TWI687444B - Hardened body, electronic parts and display elements - Google Patents

Abstract

An object of the present invention is to provide a hardened body excellent in flexibility and reliability under high temperature and high humidity environment. In addition, an object of the present invention is to provide an electronic component and a display element using the hardened body.

The present invention is a hardened body, which is a cured body of a light moisture curable resin composition containing a radically polymerizable compound and a moisture curable resin, and its storage elastic modulus at 0°C is 1.0×10 ⁷ Pa or more And the storage elastic modulus at 50°C is 5.0×10 ⁶ Pa or less.

Description

Hardened body, electronic parts and display elements

The present invention relates to a hardened body excellent in flexibility and reliability under high temperature and high humidity environment. In addition, the present invention relates to an electronic component and a display element using the hardened body.

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. In such display elements, photocurable resin compositions are generally used for sealing of liquid crystals or light emitting layers, bonding of various members such as substrates, optical films, and protective films.

In addition, in the modernization of mobile phones, portable game consoles and other mobile devices with display elements, the miniaturization of display elements is the most pursued issue. As a method of miniaturization, the image display section is narrowed (below) (Also known as narrow border design). However, in the narrow bezel design, the photo-curable resin composition may be applied to the portion where the light cannot reach sufficiently, and as a result, the photo-curable resin composition applied to the portion where the light does not reach may be insufficiently cured problem. Therefore, a photothermosetting resin composition is also used as a resin composition that can be sufficiently cured even when applied to a portion where light does not reach, and photocuring and thermal curing are used in combination, but there are components that are heated due to high temperature. The risk of adverse effects.

Furthermore, in recent years, electronic components such as semiconductor wafers have been required to be highly integrated and miniaturized. For example, a plurality of thin semiconductor wafers are bonded via an adhesive layer to form a laminate of semiconductor wafers. Such a semiconductor wafer stacking system is manufactured by a method such as, for example, coating a semiconductor wafer with an adhesive, laminating another semiconductor wafer through the adhesive, and then hardening the adhesive; at a fixed interval The method of filling the adhesive between the held semiconductor wafers and then hardening the adhesive.

As an adhesive used for the adhesion of such electronic parts, for example, Patent Document 1 discloses a thermosetting adhesive containing an epoxy compound having a number average molecular weight of 600 to 1,000. However, the thermosetting adhesive as disclosed in Patent Document 1 is not suitable for bonding electronic parts that may cause defects due to heat.

As a method for curing the resin composition without heating at high temperature, Patent Documents 2 and 3 disclose the use of amine esters having at least one isocyanate group and at least one (meth)acryloyl group contained in the molecule. The photo-moisture-curable resin composition of the prepolymer is a combination of photo-curing and moisture-curing. However, as disclosed in Patent Documents 2 and 3, the light-moisture-curable resin composition is difficult to form a hardened body excellent in both flexibility and reliability (especially resistance to creep) in a high-temperature and high-humidity environment.

Patent Document 1: Japanese Patent Laid-Open No. 2000-178342

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

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

An object of the present invention is to provide a hardened body excellent in flexibility and reliability under high temperature and high humidity environment. In addition, an object of the present invention is to provide an electronic component and a display element using the hardened body.

The present invention is a hardened body, which is a cured body of a light moisture-curable resin composition containing a radically polymerizable compound and a moisture-curable resin, and its storage elastic modulus at 0°C is 1.0×10 ⁷ Pa Above, and the storage elastic modulus at 50°C is 5.0×10 ⁶ Pa or less.

Hereinafter, the present invention will be described in detail.

The inventors of the present invention have found that in a photo-moisture-curable resin composition containing a radically polymerizable compound and a moisture-curable resin, the cured body obtained by curing the composition with photo-moisture is at 0°C If the storage elastic modulus at 50° C. is within a specific range, both the flexibility of the hardened body and the reliability in a high-temperature and high-humidity environment are excellent, and the present invention has been completed.

The storage elastic modulus of the hardened body of the present invention at 0°C is 1.0×10 ⁷ Pa or more. If the storage elastic modulus at 0° C. does not reach 1.0×10 ⁷ Pa, when the cured body of the present invention is applied to a substrate or the like, it may be too soft and the cured body may be crushed. In this case, because the width of the adhesive applied during bonding becomes wider, it cannot correspond to the narrow frame design. The storage elastic modulus at 0° C. is preferably 2.0×10 ⁷ Pa or more, and more preferably 3.0×10 ⁷ Pa or more. The upper limit of the storage elastic modulus at 0° C. is not particularly limited, but is usually 1.0×10 ⁸ Pa or less.

In addition, the storage elastic modulus of the hardened body of the present invention at 50°C is 5.0×10 ⁶ Pa or less. If the storage elastic modulus at 50° C. exceeds 5.0×10 ⁶ Pa, it may lose flexibility at high temperatures and cannot be used for bonding of substrates and the like. The storage elastic modulus at 50° C. is preferably 3.0×10 ⁶ Pa or less, more preferably 2.0×10 ⁶ Pa or less, and further preferably 1.0×10 ⁶ Pa or less. In addition, since it does not become too soft under high-temperature and high-humidity conditions and the reliability is more excellent, the storage elastic modulus at 50°C is preferably 5.0×10 ⁵ Pa or more.

The storage elastic modulus at 0°C and the storage elastic modulus at 50°C can be adjusted by adjusting the cross-linking density of the hardened body, controlling the phase structure in the composition, free radically polymerizable compounds or moisture-curable resins. The selection and adjustment of the blending amount, the selection of the filler described below and the adjustment of the blending amount are easily controlled.

In addition, the "storage elastic modulus" can be measured using a dynamic viscoelasticity measuring device (for example, "DVA-200" manufactured by IT Measurement and Control Corporation).

The hardened body of the present invention preferably has two or more glass transition temperatures, and has a glass transition temperature below 0°C and one or more glass transition temperatures exceeding 0°C. Among them, the glass transition temperature exceeding 0°C is more preferably 30°C or lower, and further preferably 25°C or lower. By having such a glass transition temperature, the hardened body of the present invention can achieve both flexibility and reliability in a high temperature and high humidity environment.

Examples of a method for making the cured body have two or more glass transition temperatures include a method in which the radically polymerizable compound and the moisture-curable resin are not completely miscible in the composition. The transition temperature (in the case of a radically polymerizable compound refers to the glass transition temperature of the homopolymer of the radically polymerizable compound) is selected from the radically polymerizable compound and the moisture-curable resin, and two or more The glass transition temperature is adjusted to the above range.

Furthermore, in this specification, the above "glass transition temperature" means the temperature at which the maximum value due to micro-Brownian motion occurs in the maximum value of the loss tangent (tan δ) obtained by dynamic viscoelasticity measurement. The previously known method of measuring the viscoelasticity measuring device.

The curing system of the present invention contains a cured body of a photo-moisture-curable resin composition of a radically polymerizable compound and a moisture-curable resin. Hereinafter, the photo-moisture-curable resin composition that becomes the cured body of the present invention by photo-moisture curing is also referred to as "photo-moisture-curable resin composition of the present invention".

The optical moisture-curable resin composition of the present invention contains a radical polymerizable compound.

The radical polymerizable compound may be a radical polymerizable compound having photopolymerization, and it is not particularly limited as long as it has a radical-reactive functional group in the molecule, and preferably has an unsaturated double bond The compound having a radical-reactive functional group is particularly preferably a compound having a (meth)acryloyl group (hereinafter also referred to as "(meth)acrylic compound") in terms of reactivity.

In addition, in this specification, the said "(meth)acrylic acid" means acrylic acid or methacrylic acid.

Examples of the (meth)acrylic compound include an urethane (meth)acrylate obtained by reacting an isocyanate compound and a (meth)acrylic acid derivative having a hydroxyl group, by A (meth)acrylate compound obtained by reacting (meth)acrylic acid with a compound having a hydroxyl group, an epoxy (meth)acrylate obtained by reacting (meth)acrylic acid with an epoxy compound, and the like. Among them, the radical polymerizable compound preferably contains aliphatic urethane (meth)acrylate. In addition, in this specification, the "(meth)acrylate" means acrylate or methacrylate. In addition, all isocyanate groups of the isocyanate compound that is the raw material of the amine ester (meth)acrylate are used to form amine ester bonds, and the amine ester (meth)acrylate does not have residual isocyanate groups.

The above-mentioned aliphatic amine ester (meth) acrylate can, for example, be The tin-based compound is obtained by reacting an aliphatic (meth)acrylic acid derivative having a hydroxyl group with an aliphatic isocyanate compound.

烷(norbornane)二異氰酸酯、環己烷-1,2-二基雙(亞甲基)二異氰酸酯、離胺酸二異氰酸酯、1,6,11-十-烷三異氰酸酯等。 Examples of the aliphatic isocyanate compound that becomes the raw material of the aliphatic amine ester (meth)acrylate include monoisocyanate alkyl esters such as n-butyl isocyanate, isophorone diisocyanate, and hexamethylene Methyl diisocyanate, trimethylhexamethylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, drop

Alkane (norbornane) diisocyanate, cyclohexane-1,2-diyl bis(methylene) diisocyanate, amine acid diisocyanate, 1,6,11-decane-triisocyanate, etc.

Furthermore, as the aliphatic isocyanate compound, ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, polycaprolactone can also be used. A chain-extended aliphatic isocyanate compound obtained by the reaction of a polyhydric alcohol such as a diol with an excess aliphatic isocyanate compound.

Examples of the aliphatic (meth)acrylic acid derivative having a hydroxyl group as the raw material of the aliphatic amine ester (meth)acrylate include ethylene glycol, propylene glycol, 1,3-propanediol, and 1,3-butane Mono(meth)acrylates of binary aliphatic alcohols such as diols, 1,4-butanediol, and polyethylene glycol; or ternary aliphatics such as trimethylolethane, trimethylolpropane, and glycerin Mono (meth) acrylate or di (meth) acrylate of alcohol; or aliphatic epoxy (meth) acrylate such as hydrogenated bisphenol epoxy (meth) acrylate.

Among the above aliphatic amine ester (meth)acrylates, as a commercially available product, for example, EBECRYL230, EBECRYL270, EBECRYL1290, EBECRYL4858, EBECRYL5129, EBECRYL8402, EBECRYL8411, EBECRYL8804, EBECRYL8807, EBECRYL9260 (all made by Daicel Cham new company) , GENOMER1122 (Made by Rahn) etc.

In the above aliphatic amine ester (meth)acrylate, since the storage elastic modulus of the obtained hardened body can be easily adjusted to the above range, the above radically polymerizable compound preferably contains a glass transition temperature of 0°C or lower. Monofunctional aliphatic amine ester (meth)acrylate.

The content of the monofunctional aliphatic amine ester (meth)acrylate having a glass transition temperature of 0°C or lower is 100 parts by weight relative to the total of the radically polymerizable compound and the moisture-curable resin, and the lower limit is preferably 5 parts by weight, the preferred upper limit is 30 parts by weight. By setting the content of the above-mentioned monofunctional aliphatic amine ester (meth)acrylate having a glass transition temperature of 0° C. or lower to this range, it is easy to adjust the storage elastic modulus of the resulting hardened body to the above range. The more preferable lower limit of the content of the above monofunctional aliphatic amine ester (meth)acrylate having a glass transition temperature of 0° C. or lower is 10 parts by weight, and the more preferable upper limit is 25 parts by weight.

As the amine ester (meth)acrylate other than the aliphatic amine ester (meth)acrylate, in addition to using the isocyanate compound other than the aliphatic isocyanate compound instead of the aliphatic isocyanate compound, the aliphatic amine Ester (meth)acrylate is obtained in the same manner.

Examples of the other isocyanate compounds include 2,4-tolyylene diisocyanate, 2,6-tolyl diisocyanate, and diphenylmethane-4,4′-diisocyanate (MDI). , Hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, tolidine diisocyanate, stubble diisocyanate (XDI), hydrogenated XDI, triphenylmethane triisocyanate, tris(isocyanatophenyl) phosphorothioate , Tetramethyl stubble diisocyanate, etc.

Among the (meth)acrylate compounds obtained by reacting the above (meth)acrylic acid with a compound having a hydroxyl group, examples of the monofunctional group include N-acryloyloxy Phthalate imide acrylates such as ethyl hexahydrophthalimide, various imide acrylates, methyl (meth)acrylate, ethyl (meth)acrylate, (methyl) Propyl acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isopropyl (meth)acrylate Octyl, n-octyl (meth)acrylate, isononyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, isomyristyl (meth)acrylate, (A Group) octadecyl acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylate 2 -Hydroxyethyl, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-methoxyethyl (meth)acrylate , 2-ethoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, methoxyethylene glycol (methyl) Acrylate, methoxypolyethylene glycol (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, (meth)acrylic acid Tetrahydrofurfuryl ester, ethyl carbitol (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate , (Meth)acrylic acid 1H,1H,5H-octafluoropentyl ester, amide imide (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate , 2-(meth)acryloyloxyethyl succinate, 2-(meth)acryloyloxyethyl hexahydrophthalate, 2-(meth)acryloyloxyethyl phthalate 2-hydroxypropyl ester, glycidyl (meth)acrylate, 2-(meth)acrylic acid ethyl phosphate.

In addition, among the above (meth)acrylate compounds, examples of bifunctional ones 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-butyl Yl-2-ethyl-1,3-propanediol di(meth)acrylate, Dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate Acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene oxide addition bisphenol A di(meth)acrylate, ethylene oxide addition double Phenol A di(meth)acrylate, ethylene oxide addition 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)acryloxypropyl (meth)acrylate, carbonic acid Esterdiol di(meth)acrylate, polyetherdiol di(meth)acrylate, polyesterdiol di(meth)acrylate, polycaprolactonediol di(meth)acrylate, poly Butadiene diol di(meth)acrylate, etc.

In addition, among the above (meth)acrylate compounds, examples of trifunctional or more include neopentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, and propylene oxide. Addition trimethylolpropane tri(meth)acrylate, ethylene oxide addition trimethylolpropane tri(meth)acrylate, caprolactone modified trimethylolpropane tri(meth)acrylic acid Ester, ethylene oxide addition isocyanurate tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, di neopentaerythritol hexa (meth) acrylate, di-tris Hydroxymethylpropane tetra (meth) acrylate, neopentaerythritol tetra (meth) acrylate, glycerol tri (meth) acrylate, propylene oxide addition glycerol tri (meth) acrylate, triphosphate ( Methyl) propylene acetylacetate and so on.

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

Examples of the epoxy compound used as a raw material for synthesizing the epoxy (meth)acrylate include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, and 2 ,2'-diallyl bisphenol A epoxy resin, hydrogenated bisphenol epoxy resin, epoxy resin Propane addition bisphenol A epoxy resin, resorcinol epoxy resin, biphenyl epoxy resin, sulfide epoxy resin, diphenyl ether epoxy resin, dicyclopentadiene epoxy resin Resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, o-cresol novolac type epoxy resin, dicyclopentadiene novolac type epoxy resin, biphenol novolac type epoxy resin, naphthol novolac type Varnish epoxy resin, epoxypropylamine epoxy resin, alkyl polyol epoxy resin, rubber modified epoxy resin, glycidyl ester compound, bisphenol A episulfide resin, etc.

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

Among the bisphenol F-type epoxy resins mentioned above, examples of commercially available products include jER806 and jER4004 (all manufactured by Mitsubishi Chemical Corporation).

Among the bisphenol S-type epoxy resins mentioned above, as a commercially available product, for example, EPICLON EXA1514 (manufactured by DIC Corporation) can be cited.

Among the above-mentioned 2,2'-diallylbisphenol A type epoxy resins, as a commercially available product, for example, RE-810NM (manufactured by Nippon Kayaku Co., Ltd.) and the like can be cited.

Among the above-mentioned hydrogenated bisphenol-type epoxy resins, as a commercially available product, for example, EPICLON EXA7015 (manufactured by DIC) can be cited.

Among the propylene oxide addition bisphenol A type epoxy resins, as a commercially available product, for example, EP-4000S (made by ADEKA Corporation) and the like can be cited.

Among the resorcinol-type epoxy resins mentioned above, examples of commercially available ones include EX-201 (manufactured by Nagase Chemicals).

Among the above biphenyl-type epoxy resins, as a commercially available one, for example, jER YX-4000H (three Manufactured by Ling Chemical Co., Ltd.).

Among the above-mentioned sulfide-type epoxy resins, YSLV-50TE (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) and the like can be exemplified as commercially available ones.

Among the above diphenyl ether type epoxy resins, YSLV-80DE (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) and the like may be mentioned as a commercially available product.

Among the above-mentioned dicyclopentadiene-type epoxy resins, as a commercially available product, for example, EP-4088S (made by ADEKA) can be cited.

Among the above naphthalene-type epoxy resins, as a commercially available product, for example, EPICLON HP4032, EPICLON EXA-4700 (all manufactured by DIC Corporation), etc. may be mentioned.

Among the phenol novolac-type epoxy resins mentioned above, as a commercially available product, for example, EPICLON N-770 (manufactured by DIC Corporation) can be cited.

Among the ortho-cresol novolac-type epoxy resins mentioned above, examples of commercially available products include EPICLON N-670-EXP-S (manufactured by DIC Corporation).

Among the above-mentioned dicyclopentadiene novolac-type epoxy resins, as a commercially available product, for example, EPICLON HP7200 (manufactured by DIC Corporation) can be cited.

Among the biphenol novolac-type epoxy resins, as a commercially available product, for example, NC-3000P (manufactured by Nippon Kayaku Co., Ltd.) can be cited.

Among the above naphthol novolak type epoxy resins, as a commercially available product, for example, ESN-165S (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) can be cited.

Among the above-mentioned glycidylamine-type epoxy resins, commercially available examples include jER630 (manufactured by Mitsubishi Chemical Corporation), EPICLON 430 (manufactured by DIC Corporation), TETRAD-X (manufactured by Mitsubishi Gas Chemical Corporation), and the like.

Among the above-mentioned alkyl polyol-type epoxy resins, examples of commercially available products include ZX-1542 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), EPICLON 726 (manufactured by DIC Corporation), and Epolight 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.) , DENACOL EX-611 (made by Nagase Chemical Co., Ltd.), etc.

Among the rubber-modified epoxy resins mentioned above, YR-450, YR-207 (all manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), EpoLead PB (manufactured by Daicel Corporation) and the like can be cited as commercially available ones.

Among the above glycidyl ester compounds, as a commercially available product, for example, DENACOL EX-147 (manufactured by Nagase Chemical Industries, Ltd.) and the like can be cited.

Among the bisphenol A-type episulfide resins mentioned above, as a commercially available product, for example, jER YL-7000 (manufactured by Mitsubishi Chemical Corporation) can be cited.

Among the above epoxy resins, as other commercially available products, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Corporation), jER1031, jER1032 (all For Mitsubishi Chemical Corporation), EXA-7120 (manufactured by DIC Corporation), TEPIC (manufactured by Nissan Chemical Corporation), etc.

Among the above-mentioned epoxy (meth)acrylates, as a commercially available product, for example, EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3800, EBECRYL6040, EEBERYL RDX63 (Made by the company), EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (all made by Shin Nakamura Chemical Industry Company), 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 ( (Made by Kyoeisha Chemical Company), Denacol Acrylate DA-141, Denacol Acrylate DA-314, Denacol Acrylate DA-911 (all made by Nagase Chemical Co., Ltd.), etc.

Moreover, other radically polymerizable compounds other than the above can also be used as appropriate.

Examples of the above-mentioned other radical polymerizable compounds include N,N-dimethyl(meth)acrylamide, N-(meth)acrylamide mofeline, and N-hydroxyethyl(methyl). Acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide (Meth) acrylamide compounds; vinyl compounds such as styrene, α-methylstyrene, N-vinylpyrrolidone, N-vinyl-ε-caprolactam, etc.

From the viewpoint of adjusting the curability and the like, the radical polymerizable compound preferably contains a monofunctional radical polymerizable compound and a polyfunctional radical polymerizable compound. By containing the above-mentioned monofunctional radically polymerizable compound and the above-mentioned multifunctional radically polymerizable compound, the obtained optical moisture curable resin composition becomes more excellent in curability and viscosity. Among them, a compound having a nitrogen atom in the molecule (which is the above-mentioned monofunctional radical polymerizable compound) and an amine ester (meth)acrylate (which is the above-mentioned multifunctional radical polymerizable compound) are more preferably used 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 total amount of the monofunctional radical polymerizable compound and the polyfunctional radical polymerizable compound is 100 parts by weight, the lower limit of the content of the above-mentioned multifunctional radical polymerizable compound is preferably 2 parts by weight, and the upper limit is preferably 45 parts by weight. When the content of the above-mentioned multifunctional radical polymerizable compound is in this range, the resulting optical moisture curable resin composition becomes more excellent in curability and viscosity. The more preferable lower limit of the content of the above-mentioned multifunctional radical polymerizable compound is 5 parts by weight, and the more preferable upper limit is 35 parts by weight.

The lower limit of the content of the radical polymerizable compound is preferably 10 parts by weight, and the preferred upper limit is 80 parts by weight with respect to the total of 100 parts by weight of the radical polymerizable compound and the moisture-curable resin. When the content of the radical polymerizable compound is within this range, the resulting optical moisture-curable resin composition becomes more excellent in photocurability and moisture curability. The more preferable lower limit of the content of the radical polymerizable compound is 25 parts by weight, the more preferable upper limit is 70 parts by weight, the more preferable lower limit is 30 parts by weight, and the more preferable upper limit is 59 parts by weight.

The optical moisture-curable resin composition of the present invention contains moisture-curable resin.

Examples of the moisture-curable resin include moisture-curable urethane resins and resins having crosslinkable silicon groups. Among them, moisture-curable urethane resins are preferred because they have excellent fast-curing properties during moisture curing. The moisture-curable urethane resin has an amine ester bond and an isocyanate group, and the isocyanate group in the molecule reacts with water in the air or the adherend to be cured.

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

The moisture-curable urethane resin preferably has a group containing an ethylenically unsaturated double bond and/or an alkoxysilyl group, and more preferably has a group containing an ethylenically unsaturated double bond and/or an alkoxy group at the end of the molecule Based on silicon.

In addition, the moisture-curable urethane resin is not included in the radical-polymerizable compound even if it has a radical polymerizable group, and is regarded as a moisture-curable urethane resin.

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

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

As the above-mentioned polyol compound, a well-known polyol compound generally used for producing polyurethanes can be used, and examples thereof include polyester polyols, polyether polyols, polyalkylene polyols, and polycarbonate polyols. . These polyol compounds may be used alone or in combination of two or more.

Examples of the polyester polyols include polyester polyols obtained by the reaction of a polycarboxylic acid and a polyol compound, and poly-ε-caprolactone polyols obtained by ring-opening polymerization of ε-caprolactone.

Examples of the above-mentioned polycarboxylic acid as the raw material of the above-mentioned 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, decamethylene-dicarboxylic acid, dodecamethylene dicarboxylic acid, etc.

Examples of the above-mentioned polyol compound that becomes the raw material of the above-mentioned polyester polyol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, and 1,5-pentanediol. Alcohol, 1,6-hexanediol, diethylene glycol, cyclohexanediol, etc.

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

The bisphenol-type polyoxyalkylene modification system described above adds the active hydrogen portion of the bisphenol-type molecular skeleton to alkylene oxide (such as ethylene oxide, propylene oxide, butylene oxide, and isobutylene oxide, etc.) The polyether polyol obtained by the formation reaction may be a random copolymer or a block copolymer. The bisphenol-type polyoxyalkylene modified body is preferably added with one or two types at both ends of the bisphenol-type molecular skeleton. More than one kind of alkylene oxide. The bisphenol type is not particularly limited, and examples thereof include type A, type F, and type S, and bisphenol type A is preferred.

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

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

Examples of the polyisocyanate compound include diphenylmethane diisocyanate (MDI), a liquid modification of MDI, polymeric MDI, tolylene diisocyanate, naphthalene-1,5-diisocyanate, and the like. Among them, MDI and its modified substances are preferred in terms of low vapor pressure, low toxicity, and ease of handling. The above-mentioned polyisocyanate compounds may be used alone or in combination of two or more.

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 body with softness and good elongation can be obtained, which becomes excellent in compatibility with the above radical polymerizable compound By.

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

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.

The weight average molecular weight of the moisture-curable urethane resin is not particularly limited, and the lower limit is preferably 800, and the upper limit is preferably 10,000. By setting the weight average molecular weight of the moisture-curable urethane resin in this range, the cross-linking density does not become too high, the resulting cured body is more excellent in flexibility, and the resulting optical moisture-curable resin composition The coatability is more excellent. The more preferable lower limit of the weight average molecular weight of the moisture-curable urethane resin is 2000, the more preferable upper limit is 8000, the more preferable lower limit is 2500, and the more preferable upper limit is 6000.

In addition, in this specification, the said weight average molecular weight is measured by the gel permeation chromatography (GPC), and it is the value calculated by polystyrene conversion. Examples of the column when measuring the weight average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko). In addition, examples of the solvent used in GPC include tetrahydrofuran.

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

Among the above-mentioned resins having a crosslinkable silicon group, examples of commercially available products include ECSTAR-S2410, S2420, S3430 (all manufactured by Asahi Glass Co., Ltd.), XMAP SA-100S (manufactured by Zhonghua Company), and the like.

The lower limit of the content of the moisture-curable resin is preferably 20 parts by weight, and the preferred upper limit is 90 parts by weight with respect to the total of 100 parts by weight of the radical polymerizable compound and the moisture-curable resin. By making the content of the above moisture-curable resin within this range, the obtained The light moisture-curable resin composition becomes more excellent in moisture curability and photocurability. The more preferable lower limit of the content of the moisture-curable resin is 30 parts by weight, the more preferable upper limit is 75 parts by weight, the more preferable lower limit is 41 parts by weight, and the more preferable upper limit is 70 parts by weight.

The optical moisture-curable resin composition of the present invention usually contains an optical radical polymerization initiator.

等。 Examples of the photo radical polymerization initiator include benzophenone-based compounds, acetophenone-based compounds, acetylphosphine oxide-based compounds, titanocene-based compounds, oxime ester-based compounds, benzoin ether-based compounds, 9-oxygen sulfur

Wait.

Among the above-mentioned photo-radical polymerization initiators, commercially available examples include IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 784, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, Lucirin TPO (all are BASF), benzoin methyl ether, benzoin ether, benzoin isopropyl ether (all made by Tokyo Chemical Industry Co., Ltd.), etc.

The lower limit of the content of the photo-radical polymerization initiator is preferably 0.01 part by weight, and the upper limit is preferably 10 parts by weight, relative to 100 parts by weight of the above-mentioned radical polymerizable compound. When the content of the photo radical polymerization initiator is within this range, the resulting photo-moisture-curable resin composition becomes more excellent in photo-curability and storage stability. The more preferable lower limit of the content of the photo radical polymerization initiator is 0.1 part by weight, and the more preferable upper limit is 5 parts by weight.

From the viewpoint of making the storage elastic modulus of the obtained cured body into a preferable range, it is preferable that the optical moisture curing resin composition of the present invention contains the above-mentioned monofunctional aliphatic amine having a glass transition temperature of 0°C or lower Ester (meth)acrylate as the above-mentioned radically polymerizable compound, and moisture-curable urethane resin containing polypropylene glycol/MDI type as the above-mentioned moisture-hardening The chemical-type resin contains the monofunctional aliphatic amine ester having a glass transition temperature of 0°C or less at a ratio of 10 to 30 parts by weight relative to 100 parts by weight of the total of the radically polymerizable compound and the moisture-curable resin ( Methacrylic acid ester, containing the above polypropylene glycol/MDI type moisture-curable urethane resin at a ratio of 20 to 50 parts by weight, and acyl phosphine oxide system at a ratio of 0.5 to 1.5 parts by weight The photopolymerization initiator serves as a photoradical polymerization initiator.

The optical moisture-curable resin composition of the present invention preferably contains a filler.

By containing the above-mentioned filler, the optical moisture-curable resin composition of the present invention has better shakeability and can sufficiently maintain the shape after coating.

The preferred lower limit of the primary particle size of the filler is 1 nm, and the preferred upper limit is 50 nm. When the primary particle diameter of the filler is within this range, the resulting optical moisture-curable resin composition becomes more excellent in coatability and shape retention after coating. The preferred lower limit of the primary particle size of the filler is 5 nm, the preferred upper limit is 30 nm, the preferred lower limit is 10 nm, and the preferred upper limit is 20 nm.

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

In addition, the filler may exist in the optical moisture-curable resin composition of the present invention as secondary particles (a combination of a plurality of primary particles), and the preferred lower limit of the particle size of such secondary particles is 5nm, the preferred upper limit is 500nm, the more preferred lower limit is 10nm, and the more preferred upper limit is 100nm. The particle size of the secondary particles of the filler can be measured by observing the optical moisture-curable resin composition of the present invention or the cured body of the present invention using a transmission electron microscope (TEM).

The filler is preferably an inorganic filler, and examples thereof include silicon oxide, Talc, titanium oxide, zinc oxide, calcium carbonate, etc. Among them, since the obtained moisture-curable resin composition is excellent in ultraviolet transmittance, silica is preferred. These fillers may be used alone or in combination of two or more.

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

Examples of the hydrophobic surface treatment include silylation treatment, alkylation treatment, and epoxidation treatment. Among them, since the effect of improving shape retention is excellent, silylation treatment is preferable, and trimethyl silylation treatment is more preferable.

As a method of subjecting the filler to a hydrophobic surface treatment, for example, a method of treating the surface of the filler with a surface treatment agent such as a silane coupling agent can be mentioned.

Specifically, for example, the trimethylsilylation-treated silica can be produced by, for example, the following method: synthesizing silica by a sol-gel method or the like, and spraying the silica in a state where it flows. Hexamethyl disilazane (hexamethyl disilazane) method: Add silicon dioxide to alcohol, toluene and other organic solvents, and then add hexamethyl disilazane and water, use an evaporator to evaporate the water and organic solvent to dry Methods.

The lower limit of the content of the filler is preferably 0.1 part by weight, and the preferred upper limit is 20 parts by weight with respect to the total of 100 parts by weight of the radical polymerizable compound and the moisture-curable resin. When the content of the filler is within this range, the obtained optical moisture curable resin composition becomes more excellent in coatability and shape retention after coating. The more preferable lower limit of the content of the filler is 1 part by weight, the more preferable upper limit is 15 parts by weight, the further preferred lower limit is 2 parts by weight, the further preferred upper limit is 10 parts by weight, and the more preferred lower limit is 3 parts by weight, especially The preferred upper limit is 5 parts by weight.

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

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 opacifier may not be black, as long as the material has the ability to make light in the visible light region difficult to transmit, the materials listed as fillers such as silica, talc, titanium oxide, etc. are also included in the opacifier . Among them, titanium black is preferred.

The above-mentioned titanium black is a substance having a higher transmittance in the vicinity of the ultraviolet region, especially light in the wavelength range of 370 to 4500 nm, compared with the average transmittance for light in the wavelength range of 300 to 800 nm. That is, the above-mentioned titanium black is a light-shielding agent that imparts light-shielding properties to the optical moisture-curable resin composition of the present invention by sufficiently shielding the light of the wavelength in the visible light region, and on the other hand, has a wavelength that makes the wavelength near the ultraviolet region The nature of light transmission. Therefore, as a photo-radical polymerization initiator, a photo-moisture-curable resin composition of the present invention can be started by using the light of a wavelength (370 to 450 nm) at which the transmittance of the titanium black becomes higher (370-450 nm) The photohardenability is further increased. On the other hand, the opacifier contained in the optical moisture-curable resin composition of the present invention is preferably a substance with high insulation, and titanium black is also preferable as an opacifier with high insulation.

The optical density (OD value) of the titanium black is preferably 3 or more, and more preferably 4 or more. In addition, the blackness (L value) of the titanium black is preferably 9 or more, and more preferably 11 or more. The higher the light-shielding property of the above-mentioned titanium black, the better. The OD value of the above-mentioned titanium black does not have a particularly preferable upper limit, and is usually 5 or less.

Even if the above titanium black is not surface-treated, it can exert sufficient effects, but it also Titanium black surface-treated with organic components such as coupling agents and those coated with inorganic components such as silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide, and magnesium oxide can be used. Among them, those that have been treated with organic components are preferred in terms of further improvement in insulation.

In addition, in the display device manufactured using the optical moisture-curable resin composition of the present invention, the optical moisture-curable resin composition has sufficient light-shielding properties, and therefore has high contrast without light leakage and excellent image display quality.

The preferable lower limit of the specific surface area of the above titanium black is 5 m ² /g, the preferable upper limit is 40 m ² /g, the more preferable lower limit is 10 m ² /g, and the more preferable upper limit is 25 m ² /g. Furthermore, in the case of mixing with resin (70% blending), the preferable lower limit of the sheet resistance of the above titanium black is 10 ⁹ Ω/□, and the more preferable lower limit is 10 ¹¹ Ω/□.

Among the above-mentioned titanium blacks, as a commercially available product, for example, 12S, 13M, 13M-C, 13R-N (all manufactured by Mitsubishi Materials Corporation), Tilack D (manufactured by Ako Chemical Corporation), etc. may be mentioned.

In the optical moisture-curable resin composition of the present invention, the primary particle size of the light-shielding agent is equal to or less than the distance between the substrates of the display device, etc., and can be 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 diameter of the above-mentioned opacifier is in this range, the obtained optical moisture-curable resin composition has more excellent applicability and workability to the substrate without greatly increasing the viscosity and shakeability. The better lower limit of the primary particle size of the above-mentioned opacifier is 50 nm, and the more preferable upper limit is 200 nm.

In addition, the particle size of the said sunscreen agent can be measured using NICOMP 380ZLS (made by PARTICLE SIZING SYSTEMS Co., Ltd.) by dispersing the said sunscreen agent in a solvent (water, organic solvent, etc.).

The above-mentioned sunscreen agent in the whole light moisture curing resin composition of the present invention The lower limit of the content is preferably 0.05% by weight, and the upper limit is preferably 10% by weight. When the content of the light-shielding agent is in this range, the resulting light-moisture-curable resin composition becomes more excellent in drawing properties, adhesion to substrates, etc., strength after curing, and light-shielding properties. The more preferable lower limit of the content of the above-mentioned opacifier is 0.1% by weight, the more preferable upper limit is 2% by weight, and the more preferable upper limit is 1% by weight.

The optical moisture-curable resin composition of the present invention may further contain additives such as colorants, ionic liquids, solvents, metal-containing particles, reactive diluents, and coupling agents, if necessary. Among them, the optical moisture-curable resin composition of the present invention preferably contains a coupling agent. By containing the above-mentioned coupling agent, the optical moisture-curable resin composition of the present invention becomes more excellent in resistance to creep.

Examples of the coupling agent include a silane coupling agent, a titanate coupling agent, and a zirconate coupling agent. Among them, a silane coupling agent is preferred because the effect of improving adhesion or anti-creep resistance is particularly excellent.

The lower limit of the content of the coupling agent is preferably 0.05 parts by weight, and the upper limit is preferably 5 parts by weight with respect to the total of 100 parts by weight of the radical polymerizable compound and the moisture-curable resin.

Examples of the method for producing the light-moisture-curable resin composition of the present invention include the use of a mixer such as a homogenous disperser, a homomixer, a universal mixer, a planetary mixer, a kneader, and a three-roll mill. Methods such as additives such as organic compounds, moisture-curable resins, photo-radical polymerization initiators, fillers, etc., if necessary.

The light moisture curable resin composition of the present invention uses a cone-plate type viscometer at 25 ℃, 1rpm, the preferred lower limit of viscosity measured 50Pa. s, the preferred upper limit is 500Pa. s. When the viscosity is in this range, when the optical moisture-curable resin composition is used as an adhesive for electronic parts or an adhesive for display elements, it is applied to a substrate such as a substrate. Sex is more excellent. The better lower limit of the above viscosity is 80Pa. s, the better upper limit is 300Pa. s, and the better upper limit is 200Pa. s.

The preferable lower limit of the rocking degree of the light moisture-curable resin composition of the present invention is 1.3, and the preferred upper limit is 5.0. When the above-mentioned rocking degree is within this range, when the optical moisture-curable resin composition is used as an adhesive for electronic parts or an adhesive for display elements, the workability when applied to a substrate such as a substrate Even better. The better lower limit of the above-mentioned rocking degree is 1.5, and the better upper limit is 4.0.

Furthermore, in this specification, the above-mentioned rocking degree means the viscosity measured using a cone-plate viscometer at 25°C and 1 rpm divided by the viscosity measured using a cone-plate viscometer at 25°C and 10 rpm. Value.

Examples of the adherend to which the optical moisture-curable resin composition of the present invention can be adhered include various adherends such as metal, glass, and plastic. Examples of the shape of the adherend include a film shape, a sheet shape, a plate shape, a panel shape, a disk shape, a rod (rod shape) shape, a box shape, and a cabinet shape.

Examples of the above-mentioned metals include iron steel, stainless steel, aluminum, copper, nickel, chromium, and alloys thereof.

Examples of the glass include alkali glass, alkali-free glass, and quartz glass.

Examples of the plastics include polyolefin resins such as high-density polyethylene, ultra-high-molecular-weight polyethylene, syntactic 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 copolymerization (N6/66/610), nylon MXD6 (MXD6), nylon 6T, nylon 6/6T Copolymer, nylon 66/PP copolymer, nylon 66/PPS copolymer and other polyamide resins; polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyisophthalene Ethylene dicarboxylate (PEI), PET/PEI copolymer, polyarylate (PAR), polybutylene naphthalate (PBN), liquid crystal polyester, polyoxyalkylene diimide diacid/poly Aromatic polyester resins such as butylene terephthalate copolymer; polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile/styrene copolymer (AS), methacrylonitrile/styrene copolymer , Methacrylonitrile/styrene/butadiene copolymer and other polynitrile resins, polycarbonate, polymethyl methacrylate (PMMA), polyethyl methacrylate (polyethyl methacrylate) and other polymethacrylates Resin, polyvinyl alcohol (PVA), vinyl alcohol/ethylene copolymer (EVOH), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), vinyl chloride/vinylidene chloride copolymer, vinylidene chloride /Methylene acrylate copolymer and other polyethylene resins.

In addition, as the 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 in which a passivation film is formed by passivating a metal surface can also be cited. Examples of the passivating treatment include heat treatment and anodizing treatment. Especially in the case of aluminum alloys of the international aluminum alloy name 6000 type material, by performing sulfuric acid aluminum acid treatment or phosphoric acid aluminum acid treatment as the above-mentioned passivation treatment, the adhesion can be improved.

As a method of using the photo-moisture-curable resin composition of the present invention followed by an adherend, for example, a method including the following steps may be mentioned: applying the photo-moisture-curable resin composition of the present invention to the first member; The light-moisture-curing type of the present invention disposed on the first member The resin composition is irradiated with light to harden the radically polymerizable compound in the light moisture-curable resin composition of the present invention (first curing step); and through the light moisture-curable resin composition after the first curing step Laminating the first member and the second member (laminating step); and after the laminating step, by moisture curing of the moisture curing resin in the optical moisture curing resin composition of the present invention, the The first member is bonded to the second member (second curing step); preferably, the step of irradiating light is included after the bonding step. Since the step of irradiating light is included after the above-mentioned bonding step, the adhesiveness (initial adhesiveness) immediately after the bonding with the adherend can be improved. When the first member and/or the second member are light-transmitting materials, it is preferable to irradiate light through the transparent first member and/or the second member, and the first member and/or the When the second member is a material that is hard to transmit light, it is preferable that the side surface of the structure formed by bonding the first member and the second member via the optical moisture curing resin composition, that is, the optical moisture curing type The exposed portion of the resin composition is irradiated with light.

The optical moisture-curable resin composition of the present invention can be particularly preferably used as an adhesive for electronic parts or an adhesive for display elements.

As a method for manufacturing the cured body of the present invention by curing the optical moisture-curable resin composition of the present invention with light moisture, for example, a method having the following steps may be mentioned: irradiation of the optical moisture-curable resin composition of the present invention 500~3000mJ/cm ² of light to harden it; and the light-hardened light moisture-curable resin composition of the present invention is exposed to an environment of 20-30°C and 40-60%RH for 8-24 hours and Let it harden with moisture.

The optical density (OD value) when the hardened body of the present invention is made 1 mm thick is preferably 1 or more. By setting the OD value to 1 or more, the light-shielding property is excellent, and when used in a display device, leakage of light can be prevented and high contrast can be obtained. The above OD value is more preferably 1.5 or more.

The higher the above OD value, the better. However, if a large amount of sunscreen is blended in order to increase the above OD value, the workability due to thickening will be reduced. Therefore, in order to balance the blending amount with the sunscreen, The preferred upper limit of the OD value of the hardened body is 4.

Furthermore, the OD value of the hardened body of the present invention can be measured using an optical densitometer.

The lower limit of the tensile elastic modulus of the hardened body of the present invention at 25°C is preferably 0.5 kgf/cm ² , and the preferred upper limit is 5 kgf/cm ² . With the above-mentioned tensile elastic modulus being in this range, it becomes more excellent in flexibility without greatly reducing the adhesive force. The more preferable lower limit of the above tensile elastic modulus is 1 kgf/cm ² , and the more preferable upper limit is 4 kgf/cm ² .

In addition, in this specification, the above-mentioned "tensile elastic modulus" means using a tensile testing machine (for example, "EZ-Graph" manufactured by Shimadzu Corporation) to stretch the hardened body at a speed of 10 mm/min as The value measured by the force at 10% elongation.

The hardened body of the present invention can be particularly preferably used for electronic parts and display elements. Electronic components having a substrate and a hardened body of the present invention, and a display device having a substrate and a hardened body of the present invention are also one of the present invention.

According to the present invention, a hardened body excellent in flexibility and reliability in a high-temperature and high-humidity environment can be provided. Furthermore, according to the present invention, it is possible to provide an electronic component and a display element using the hardened body.

1‧‧‧Polycarbonate substrate

2‧‧‧Light moisture curing resin composition

3‧‧‧glass plate

FIG. 1(a) is a schematic diagram showing a case where the sample for anti-creep evaluation is viewed from above, and FIG. 1(b) is a schematic diagram showing the case where the sample for anti-creep evaluation is viewed from the side.

Hereinafter, the present invention will be further described in detail with examples, but the present invention is not limited to these examples.

(Synthesis Example 1 (Preparation of moisture-curable urethane resin A))

As a polyol compound, put 100 parts by weight of polytetramethylene ether glycol (manufactured by Mitsubishi Chemical Corporation, "PTMG-2000") and 0.01 parts by weight of dibutyltin dilaurate into a separable flask of 500 mL capacity , Under vacuum (20mmHg or less), stir at 100°C for 30 minutes to mix. Then, it was set to normal pressure, 26.5 parts by weight of diphenylmethane diisocyanate (manufactured by Nissho Corporation, "Pure MDI") was added as a polyisocyanate compound, and the mixture was stirred at 80°C for 3 hours for reaction to obtain isocyanate groups at both ends. The moisture-curable urethane resin A (weight average molecular weight 2700).

(Synthesis Example 2 (Preparation of moisture-curable urethane resin B))

As a polyol compound, put 100 parts by weight of polypropylene glycol (manufactured by Asahi Glass Co., Ltd., "EXCENOL 2020") and 0.01 parts by weight of dibutyltin dilaurate in a separable flask of 500 mL capacity under vacuum (20 mmHg or less) , Stir at 100°C for 30 minutes to mix. Then, it was set to normal pressure, 26.5 parts by weight of diphenylmethane diisocyanate (manufactured by Nissho Corporation, "Pure MDI") was added as a polyisocyanate compound, and the mixture was stirred at 80°C for 3 hours for reaction to obtain isocyanate groups at both ends. The moisture-curable urethane resin B (weight average molecular weight 2900).

(Synthesis Example 3 (Preparation of moisture-curable urethane resin C))

After containing 100 parts by weight of the moisture-curable urethane resin A obtained in the same manner as in Synthesis Example 1, To the reaction vessel, 9.8 parts by weight of 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-803") was added, and the mixture was stirred and mixed at 80°C for 1 hour to obtain an organosilicon group-containing amine ester resin. Moisture-curable urethane resin C (weight average molecular weight 3100) having isocyanate group and trimethoxysilyl group at the molecular terminal.

(Examples 1-7, Comparative Examples 1-5)

According to the blending ratios listed in Tables 1 and 2, the materials were mixed by a planetary stirring device (manufactured by Shiny (Thinky) Co., Ltd., "Defoaming Taro"), and then evenly mixed by a ceramic three-roll mill. A light moisture-curable resin composition was obtained.

A part of the obtained light moisture curable resin composition was filled into a Teflon (registered trademark) mold frame with a width of 3 mm, a length of 50 mm, and a height of 1 mm. Then, by irradiating ultraviolet light at 1000 mJ/cm ² using a high-pressure mercury lamp, the photo-moisture-curable resin composition is photo-hardened, and then allowed to stand for more than one night to harden the moisture to obtain a cured body.

<evaluation>

The following evaluation was performed about each photo-moisture-curable resin composition and each cured body obtained in Examples and Comparative Examples. The results are shown in Tables 1 and 2.

(Storage elastic modulus and glass transition temperature)

Each hardened body obtained in the examples and comparative examples was cut out with a width of 3 mm, a length of 20 mm, and a height of 0.8 mm, using a dynamic viscoelasticity measuring device (manufactured by IT Measurement and Control Corporation, "DVA-200") in the deformation mode: stretching 1. Under the conditions of setting strain 1%, measuring frequency 1Hz, heating rate 5℃/min, measure the dynamic viscoelasticity within the range of -70℃~100℃, and find the storage elastic modulus of 0℃ and 50℃. Furthermore, the temperature at which the maximum value of the loss tangent (tan δ) is obtained is taken as the glass transition temperature.

(Anti-creep resistance (reliability evaluation))

Using a drip coating device, each of the optical moisture-curable resin compositions obtained in Examples and Comparative Examples was applied to a carbonate substrate with a width of about 2 mm. Then, UV-LED (wavelength 365 nm) was used to irradiate ultraviolet rays at 1000 mJ/cm ² , thereby photocuring the photo-moisture-curable resin composition. Then, a glass plate was bonded to the polycarbonate substrate, a weight of 20 g was placed, and left overnight to harden it with moisture to obtain a sample for evaluation of creep resistance.

FIG. 1 shows a schematic diagram of the case where the sample for anti-creep evaluation is viewed from above (FIG. 1( a )), and a schematic diagram of the case where the sample for anti-creep evaluation is viewed from the side (FIG. 1( b )). Hang the obtained sample for evaluation of creep resistance perpendicular to the ground, hang a 100 g weight on the end of the polycarbonate substrate, put it in a constant temperature and humidity machine at 50°C and 80% RH in this state, and let it stand 24 hours. After standing for 24 hours, the case where the polycarbonate substrate and the glass plate are not peeled is recorded as "○", and the case where the polycarbonate substrate and the glass plate is partially peeled is recorded as "△", and the polycarbonate substrate and the glass plate The case of complete peeling is recorded as “×”, and the creep resistance of the light moisture-curable resin composition is evaluated.

(Flexibility)

For the test pieces obtained by punching each hardened body obtained in the examples and comparative examples into a dumbbell shape (No. 6 shape prescribed by "JIS K 6251"), a tensile tester (manufactured by Shimadzu Corporation, "EZ -Graph"), stretching at a speed of 10 mm/min, and determining the force at 10% elongation as the tensile modulus of elasticity.

[Industry availability]

According to the present invention, a hardened body excellent in flexibility and reliability in a high-temperature and high-humidity environment can be provided. Furthermore, according to the present invention, it is possible to provide an electronic component and a display element using the hardened body.

Claims (11)

A hardened body comprising a photo-moisture-curable resin composition containing a radically polymerizable compound and a moisture-curable resin, characterized in that the photo-moisture-curable resin composition is polymerized relative to the radical The total amount of the chemical compound and the moisture-curable resin is 100 parts by weight, and the radical-polymerizable compound contains 10 parts by weight or more and 80 parts by weight or less, and the moisture-curable resin is 20 parts by weight or more and 90 parts by weight or less. The cured body has a storage elastic modulus of 1.0×10 ⁷ Pa or more at 0° C., and a storage elastic modulus of 5.0×10 ⁶ Pa or less at 50° C., and has two or more glass transition temperatures and has a temperature of 0° C. or less The glass transition temperature and the glass transition temperature exceeding 0°C and below 30°C are each one or more. The hardened body as claimed in item 1 of the patent application, wherein the radically polymerizable compound contains a compound having a (meth)acryloyl group. The hardened body as claimed in item 1 or 2 of the patent application, wherein the radically polymerizable compound contains an aliphatic urethane (meth)acrylate. For example, in the cured body of claim 1 or 2, the moisture-curable resin is a moisture-curable urethane resin. For example, in the cured body of claim 4, the moisture-curable urethane resin has a group containing an ethylenically unsaturated double bond and/or an alkoxysilyl group. For example, in the hardened body according to item 1 or 2 of the patent application range, the light-moisture-curable resin composition contains a filler having a primary particle diameter of 1 to 50 nm. For example, the hardened body of patent application item 1 or 2, in which the light moisture curing resin composition The object contains sunscreen. As in the hardened body according to item 1 or 2 of the patent application, the light moisture curing resin composition contains a photo radical polymerization initiator. The hardened body as claimed in item 1 or 2 of the patent application, wherein the light moisture curing resin composition contains a coupling agent. An electronic part having a substrate and a hardened body of items 1, 2, 3, 4, 5, 6, 7, 8, or 9 of the patent application range. A display element having a substrate and a hardened body of items 1, 2, 3, 4, 5, 6, 7, 8, or 9 of the patent application range.

Images