adhesion and excellent in high-temperature and high-humidity environments. Moreover, an object of the present invention is to provide an adhesive for an electronic component and an adhesive for a display element which are obtained by using the light and moisture-curable resin composition.

The present invention relates to a light and moisture-curable resin composition comprising a radical polymerizable compound, a moisture-curing amine ester resin, and a photoradical polymerization initiator, and the moisture-curable amine ester resin comprises: An urethane bond, a group represented by the following formula (1), and a compound of an isocyanate group.

In the formula (1), R ¹ and R ² are hydrogen, an alkyl group having 1 to 5 carbon atoms or an aryl group, and R ¹ and R ² may be the same or different. x is 0~2.

Description

Light and moisture curing resin composition, adhesive for electronic parts, and adhesive for display elements

The present invention relates to a light and moisture-curable resin composition excellent in adhesion and excellent in high-temperature and high-humidity environments. Moreover, the present invention relates to an adhesive for an electronic component and an adhesive for a display element which are obtained by using the light and 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 characteristics such as thinness, light weight, and low power consumption. Among these display elements, a photocurable resin composition is usually used in the sealing of a liquid crystal or a light-emitting layer, a substrate, an optical film, a protective film, or a combination of various members.

In addition, various types of mobile devices, such as mobile phones and portable game machines, are becoming more and more popular, and the miniaturization of display elements is the most demanding problem. As a method of miniaturization, the narrow side of the image display unit is implemented. Initiative (hereinafter, also known as narrow edge design). However, in the narrow-edge design, there is a case where a photocurable resin composition is applied to a portion where light does not sufficiently reach, and as a result, there is insufficient hardening of the photocurable resin composition applied to a portion where light does not reach. The problem. Therefore, a light and thermosetting resin composition is also used as a resin composition which can be sufficiently cured when applied to a portion where light does not reach, and is used together with photohardening and thermal hardening, but is heated by high temperature. Defective effects on components, etc.

As a method of hardening the resin composition by heating at a high temperature, Patent Document 1 discloses a method of using a light-and-moisture-curing resin composition containing an amine ester prepolymer having at least one isocyanate group and at least one (meth) acrylonitrile group in a molecule, and using light together. Hardening and moisture hardening. However, when the light-and-moisture-curing resin composition disclosed in Patent Document 1 is used, there is a possibility of adhering to a substrate such as a substrate, or a high-temperature and high-humidity environment (especially resistance). Creep is insufficient.

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Laid-Open Patent Publication No. 2008-274131

An object of the present invention is to provide a light and moisture-curable resin composition excellent in adhesion and excellent in high-temperature and high-humidity environments. Moreover, an object of the present invention is to provide an adhesive for an electronic component and an adhesive for a display element which are obtained by using the light and moisture-curable resin composition.

The present invention relates to a light and moisture-curable resin composition comprising a radical polymerizable compound, a moisture-curing amine ester resin, and a photoradical polymerization initiator, and the moisture-curable amine ester resin comprises: An urethane bond, a group represented by the following formula (1), and a compound of an isocyanate group.

-Si(R ¹ ) _x (OR ² ) _3-x  (1)

In the formula (1), R ¹ and R ² are hydrogen, an alkyl group having 1 to 5 carbon atoms or an aryl group, and R ¹ and R ² may be the same or different. x is 0~2.

The invention is described in detail below.

The present inventors have surprisingly found that light and moisture-curable resin compositions containing a radical polymerizable compound, a moisture-curing amine ester resin, and a photo-radical polymerization initiator are specific by use. The functional group compound is a moisture-curable amine ester resin, and a light-and-moisture-curing resin composition excellent in adhesion and high-temperature and high-humidity environment can be obtained, and the present invention has been completed.

The light and moisture-curable resin composition of the present invention contains a moisture-curable amine ester resin. The isocyanate group in the molecule of the above-mentioned moisture-curing amine ester resin is hardened by reacting with moisture in the air or in the adherend.

The moisture-curable amine ester resin contains a compound having an amine ester bond, a group represented by the above formula (1), and an isocyanate group (hereinafter also referred to as "an organic sulfhydryl group-containing urethane resin"). The light-and-moisture-curable resin composition of the present invention is excellent in reliability in the adhesiveness and high-temperature and high-humidity environment by using the above-described organic sulfhydryl group-containing amine ester resin as the moisture-curable amine ester resin.

The above-mentioned organic mercapto group-containing amine ester resin has a group represented by the above formula (1). In the above formula (1), R ¹ and R ^{2 are} preferably an alkyl group having 1 to 5 carbon atoms, and more preferably A, in terms of improving the adhesion and the effect of reliability in a high-temperature and high-humidity environment. Base, ethyl.

In the case where R ¹ and R ² are an aryl group, examples of the aryl group include a phenyl group, a naphthyl group, and a 2-methylphenyl group.

Further, the case where x in the above formula (1) is 0 means that the ruthenium atom is not bonded to the atom or the group represented by R ^{1 and} is bonded to the three -OR ² groups.

The above organic thiol-containing amine ester resin has an isocyanate group.

The above-mentioned organic mercapto group-containing amine ester resin may have only one isocyanate group in one molecule, or may have two or more.

The above-mentioned organic mercapto group-containing amine ester resin preferably has the above-mentioned respective ends a group represented by the formula (1) and the above isocyanate group.

The above organic thiol-containing amine ester resin can be obtained by: A polyol compound having two or more hydroxyl groups in a molecule is reacted with a polyisocyanate compound having two or more isocyanate groups in one molecule to obtain a compound having an amine ester bond and an isocyanate group, and the obtained compound and a reactive functional group are obtained. The compound represented by the formula (1) is reacted to obtain it. Further, the above "reactive functional group" means a group which can react with the above compound having an amine ester bond and an isocyanate group.

The reaction of the above polyol compound with the above polyisocyanate compound is usually The molar ratio of the hydroxyl group (OH) in the above polyol compound to the isocyanate group (NCO) in the above polyisocyanate compound is in the range of [NCO] / [OH] = 2.0 to 2.5.

As the above polyol compound, a commonly used one in the production of a polyurethane can be used. The known polyol compound may, for example, be a polyester polyol, a polyether polyol, a polyalkylene polyol or a polycarbonate polyol. These polyol compounds may be used singly or in combination of two or more.

As the polyester polyol, for example, a polyvalent carboxylic acid and a polyhydric alcohol can be exemplified. Polyester polyol obtained by the reaction, or polyε- obtained by ring-opening polymerization of ε-caprolactone Caprolactone polyols and the like.

The above polycarboxylic acid which is a raw material of the above polyester polyol can be listed, for example. For: terephthalic acid, isophthalic acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, bismuth Acid, sebacic acid, phthalic acid, dodecane dicarboxylic acid, and the like.

The above polyol which is a raw material of the above polyester polyol can be listed, for example. Lift: ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, diethylene Alcohol, cyclohexanediol, and the like.

Examples of the polyether polyol include ethylene glycol, propylene glycol, and tetrahydrogen. a ring-opening polymerization compound of furan or 3-methyltetrahydrofuran, and a random copolymer or block copolymer of these or its derivatives, or a bisphenol type polyoxyalkylene modified product.

The above bisphenol type polyoxyalkylene modified system is an alkylene oxide (for example, ethylene oxide, a polyether polyol obtained by an addition reaction of a propylene oxide, butylene oxide, isobutylene oxide or the like with an active hydrogen moiety of a bisphenol type molecular skeleton, which may be a random copolymer or a block. Copolymer. The bisphenol type polyoxyalkylene modified product preferably has one or more kinds of 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 a bisphenol A type is preferable.

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

Examples of the polycarbonate polyol include polyhexamethylene carbonate polyol and polycyclohexane dimethylene carbonate polyol.

As the polyisocyanate compound, for example, diphenylmethane diiso is mentioned Cyanate ester, liquid modified product of diphenylmethane diisocyanate, polymerized MDI (methane diisocyanate), toluene diisocyanate, naphthalene-1,5-diisocyanate, and the like. Among them, diphenylmethane diisocyanate and a modified product thereof are preferred in terms of low vapor pressure or low toxicity and easy handling. These polyisocyanate compounds may be used alone or in combination of two or more.

As the compound having a reactive functional group and a group represented by the formula (1), For example, 3-mercaptopropyltrimethoxydecane, 3-mercaptopropyltriethoxydecane, 3-mercaptopropylmethyldimethoxydecane, 3-mercaptopropylmethyldiethoxydecane , 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 3-ring Oxypropoxypropylmethyldiethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 3-Aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-(2-aminoethyl)aminopropyltrimethoxydecane, 3-(2-Amino B Aminopropyltriethoxydecane, 3-(2-aminoethyl)aminopropylmethyldimethoxydecane, 3-(methyl)propenyloxypropyltrimethoxydecane , 3-(methyl)propenyloxypropyltriethoxydecane, 3-(meth)acryloxypropylmethyldimethoxydecane, 3-(methyl)propeneoxypropane Methyldiethoxydecane, vinyltrimethoxydecane, vinyltriethoxydecane, 3-isocyanatepropyltrimethoxy Silane like. Among them, from the viewpoint of reactivity, a thiol group is preferred as the reactive functional group.

In the present specification, the above "(meth)acryloyl group" means an acryloyl group or a methacryl group.

The content of the above organic thiol-containing amine ester resin relative to the radical polymerizability The total amount of the compound and the moisture-curable amine ester resin is 100 parts by weight, preferably a lower limit of 1 part by weight, preferably an upper limit of 50 parts by weight. If the content of the above amino group-containing amine ester resin is less than one weight In the case of the amount, the effect of improving the adhesion and the reliability in a high-temperature and high-humidity environment is not sufficiently exhibited. When the content of the above-mentioned organic mercapto group-containing amine ester resin exceeds 50 parts by weight, the reaction of the moisture-curable amine ester resin is inhibited, and the elastic modulus of the cured product is lowered, and sufficient adhesion cannot be ensured. A more preferred lower limit of the content of the above-mentioned organic mercapto group-containing amine ester resin is 2 parts by weight, more preferably 30 parts by weight, still more preferably 5 parts by weight, and still more preferably 25 parts by weight.

The light and moisture-curable resin composition of the present invention preferably further contains A moisture-curing urethane resin other than an organic sulfhydryl amide resin. The curability is easily adjusted by containing a moisture-curing amine ester resin other than the amine ester resin containing an organic mercapto group.

As the above other moisture-curable amine ester resin, the above compound having an amine ester bond and an isocyanate group is preferably used.

Hereinafter, a matter common to the moisture-curable urethane resin containing the above-described organic thiol-containing urethane resin is simply referred to as "moisture-curing urethane resin".

The above moisture-curable urethane resin is preferably used in the form of the following formula (2). Obtained as a polyol compound of the structure shown. By using a polyol compound having a structure represented by the following formula (2), a composition excellent in adhesion or a cured product which is soft and preferably stretched can be obtained, and the compatibility with the radical polymerizable compound is excellent. . Further, the moisture-curable urethane resin preferably has a branch.

Among them, a polyether polyol composed of a ring-opening polymerization compound of a 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 is preferably used.

In the formula (2), R represents hydrogen, methyl or ethyl, and n is an integer of 1 to 10, L It is an integer from 0 to 5, and m is an integer from 1 to 500. n is preferably from 1 to 5, L is preferably from 0 to 4, and m is preferably from 50 to 200.

Furthermore, the case where L is 0 means that the carbon bonded to R is directly bonded to oxygen.

Further, the moisture-curable amine ester resin may have a radical polymerizable group.

The radical polymerizable group which the above-mentioned moisture-curable amine ester resin can have is preferably a group having an unsaturated double bond, and more preferably a (meth) acrylonitrile group in terms of reactivity.

Further, the moisture-curable amine ester resin having a radical polymerizable group is not contained in the radically polymerizable compound, and is considered to be a moisture-curable amine ester resin.

a preferred lower limit of the weight average molecular weight of the above moisture-curing amine ester resin It is 800, and the upper limit is preferably 10,000. When the weight average molecular weight of the moisture-curable urethane resin is less than 800, the crosslinking density becomes high and the flexibility is impaired. When the weight average molecular weight of the moisture-curable urethane resin exceeds 10,000, the obtained light and moisture-curable resin composition may be inferior in coatability. A lower limit of the weight average molecular weight of the above moisture-curable amine ester resin is 2,000, more preferably 8,000, and still more preferably 2,500, and still more preferably 6,000.

In the present specification, the weight average molecular weight is measured by gel permeation chromatography (GPC) and is determined by polystyrene conversion. As a column for measuring the weight average molecular weight obtained by the polystyrene conversion by GPC, for example, Shodex LF-804 (manufactured by Showa Denko Co., Ltd.) or the like can be mentioned. Further, as a solvent used in GPC, tetrahydrofuran may be mentioned. Wait.

The content of the above moisture-curable amine ester resin relative to the above radical polymerization property The total amount of the compound and the above moisture-curable amine ester resin is 100 parts by weight, preferably 20 parts by weight, and preferably 90 parts by weight. When the content of the moisture-curable urethane resin is less than 20 parts by weight, the obtained light and moisture-curable resin composition may be inferior in moisture hardenability. When the content of the moisture-curable urethane resin exceeds 90 parts by weight, the obtained light and moisture-curable resin composition may be inferior in photocurability. A more preferred lower limit of the content of the above moisture-curable amine ester resin is 30 parts by weight, more preferably an upper limit of 75 parts by weight, still more preferably a lower limit of 41 parts by weight, and still more preferably an upper limit of 70 parts by weight.

The light-and-moisture-curing resin composition of the present invention contains radical polymerizable Compound.

The radically polymerizable compound is not particularly limited as long as it is a photopolymerizable radical polymerizable compound, and is preferably a compound having a radical polymerizable group in the molecule, and preferably has an unsaturated double bond. The compound having a radical polymerizable group is preferably a compound having a (meth) acrylonitrile group (hereinafter also referred to as "(meth)acrylic compound"), in particular, in terms of reactivity.

In the present specification, the above "(meth)acrylic group" means an acrylic group or a methacryl group.

Examples of the (meth)acryl-based compound include, by way of example, An ester compound obtained by reacting a hydroxy compound with (meth)acrylic acid, an epoxy (meth) acrylate obtained by reacting (meth)acrylic acid with an epoxy compound, by having a hydroxyl group ( Amine (meth) propylene obtained by reacting a methyl methacrylate derivative with an isocyanate compound Acid esters, etc.

In the present specification, the above "(meth) acrylate" means acrylate or methacrylate. Further, all of the isocyanate groups of the isocyanate compound which is a raw material of the above amine ester (meth) acrylate are used to form an amine ester bond, and the above amine ester (meth) acrylate does not have a residual isocyanate group.

As the monofunctional one of the above ester compounds, for example, (meth) propylene is exemplified 2-hydroxyethyl acid, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, isobutyl (meth)acrylate, ( Tert-butyl methacrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isodecyl (meth) acrylate, (meth) acrylate ring Hexyl ester, 2-methoxyethyl (meth)acrylate, methoxyethylene glycol (meth) acrylate, 2-ethoxyethyl (meth) acrylate, tetrahydroanthracene (meth) acrylate Ester, benzyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxy diethylene glycol (meth) acrylate, phenoxy Polyethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, (meth) acrylate 2, 2, 3,3-tetrafluoropropyl ester, (meth)acrylic acid 1H, 1H, 5H-octafluoropentyl ester, quinone imine (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate , n-butyl (meth)acrylate, propyl (meth)acrylate, cyclohexyl (meth)acrylate, (methyl) ) 2-ethylhexyl acrylate, n-octyl (meth) acrylate, isodecyl (meth) acrylate, isomyristyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-phenoxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, isodecyl (meth)acrylate, diethylaminoethyl (meth)acrylate, (meth)acrylic acid Dimethylaminoethyl ester, 2-(methyl) propylene methoxyethyl succinate, 2-(methyl) propylene methoxyethyl hexaphthalate, 2-(phthalic acid) Methyl)propenyloxyethyl 2-hydroxypropyl ester, glycidyl (meth)acrylate, phosphoric acid Phthalic imine acrylate such as 2-(meth) propylene methoxyethyl ester or N-propylene methoxyethyl hexahydrophthalimide or various quinone acrylates.

Further, as the two-functional one of the above ester compounds, for example, 1,4-butyl Diol (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,6-hexanediol di(meth) acrylate Ester, 1,9-nonanediol di(meth)acrylate, 1,10-nonanediol di(meth)acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di Methyl) acrylate, dipropylene glycol di(meth) acrylate, tripropylene glycol di(meth) acrylate, polypropylene glycol (meth) acrylate, ethylene glycol di(meth) acrylate, diethylene glycol Di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene oxide addition bisphenol A di(meth)acrylate, epoxy Ethane addition bisphenol A di(meth) acrylate, ethylene oxide addition bisphenol F di(meth) acrylate, di(hydroxy)dicyclopentadienyl di(meth)acrylate, 1 , 1,3-butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide modified iso-cyanuric acid Di(meth)acrylate, 2-hydroxy-3-(methyl)propenyloxypropyl (meth)acrylate, carbonate diol II (Meth) acrylate, polyether diol di(meth) acrylate, polyester diol di(meth) acrylate, polycaprolactone diol di(meth) acrylate, polybutadiene II Alcohol di(meth)acrylate and the like.

Further, as the trifunctional or higher one of the above ester compounds, for example, new Pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, propylene oxide addition trimethylolpropane tri(meth)acrylate, ethylene oxide addition trishydroxyl Methylpropane tri(meth)acrylate, caprolactone modified trimethylolpropane tri(meth)acrylate, ethylene oxide addition isocyanuric acid tris(meth)acrylate, two new Pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, di-trimethylolpropane tetra (meth) acrylate, neopentyl alcohol tetra (meth) acrylate Ester, glycerol tri(meth) acrylate, propylene oxide addition glycerol tri(meth) acrylate, tris(meth) propylene methoxyethyl phosphate, and the like.

The epoxy (meth) acrylate is exemplified by a conventional one. A method in which an epoxy compound is reacted with (meth)acrylic acid in the presence of a basic catalyst, and the like.

Epoxy which becomes a raw material for synthesizing the above epoxy (meth) acrylate Examples of the compound include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, 2,2'-diallyl bisphenol A type epoxy resin, and hydrogenated bisphenol. Type epoxy resin, propylene oxide addition bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, thioether type epoxy resin, diphenyl ether type epoxy resin, two Cyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol novolak type epoxy resin, o-cresol novolac type epoxy resin, dicyclopentadiene novolac type epoxy resin, biphenol novolak type varnish Type epoxy resin, naphthol novolak type epoxy resin, epoxy propylamine type epoxy resin, alkyl polyol type epoxy resin, rubber modified epoxy resin, glycidyl ester compound, bisphenol A type ring Sulfur resin, etc.

As a commercial item among the said bisphenol A type epoxy resin, the following are mentioned, for example: Epikote 828EL, Epikote 1001, Epikote 1004 (all manufactured by Mitsubishi Chemical Corporation), Epiclon 850-S (manufactured by DIC Corporation), and the like.

For example, Epikote 806 and Epikote 4004 (all manufactured by Mitsubishi Chemical Corporation) and the like are mentioned as a commercial product of the bisphenol F-type epoxy resin.

As a commercial item of the said bisphenol S type epoxy resin, Epiclon EXA1514 (made by the DIC company) etc. are mentioned, for example.

The commercially available one of the 2,2'-diallyl bisphenol A type epoxy resins is, for example, RE-810NM (manufactured by Nippon Kayaku Co., Ltd.).

As a commercial item of the said hydrogenated bisphenol type epoxy resin, Epiclon EXA7015 (made by the DIC company) etc. are mentioned, for example.

The commercially available one of the above-mentioned propylene oxide-added bisphenol A-type epoxy resins is, for example, EP-4000S (manufactured by Adeka Co., Ltd.).

The commercially available one of the resorcinol-type epoxy resins is, for example, EX-201 (manufactured by Nagase ChemteX Co., Ltd.).

As a commercial item of the above-mentioned biphenyl type epoxy resin, Epikote YX-4000H (made by Mitsubishi Chemical Corporation), etc. are mentioned, for example.

For example, YSLV-50TE (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) or the like can be mentioned as a commercially available one of the above-mentioned thioether type epoxy resins.

For example, YSLV-80DE (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) and the like can be cited as a commercially available one of the above-mentioned diphenyl ether type epoxy resins.

The commercially available one of the above-mentioned dicyclopentadiene type epoxy resins is, for example, EP-4088S (manufactured by Adeka Co., Ltd.).

Examples of the commercially available ones of the naphthalene type epoxy resins include Epiclon HP 4032 and Epiclon EXA-4700 (all manufactured by DIC Corporation).

For example, Epiclon N-770 (manufactured by DIC Corporation) can be mentioned as a commercially available one of the phenolic novolac type epoxy resins.

As a commercial item of the above-mentioned o-cresol novolak-type epoxy resin, Epiclon N-670-EXP-S (made by DIC Corporation) etc. are mentioned, for example.

The commercially available one of the above-mentioned dicyclopentadiene novolac type epoxy resins is Epiclon HP7200 (manufactured by DIC Corporation).

The commercially available one of the above-mentioned biphenyl novolak type epoxy resins is, for example, NC-3000P (manufactured by Nippon Kayaku Co., Ltd.).

As a commercial item of the above-mentioned naphthol novolac type epoxy resin, ESN-165S (made by Nippon Steel & Sumitomo Chemical Co., Ltd.), etc. are mentioned, for example.

For example, Epikote 630 (manufactured by Mitsubishi Chemical Corporation), Epiclon 430 (manufactured by DIC Corporation), TETRAD-X (manufactured by Mitsubishi Gas Chemical Co., Ltd.), and the like are mentioned.

For example, ZX-1542 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), Epiclon 726 (manufactured by DIC Corporation), and Epolight 80MEA (manufactured by Kyoeisha Chemical Co., Ltd.) are mentioned as a commercial product of the above-mentioned alkyl polyol type epoxy resin. ), Denacol EX-611 (manufactured by Nagase ChemteX), and the like.

For example, YR-450, YR-207 (all manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), Epolead PB (manufactured by Daicel Chemical Industry Co., Ltd.), and the like are exemplified as the commercially available ones of the rubber-modified epoxy resins.

The commercially available one of the above-mentioned glycidyl ester compounds is, for example, Denacol. EX-147 (manufactured by Nagase ChemteX Co., Ltd.).

For example, Epikote YL-7000 (manufactured by Mitsubishi Chemical Corporation) and the like are mentioned as a commercial product of the bisphenol A-type episulfide resin.

For example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Co., Ltd.), Epikote 1031, Epikote, etc., may be mentioned. 1032 (all manufactured by Mitsubishi Chemical Corporation), EXA-7120 (manufactured by DIC Corporation), TEPIC (manufactured by Nissan Chemical Co., Ltd.), and the like.

As a commercial one of the above-mentioned epoxy (meth)acrylate, for example, the following are mentioned: EBECRYL 860, EBECRYL 3200, EBECRYL 3201, EBECRYL 3412, EBECRYL 3600, EBECRYL 3700, EBECRYL 3701, EBECRYL 3702, EBECRYL 3703, EBECRYL 3800, EBECRYL 6040, EBECRYL RDX63182 (all manufactured by Daicel-Allnex); 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 Kyoei Chemical Co., Ltd.); Denacol Acrylate DA-141, Denacol Acrylate DA-314 , Denacol Acrylate DA-911 (all manufactured by Nagase ChemteX) and the like.

The above amine ester (meth) acrylate can be, for example, tin-based compound due to the amount of catalyst It is obtained by reacting an isocyanate compound with a (meth)acrylic acid derivative having a hydroxyl group in the presence of a substance.

Isocyanate compound as a raw material of the above amine ester (meth) acrylate Examples of the substance include isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and diphenylmethane. -4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, benzodimethyl diisocyanate (XDI), hydrogenated XDI And phthalic acid diisocyanate, triphenylmethane triisocyanate, tris(isocyanate phenyl) thiophosphate, tetramethyl xylene diisocyanate, 1,6,11-undecane triisocyanate, and the like.

Further, as the above isocyanate compound, for example, ethylene glycol can be used. Glycerin, sorbitol, trimethylolpropane, (poly)propylene glycol, carbonate diol, polyether diol, polyester A chain extended isocyanate compound obtained by reacting a polyhydric alcohol such as a diol or a polycaprolactone diol with an excess of an isocyanate compound.

As a raw material of the above amine ester (meth) acrylate, having a hydroxyl group (A) Examples of the acrylic acid derivative include glycols such as ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,3-butylene glycol, 1,4-butanediol, and polyethylene glycol. Single (meth) acrylate, or mono (meth) acrylate or di(meth) acrylate of trihydric alcohol such as trimethylolethane, trimethylolpropane or glycerin, or bisphenol A type Epoxy (meth) acrylate such as epoxy (meth) acrylate.

As a commercial one of the above-mentioned amine ester (meth) acrylate, for example, M-1100, M-1200, M-1210, M-1600 (all manufactured by Toagosei Co., Ltd.); EBECRYL 230, EBECRYL 270, EBECRYL 4858, EBECRYL 8402, EBECRYL 8411, EBECRYL 8412, EBECRYL 8413, EBECRYL 8804, EBECRYL 8803 , EBECRYL 8807, EBECRYL 9260, EBECRYL 1290, EBECRYL 5129, EBECRYL 4842, EBECRYL 210, EBECRYL 4827, EBECRYL 6700, EBECRYL 220, EBECRYL 2220, KRM 7735, KRM-8295 (all manufactured by Daicel-Allnex); Artresin UN- 9000H, Artresin UN-9000A, Artresin UN-7100, Artresin UN-1255, Artresin UN-330, Artresin UN-3320HB, Artresin UN-1200TPK, Artresin SH-500B (all manufactured by Gensei Industrial 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 (made by Xinzhongcun Chemical Industry Co., Ltd.); AI-600, AH-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA-306T (all are Gongrongsha Chemical company manufacturing) and so on.

Further, other radical polymerizable compounds other than the above may be suitably used. Examples of the other radically polymerizable compound include N,N-dimethyl(meth)acrylamide, N-(methyl)propenyl rufofen, and N-hydroxyethyl (methyl). Acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide A (meth)acrylamide compound or a vinyl compound such as styrene, α-methylstyrene, N-vinylpyrrolidone or N-vinylcaprolactone.

The content of the above radical polymerizable compound relative to the above radical polymerizable property The total amount of the compound and the above moisture-curable amine ester resin is 100 parts by weight, preferably 10 parts by weight, and preferably 80 parts by weight. When the content of the radical polymerizable compound is less than 10 parts by weight, the obtained light and the moisture-curable resin composition may be inferior in photocurability. When the content of the radically polymerizable compound exceeds 80 parts by weight, the obtained light and moisture-curable resin composition may be inferior in moisture hardenability. A more preferred lower limit of the content of the above radical polymerizable compound is 25 parts by weight, more preferably 70 parts by weight, still more preferably 30 parts by weight, and still more preferably an upper limit of 59 parts by weight.

The above radical polymerizable compound is preferred from the viewpoint of adjusting the hardenability and the like. It is a monofunctional radically polymerizable compound and a polyfunctional radically polymerizable compound. When only a monofunctional radically polymerizable compound is used, the obtained light and moisture-curable resin composition may be inferior in hardenability, and when only a polyfunctional radical polymerizable compound is used, The obtained light and the moisture-curable resin composition are inferior in adhesion. In particular, it is more preferable to use a compound having a nitrogen atom in the molecule of the monofunctional radically polymerizable compound and an amine ester (meth) acrylate as the polyfunctional radical polymerizable compound. Further, the polyfunctional radically polymerizable compound is preferably a bifunctional or trifunctional group. More preferably, it is a bifunctional.

The above radical polymerizable compound contains the above monofunctional radical polymerizable property In the case of the compound and the above polyfunctional radically polymerizable compound, the content of the polyfunctional radically polymerizable compound is 100 parts by weight based on 100 parts by weight of the total of the monofunctional radically polymerizable compound and the polyfunctional radically polymerizable compound. The lower limit is preferably 2 parts by weight, and preferably the upper limit is 45 parts by weight. When the content of the polyfunctional radical polymerizable compound is less than 2 parts by weight, the obtained light and the moisture-curable resin composition may be inferior in curability. When the content of the polyfunctional radically polymerizable compound exceeds 45 parts by weight, the obtained light and the moisture-curable resin composition may be inferior in adhesion. A more preferred lower limit of the content of the above polyfunctional radically polymerizable compound is 5 parts by weight, and a more preferred upper limit is 35 parts by weight.

The light and moisture curing resin composition of the present invention contains photoradical polymerization Starting agent.

Examples of the photoradical polymerization initiator include a benzophenone compound, an acetophenone compound, a fluorenyl phosphine oxide compound, a titanocene compound, an oxime ester compound, and a benzoin ether compound. 9-oxygen sulfur Wait.

As a commercial one of the above-mentioned photoradical polymerization initiators, for example, IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 784, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, Lucirin TPO (all manufactured by BASF Japan); benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether ( All are manufactured by Tokyo Chemical Industry Co., Ltd.).

The content of the above photoradical polymerization initiator is relative to the above radical polymerizability The compound has a lower limit of 0.01 parts by weight, preferably 10 parts by weight, based on 100 parts by weight of the compound. When the content of the photoradical polymerization initiator is less than 0.01 part by weight, the obtained light and the moisture-curable resin composition may not be sufficiently photocured. When the content of the photoradical polymerization initiator is more than 10 parts by weight, the storage stability of the obtained light and the moisture-curable resin composition may be lowered. A more preferred lower limit of the content of the above photoradical polymerization initiator is 0.1 part by weight, and a more preferred upper limit is 5 parts by weight.

Adjusting the coating property or shape of the light and moisture-curable resin composition obtained The light and moisture-curable resin composition of the present invention may further contain a filler from the viewpoint of shape retention and the like.

A preferred lower limit of the primary particle diameter of the above filler is 1 nm, and a preferred upper limit is 50 nm. When the primary particle diameter of the above filler is less than 1 nm, the obtained light and the moisture-curable resin composition are inferior in coatability. When the primary particle diameter of the filler exceeds 50 nm, the obtained light and the moisture-curable resin composition are inferior in shape retention after coating. A lower limit of the primary particle diameter of the above filler is 5 nm, more preferably 30 nm, and further preferably a lower limit of 10 nm, and further preferably an upper limit of 20 nm.

In addition, the primary particle diameter of the above-mentioned filler can be measured by dispersing the above-mentioned filler in a solvent (water, an organic solvent, etc.) using NICOMP 380ZLS (manufactured by PARTICLE SIZING SYSTEMS).

Further, the above-mentioned filler is present in the form of secondary particles (a plurality of primary particles are aggregated) in the light-and-moisture-curable resin composition of the present invention, and the particle diameter of such secondary particles is relatively The lower limit is preferably 5 nm, preferably the upper limit is 500 nm, more preferably the lower limit is 10 nm, and the more preferred upper limit is 100 nm. The particle diameter of the secondary particles of the above filler can be measured by observing the light and moisture-curable resin composition of the present invention or a cured product thereof using a transmission electron microscope (TEM). set.

Examples of the filler include silica, talc, and Titanium oxide, zinc oxide, and the like. Among them, in view of the fact that the obtained light and moisture-curable resin composition is excellent in UV light transmittance, cerium oxide is preferred. These fillers may be used singly or in combination of two or more.

The above filler is preferably subjected to a hydrophobic surface treatment. By the above hydrophobic table In the surface treatment, the obtained light and moisture-curable resin composition are more excellent in shape retention after coating.

Examples of the hydrophobic surface treatment include a thiolation treatment, an alkylation treatment, and an epoxidation treatment. Among them, in terms of improving the effect of improving the shape retainability, the thiolation treatment is preferred, and the trimethyl thiolation treatment is more preferred.

As a method of performing hydrophobic surface treatment on the above filler, for example, A method of treating the surface of the filler with a surface treatment agent such as a decane coupling agent or the like.

Specifically, for example, the above-described trimethyl thiolated cerium oxide can be produced, for example, by synthesizing cerium oxide by a method such as a sol-gel method, and ejecting a mist in a state in which cerium oxide flows. a method of adding hexamethyldioxane; or adding cerium oxide to an organic solvent such as an alcohol or toluene, and further, after adding hexamethyldioxane and water, evaporating and drying the water and the organic solvent by an evaporator Method, etc.

The content of the above filler is the light and moisture hardening resin composition of the present invention. A preferred lower limit is 1 part by weight, and a preferred upper limit is 20 parts by weight, based on 100 parts by weight of the whole. When the content of the filler is less than 1 part by weight, the obtained light and the moisture-curable resin composition may be inferior in shape retention after coating. If the content of the above filler exceeds 20 In the case of the amount of the light, the obtained light and the moisture-curable resin composition may be inferior in coatability. A more preferred lower limit of the content of the above filler is 2 parts by weight, more preferably 15 parts by weight, still more preferably 3 parts by weight, still more preferably 10 parts by weight, and even more preferably 4 parts by weight.

The light and moisture-curable resin composition of the present invention may also contain an opacifier. By In the light-shielding-hardening resin composition of the present invention, the light-shielding-hardening resin composition of the present invention is excellent in light-shielding property, and light leakage of the display element can be prevented.

Furthermore, in the present specification, the term "sunscreen agent" means a material having an ability to easily penetrate light in a visible light region.

Examples of the sunscreen agent include iron oxide, titanium black, nigrosine, and flowers. Cyan, fullerene, carbon black, resin-coated carbon black, and the like. Further, the light-shielding agent may not be black, and the material exemplified as a filler such as cerium oxide, talc or titanium oxide is also included in the above-mentioned sunscreen agent as long as it has a ability to penetrate light in a visible light region. in. Among them, titanium black is preferred.

The titanium black system has a higher transmittance to light in the vicinity of the ultraviolet region, particularly at a wavelength of 370 to 450 nm, as compared with the average transmittance of light having a wavelength of 300 to 800 nm. In other words, the titanium black imparts light-shielding property to the light-and-moisture-curable resin composition of the present invention by sufficiently shielding light of a wavelength in the visible light region, and has a property of penetrating light of a wavelength near the ultraviolet region. Sunscreen. Therefore, the light and moisture-curable resin of the present invention can be obtained by using a light having a wavelength (370 to 450 nm) in which the transmittance of titanium black is high to start the reaction as a photoradical polymerization initiator. The photohardenability of the composition is further increased. Further, on the other hand, as the light shielding agent contained in the light- and moisture-curable resin composition of the present invention, it is preferred. A material having a high insulating property is preferably titanium black as a light-shielding agent having a high insulating property.

The optical density (OD value) of the above titanium black is preferably 3 or more, more preferably 4 or more. Further, the blackness (L value) of the titanium black is preferably 9 or more, and more preferably 11 or more. The higher the light blocking property of the titanium black, the better, and the OD value of the titanium black is not particularly preferably a preferred upper limit, and is usually 5 or less.

The titanium black may exhibit sufficient effects even if it is not subjected to surface treatment, but may be treated with an organic component such as a coupling agent, or by cerium oxide, titanium oxide, cerium oxide, aluminum oxide, zirconium oxide, or oxidation. A surface-treated titanium black such as an inorganic component such as magnesium. Among them, it is preferable that the organic component is processed to further improve the insulation property.

Further, in the display element produced by using the light-and-moisture-curing resin composition of the present invention, since the light and the moisture-curable resin composition have sufficient light-shielding property, light leakage does not occur, and the display element has a high level. Contrast, and has excellent image display quality.

As a commercial one of the above-mentioned titanium black, for example, 12S, 13M, 13M-C, 13R-N (both manufactured by Mitsubishi Materials Corporation) and Tilack D (manufactured by Ako Chemical Co., Ltd.).

A preferred lower limit of the specific surface area of the above titanium black is 5 m ² /g, preferably an upper limit of 40 m ² /g, a more preferred lower limit of 10 m ² /g, and a more preferred upper limit of 25 m ² /g.

Further, in the case of mixing with a resin (70% blending), the lower limit of the sheet resistance of the above titanium black is preferably 10 ⁹ Ω/□, and more preferably the lower limit is 10 ¹¹ Ω/□.

In the light and moisture-curable resin composition of the present invention, one of the above-mentioned sunscreen agents The secondary particle diameter is equal to or less than the distance between the substrates of the display element, and is appropriately selected depending on the application. A preferred lower limit is 30 nm, and a preferred upper limit is 500 nm. When the primary particle diameter of the above-mentioned sunscreen agent is less than 30 nm, the viscosity and the shakenness of the obtained light and the moisture-curable resin composition are greatly increased, and the workability is deteriorated. If the primary particle diameter of the above-mentioned sunscreen exceeds 500 nm, the obtained light is obtained. The dispersibility of the light-shielding agent in the moisture-curable resin composition is lowered, and the light-shielding property is lowered. A more preferred lower limit of the primary particle diameter of the above-mentioned opacifier is 50 nm, and a more preferred upper limit is 200 nm.

In addition, the particle size of the above-mentioned light-shielding agent can be measured by dispersing the light-shielding agent in a solvent (water, an organic solvent, etc.) using the NICOMP 380ZLS (made by PARTICLE SIZING SYSTEMS), and determining the average particle diameter.

The content of the above-mentioned light shielding agent in the entire light and moisture-curable resin composition of the present invention is not particularly limited, and a preferred lower limit is 0.05% by weight, and a preferred upper limit is 10% by weight. If the content of the above-mentioned sunscreen agent is less than 0.05% by weight, sufficient light-shielding properties may not be obtained. When the content of the light-shielding agent is more than 10% by weight, the strength of the obtained light and the moisture-curable resin composition to the substrate or the like may be lowered or the drawing property may be lowered. A more preferred lower limit of the content of the above-mentioned sunscreen agent is 0.1% by weight, more preferably an upper limit of 2% by weight, and still more preferably an upper limit of 1% by weight.

The light-and-moisture-curing resin composition of the present invention may further contain an additive such as a colorant, an ionic liquid, a solvent, a metal-containing particle, or a reactive diluent, as needed.

As a method of producing the light-and-moisture-curing resin composition of the present invention, for example, a method such as a homogenous phase disperser, a homomixer, a universal mixer, a planetary mixer, a kneader, or a three-roll mill can be used. In a mixer, a radical polymerizable compound, a moisture-curing amine ester resin, a photoradical polymerization initiator, and an additive to be added as needed are mixed.

The lower limit of the viscosity of the light and moisture-curable resin composition of the present invention measured by a cone-and-plate type viscometer at 25 ° C and 1 rpm is 50 Pa. s, the upper limit is preferably 500Pa. s. If the above viscosity is less than 50Pa. s or more than 500Pa. s, when the light and moisture-curable resin composition is used for an adhesive for electronic parts or an adhesive for display elements, There is a case where the workability when applied to a member to be bonded such as a substrate is deteriorated. The lower limit of the above viscosity is 80 Pa. s, the upper limit is 300Pa. s, and thus the upper limit is preferably 200 Pa. s.

The rocking index of the light and moisture hardening resin composition of the present invention is preferably The lower limit is 1.3, and the preferred upper limit is 5.0. When the light-and-moisture-curable resin composition is used for an adhesive for an electronic component or an adhesive for a display element, the image is applied to a substrate such as a substrate. The situation in which the workability deteriorates. A lower limit of the above-mentioned rocking index is 1.5, and a lower limit is 4.0.

Furthermore, in the present specification, the above-mentioned rocking index means that the viscosity measured by using a cone-and-plate type viscometer at 25 ° C and 1 rpm is divided by using a cone-and-plate type viscometer at 25 ° C and 10 rpm. The value obtained by the viscosity.

With respect to the light-and-moisture-curing resin composition of the present invention, a preferred lower limit of the tensile modulus of the cured product at 25 ° C is 0.5 kgf / cm ² , preferably an upper limit of 6 kgf / cm ² . When the tensile modulus of elasticity is less than 0.5 kgf/cm ² , it is too soft, the cohesive force is weak, and the force is lowered. When the tensile elastic modulus exceeds 6 kgf/cm ² , the flexibility may be impaired. A more preferable lower limit of the above tensile elastic modulus is 1 kgf/cm ² , and a more preferable upper limit is 4 kgf/cm ² .

In the present specification, the above-mentioned "tensile elastic modulus" means that a cured product is stretched at a speed of 10 mm/min using a tensile tester (for example, "EZ-Graph" manufactured by Shimadzu Corporation). The value obtained by measuring the form of the force at 50% elongation.

The light and moisture-curable resin composition of the present invention can be preferably used as an electron zero The adhesive for the piece or the adhesive for the display element. Further, an adhesive for an electronic component obtained by using the light-and-moisture-curing resin composition of the present invention and an adhesive for a display element using the light-and-moisture-curing resin composition of the present invention are also One of the inventions.

According to the present invention, it is possible to provide a light and moisture-curable resin composition excellent in adhesion and excellent in high-temperature and high-humidity environments. Moreover, according to the present invention, an adhesive for electronic parts and an adhesive for display elements using the light and moisture-curable resin composition can be provided.

1‧‧‧ polycarbonate substrate

2‧‧‧Light and moisture hardening resin composition

3‧‧‧ glass plate

Fig. 1(a) is a schematic view showing a state in which a sample for adhesion evaluation is observed from above, and Fig. 1(b) is a view showing a state in which a sample for adhesion evaluation is observed from a lateral direction.

The invention is explained in more detail below with reference to examples, but the invention is not limited to the examples.

(Synthesis Example 1 (Production of Amine Prepolymer A))

100 parts by weight of polytetramethylene ether glycol ("MGMG-2000" manufactured by Mitsubishi Chemical Corporation) and 0.01 part by weight of dibutyltin dilaurate as a separable formula of 500 mL capacity The flask was mixed under vacuum (20 mmHg or less) at 100 ° C for 30 minutes. Then, 26.5 parts by weight of diphenylmethane diisocyanate ("Mure", manufactured by Rixo Co., Ltd.), which is a polyisocyanate compound, was added at a normal pressure, and the mixture was stirred at 80 ° C for 3 hours to obtain an amine. Ester prepolymer A (weight average molecular weight 2700).

(Synthesis Example 2 (Production of Amine Prepolymer B))

100 parts by weight of polypropylene glycol ("EXCENOL 2020" manufactured by Asahi Glass Co., Ltd.) and 0.01 part by weight of dibutyltin dilaurate as a polyol compound are added to a capacity of 500 mL. The separable flask was mixed under vacuum (20 mmHg or less) at 100 ° C for 30 minutes. Then, 26.5 parts by weight of diphenylmethane diisocyanate ("Mure", manufactured by Rixo Co., Ltd.), which is a polyisocyanate compound, was added at a normal pressure, and the mixture was stirred at 80 ° C for 3 hours to obtain an amine. Ester prepolymer B (weight average molecular weight 2900).

(Synthesis Example 3 (Production of Amine Prepolymer C))

1.3 parts by weight of hydroxyethyl methacrylate and N-nitrosophenylhydroxylamine as a polymerization inhibitor were added to a reaction vessel containing 100 parts by weight of the amine ester prepolymer A obtained in the same manner as in Synthesis Example 1. 0.14 parts by weight of aluminum salt ("Q-1301" manufactured by Wako Pure Chemical Industries, Ltd.), and stirred and mixed at 80 ° C for 1 hour under a nitrogen stream to obtain an amine ester prepolymerized with an isocyanate group and a methacryl oxime group at the molecular terminal. Compound C (weight average molecular weight 2900).

(Synthesis Example 4 (Production of Amine Prepolymer D))

To a reaction vessel containing 100 parts by weight of the amine ester prepolymer A obtained in the same manner as in Synthesis Example 1, 3-mercaptopropyltrimethoxydecane ("KBM-803", manufactured by Shin-Etsu Chemical Co., Ltd.) was added to 9.8 weight. The mixture was stirred and mixed at 80 ° C for 1 hour to obtain an amine ester prepolymer D (weight average molecular weight: 3,100) having an isocyanate group and a trimethoxyindenyl group at the molecular terminal as an amino group-containing amine ester resin.

(Examples 1 to 15, Comparative Examples 1, 2)

According to the blending ratios shown in Tables 1 and 2, each material was stirred by a planetary stirring device (manufactured by Thinky Co., Ltd., "Debuxing Stirring Taro"), and then uniformly mixed by a ceramic three-roll mill to obtain Example 1 ~15, Light and moisture-curable resin compositions of Comparative Examples 1 and 2.

In addition, the "amine ester prepolymer A" in Tables 1 and 2 is an amine ester prepolymer having an isocyanate group at both ends described in Synthesis Example 1, and the "aminoester prepolymer B" is a synthesis example 2 Recorded at the end of the two An amine ester prepolymer having an isocyanate group at the end, and an "amine ester prepolymer C" is an amine ester prepolymer having an isocyanate group and a methacryl oxime group at the molecular terminal described in Synthesis Example 3, "amine ester prepolymerization" The material D" is an amine ester prepolymer having an isocyanate group and a trimethoxyindenyl group at the molecular terminal described in Synthesis Example 4.

<evaluation>

Each of the light and moisture-curable resin compositions obtained in the examples and the comparative examples was evaluated as follows. The results are shown in Tables 1 and 2.

Further, in the light and moisture-curable resin composition obtained in Comparative Example 2, the light and the moisture-curable resin composition were crushed when the substrate was bonded, and the samples in each evaluation were not produced, so the following were not performed. Evaluation.

(adhesive)

Each of the light and moisture-curable resin compositions obtained in the examples and the comparative examples was applied to a polycarbonate substrate at a width of about 2 mm using a dispensing device. Thereafter, the UV-LED (wavelength: 365 nm) was irradiated with ultraviolet rays of 1000 mJ/cm ² to photoharden the light and the moisture-curable resin composition. Thereafter, the glass plate was bonded to a polycarbonate substrate, and a weight of 20 g was placed thereon, and the mixture was allowed to stand overnight to be moisture-hardened to obtain a sample for evaluation of adhesion. Fig. 1 is a schematic view showing a state in which a sample for adhesion evaluation is observed from above (Fig. 1 (a)), and a schematic view showing a state in which a sample for adhesion evaluation is observed from the lateral direction (Fig. 1 (b)).

The tensile tester ("Ez-Graph", manufactured by Shimadzu Corporation) was used to stretch the produced adhesion evaluation sample at a speed of 5 mm/sec in the shear direction, and the polycarbonate substrate and the glass plate were measured. Strength at the time of peeling.

(High temperature and high humidity reliability (creep resistance))

A sample for evaluation of high-temperature and high-humidity reliability was produced in the same manner as the sample for evaluation of adhesion in the evaluation of "(adhesion)". The sample for high-temperature and high-humidity reliability evaluation obtained was suspended vertically with respect to the ground, and placed in a constant-temperature and constant-humidity oven at 60 ° C and 95% RH in a state in which a weight of 120 g was attached to the end of the polycarbonate substrate. In, stay for 24 hours. The case where the polycarbonate substrate and the glass plate were not peeled off after standing for 24 hours was set to "○", and the case where the polycarbonate substrate and the glass plate were partially peeled off was set to "Δ", and the polycarbonate substrate and the glass plate were placed. In the case of complete peeling, "X" was evaluated to evaluate the high-temperature and high-humidity reliability (creep resistance) of the light-and-moisture-curing resin composition.

(softness)

Each of the light obtained in the examples and the comparative examples and the moisture-curable resin composition were photocured by using a high-pressure mercury lamp and irradiated with ultraviolet rays of 1000 mJ/cm ² , and then allowed to stand overnight to thereby harden the moisture. The obtained cured product was punched into a dumbbell shape ("No. 6 shape as defined by JIS K 6251") to obtain a test piece, and the obtained test piece was obtained using a tensile tester ("EZ-Graph", manufactured by Shimadzu Corporation). The tensile force was carried out at a speed of 10 mm/min, and the force at the elongation of 50% was determined as the elastic modulus.

[Industrial availability]

According to the present invention, it is possible to provide a light and moisture-curable resin composition excellent in adhesion and excellent in high-temperature and high-humidity environments. Moreover, according to the present invention, an adhesive for electronic parts and an adhesive for display elements using the light and moisture-curable resin composition can be provided.

Claims (9)

A light and moisture-curable resin composition containing a radical polymerizable compound, a moisture-curing amine ester resin, and a photoradical polymerization initiator, and the moisture-curable amine ester resin contains: an amine ester ( a urethane) bond, a compound represented by the following formula (1), and an isocyanate group-containing compound; -Si(R ¹ ) _x (OR ² ) _3-x (1) In the formula (1), R ¹ and R ² are hydrogen And an alkyl group or an aryl group having 1 to 5 carbon atoms, and R ¹ and R ² respectively may be the same or different; x is 0 to 2. The light-and-moisture-curing resin composition of the first aspect of the invention, wherein the content of the compound having an amine ester bond, a group represented by the formula (1), and an isocyanate group is relative to the radical polymerizable compound and moisture The total amount of the curable amine ester resin is from 1 to 50 parts by weight based on 100 parts by weight. The light-and-moisture-curing resin composition according to claim 1 or 2, further comprising: a moisture-curing type other than a compound having an amine ester bond, a group represented by the formula (1), and an isocyanate group; Amine ester resin. The light-and-moisture-curing resin composition of the first or second aspect of the invention, wherein the radically polymerizable compound contains a monofunctional radically polymerizable compound and a polyfunctional radically polymerizable compound. The light-and-moisture-curing resin composition of the fourth aspect of the invention, wherein the content of the polyfunctional radically polymerizable compound is 100% by weight based on the total of the monofunctional radically polymerizable compound and the polyfunctional radically polymerizable compound. The serving is 2 to 45 parts by weight. A light-and-moisture-curing resin composition according to claim 1 or 2, which contains a A filler having a secondary particle size of 1 to 50 nm. A light-and-moisture-curing resin composition according to claim 1 or 2, which contains an opacifier. An adhesive for electronic parts obtained by using a light-and-moisture-curing resin composition of the first, second, third, fourth, fifth, sixth or seventh aspect of the patent application. An adhesive for a display element which is obtained by using a light-and-moisture-curing resin composition of the first, second, third, fourth, fifth, sixth or seventh aspect of the patent application.