TWI720976B - Light and moisture curable resin composition, adhesive for electronic parts, and adhesive for display elements - Google Patents

Abstract

The object of the present invention is to provide a light and moisture curable resin composition having excellent coating properties, shape retention properties, adhesive properties, and gap retention properties. In addition, an object of the present invention is to provide an adhesive for electronic parts and an adhesive for display elements formed using the light and moisture curable resin composition.

The present invention is a light and moisture curable resin composition, which contains a radical polymerizable compound, a moisture curable resin, a photoradical polymerization initiator, and spacer particles.

Description

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

The present invention relates to a light and moisture curable resin composition having excellent coating properties, shape retention properties, adhesive properties, and gap retention properties. In addition, the present invention relates to an adhesive for electronic parts and an adhesive for display elements formed using the light and moisture curable resin composition.

In recent years, liquid crystal display elements, organic EL display elements, etc. have been widely used as display elements with characteristics such as thinness, light weight, and low power consumption. In these display elements, a photocurable resin composition is generally used when sealing various members such as a liquid crystal, a light-emitting layer, an adhesive substrate, an optical film, and a protective film.

However, in the modern age where various mobile devices with display elements such as mobile phones and portable game consoles are becoming popular, the miniaturization of display elements is the most sought-after issue. As a method of miniaturization, narrow the edges of the image display are implemented. (Hereinafter, also referred to as narrow-edge design). However, in the narrow-edge design, the photo-curable resin composition may be applied to the part where the light does not reach enough. As a result, there is insufficient curing of the photo-curable resin composition applied to the part where the light does not reach. The problem. Therefore, the following steps are also carried out: using a light and thermosetting resin composition as a resin composition that can be cured sufficiently when applied to a portion where light does not reach, and combining light curing and Thermal hardening, but there is a risk of adverse effects on components due to heating at high temperatures.

In addition, in recent years, there has been a demand for higher integration and miniaturization in electronic parts such as semiconductor wafers. For example, a laminate of semiconductor wafers is obtained by bonding a plurality of thin semiconductor wafers through an adhesive layer. Such a semiconductor wafer laminate can be manufactured by, for example, the following method: after coating an adhesive on a semiconductor wafer, laminating another semiconductor wafer through the adhesive, and then hardening the adhesive; or leaving a certain interval An adhesive is filled between the semiconductor wafers held on the ground, and then the adhesive is cured.

As an adhesive used for bonding of such electronic parts, for example, Patent Document 1 discloses a thermosetting adhesive containing an epoxy compound with a number average molecular weight of 600 to 1000. However, the thermosetting adhesive disclosed in Patent Document 1 is not suitable for bonding electronic parts that may be damaged by heat.

Patent Documents 2 and 3 disclose the following method: using a light and moisture curable resin composition containing a urethane prepolymer having at least one isocyanate group and at least one (meth)acryloyl group in the molecule, And use light hardening and moisture hardening together. It is considered that if such a light and moisture curable resin composition is used, the resin composition can be cured without heating at a high temperature. However, when the light and moisture curable resin composition disclosed in Patent Document 2 or Patent Document 3 is used, the shape of the resin composition after coating cannot be maintained and may expand, or the substrate may be stuck. The problem that the adhesiveness becomes insufficient when the body is attached.

In addition, in electronic equipment, display devices, etc., it is necessary to minimize the unevenness of the gaps between electronic components and between substrates, etc. Therefore, there is a demand for adhesives for electronic components and display devices that can have both gap retention and adhesiveness. Use adhesive.

Patent Document 1: Japanese Patent Application Publication No. 2000-178342

Patent Document 2: Japanese Patent Application Laid-Open No. 2008-274131

Patent Document 3: Japanese Patent Laid-Open No. 2008-63406

The object of the present invention is to provide a light and moisture curable resin composition having excellent coating properties, shape retention properties, adhesive properties, and gap retention properties. In addition, an object of the present invention is to provide an adhesive for electronic parts and an adhesive for display elements formed using the light and moisture curable resin composition.

The present invention is a light and moisture curable resin composition, which contains a radical polymerizable compound, a moisture curable resin, a photoradical polymerization initiator, and spacer particles.

The present invention will be described in detail below.

Surprisingly, the inventors discovered that a light and moisture-curing resin composition containing a radical polymerizable compound, a moisture-curing resin, a photo-radical polymerization initiator, and spacer particles can be used for coating It is excellent in all aspects of performance, shape retention, adhesiveness, and gap retention, thereby completing the present invention.

The light and moisture curable resin composition of the present invention contains a radical polymerizable compound.

As the above-mentioned radically polymerizable compound, as long as it is a radically polymerizable compound having photopolymerization properties, it is not particularly limited as long as it has a radically reactive functional group in the molecule, and it preferably has an unsaturated double bond. As a compound with a radical reactive functional group, in terms of reactivity, a compound having a (meth)acryloyl group (hereinafter, also referred to as "(former) 基)Acrylic compound").

In addition, in this specification, the above-mentioned "(meth)acryloyl group" means acryloyl group or methacryloyl group, and the above-mentioned "(meth)acrylic acid" means acrylic acid or methacrylic acid.

As the (meth)acrylic compound, for example, a (meth)acrylate compound obtained by reacting a compound having a hydroxyl group with (meth)acrylic acid, and a (meth)acrylic acid compound obtained by reacting (meth)acrylic acid with epoxy Epoxy (meth)acrylate obtained by reacting a compound, amine ester (meth)acrylate obtained by reacting a (meth)acrylic acid derivative having a hydroxyl group with an isocyanate compound, and the like.

In addition, in this specification, the above-mentioned "(meth)acrylate" means acrylate or methacrylate. In addition, all the isocyanate groups of the isocyanate compound used as the raw material of the urethane (meth)acrylate are used to form urethane bonds, and the urethane (meth)acrylate does not have residual isocyanate groups.

Examples of the monofunctional ones in the above (meth)acrylate compounds include: phthalimide acrylates such as N-acryloyloxyethylhexahydrophthalimide, and various alcohols. Imine acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, (meth)acrylate ) Tert-butyl acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isononyl (meth)acrylate, (meth)acrylate Base) isodecyl acrylate, lauryl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, isocamphor (meth)acrylate Ester, dicyclopentenyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylic acid- 2-hydroxybutyl ester, (meth)acrylic acid-4-hydroxyl Butyl butyl ester, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, (meth) Methoxy glycol acrylate, methoxy polyethylene glycol (meth)acrylate, ethyl carbitol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, (meth)acrylic acid -2-Phenoxy ethyl ester, phenoxy diethylene glycol (meth)acrylate, phenoxy polyethylene glycol (meth)acrylate, -2,2,2-tri (meth)acrylate Fluoroethyl, (meth)acrylic acid-2,2,3,3-tetrafluoropropyl ester, (meth)acrylic acid-1H,1H,5H-octafluoropentyl ester, (meth)acrylic acid dimethylamino group Ethyl, diethylaminoethyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, hexahydrophthalic acid-2-(meth)acryloyloxyethyl Esters, phthalic acid-2-(meth)acryloyloxyethyl-2-hydroxypropyl, glycidyl(meth)acrylate, phosphoric acid-2-(meth)acryloyloxyethyl Wait.

In addition, examples of the bifunctional ones in the above-mentioned (meth)acrylate compounds include 1,3-butanediol di(meth)acrylate and 1,4-butanediol di(meth)acrylate , 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 2-n-butane 2-ethyl-1,3-propanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate Base) acrylate, polyethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol (meth)acrylate, ethylene oxide Addition of bisphenol A di(meth)acrylate, propylene oxide addition of bisphenol A di(meth)acrylate, ethylene oxide addition of bisphenol F di(meth)acrylate, dimethylol Dicyclopentadienyl di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide modified isocyanurate di(meth)acrylate, 2-hydroxy-3- (Meth) acryloxy propyl (meth)acrylate, carbonate diol di(meth)acrylate, poly Etherdiol di(meth)acrylate, polyesterdiol di(meth)acrylate, polycaprolactonediol di(meth)acrylate, polybutadienediol di(meth)acrylate Wait.

In addition, examples of the above-mentioned (meth)acrylate compounds having trifunctional or higher functions include trimethylolpropane tri(meth)acrylate, ethylene oxide addition trimethylolpropane tri(methyl) )Acrylate, propylene oxide addition trimethylolpropane tri(meth)acrylate, caprolactone modified trimethylolpropane tri(meth)acrylate, neopentylerythritol tri(meth)acrylic acid Ester, ethylene oxide addition isocyanuric acid tri(meth)acrylate, glycerol tri(meth)acrylate, propylene oxide addition glycerol tri(meth)acrylate, tri(meth)propylene Acetoxyethyl phosphate, di-trimethylolpropane tetra (meth) acrylate, neopentyl erythritol tetra (meth) acrylate, dine pentaerythritol penta (meth) acrylate, two new Pentaerythritol hexa(meth)acrylate and the like.

As said epoxy (meth)acrylate, the thing obtained by reacting an epoxy compound and (meth)acrylic acid in the presence of a basic catalyst according to a conventional method, etc. are mentioned, for example.

As the epoxy compound used as a raw material for synthesizing the above-mentioned epoxy (meth)acrylate, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, 2 , 2'-diallyl bisphenol A epoxy resin, hydrogenated bisphenol epoxy resin, propylene oxide addition bisphenol A epoxy resin, resorcinol epoxy resin, biphenyl ring Oxygen resin, thioether type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol novolak type epoxy resin, o-cresol novolak type ring Oxygen resin, dicyclopentadiene novolak type epoxy resin, biphenol novolak type epoxy resin, naphthol novolak type epoxy resin, glycidamine type epoxy resin, alkyl polyol type epoxy resin, Rubber modified epoxy resin, Glycidyl ester compound, bisphenol A type episulfide resin, etc.

Examples of commercially available products among the above-mentioned bisphenol A epoxy resins include jER828EL, jER1001, jER1004 (all manufactured by Mitsubishi Chemical Corporation), EPICLON 850-S (manufactured by DIC Corporation), and the like.

As a commercial item among the said bisphenol F type epoxy resin, jER806, jER4004 (all are manufactured by Mitsubishi Chemical Corporation) etc. are mentioned, for example.

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

Examples of commercially available products among the above-mentioned 2,2'-diallylbisphenol A epoxy resins include RE-810NM (manufactured by Nippon Kayaku Co., Ltd.).

As a commercial item among the said hydrogenated bisphenol-type epoxy resin, EPICLON EXA7015 (made by DIC Corporation) etc. are mentioned, for example.

As a commercial item among the said propylene oxide addition bisphenol A type epoxy resin, EP-4000S (made by ADEKA Corporation) is mentioned, for example.

As a commercial item among the said resorcinol type epoxy resin, EX-201 (manufactured by Nagase ChemteX Corporation) etc. are mentioned, for example.

As a commercial item among the said biphenyl type epoxy resin, jER YX-4000H (manufactured by Mitsubishi Chemical Corporation) etc. are mentioned, for example.

As a commercial item among the said sulfide-type epoxy resin, YSLV-50TE (manufactured by NIPPON STEEL & SUMIKIN CHEMICAL CO., LTD.) etc. are mentioned, for example.

As a commercial item among the said diphenyl ether type epoxy resin, YSLV-80DE (manufactured by NIPPON STEEL & SUMIKIN CHEMICAL CO., LTD.) etc. are mentioned, for example.

As a commercial item among the said dicyclopentadiene type epoxy resin, EP-4088S (made by ADEKA Corporation) etc. are mentioned, for example.

Examples of commercially available products among the above-mentioned naphthalene-type epoxy resins include EPICLON HP4032, EPICLON EXA-4700 (all manufactured by DIC Corporation), and the like.

As a commercial item among the said phenolic novolak type epoxy resin, EPICLON N-770 (made by DIC Corporation) etc. are mentioned, for example.

As a commercial item among the said ortho-cresol novolak type epoxy resin, EPICLON N-670-EXP-S (made by DIC Corporation) etc. are mentioned, for example.

As a commercial item among the said dicyclopentadiene novolak type epoxy resin, EPICLON HP7200 (made by DIC Corporation) etc. are mentioned, for example.

As a commercial item of the said biphenol novolak type epoxy resin, NC-3000P (manufactured by Nippon Kayaku Co., Ltd.) etc. are mentioned, for example.

As a commercial item among the said naphthol novolak type epoxy resin, ESN-165S (manufactured by NIPPON STEEL & SUMIKIN CHEMICAL CO., LTD.) etc. are mentioned, for example.

Examples of commercially available products among the above-mentioned glycidamine-type epoxy resins include jER630 (manufactured by Mitsubishi Chemical Corporation), EPICLON 430 (manufactured by DIC Corporation), TETRAD-X (manufactured by MITSUBISHI GAS CHEMICAL COMPANY, INC.), and the like.

Examples of commercially available products among the aforementioned alkyl polyol type epoxy resins include ZX-1542 (manufactured by NIPPON STEEL & SUMIKIN CHEMICAL CO., LTD.), EPICLON 726 (manufactured by DIC Corporation), and EPOLIGHT 80MFA (Kyoeisha) Chemical Company), DENACOL EX-611 (manufactured by Nagase ChemteX Corporation), etc.

Examples of commercially available products among the above-mentioned rubber-modified epoxy resins include YR-450, YR -207 (all manufactured by NIPPON STEEL & SUMIKIN CHEMICAL CO., LTD.), EPOLEAD PB (manufactured by Daicel Corporation), etc.

As a commercial item among the said glycidyl ester compounds, DENACOL EX-147 (manufactured by Nagase ChemteX Corporation) etc. are mentioned, for example.

As a commercial item among the said bisphenol A type episulfide resin, jER YL-7000 (manufactured by Mitsubishi Chemical Corporation) etc. are mentioned, for example.

As other commercially available products among the above epoxy resins, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by NIPPON STEEL & SUMIKIN CHEMICAL CO., LTD.), XAC4151 (manufactured by Asahi Kasei Corporation), jER1031, jER1032 (all manufactured by Mitsubishi Chemical Corporation), EXA-7120 (manufactured by DIC Corporation), TEPIC (manufactured by NISSAN CHEMICAL INDUSTRIES, LTD.), etc.

Examples of commercially available products among the above epoxy (meth)acrylates include: EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3800, EBECRYL6040, EBNEXDA LTD.), EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (all manufactured by SHIN-NAKAMURA CHEMICAL 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 400 CHEA (all KYO, SHA LTD.), DENACOL Acrylate DA-141, DENACOL Acrylate DA-314, DENACOL Acrylate DA-911 (all manufactured by Nagase ChemteX Corporation) and the like.

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

Examples of the isocyanate compound used as the raw material of the amine ester (meth)acrylate include: isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, and hexamethylene diisocyanate , Trimethylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, toluidine Diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris(isocyanatophenyl) phosphorothioate, tetramethylxylene diisocyanate, 1 , 6,11-Undecane triisocyanate, etc.

In addition, as the aforementioned isocyanate compound, for example, ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, and polycaprolactone can also be used. A chain-extended isocyanate compound obtained by the reaction of a polyol such as a diol and an excess isocyanate compound.

Examples of (meth)acrylic acid derivatives having hydroxyl groups used as raw materials for the above amine ester (meth)acrylates include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, and 1 ,4-Butanediol, polyethylene glycol and other glycol mono(meth)acrylate, trimethylolethane, trimethylolpropane, glycerin and other triol mono(meth)acrylate Or epoxy (meth)acrylates such as di(meth)acrylate and bisphenol A epoxy (meth)acrylate.

As the commercially available products among the above-mentioned urethane (meth)acrylates, for example: M-1100, M-1200, M-1210, M-1600 (all manufactured by Toagosei Co., Ltd.), EBECRYL230, EBECRYL270, EBECRYL4858, EBECRYL8402, EBECRYL8411, EBECRYL8412, EBECRYL8413, EBECRYL8804, EBECRYL8803, EBECRYL1290, EBECRYL9260, EBECRYL4842, EBECRYL210, EBECRYL4827, EBECRYL6700, EBECRYL220, EBECRYL2220, KRM7735, KRM-8295 (all manufactured by DAICEL-ALLNEX LTD.), 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 Negami Chemical 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 (all are SHIN-NAKAMURA CHEMICAL CO.,LTD. Manufacturing), AI-600, AH-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA-306T (all manufactured by Kyoeisha Chemical Co., Ltd.), CN-902, CN -973, CN-9021, CN-9782, CN-9833 (all manufactured by SARTOMER Corporation), etc.

In addition, other radically polymerizable compounds other than the above can also be suitably used.

As the above-mentioned other radically polymerizable compounds, for example, N,N-dimethyl(meth)acrylamide, N-(meth)acrylomorpholine, N-hydroxyethyl(meth)propylene Amide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N,N-dimethyl (Meth)acrylamide compounds such as aminopropyl (meth)acrylamide, styrene, α-methylstyrene, N-vinylpyrrolidone, N-vinyl-ε-caprolactone Vinyl compounds such as amines, etc.

From the viewpoint of adjusting curability, etc., the radically polymerizable compound preferably contains a monofunctional radically polymerizable compound and a polyfunctional radically polymerizable compound. By containing the above-mentioned monofunctional radical polymerizable compound and the above-mentioned polyfunctional radical polymerizable compound, the obtained light and moisture curable resin composition can be more excellent in curability and adhesiveness. Among them, it is more preferable to use a compound having a nitrogen atom in the molecule as the monofunctional radical polymerizable compound and an amine ester (meth)acrylate as the polyfunctional radical polymerizable compound in combination. In addition, 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 relative to the monofunctional radical polymerizable compound and the polyfunctional radical polymerizable compound. The total amount of the functional radical polymerizable compound is 100 parts by weight, the lower limit is preferably 2 parts by weight, and the upper limit is preferably 45 parts by weight. By setting the content of the polyfunctional radical polymerizable compound within this range, the obtained light and moisture curable resin composition can be made more excellent in curability and adhesiveness. The lower limit of the content of the polyfunctional radical polymerizable compound is more preferably 5 parts by weight, and the upper limit is more preferably 35 parts by weight.

The content of the radical polymerizable compound relative to 100 parts by weight of the total of the radical polymerizable compound and the moisture-curing resin, the lower limit is preferably 10 parts by weight, and the upper limit is preferably 80 parts by weight. By setting the content of the above radical polymerizable compound to this range, It is possible to make the obtained light and moisture curable resin composition more excellent in light curability and moisture curability. The lower limit of the content of the radical polymerizable compound is more preferably 25 parts by weight, the upper limit is more preferably 70 parts by weight, the lower limit is still more preferably 30 parts by weight, and the upper limit is still more preferably 59 parts by weight.

The light and moisture hardening resin composition of the present invention contains moisture hardening resin.

As said moisture hardening type resin, moisture hardening type urethane resin, resin which has a crosslinkable silicon group, etc. are mentioned. Among them, the moisture-curable urethane resin is preferred in terms of its excellent rapid curing properties during moisture curing. The moisture curable urethane resin has an urethane bond and an isocyanate group, and the isocyanate group in the molecule reacts with moisture in the air or in the adherend to be cured.

The moisture-curable urethane resin preferably has the isocyanate group at the molecular terminal.

The moisture-curable urethane resin may have only one isocyanate group in one molecule, or may have two or more. Among them, it is preferable to have an isocyanate group at both ends.

The moisture-curable urethane resin can be obtained by reacting a polyol compound having two or more hydroxyl groups in one molecule and a polyisocyanate compound having two or more isocyanate groups in one molecule.

The reaction between the polyol compound and the polyisocyanate compound is usually in the molar ratio of the hydroxyl group (OH) in the polyol compound and the isocyanate group (NCO) in the polyisocyanate compound as [NCO]/[OH]=2.0~ Within the scope of 2.5.

As the above-mentioned polyol compound, well-known polyol compounds commonly used in the production of polyurethane can be used, for example, polyester polyols, polyether polyols, polyalkylene polyols, polycarbonate polyols, etc. . These polyol compounds may be used alone or in combination of two or more kinds.

Examples of the polyester polyols include polyester polyols obtained by the reaction of polycarboxylic acids and polyol compounds, and polyε-caprolactone polyols obtained by ring-opening polymerization of ε-caprolactone. Alcohol etc.

Examples of the polycarboxylic acid used as the raw material of the polyester polyol include terephthalic acid, isophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, succinic acid, and glutaric acid. Acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, sebacic acid, dodecane dicarboxylic acid, etc.

Examples of the polyols used as the raw materials of the polyester polyols include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, and 1,5-pentanediol. , 1,6-hexanediol, diethylene glycol, cyclohexanediol, etc.

As the above-mentioned polyether polyols, for example, ring-opening polymers of ethylene glycol, propylene glycol, tetrahydrofuran, ring-opening polymers of 3-methyltetrahydrofuran, and random copolymers or blocks of these or derivatives thereof Copolymer, or bisphenol type polyoxyalkylene modified body, etc.

The above-mentioned bisphenol-type polyoxyalkylene modification system makes alkylene oxide (for example, ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, etc.) and the active hydrogen of the bisphenol-type molecular skeleton The polyether polyol obtained by partial addition reaction may be a random copolymer or a block copolymer. The above-mentioned bisphenol-type polyoxyalkylene modification body preferably has one or more alkylene oxides added to both ends of the bisphenol-type molecular skeleton. It does not specifically limit as a bisphenol type, A type, F type, S type, etc. are mentioned, A bisphenol A type is preferable.

As said polyalkylene polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, hydrogenated polyisoprene polyol, etc. are mentioned, for example.

Examples of the above polycarbonate polyol include: polyhexamethylene carbonate Polyol, polycyclohexane dimethylene carbonate polyol, etc.

As said polyisocyanate compound, diphenylmethane-4,4'-diisocyanate (MDI), the liquid modification of MDI, polymeric MDI, toluene diisocyanate, naphthalene-1,5-diisocyanate, etc. are mentioned, for example. Among them, from the viewpoints of low vapor pressure and toxicity, and easy handling, diphenylmethane diisocyanate and its modified products are preferred. The above-mentioned polyisocyanate compounds may be used alone or in combination of two or more kinds.

In addition, 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 with excellent adhesiveness and a hardened product that is soft and well stretched can be obtained, and it has excellent compatibility with the radical polymerizable compound.

Among them, it is preferable to use a polyether polyol composed of a ring-opening polymer compound of propylene glycol, a tetrahydrofuran (THF) compound, or a ring-opening polymer compound of a tetrahydrofuran compound having a substituent such as a methyl group.

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

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

Furthermore, the moisture hardening type 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 preferred, and especially in terms of reactivity, it is more preferably a (meth)acryloyl group .

In addition, the moisture-curable urethane resin having a radically polymerizable functional group is not included in the radically polymerizable compound, but is regarded as a moisture-curable urethane resin.

The weight average molecular weight of the moisture curable urethane resin is not particularly limited, and the preferred lower limit is 800, and the preferred upper limit is 10,000. With the weight average molecular weight of the moisture-curing urethane resin in this range, the crosslinking density will not be too high, and the obtained light and moisture-curing resin composition will have more excellent coatability, and The obtained hardened product becomes more excellent in flexibility. The lower limit of the weight average molecular weight of the moisture curable urethane resin is more preferably 2000, the upper limit is more preferably 8000, the lower limit is still more preferably 2500, and the upper limit is still more preferably 6000.

In addition, in this specification, the said weight average molecular weight is the value calculated|required by the polystyrene conversion measured by gel permeation chromatography (GPC). As a column for the weight average molecular weight measured by GPC and converted from polystyrene, for example, Shodex LF-804 (manufactured by Showa Denko Co., Ltd.) can be cited. Moreover, as a solvent used in GPC, tetrahydrofuran etc. are mentioned.

As the resin having a crosslinkable silicon group, it is preferable to have a crosslinkable silicon group at the end.

Examples of commercially available products among the above-mentioned cross-linkable silicone resins include: EXSTAR-S2410, S2420, S3430 (all manufactured by Asahi Glass Co., Ltd.), XMAP SA-100S (KANEKA Company manufacturing) and so on.

The content of the moisture-curing resin is preferably a lower limit of 20 parts by weight, and a preferably upper limit of 90 parts by weight with respect to 100 parts by weight of the total of the radical polymerizable compound and the moisture-curing resin. By setting the content of the moisture-curing resin in this range, the obtained light and moisture-curing resin composition can be made more excellent in moisture-curing properties and light-curing properties. The lower limit of the content of the moisture curable resin is more preferably 30 parts by weight, the upper limit is more preferably 75 parts by weight, the lower limit is still more preferably 41 parts by weight, and the upper limit is more preferably 70 parts by weight.

The light and moisture curable resin composition of the present invention contains a photoradical polymerization initiator.

等。 Examples of the aforementioned photoradical polymerization initiator include benzophenone-based compounds, acetophenone-based compounds, phosphine oxide-based compounds, titanocene-based compounds, oxime ester-based compounds, benzoin ether-based compounds, 9-oxysulfur

Wait.

Examples of commercially available photo radical polymerization initiators include IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 784, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, Lucirin TPO (all Manufactured by BASF Corporation); Benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether (all manufactured by Tokyo Chemical Industry Co., Ltd.), etc.

The content of the photo-radical polymerization initiator is preferably 0.01 parts by weight in the lower limit and 10 parts by weight in the upper limit with respect to 100 parts by weight of the radically polymerizable compound. By setting the content of the aforementioned photoradical polymerization initiator within this range, the obtained light and moisture curable resin composition can maintain excellent storage stability and make the photocurability more excellent. The lower limit of the content of the photo radical polymerization initiator is more preferably 0.1 parts by weight, and the upper limit is more preferably 5 parts by weight.

The light and moisture curable resin composition of the present invention may contain spacer particles. By containing the above-mentioned spacer particles, the light and moisture curable resin composition of the present invention has excellent gap retention properties, and the gap between the electronic components and the like can be kept constant when a plurality of electronic components are laminated and then connected.

The shape of the spacer particles is preferably spherical.

The preferred upper limit of the aspect ratio of the spacer particles is 1.1. By making the aspect ratio of the aforementioned spacer particles to be 1.1 or less, the interval between the electronic components and the like can be stably kept constant when the electronic components and the like are laminated.

In addition, in this specification, the above-mentioned "aspect ratio" refers to the ratio of the length of the long diameter of the particle to the length of the short diameter of the particle (the length of the long diameter/the length of the short diameter). The closer the value of the aspect ratio is to 1, the closer the shape of the spacer particles is to a true sphere.

The preferred lower limit of the average particle diameter of the spacer particles is 3 μm, and the preferred upper limit is 200 μm. By setting the average particle size of the spacer particles in this range, the effect of keeping the interval between electronic parts and the like constant becomes more excellent. The lower limit of the average particle diameter of the spacer particles is more preferably 5 μm, and the upper limit is more preferably 50 μm.

Furthermore, the average particle diameter of the aforementioned spacer particles is preferably 1.1 times or more the average particle diameter of other solid components added in addition to the spacer particles. By making the average particle size of the spacer particles 1.1 times or more the average particle size of other solid components, the effect of keeping the interval between electronic parts and the like constant becomes more excellent. The average particle diameter of the aforementioned spacer particles is more preferably 1.2 times or more the average particle diameter of other solid components added in addition to the spacer particles.

In addition, the average particle diameter of the spacer particles can be measured by dispersing the spacer particles in a solvent (water, organic solvent, etc.) using a particle size distribution measuring device such as NICOMP 380ZLS (manufactured by PARTICLE SIZING SYSTEMS).

The preferred upper limit of the CV value of the particle diameter of the spacer particles is 10%. By setting the CV value of the particle diameter of the spacer particles to 10% or less, the difference in particle diameter becomes smaller, and the effect of keeping the interval between electronic parts and the like constant becomes more excellent. The more preferable upper limit of the CV value of the particle diameter of the spacer particles is 8%, and the more preferable upper limit is 6%.

In addition, in this specification, the above-mentioned "CV value of particle diameter" refers to a value obtained by the following formula.

CV value of particle size (%)=(standard deviation of particle size/average particle size)×100

The preferred lower limit of the K value represented by the following formula of the spacer particles is 980 N/mm ² , and the more preferred upper limit is 4900 N/mm ² . By keeping the K value of the above-mentioned spacer particles in this range, it is possible to prevent damage to the electronic parts, etc., or deformation of the spacer particles due to extrusion when a plurality of electronic parts are stacked and connected, and the interval between the electronic parts, etc. is kept constant The effect becomes more excellent.

K=(3/√2)‧F‧S ^-3/2 ‧R ^-1/2

In the above formula, F represents the load value (kgf) of the spacer particle during 10% compression deformation, S represents the compression displacement (mm) of the spacer particle during 10% compression deformation, and R represents the radius (mm) of the spacer particle.

Furthermore, the above-mentioned "K value of spacer particles" can be measured by the following method.

First, spread the above-mentioned spacer particles on a steel plate with a smooth surface, and then select one particle from it, and compress the spacer particles using the smooth end surface of a diamond-made cylinder with a diameter of 50 mm using a micro compression tester. At this time, the compression load is electrically detected in the form of electromagnetic force, and the compression displacement is detected electrically in the form of displacement caused by the differential transformer. Then, calculate the load value and compression displacement at 10% compression deformation based on the obtained compression shift-load relationship, and use the obtained result to calculate the K value.

Compression of the above-mentioned spacer particles when they are released from the state of compression deformation at 20°C and 10% The lower limit of the recovery rate is preferably 20%. In the case of using spacer particles with such a compression recovery rate, even if there are large particles between the laminated electronic parts, the shape can be restored by compression and deformation, thereby functioning as a gap adjuster. Therefore, electronic components and the like can be layered horizontally at more stable intervals.

In addition, the compression recovery rate of the spacer particles can be measured by the following method.

By the same method as in the case of the above K value measurement, the compression displacement is electrically detected in the form of displacement caused by the differential transformer, and compressed until the load value is reversed, then the load is removed and the measurement The relationship between load and compression shift at this time. Calculate the compression recovery rate from the obtained measurement results. However, the end point when the load is unloaded is not set to a load value of zero, but set to a load value of 0.1g or more at the origin.

The spacer particles are not particularly limited as long as they are particulate, and examples thereof include resin particles, inorganic particles, organic-inorganic hybrid particles, and the like. Among them, resin particles or organic-inorganic hybrid particles are preferred, and resin particles are more preferred.

聚合物等交聯樹脂。其中，交聯樹脂由於易於調整間隔粒子之硬度與壓縮回復率，且可使所得到之光與濕氣硬化型樹脂組成物之硬化物的耐熱性提高，因此較佳，更佳為二乙 烯苯聚合物、二乙烯苯-苯乙烯共聚物、二乙烯苯-(甲基)丙烯酸酯共聚物、鄰苯二甲酸二烯丙酯聚合物。 As the resin constituting the above-mentioned resin particles, polyethylene, polypropylene, polymethylpentene, polyvinyl chloride, polytetrafluoroethylene, polystyrene, polymethyl acrylate, polymethyl methacrylate, poly(p-methyl) Non-crosslinked resins such as ethylene phthalate), poly(butylene terephthalate), polyamide, polyimide, polysulfide, polyphenylene ether, polyacetal, etc., or epoxy resin, phenol resin , Melamine resin, unsaturated polyester resin, divinylbenzene polymer, divinylbenzene-styrene copolymer, divinylbenzene-acrylate copolymer, diallyl phthalate polymer, three Triallyl isocyanurate polymer, benzoguanidine

Cross-linked resins such as polymers. Among them, the cross-linked resin is preferred because it is easy to adjust the hardness and compression recovery rate of the spacer particles, and can improve the heat resistance of the cured product of the obtained light and moisture-curable resin composition, and therefore, divinylbenzene is more preferred Polymers, divinylbenzene-styrene copolymers, divinylbenzene-(meth)acrylate copolymers, diallyl phthalate polymers.

Examples of the organic-inorganic hybrid particles include particles mainly composed of a polymer of alkoxysilane.

The above-mentioned particles containing a polymer of alkoxysilane as a main component can be obtained, for example, by hydrolyzing and condensing an alkoxysilane according to the description of Japanese Patent No. 2698541.

The aforementioned spacer particles can also be surface-treated as needed. By applying surface treatment to the spacer particles, the viscosity of the obtained light and moisture curable resin composition can be easily adjusted to a desired range, and the coating properties can be improved.

As a method of surface-treating the spacer particles, for example, the following method can be cited: when the light and moisture curable resin composition is hydrophobic as a whole, a hydrophilic group is provided to the surface of the spacer particles.

As a method of imparting a hydrophilic group to the surface of the spacer particles, for example, the following method may be mentioned: when the resin particle is used as the spacer particle, the surface of the resin particle is treated with a coupling agent having a hydrophilic group.

The aforementioned spacer particles may be conductive. Hereinafter, spacer particles having conductivity are also referred to as "conductive spacer particles".

As an anisotropic conductive material used for conductive connection between electrodes, for example, Japanese Patent Laid-Open No. 2005-314696 discloses the following film-like anisotropic conductive circuit connecting material, which is a film-like anisotropic conductive circuit connecting material It is a hardener that can generate free radicals by heating, hydroxyl-containing resins with a molecular weight of 10,000 or more, phosphate esters, radical polymerizable substances, and conductive particles as essential components; in Japanese Patent Application Publication No. 2006-16580 Reveals the presence of curable ingredients, silylation Adhesive composition of compound, conductive particle. However, in recent years, in electronic parts such as semiconductor wafers, due to the requirements for higher integration and miniaturization, the electrode width and electrode interval have become extremely narrow, and the use of conventional anisotropic conductive materials has become impossible to obtain sufficient Adherence and connection reliability. Therefore, by using the light and moisture curable resin composition of the present invention containing conductive spacer particles as the spacer particles as the anisotropic conductive material, highly reliable conductive connection can be achieved.

In other words, the above-mentioned conductive spacer particles not only have the effect of making the obtained light and moisture curable resin composition excellent in gap retention, but also have the effect of ensuring the insulation between connected electrodes. The effect of connecting all electrodes together.

The conductive spacer particles are not particularly limited as long as they are particles with conductivity at least on the surface. Examples include organic particles, inorganic particles, organic-inorganic hybrid particles, and other conductive particles whose surfaces are coated with a metal layer, and are essentially composed of only metal. The metal particles and so on.

Among them, it is preferable that the conductive spacer particles have resin particles and a conductive layer formed on the surface of the resin particles from the viewpoint of further improving the connection reliability between electrodes and the viewpoint of preventing damage to the electrodes and the like.

Examples of the conductive layer include a gold layer, a silver layer, a copper layer, a nickel layer, a palladium layer, and a metal layer containing tin. The above-mentioned conductive fine particles may be conductive fine particles in which at least the outer surface layer of the conductive layer is a solder layer.

The material constituting the solder layer is not particularly limited, but it is preferably a fusible material in accordance with JIS Z3001: Solvent term and a liquidus temperature of 450° C. or less.

Examples of the composition of the solder layer include metal compositions containing zinc, gold, lead, copper, tin, bismuth, and indium. Among them, it is preferable not to contain lead, and it is more preferable to be tin with a low melting point and lead-free- Indium series (117°C eutectic) or tin-bismuth series (139°C eutectic).

The preferred lower limit of the thickness of the aforementioned conductive layer is 5 nm, and the preferred upper limit is 40,000 nm. When the thickness of the conductive layer is 5 nm or more, it can be more excellent in conductivity. When the thickness of the conductive layer is 40,000 nm or less, the difference in the thermal expansion coefficient between the resin particles and the conductive layer can be reduced, making it difficult for the conductive layer to peel off. A more preferable lower limit of the thickness of the above-mentioned conductive layer is 10 nm, a more preferable upper limit is 30,000 nm, a further more preferable lower limit is 20 nm, a still more preferable upper limit is 20,000 nm, and a particularly preferable upper limit is 10,000 nm.

The preferred lower limit of the average particle diameter of the conductive spacer particles is 0.5 μm, and the preferred upper limit is 100 μm. When the average particle diameter of the conductive fine particles is 0.5 μm or more, agglomeration of the conductive spacer particles can be suppressed, and the connection reliability can be more excellent. Since the average particle diameter of the above-mentioned conductive fine particles is 100 μm or less, it can be easily used even when the electrode width and the electrode interval are narrow when the connection is made. The lower limit of the average particle diameter of the conductive fine particles is more preferably 1 μm, and the upper limit is more preferably 30 μm.

The lower limit of the content of the spacer particles is preferably 0.01 parts by weight relative to 100 parts by weight of the total of the radical polymerizable compound and the moisture curable resin, and the upper limit is preferably 10 parts by weight. When the content of the spacer particles is 0.01 parts by weight or more, the effect of keeping the distance between electronic parts and the like constant can be more excellent. When the content of the spacer particles is 10 parts by weight or less, the obtained light and moisture curable resin composition can be more excellent in coating properties and flexibility of the cured product. The lower limit of the content of the spacer particles is more preferably 0.05 parts by weight, the upper limit is more preferably 1 part by weight, and the upper limit is more preferably 0.5 parts by weight.

Furthermore, when the above-mentioned conductive spacer particles are used as the above-mentioned spacer particles, the preferred lower limit of the content of the above-mentioned conductive spacer particles is relative to the above-mentioned radical polymerizable compound and the upper limit. The total 100 parts by weight of the moisture curable resin is 0.5 parts by weight, and the preferred upper limit is 30 parts by weight. When the content of the conductive spacer particles is within this range, the following effects can be more excellent. The effect is to suppress the deterioration of the electrical connection between the unconnectable electrodes and the coatability, and to make the electrodes stable Make conductive connections. The lower limit of the content of the conductive fine particles is more preferably 1 part by weight, and the upper limit is more preferably 20 parts by weight.

The light and moisture curable resin composition of the present invention preferably contains a filler. By containing the above-mentioned filler, the light and moisture curable resin composition of the present invention has better thixotropy and can sufficiently maintain the shape after coating.

The preferred lower limit of the primary particle size of the above filler is 1 nm, and the preferred upper limit is 50 nm. When the primary particle size of the filler is in this range, the obtained light and moisture-curable resin composition will be more excellent in coating properties and shape retention after coating. The lower limit of the primary particle size of the filler is more preferably 5 nm, the upper limit is more preferably 30 nm, the lower limit is still more preferably 10 nm, and the upper limit is still more preferably 20 nm.

In addition, the primary particle size of the filler can be measured in the same manner as the average particle size of the spacer particles.

In addition, there are cases where the above-mentioned filler is present in the form of secondary particles (a collection of a plurality of primary particles) in the light and moisture curable resin composition of the present invention. The particle size of such secondary particles is compared The lower limit is preferably 5 nm, the upper limit is preferably 500 nm, the lower limit is more preferably 10 nm, and the upper limit is more preferably 100 nm. The particle size of the secondary particles of the filler can be measured by observing the light and moisture curable resin composition of the present invention or its cured product using a transmission electron microscope (TEM).

The filler is preferably an inorganic filler, and examples thereof include silica, talc, titanium oxide, zinc oxide, calcium carbonate, and the like. Among them, the light and humidity obtained In terms of the gas-curable resin composition having excellent ultraviolet light transmittance, silicon dioxide is preferable. These fillers may be used alone or in combination of two or more kinds.

The above-mentioned filler is preferably subjected to hydrophobic surface treatment. Through the above-mentioned hydrophobic surface treatment, the obtained light and moisture-curable resin composition has more excellent shape retention after coating.

Examples of the hydrophobic surface treatment include silicidation treatment, alkylation treatment, and epoxidation treatment. Among them, in terms of the excellent effect of improving the shape retention, the silicidation treatment is preferred, and the trimethyl silicidation treatment is more preferred.

As a method of performing a hydrophobic surface treatment on the above-mentioned filler, for example, a method of using a surface treatment agent such as a silane coupling agent to treat the surface of the filler and the like can be cited.

Specifically, for example, the above-mentioned trimethyl silylated silica can be produced by, for example, the following method: synthesizing silica by a sol-gel method or the like, spraying hexamethyl while the silica is flowing The method of disilazane; or the method of adding silicon dioxide to organic solvents such as alcohol and toluene, and then adding hexamethyldisilazane and water, and then using an evaporator to evaporate and dry the water and organic solvent, etc.

The lower limit of the content of the filler is preferably 1 part by weight per 100 parts by weight of the total of the radical polymerizable compound and the moisture curable resin, and the upper limit is preferably 20 parts by weight. When the content of the filler is within this range, the obtained light and moisture curable resin composition will be more excellent in coating properties and shape retention after coating. The lower limit of the filler content is more preferably 2 parts by weight, the upper limit is more preferably 15 parts by weight, the lower limit is still more preferably 3 parts by weight, the upper limit is more preferably 10 parts by weight, and the lower limit is more preferably 4 parts by weight.

The light and moisture curable resin composition of the present invention preferably contains A compound of at least one group in the group consisting of an isocyanate group, an isothiocyanate group, and a carbodiimide group. The compound having at least one group selected from the group consisting of isocyanate group, isothiocyanate group, and carbodiimide group has high reactivity with water, and has a type that prevents moisture hardening during storage The role of the reaction between resin and moisture. Furthermore, a compound having a urethane bond and an isocyanate group is regarded as the above-mentioned moisture-curable urethane resin.

The above-mentioned compound having at least one group selected from the group consisting of isocyanate group, isothiocyanate group, and carbodiimide group is preferable because it must move in the system and react quickly with moisture Because the molecular weight is relatively small, especially in the case of compounds having isocyanate groups and/or isothiocyanate groups, the preferred upper limit of the molecular weight is 500, and the more preferred upper limit is 300. In addition, from the viewpoint of accelerating the reaction rate with moisture and effectively removing moisture, a compound containing an isocyanate group having an aromatic ring or a compound having an isothiocyanate group having an aromatic ring is preferred. Furthermore, the compound having a carbodiimide group is not particularly limited. In addition, a compound having at least one group selected from the group consisting of an isocyanate group, an isothiocyanate group, and a carbodiimide group that has not reacted with moisture contributes to the moisture-curing resin It is cured to increase the cross-linking density, and the cured product of the light and moisture-curable resin composition obtained thereby has excellent adhesion.

The above-mentioned compound having at least one group selected from the group consisting of isocyanate group, isothiocyanate group, and carbodiimide group may be monofunctional or polyfunctional, and has moderate moisture resistance. From the viewpoint of reactivity, bifunctional is preferred.

Furthermore, the above-mentioned compound having at least one group selected from the group consisting of isocyanate group, isothiocyanate group, and carbodiimide group is one that chemically removes moisture, but is blended with the present invention Before each material used in the light and moisture curable resin composition, it can also be pre-determined Physical treatment of each material (using a moisture adsorbent such as zeolite to remove moisture).

Among the above-mentioned compounds having at least one group selected from the group consisting of isocyanate groups, isothiocyanate groups, and carbodiimide groups, the crosslinking density is increased, and the obtained light and moisture harden From the viewpoint that the cured product of the type resin composition is excellent in adhesiveness, a compound having an isocyanate group is preferred.

The compound having an isocyanate group may be the same compound as the polyisocyanate compound used as the raw material of the moisture curable urethane resin, or may be a compound different therefrom.

Specific examples of the compound having an isocyanate group include isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate. Methylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate (NDI), norbornane diisocyanate, toluidine diisocyanate , Xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris(isocyanatophenyl) phosphorothioate, tetramethylxylene diisocyanate, 1,6 , 11-Undecane triisocyanate and so on.

In addition, as a compound having an isothiocyanate group, specific examples include benzyl isothiocyanate, phenyl isothiocyanate, 4-phenylbutyl isothiocyanate, and isothiocyanate. 3-phenylpropyl ester and so on.

In addition, as a compound having a carbodiimide group, specifically, for example, N,N-dicyclohexylcarbodiimide, N,N-diisopropylcarbodiimide, 1- Ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, bis(2,6-diisopropylphenyl)carbodiimide, etc. are commercially available, For example, Carbodilite LA-1 (manufactured by Nisshinbo Co., Ltd.) etc. are mentioned.

These can be used alone or in combination of two or more kinds.

The content of the compound having at least one group selected from the group consisting of isocyanate groups, isothiocyanate groups, and carbodiimide groups is included in the light and moisture curable resin composition of the present invention as a whole In 100 parts by weight, the preferred lower limit is 0.05 parts by weight, and the preferred upper limit is 10 parts by weight. When the content of the compound having at least one group selected from the group consisting of isocyanate group, isothiocyanate group, and carbodiimide group is within this range, the moisture-curing resin can be prevented from being When the degree of crosslinking during curing increases excessively, it becomes hard and brittle, and the obtained light and moisture-curable resin composition is more excellent in storage stability and adhesiveness. The lower limit of the content of the compound having at least one group selected from the group consisting of isocyanate groups, isothiocyanate groups, and carbodiimide groups is more preferably 0.1 parts by weight, and the upper limit is more preferably 3.0 parts by weight. Parts, the lower limit is more preferably 0.2 parts by weight, and the upper limit is more preferably 1.5 parts by weight.

The light and moisture curable resin composition of the present invention may contain a sunscreen agent. By containing the above-mentioned light-shielding agent, the light-and-moisture-curable resin composition of the present invention has excellent light-shielding properties, and can prevent light leakage when used in a display device, for example. In addition, a display element prepared using the light and moisture-curing resin composition of the present invention blended with the above-mentioned light-shielding agent does not leak light because the light- and moisture-curing resin composition has sufficient light-shielding properties. With high contrast, it becomes the one with excellent image display quality.

Furthermore, in this specification, the above-mentioned "shading agent" means a material that has the ability to not easily penetrate light in the visible light region.

Examples of the light-shielding agent include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. In addition, the above-mentioned light-shielding agent may not be black, as long as it is a material that does not easily allow light in the visible light region to penetrate, the materials listed as fillers such as silica, talc, and titanium oxide are also included in the above In the sunscreen. among them, Preferably it is titanium black.

The above-mentioned titanium black is a substance that has a higher transmittance in the vicinity of the ultraviolet region, especially light with a wavelength of 370 to 450 nm, compared to the average transmittance of light with a wavelength of 300 to 800 nm. That is, the above-mentioned titanium black is a light-shielding agent that imparts light-shielding properties to the light and moisture-curing resin composition of the present invention by sufficiently shielding light of a wavelength in the visible light region, and on the other hand, has a wavelength near the ultraviolet region The nature of light penetration. Therefore, by using the light of the wavelength (370~450nm) at which the transmittance of the above titanium black becomes higher, and the light that can start the reaction is used as the photoradical polymerization initiator, the light and moisture curable resin of the present invention can be used. The photocurability of the composition is further increased. On the other hand, as the sunscreen contained in the light and moisture curable resin composition of the present invention, a substance with higher insulation is preferred, and as a sunscreen with higher insulation, titanium is also preferred. black.

The optical density (OD value) of the titanium black is preferably 3 or more, more preferably 4 or more. In addition, the blackness (L value) of the titanium black is preferably 9 or more, 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 does not particularly have a preferred upper limit, which is usually 5 or less.

The above-mentioned titanium black exhibits sufficient effects even if it is not surface-treated, but the surface can be treated with organic components such as coupling agents, or it may be treated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide, or oxide. Surface-treated titanium black coated with magnesium and other inorganic components. Among them, those processed with organic components are preferred in terms of further improving insulation.

Examples of commercially available titanium blacks include 12S, 13M, 13M-C, 13R-N (all manufactured by Mitsubishi Materials Corporation), Tilack D (manufactured by Ako Chemicals Co., Ltd.), and the like.

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

In the light and moisture curable resin composition of the present invention, the primary particle size of the above-mentioned light-shielding agent is less than or equal to the distance between the substrates of the display element, etc., and is appropriately selected according to the application. The preferred lower limit is 30 nm, and the preferred upper limit is 500 nm. When the primary particle size of the light-shielding agent is in this range, the viscosity or thixotropy will not increase significantly, and the obtained light and moisture-curable resin composition will be more excellent in coating properties and workability to the substrate. The lower limit of the primary particle size of the above-mentioned sunscreen is more preferably 50 nm, and the more preferable upper limit is 200 nm.

Furthermore, the primary particle size of the aforementioned light-shielding agent can be measured in the same manner as the average particle size of the aforementioned spacer particles.

The lower limit of the content of the sunscreen in the entire light and moisture curable resin composition of the present invention is preferably 0.05% by weight, and the upper limit is preferably 10% by weight. When the content of the above-mentioned light-shielding agent is within this range, the obtained light and moisture-curable resin composition will have better light-shielding properties while maintaining excellent drawing properties, adhesion to substrates, etc., and strength after curing. For the excellent. The lower limit of the content of the sunscreen is more preferably 0.1% by weight, the upper limit is more preferably 2% by weight, and the upper limit is more preferably 1% by weight.

The light and moisture-curable resin composition of the present invention may further contain additives such as colorants, ionic liquids, solvents, metal-containing particles, and reactive diluents as needed.

As a method of manufacturing the light and moisture curable resin composition of the present invention, for example, the following methods can be cited: using a homogeneous disperser, a homomixer, a universal mixer, a planetary mixer, a kneader, and a three-roll mill Mixers such as free radical polymerizable compounds, moisture-curing resins, photo-radical polymerization initiators, spacer particles, and additives as necessary mixing.

The light and moisture curable resin composition of the present invention preferably has a moisture content of 100 ppm or less. When the moisture content is 100 ppm or less, it is possible to suppress the moisture-curable resin from reacting with moisture during storage, and the light and moisture-curable resin composition has more excellent storage stability. The above-mentioned moisture content is more preferably 80 ppm or less.

In addition, the above-mentioned moisture content can be measured by a Karl Fischer moisture measuring device.

The preferred lower limit of the viscosity of the light and moisture-curable resin composition of the present invention measured using a cone-plate viscometer at 25°C and 1 rpm is 50 Pa‧s, and the preferred upper limit is 1000 Pa‧s. When the above-mentioned viscosity is in this range, when the light and moisture curable resin composition is used in an adhesive for electronic parts or an adhesive for display devices, it becomes workability when applied to a substrate or other adherend. Become more excellent. The lower limit of the above viscosity is more preferably 80Pa‧s, the more preferable upper limit is 500Pa‧s, and the more preferable upper limit is 400Pa‧s.

Furthermore, when the viscosity of the light and moisture curable resin composition of the present invention is too high, the coating properties can be improved by heating during coating.

The preferred lower limit of the thixotropic index of the light and moisture curable resin composition of the present invention is 1.3, and the preferred upper limit is 5.0. With the above-mentioned thixotropic index being in this range, when the light and moisture curable resin composition is used in an adhesive for electronic parts or an adhesive for display elements, it becomes the most important thing when it is applied to a substrate or other adherend. Those who have become more excellent in workability. A more preferable lower limit of the aforementioned tremor index is 1.5, and a more preferable upper limit is 4.0.

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

Regarding the light and moisture curable resin composition of the present invention, the optical density (OD value) of the cured product with a thickness of 1 mm after curing is preferably 1 or more. With the above-mentioned OD value of 1 or more, the effect of suppressing light leakage that occurs when it is used in a display element or the like is more excellent, and high contrast can be obtained. The above-mentioned OD value is more preferably 1.5 or more.

The higher the above OD value is, the better. However, if too much sunscreen is blended to increase the above OD value, workability will decrease due to thickening. Therefore, it is necessary to maintain the balance of the blending amount with the sunscreen. The preferred upper limit of the OD value of the above-mentioned hardened body is 4.

Furthermore, the OD value of the light and moisture-curable resin composition after curing can be measured using an optical densitometer.

As an adherend that can be bonded using the light and moisture curable resin composition of the present invention, various adherends such as metal, glass, and plastic can be cited.

As the shape of the adherend, for example, a film shape, a sheet shape, a plate shape, a panel shape, a tray shape, a rod (rod) shape, a box shape, a shell shape, etc. can be mentioned.

As said metal, steel, stainless steel, aluminum, copper, nickel, chromium, or its alloy etc. are mentioned, for example.

As said glass, alkali glass, alkali-free glass, quartz glass, etc. are mentioned, for example.

Examples of the above-mentioned plastics 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 ), 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 Copolymer (N6/66/610), nylon MXD6 (MXD6), nylon 6T, nylon 6/6T Copolymers, nylon 66/PP copolymers, nylon 66/PPS copolymers and other polyamide resins; polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyisophenylene Ethylene Dicarboxylate (PEI), PET/PEI Copolymer, Polyarylate (PAR), Polybutylene Naphthalate (PBN), Liquid Crystal Polyester, Polyoxyalkylene Diimine Diacid/Poly Aromatic polyester resins such as butyrate terephthalate copolymer; polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile/styrene copolymer (AS), methacrylonitrile/styrene Copolymers, methacrylonitrile/styrene/butadiene copolymers and other polynitrile resins; polycarbonate, polymethyl methacrylate (PMMA), polyethyl methacrylate and other polymethacrylate resins ; Ethylene/vinyl acetate copolymer (EVA), polyvinyl alcohol (PVA), vinyl alcohol/ethylene copolymer (EVOH), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), vinyl chloride/vinylidene chloride Polyethylene resins such as vinyl chloride copolymers, vinylidene chloride/methyl acrylate copolymers, etc.

In addition, as the above-mentioned adherend, a composite material having a metal plating layer on the surface can also be cited, and as a base material for plating of the composite material, for example, the above-mentioned metal, glass, plastic, etc. can be cited.

Furthermore, as the above-mentioned adherend, a material that forms a passive film by subjecting a metal surface to a passivation treatment can also be cited. Examples of the passivation treatment include heat treatment, anodization treatment, and the like. Especially when the international aluminum alloy name is 6000 series of materials such as aluminum alloy, as the above passivation treatment, the sulfuric acid method anodized aluminum treatment or the phosphoric acid method anodized aluminum treatment can improve the adhesion.

As a method of bonding the adherend using the light and moisture curable resin composition of the present invention, for example, a method including the following steps: coating the light and moisture curable resin composition of the present invention on the first member ; For the light and wetness of the present invention coated on the above-mentioned first member The air-curing resin composition is irradiated with light to harden the radical polymerizable compound in the light-and-moisture-curing resin composition of the present invention (first curing step); light and moisture curing after the above-mentioned first curing step Type resin composition bonding the first member and the second member (bonding step); and after the bonding step, the moisture-curable resin in the light and moisture-curable resin composition of the present invention Moisture curing connects the first member and the second member (the second curing step); preferably, the step of irradiating light is included after the bonding step. By including the step of irradiating light after the above-mentioned bonding step, the adhesiveness (initial adhesiveness) immediately after bonding with the adherend can be improved. When the first member and/or the second member are made of a material that allows light to pass through, it is preferable to irradiate light through the first member and/or the second member that allows light to pass through. When the first member and/or the second member are made of a material that is difficult to transmit light, it is preferable to bond the first member and the second member through the light and moisture curable resin composition. The side surface of the structure is exposed to light and the part of the moisture-curable resin composition is irradiated with light.

The light and moisture-curable resin composition of the present invention can be particularly preferably used as an adhesive for electronic parts or an adhesive for display devices. In addition, the adhesive for electronic parts formed by using the light and moisture curable resin composition of the present invention and the adhesive for display elements formed by using the light and moisture curable resin composition of the present invention are also respectively One of the inventions.

According to the present invention, it is possible to provide a light and moisture curable resin composition having excellent coating properties, shape retention properties, adhesive properties, and gap retention properties. Furthermore, according to the present invention, it is possible to provide an adhesive for electronic parts and an adhesive for display elements formed using the light and moisture curable resin composition.

1‧‧‧Aluminum substrate

2‧‧‧Light and moisture hardening resin composition

Fig. 1(a) is a schematic diagram showing the state of observing the adhesive evaluation sample from above, and Fig. 1(b) is a schematic diagram showing the state of observing the adhesive evaluation sample from the side.

Examples are disclosed below to explain the present invention in more detail, but the present invention is not limited to these examples.

(Synthesis Example 1 (Production of Moisture Curing Urethane Resin A))

Add 100 parts by weight of polytetramethylene ether glycol (manufactured by Mitsubishi Chemical Corporation, "PTMG-2000") as a polyol and 0.01 parts by weight of dibutyltin dilaurate to a 500mL volume. In a separable flask, the mixture was stirred and mixed at 100°C under vacuum (20 mmHg or less). Thereafter, the pressure was set to normal pressure, 26.5 parts by weight of Pure MDI (manufactured by Nissho Corporation) was added as a diisocyanate, and the mixture was stirred at 80°C for 3 hours to react to obtain moisture-curing urethane resin A (weight Average molecular weight 2700).

(Examples 1-10, Comparative Example 1)

According to the blending ratio described in Table 1, each material was stirred with a planetary stirring device (manufactured by Thinky, "Defoaming Stirring Taro"), and then uniformly mixed with a ceramic three-roll mill to obtain Example 1~ 9. The light and moisture curable resin composition of Comparative Example 1.

<evaluation>

The following evaluations were performed on each light and moisture curable resin composition obtained in the examples and comparative examples. The results are shown in Table 1.

In addition, the "conductive spacer particles" in Table 1 are the following conductive fine particles (average particle size It is 10μm, and the CV value of the particle size is 4%): A nickel-plated layer is formed on the surface of the divinylbenzene resin particles, and a gold-plated layer is formed on the surface of the nickel-plated layer.

(Coatability (pore penetration))

A filter paper of 150 mesh was laid on a filter device with a diameter of 4 cm, and 30 g of each light and moisture curable resin composition obtained in the examples and comparative examples was pressure-filtered at a pressure of 0.2 MPa, and the passing time was evaluated. If the time required for passing is less than 30 seconds is evaluated as "○", if the time required for passing is more than 30 seconds and less than 5 minutes is evaluated as "△", the time required for passing is 5 minutes The above cases were evaluated as "×", and the coating properties (pore penetration properties) of the light and moisture curable resin composition were evaluated.

(Shape retention)

The light and moisture curable resin compositions obtained in the Examples and Comparative Examples were coated on the aluminum substrate in a manner of a width of about 1 mm and a length of about 30 mm using a dispensing device. Next, a UV-LED (wavelength: 365 nm) was used to ^{irradiate ultraviolet rays at 3000 mJ/cm 2} to photoharden the light and moisture-curable resin composition, and the line width (t ₀ ) and height (t ₁ ) were measured. The case where t ₁ /t ₀ is 0.3 or more is evaluated as "○", and the case where t ₁ /t _{0 is} less than 0.3 is evaluated as "×", and the shape retention of the light and moisture curable resin composition is evaluated.

(Adhesion)

The light and moisture curable resin compositions obtained in the examples and comparative examples were coated on the aluminum substrate with a width of about 2 mm using a dispensing device. Next, use UV-LED (wavelength 365nm) to ^{irradiate ultraviolet rays at 3000mJ/cm 2} to harden the light and moisture-curing resin composition, and then overlap another aluminum substrate, and place a 20g plumb weight and leave it overnight By this, it was cured by moisture, and a sample for adhesive evaluation was obtained.

Fig. 1 shows a schematic diagram when the adhesive evaluation sample is viewed from above (Fig. 1(a)) and a schematic diagram when the adhesive evaluation sample is viewed from the side (Fig. 1(b)).

Put each obtained sample for adhesive evaluation into a constant temperature and humidity oven at 85° C. and 85 RH%, and hang a 50 g plumb weight vertically with respect to the ground, and let it stand for 24 hours. The case where the deviation after standing for 24 hours is 1mm or less is evaluated as "○", the case exceeding 1mm and less than 3mm is evaluated as "△", the case exceeding 3mm is evaluated as "×", and the light and Adhesion of moisture-curing resin composition.

(Flexibility)

For each light and moisture curable resin composition obtained in the Examples and Comparative Examples, UV-LED (wavelength 365nm) was used to ^{irradiate ultraviolet rays at 3000mJ/cm 2} to be photocured, and then left to stand overnight. And it hardens the moisture. For each cured product obtained, the hardness was measured using a type A hardness tester (manufactured by ASKER Kobe Keki Co., Ltd.). The case where the hardness is 40 or less is set as "○", and the case where the hardness exceeds 40 is set as "×", and the flexibility is evaluated.

(Gap retention)

The light and moisture curable resin compositions obtained in the examples and comparative examples were coated on a glass substrate using a dispensing device, and another glass substrate was superimposed on the top of the coated light and moisture curable resin composition A UV-LED (wavelength: 365nm) was used to ^{irradiate ultraviolet rays at 3000mJ/cm 2} to be cured to prepare a test piece for evaluation of gap retention. For the obtained gap retention evaluation test piece, when using a high-precision shape measurement system ("KS-1100", manufactured by KEYENCE) equipped with a laser displacement meter ("LT9010M", manufactured by KEYENCE), when measuring laminated semiconductor wafers The distance between the gaps. One test piece is measured at 20 points, and when either the maximum point or the minimum point of the distance between the gaps is within ±10% of the average value, it is evaluated as "○", and the maximum point of the gap between the gaps , If at least any one of the minimum points is outside the range of ±10% of the average value and within the range of ±20%, it is evaluated as "△", and at least either the maximum point or the minimum point of the distance between the gaps The case where one is outside the range of ±20% of the average is evaluated as "×", and the gap retention is evaluated.

(Connection reliability)

For each light and moisture curable resin composition obtained in Examples 5 to 8 using conductive spacer particles, the connection reliability was evaluated by the following method.

Prepare a glass substrate on which an aluminum electrode pattern with L/S of 100 μm/100 μm and a length of 1 mm is formed. In addition, a flexible printed circuit board on which a gold-plated Cu electrode pattern with L/S of 100 μm/100 μm and a length of 2 mm is formed on the lower surface is prepared.

The light and moisture-curing resin compositions obtained in Examples 5 to 8 were coated on the glass substrate using a dispensing device to have a width of 1 mm and a thickness of 40 μm. UV-LED (wavelength: 365 nm) was used at 3000 mJ/ cm ^{2 is} irradiated with ultraviolet rays to make it photohardenable. Then, the flexible printed circuit board is laminated on the light and moisture curable resin composition so that the electrodes face each other. Then, a 5 kg plumb weight was placed on the above-mentioned flexible printed circuit board and left overnight to make it moisture hardened, thereby obtaining a test piece for connection reliability evaluation.

The connection resistance between the upper and lower electrodes of each test piece for connection reliability evaluation obtained was measured by the 4-terminal method, and the average value of the connection resistance at 100 locations was calculated. Furthermore, the connection resistance can be obtained by measuring the voltage when a certain current flows through the relationship of voltage=current×resistance. The case where the average value of the connection resistance is less than 3Ω is evaluated as "○", the case where the connection resistance is more than 3Ω and less than 5Ω is evaluated as "△", and the case of 5Ω or more is evaluated as "×", and the connection reliability is evaluated.

[Industrial availability]

According to the present invention, it is possible to provide a light and moisture curable resin composition having excellent coating properties, shape retention properties, adhesive properties, and gap retention properties. Furthermore, according to the present invention, it is possible to provide an adhesive for electronic parts and an adhesive for display elements formed using the light and moisture curable resin composition.

1‧‧‧Aluminum substrate

2‧‧‧Light and moisture hardening resin composition

Claims (8)

An adhesive for electronic parts is composed of a light and moisture hardening resin composition containing a radical polymerizable compound, a moisture hardening urethane resin, a photo radical polymerization initiator, and spacer particles. For example, the adhesive for electronic parts in the first item of the scope of patent application, wherein the CV value of the particle diameter of the spacer particles is 10% or less. For example, the adhesive for electronic parts of item 1 or 2 of the scope of patent application, wherein the spacer particles are resin particles or organic-inorganic mixed particles. For example, the adhesive for electronic parts in item 1 or 2 of the scope of patent application contains a sunscreen agent. An adhesive for display elements is composed of a light and moisture hardening resin composition containing a radical polymerizable compound, a moisture hardening urethane resin, a photo radical polymerization initiator, and spacer particles. For example, the adhesive for display elements in the fifth item of the scope of patent application, wherein the CV value of the particle diameter of the spacer particles is 10% or less. For example, the adhesive for display devices of item 5 or 6 in the scope of patent application, wherein the spacer particles are resin particles or organic-inorganic mixed particles. For example, the adhesive for display elements of item 5 or 6 of the scope of patent application contains a light-shielding agent.

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