JP6698524B2 - Cured body, electronic component, display element, and light moisture curable resin composition - Google Patents

Description

The present invention relates to a cured product having excellent flexibility and reliability. The present invention also relates to an electronic component and a display element using the cured product. Furthermore, the present invention relates to a photo-moisture curable resin composition that is suitable for producing the cured product and is excellent in coating properties, shape retention properties, and adhesive properties.

In recent years, liquid crystal display elements, organic EL display elements, and the like have been widely used as display elements having features such as thinness, light weight, and low power consumption. In these display elements, a photocurable resin composition is usually used for sealing liquid crystal or a light emitting layer, adhering various members such as a substrate, an optical film and a protective film.
By the way, in the present age where mobile devices with various display elements such as mobile phones and portable game machines are prevalent, miniaturization of the display element is the most demanded issue. Frames are being made (hereinafter also referred to as narrow frame designs). However, in a narrow frame design, a photocurable resin composition may be applied to a portion where light does not reach sufficiently, and as a result, the photocurable resin composition applied to a portion where light does not reach is cured. There was a problem that was insufficient. Therefore, a photothermosetting resin composition is used as a resin composition that can be sufficiently cured even when applied to a portion where light does not reach, and it is also possible to use both photocuring and heat curing at the same time. There is a possibility that the element may be adversely affected by heating.

Further, in recent years, electronic components such as semiconductor chips have been required to be highly integrated and miniaturized. For example, a plurality of thin semiconductor chips may be joined via an adhesive layer to form a laminated body of semiconductor chips. Has been done. Such a laminated body of semiconductor chips has, for example, a method of applying an adhesive on one semiconductor chip, laminating the other semiconductor chip via the adhesive, and then curing the adhesive, by a fixed method. It is manufactured by a method of filling an adhesive between semiconductor chips held at intervals and then curing the adhesive.
As an adhesive used for bonding such electronic components, 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 disclosed in Patent Document 1 is not suitable for bonding electronic components that may be damaged by heat.

As a method for curing a resin composition without heating at a high temperature, Patent Documents 2 and 3 contain a urethane prepolymer having at least one isocyanate group and at least one (meth)acryloyl group in the molecule. There is disclosed a method of using photocurable and moisture-curable resin composition in combination with photocurable and moisture-curable. However, when the photo-moisture curable resin composition as disclosed in Patent Documents 2 and 3 is used, the resin composition after coating cannot hold its shape and spreads or adheres to an adherend such as a substrate. There was a problem that the adhesiveness when doing was insufficient.
In addition, in electronic devices, display elements, etc., it is necessary that no problems occur even when a force is applied in the shearing direction or the bending direction, thermal stress occurs due to temperature change, etc. There has been a demand for an adhesive for electronic parts and an adhesive for display elements, which has high flexibility and is capable of relieving stress even under conditions, and which maintains high adhesiveness and is excellent in reliability.

JP 2000-178342 A JP, 2008-274131, A JP, 2008-63406, A

An object of the present invention is to provide a cured product having excellent flexibility and reliability. Another object of the present invention is to provide an electronic component and a display device using the cured product. A further object of the present invention is to provide a photo-moisture curable resin composition that is suitable for producing the cured product and is excellent in coating properties, shape retention properties, and adhesive properties.

The present invention is a cured product of a photo-moisture curable resin composition containing a radically polymerizable compound and a moisture curable resin, wherein the tensile strength at 400% elongation at 25° C. is 3 kgf/cm ² or more, 20 kgf. /Cm ² or less is a cured product.
The present invention is described in detail below.

The present inventors have surprisingly found that in a photo-moisture curable resin composition containing a radically polymerizable compound and a moisture-curable resin, a cured product obtained by photo-moisture curing the composition at 25° C. By setting the tensile strength at 400% elongation to fall within a specific range, it is possible to obtain excellent coating properties, shape retention, adhesiveness, flexibility of the cured product, and reliability. The present invention has been completed and the present invention has been completed.

Cured product of the present invention, the lower limit of the tensile strength at 400% elongation at 25 ° C. is 3 kgf / cm ^2, the upper limit is 20 kgf / cm ^2. When the tensile strength at 400% elongation at 25° C. is within this range, the cured product of the present invention can be heated by a temperature change when a force is applied to the adherend in the shear direction or the bending direction. Even when stress is generated, excellent adhesiveness and flexibility can be maintained. A preferred lower limit of the tensile strength at 400% elongation in the 25 ° C. is 5 kgf / cm ^2, a preferred upper limit 17 kgf / cm ^2, more preferred lower limit is 8 kgf / cm ^2.
In addition, the tensile strength at the time of 400% elongation at 25° C. means the force at the time of elongation up to 4 times before being pulled in the tensile test. Specifically, for example, after the photo-moisture-curable resin composition is photo-cured by irradiating ultraviolet rays having a wavelength of 365 nm with 1000 mJ/cm ² using an ultraviolet LED (UV-LED), 25° C., 50% RH The resulting cured product was allowed to stand for 72 hours or more under the conditions of No. 1 to be moisture-cured, and the resulting cured product was punched out into a dumbbell shape (No. 6 type defined in "JIS K 6251") at 25°C. It can be obtained as a force when a tensile tester (for example, "EZ-Graph" manufactured by Shimadzu Corp.) is pulled at a speed of 5 mm/min, and the tensile force is extended to 4 times before pulling.
Further, when the cured product is used for bonding substrates and the like in electronic parts and the like, the above-mentioned tensile strength and tensile rupture elongation, etc., are measured in a state in which the bonded substrates and the like are peeled off. To do. Even if it does not form a dumbbell shape, it can be obtained in the same manner by converting the thickness and width of the cured product in the peeled state.

The preferred lower limit of the tensile elongation at break at 25° C. of the cured product of the present invention is 500%. Since the tensile elongation at break at 25° C. is 500% or more, the cured product of the present invention generates thermal stress due to temperature change when a force is applied to the adherend in the shear direction or the bending direction. In this case, the effect of maintaining excellent adhesiveness and flexibility will be excellent. The more preferable lower limit of the tensile elongation at break at 25°C is 600%.
The tensile elongation at break at 25° C. is, for example, obtained by photo-curing the photo-moisture-curable resin composition by irradiating ultraviolet rays having a wavelength of 365 nm with 1000 mJ/cm ² using an ultraviolet LED lamp or the like. After that, it is moisture-cured by allowing it to stand for 72 hours or more under the conditions of 25° C. and 50% RH, and the obtained cured product is punched out into a dumbbell shape (No. 6 type specified in “JIS K 6251”). It is possible to obtain the elongation at the break point when the obtained test piece is pulled at a rate of 5 mm/min using a tensile tester (for example, "EZ-Graph" manufactured by Shimadzu Corporation) at 25°C.

In the cured product of the present invention, the preferred lower limit of the tensile shear adhesive strength to polycarbonate and glass measured at 25° C. according to JIS K 6850 is 10 kgf/cm ² . Since the tensile shear adhesive strength to the above-mentioned polycarbonate and glass is 10 kgf/cm ² or more, the cured product of the present invention has a temperature change when a force is applied to the adherend in the shear direction or the bending direction. When thermal stress is generated, it is more excellent due to the effect of maintaining excellent adhesiveness. A more preferable lower limit of the tensile shear adhesive strength to the polycarbonate and glass is 15 kgf/cm ² .
The tensile shear adhesive strength with respect to the above-mentioned polycarbonate and glass is specifically, for example, that a light moisture-curable resin composition is applied on a polycarbonate substrate in a width of about 1 mm, and a wavelength of 365 nm is obtained using an ultraviolet LED lamp or the like. After the photo-moisture-curable resin composition is photo-cured by irradiating with ultraviolet rays at 1000 mJ/cm ² , glass substrates are stacked, a weight of 20 g is placed, and the glass substrate is allowed to stand for 72 hours or more under the conditions of 25° C. and 50% RH. The test piece obtained by moisture-curing the light-moisture curable resin composition by doing so is 10 mm in the shear direction at 25° C. using a tensile tester (for example, “EZ-Graph” manufactured by Shimadzu Corporation). It can be measured by pulling at a speed of /min.

In the cured product of the present invention, the storage elastic modulus at 80° C. has a preferable lower limit of 1×10 ⁵ Pa and a preferable upper limit of 1×10 ⁷ Pa. When the storage elastic modulus at 80° C. is within this range, the cured product of the present invention has suitable flexibility even at high temperatures and is excellent in reliability. The more preferable lower limit of the storage elastic modulus at 80° C. is 8×10 ⁵ Pa, and the more preferable upper limit thereof is 5×10 ⁶ Pa.
The storage elastic modulus at 80°C can be measured by using a dynamic viscoelasticity measuring device (for example, "DVA-200" manufactured by IT measurement control company).

The cured product of the present invention is a cured product of a photo-moisture curable resin composition containing a radically polymerizable compound and a moisture curable resin. A photo-moisture-curable resin composition that becomes a cured product of the present invention by curing with light-moisture, that is, a photo-moisture-curable resin composition containing a radically polymerizable compound and a moisture-curable resin, A photo-moisture curable resin composition having a tensile strength at 400% elongation of 25° C. of 3 to 20 kgf/cm ² is also one aspect of the present invention.
The above-mentioned radically polymerizable compound tends to have high flexibility (low tensile strength) of the cured product, low adhesive strength, and good elongation (high elongation at break). On the other hand, the above-mentioned moisture-curable resin tends to have low flexibility of the cured product, strong adhesive force, and good elongation. Therefore, the tensile strength and the like of the cured product can be adjusted to the above-mentioned range by adjusting the types of compounds used as these components, the compounding ratio thereof, the glass transition temperature, the crosslinking density, and the like. Further, the tensile strength and the like of the cured product can be adjusted to the above-mentioned range by adjusting the kind and the blending amount of the filler and the like described later as long as the object of the present invention is not impaired.

The photo-moisture curable resin composition of the present invention contains a radically polymerizable compound.
The radical-polymerizable compound is not particularly limited as long as it is a compound having a radical-reactive functional group in the molecule, as long as it is a photo-polymerizable radical-polymerizable compound. A compound having a heavy bond is preferable, and a compound having a (meth)acryloyl group (hereinafter, also referred to as “(meth)acrylic compound”) is particularly preferable in terms of reactivity.
In the present specification, the “(meth)acryloyl” means acryloyl or methacryloyl, and the “(meth)acryl” means acryl or methacryl.

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

Examples of monofunctional compounds among the (meth)acrylic acid ester compounds include phthalimide acrylates such as N-acryloyloxyethylhexahydrophthalimide, various imide acrylates, methyl (meth)acrylate, ethyl (meth)acrylate, propyl. (Meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isononyl (Meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, Benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-methoxyethyl (meth)acrylate , 2-ethoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, methoxyethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, ethylcarbitol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate , 2-phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (Meth)acrylate, 1H,1H,5H-octafluoropentyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth ) Acryloyloxyethyl hexahydrophthalic acid, 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalate, glycidyl (meth)acrylate, 2-(meth)acryloyloxyethyl phosphate and the like can be mentioned.

In addition, examples of the bifunctional compound of the (meth)acrylic acid ester compound include, for example, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, and 1,6-hexane. Diol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di(meth ) Acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth) ) Acrylate, polypropylene glycol di(meth)acrylate, ethylene oxide-added bisphenol A di(meth)acrylate, propylene oxide-added bisphenol A di(meth)acrylate, ethylene oxide-added bisphenol F di(meth)acrylate, dimethyloldicyclopentadienyldi (Meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide-modified isocyanuric acid di(meth)acrylate, 2-hydroxy-3-(meth)acryloyloxypropyl(meth)acrylate, carbonate diol di(meth)acrylate, Examples include polyether diol di(meth)acrylate, polyester diol di(meth)acrylate, polycaprolactone diol di(meth)acrylate, polybutadiene diol di(meth)acrylate and the like.

Examples of trifunctional or higher functional compounds of the (meth)acrylic acid ester compound include, for example, trimethylolpropane tri(meth)acrylate, ethylene oxide-added trimethylolpropane tri(meth)acrylate, and propylene oxide-added trimethylolpropane tri( (Meth)acrylate, caprolactone-modified trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ethylene oxide-added isocyanuric acid tri(meth)acrylate, glycerin tri(meth)acrylate, propylene oxide-added glycerin tri(meth)acrylate, Examples thereof include tris(meth)acryloyloxyethyl phosphate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate.

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

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

Examples of commercially available bisphenol A type epoxy resins include jER828EL, jER1001, jER1004 (all manufactured by Mitsubishi Chemical Corporation), Epicron 850-S (manufactured by DIC Corporation) and the like.
Examples of commercially available bisphenol F type epoxy resins include jER806 and jER4004 (both manufactured by Mitsubishi Chemical Corporation).
Examples of commercially available bisphenol S-type epoxy resins include Epiclon EXA1514 (manufactured by DIC) and the like.
Examples of commercially available 2,2′-diallyl bisphenol A type epoxy resins include RE-810NM (manufactured by Nippon Kayaku Co., Ltd.) and the like.
Examples of commercially available hydrogenated bisphenol type epoxy resins include Epiclon EXA7015 (manufactured by DIC).
Examples of commercially available propylene oxide-added bisphenol A type epoxy resins include EP-4000S (manufactured by ADEKA).
Examples of commercially available resorcinol type epoxy resins include EX-201 (manufactured by Nagase Chemtex) and the like.
Examples of commercially available biphenyl type epoxy resins include jER YX-4000H (manufactured by Mitsubishi Chemical Corporation) and the like.
Examples of commercially available sulfide type epoxy resins include YSLV-50TE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) and the like.
Examples of commercially available diphenyl ether type epoxy resins include YSLV-80DE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) and the like.
Examples of commercially available dicyclopentadiene type epoxy resins include EP-4088S (manufactured by ADEKA) and the like.
Examples of commercially available naphthalene type epoxy resins include Epiclon HP4032 and Epiclon EXA-4700 (both manufactured by DIC).
Examples of commercially available phenol novolac type epoxy resins include Epicron N-770 (manufactured by DIC).
Examples of commercially available ortho-cresol novolac type epoxy resins include Epiclon N-670-EXP-S (manufactured by DIC).
Examples of commercially available dicyclopentadiene novolac type epoxy resins include Epiclon HP7200 (manufactured by DIC).
Examples of commercially available biphenyl novolac type epoxy resins include NC-3000P (manufactured by Nippon Kayaku Co., Ltd.) and the like.
Examples of commercially available naphthalenephenol novolac type epoxy resins include ESN-165S (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
Examples of commercially available glycidylamine type epoxy resins include jER630 (manufactured by Mitsubishi Chemical Corporation), Epicron 430 (manufactured by DIC Corporation), TETRAD-X (manufactured by Mitsubishi Gas Chemical Company) and the like.
Among the above-mentioned alkyl polyol type epoxy resins, commercially available products include, for example, ZX-1542 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Epicron 726 (manufactured by DIC Co., Ltd.), Epolite 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), and Denacol EX-611. (Manufactured by Nagase Chemtex) and the like.
Examples of commercially available rubber-modified epoxy resins include YR-450, YR-207 (all manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), and Epolide PB (manufactured by Daicel).
Examples of commercially available glycidyl ester compounds include Denacol EX-147 (manufactured by Nagase Chemtex) and the like.
Examples of commercially available bisphenol A type episulfide resins include jER YL-7000 (manufactured by Mitsubishi Chemical Corporation) and the like.
Other commercially available epoxy compounds include, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Corporation), jER1031, jER1032 (any one). And Mitsubishi Chemical Co., Ltd.), EXA-7120 (manufactured by DIC), TEPIC (manufactured by Nissan Chemical Co., Ltd.) and the like.

As those commercially available among the epoxy (meth) acrylate, for example, EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3800, EBECRYL6040, EBECRYL RDX63182 (both manufactured by Daicel-Orunekusu Inc. ), 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 400EA (all manufactured by Kyoeisha Chemical Co., Ltd.), Denacol acrylate DA-141 , Denacol Acrylate DA-314, Denacol Acrylate DA-911 (all manufactured by Nagase Chemtex) and the like.

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

Examples of the isocyanate compound as a raw material of the urethane (meth)acrylate include, for example, isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4. '-Diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanate Phenyl) thiophosphate, tetramethyl xylylene diisocyanate, 1,6,11-undecane triisocyanate and the like can be mentioned.

As the above-mentioned isocyanate compound, for example, it is obtained by a reaction between a polyol such as ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, polycaprolactone diol, etc. and an excess isocyanate compound. Chain-extended isocyanate compounds can also be used.

Examples of the (meth)acrylic acid derivative having a hydroxyl group, which is a raw material of the urethane (meth)acrylate, include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, and 1,4-butane. Mono(meth)acrylates of dihydric alcohols such as diols and polyethylene glycols, mono(meth)acrylates or di(meth)acrylates of trihydric alcohols such as trimethylolethane, trimethylolpropane and glycerin, bisphenol A type epoxy ( Examples thereof include epoxy (meth)acrylates such as (meth)acrylate.

Examples of commercially available urethane (meth)acrylates include, 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, EBECRYL8807, EBECRYL9260, EBECRYL1290, EBECRYL5129, EBECRYL4842, EBECRYL210, EBECRYL4827, EBECRYL6700, EBECRYL220, EBECRYL2220, KRM7735, KRM-8295 (all manufactured by Daicel-Orunekusu Co., Ltd.), Art resin UN-9000H , Art Resin UN-9000A, Art Resin UN-7100, Art Resin UN-1255, Art Resin UN-330, Art Resin UN-3320HB, Art Resin UN-1200TPK, Art Resin SH-500B (all manufactured by Negami Kogyo Co., Ltd.) , U-2HA, U-2PHA, U-3HA, U-4HA, U-6H, U-6LPA, U-6HA, U-10H, U-15HA, U-122A, U-122P, U-108, U. -108A, U-324A, U-340A, U-340P, U-1084A, U-2061BA, UA-340P, UA-4100, UA-4000, UA-4200, UA-4400, UA-5201P, UA-7100. , UA-7200, UA-W2A (all manufactured by Shin-Nakamura Chemical Co., Ltd.), 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) and the like.

Further, other radically polymerizable compounds other than those mentioned above can also be used as appropriate.
Examples of the other radically polymerizable compound include N,N-dimethyl(meth)acrylamide, N-(meth)acryloylmorpholine, N-hydroxyethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N. -(Meth)acrylamide compounds such as isopropyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, vinyl compounds such as styrene, α-methylstyrene, N-vinylpyrrolidone, N-vinyl-ε-caprolactam, etc. Is mentioned.

From the viewpoint of adjusting curability and the like, it is preferable that the radically polymerizable compound contains a monofunctional radically polymerizable compound and a polyfunctional radically polymerizable compound. By containing the monofunctional radically polymerizable compound and the polyfunctional radically polymerizable compound, the obtained photo-moisture curable resin composition becomes more excellent in curability and tackiness. Above all, it is more preferable to use a compound having a nitrogen atom in the molecule as the monofunctional radically polymerizable compound and a urethane (meth)acrylate as the polyfunctional radically polymerizable compound. The polyfunctional radically polymerizable compound is preferably bifunctional or trifunctional, and more preferably bifunctional.

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

Regarding the content of the radically polymerizable compound, a preferable lower limit is 10 parts by weight and a preferable upper limit is 80 parts by weight with respect to 100 parts by weight as a total of the radically polymerizable compound and the moisture-curable resin. When the content of the radically polymerizable compound is within this range, the obtained photo-moisture curable resin composition becomes more excellent in photo-curability and moisture-curability. The more preferable lower limit of the content of the radically polymerizable compound is 25 parts by weight, the more preferable upper limit is 70 parts by weight, the still more preferable lower limit is 30 parts by weight, and the still more preferable upper limit is 59 parts by weight.

The light moisture curable resin composition of the present invention contains a moisture curable resin.
Examples of the moisture-curable resin include a moisture-curable urethane resin and a resin having a crosslinkable silyl group. Of these, a moisture-curable urethane resin is preferable because it has excellent quick-curing properties when moisture-curing. The moisture-curable urethane resin has a urethane bond and an isocyanate group, and the isocyanate group in the molecule reacts with moisture in the air or the adherend to be cured.
The moisture-curable urethane resin preferably has the isocyanate group at the terminal of the molecule.

The moisture-curable urethane resin may have only one isocyanate group in one molecule, or may have two or more isocyanate groups. Above all, 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 with a polyisocyanate compound having two or more isocyanate groups in one molecule.

The reaction between the above-mentioned polyol compound and the polyisocyanate compound is usually carried out by [NCO]/[OH]=2.0-in molar ratio of the hydroxyl group (OH) in the polyol compound and the isocyanate group (NCO) in the polyisocyanate compound It is performed in the range of 2.5.

As the above-mentioned polyol compound, a known polyol compound which is usually used in the production of polyurethane can be used, and examples thereof include polyester polyol, polyether polyol, polyalkylene polyol and polycarbonate polyol. 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 polycarboxylic acid as a raw material of the polyester polyol include terephthalic acid, isophthalic acid, 1,5-naphthalic acid, 2,6-naphthalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, and suberin. Acids, azelaic acid, sebacic acid, decamethylenedicarboxylic acid, dodecamethylenedicarboxylic acid and the like can be mentioned.

Examples of the polyol compound as a raw material of the polyester polyol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6- Hexanediol, diethylene glycol, cyclohexanediol and the like can be mentioned.

Examples of the polyether polyol include ethylene glycol, propylene glycol, a ring-opening polymer of tetrahydrofuran, a ring-opening polymer of 3-methyltetrahydrofuran, and a random copolymer or block copolymer of these or derivatives thereof, bisphenol. Examples include modified polyoxyalkylenes of the type.

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

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

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

Examples of the polyisocyanate compound include diphenylmethane-4,4'-diisocyanate (MDI), a liquid modified product of MDI, polymeric MDI, tolylene diisocyanate, and naphthalene-1,5-diisocyanate. Of these, diphenylmethane diisocyanate and its modified products are preferable from the viewpoints of low vapor pressure, low toxicity, and easy handling. The polyisocyanate compound may be used alone or in combination of two or more kinds.

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), it is possible to obtain a composition having excellent adhesiveness and a cured product having flexibility and good elongation, and compatibility with the radically polymerizable compound. Will be excellent.
Of these, those using a polyether polyol composed of a ring-opening polymerized compound of propylene glycol, a tetrahydrofuran (THF) compound, or a tetrahydrofuran compound having a substituent such as a methyl group are preferable.

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

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

The weight average molecular weight of the moisture-curable urethane resin is not particularly limited, but the preferred lower limit is 800 and the preferred upper limit is 10,000. When the weight average molecular weight of the moisture-curable urethane resin is within this range, the crosslinking density does not become too high, the resulting cured product is more flexible, and the resulting light-moisture-curable resin composition has applicability. Will be better. 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 8,000, the still more preferable lower limit is 2500, and the still more preferable upper limit is 6000.
In addition, in this specification, the said weight average molecular weight is a value calculated|required by polystyrene conversion by measuring by gel permeation chromatography (GPC). Examples of the column for measuring the weight average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (Showa Denko KK). Moreover, tetrahydrofuran etc. are mentioned as a solvent used by GPC.

The resin having a crosslinkable silyl group preferably has a crosslinkable silyl group at the terminal.
Examples of commercially available resins having a crosslinkable silyl group include Exter S2410, S2420, S3430 (all manufactured by Asahi Glass Co., Ltd.), XMAP SA-100S (manufactured by Kaneka Corporation), and the like.

With respect to the content of the moisture-curable resin, a preferable lower limit is 20 parts by weight and a preferable upper limit is 90 parts by weight with respect to a total of 100 parts by weight of the radical-polymerizable compound and the moisture-curable resin. When the content of the moisture-curable resin is within this range, the obtained 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 thereof is 75 parts by weight, the still more preferable lower limit thereof is 41 parts by weight, and the still more preferable upper limit thereof is 70 parts by weight.

The photo-moisture curable resin composition of the present invention usually contains a photo radical polymerization initiator.
Examples of the photoradical polymerization initiator include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, and thioxanthone.

Examples of commercially available photoradical polymerization initiators include, for example, IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 784, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXEROXIOR, and IRGACURE LIN. BASF Corporation), benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether (all manufactured by Tokyo Chemical Industry Co., Ltd.) and the like.

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

The light moisture curable resin composition of the present invention preferably contains a filler. By containing the above-mentioned filler, the photo-moisture curable resin composition of the present invention has suitable thixotropy and can sufficiently retain its shape after application.

The filler has a preferable lower limit of primary particle diameter of 1 nm and a preferable upper limit of 50 nm. When the primary particle diameter of the above-mentioned filler is in this range, the obtained photo-moisture-curable resin composition becomes more excellent in coatability and shape retention after coating. The more preferable lower limit of the primary particle diameter of the filler is 5 nm, the more preferable upper limit thereof is 30 nm, the still more preferable lower limit thereof is 10 nm, and the still more preferable upper limit thereof is 20 nm.
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). it can.
Further, the filler may be present as secondary particles (aggregates of a plurality of primary particles) in the light moisture curable resin composition of the present invention, and a preferable lower limit of the particle diameter of such secondary particles. Is 5 nm, the preferred upper limit is 500 nm, the more preferred lower limit is 10 nm, and the more preferred upper limit is 100 nm. The particle size of the secondary particles of the filler can be measured by observing the light moisture curable resin composition of the present invention or a cured product thereof 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. Of these, silica is preferable because the resulting light-humidity-curable resin composition has excellent ultraviolet light transmittance. These fillers may be used alone or in combination of two or more.

The above-mentioned filler is preferably subjected to hydrophobic surface treatment. By the above hydrophobic surface treatment, the obtained photo-moisture-curable resin composition is more excellent in shape retention after coating.
Examples of the hydrophobic surface treatment include silylation treatment, alkylation treatment and epoxidation treatment. Among them, the silylation treatment is preferable, and the trimethylsilylation treatment is more preferable, because it is excellent in the effect of improving the shape retention property.

Examples of the method for treating the surface of the filler with a hydrophobic property include a method of treating the surface of the filler with a surface treatment agent such as a silane coupling agent.
Specifically, for example, the trimethylsilylation-treated silica is, for example, a method in which silica is synthesized by a method such as a sol-gel method, and hexamethyldisilazane is sprayed in a state where the silica is fluidized, alcohol, in an organic solvent such as toluene. It can be prepared by a method such as adding silica to the above, further adding hexamethyldisilazane and water, and then evaporating and drying the water and the organic solvent with an evaporator.

The content of the filler is preferably 1 part by weight and 20 parts by weight with respect to 100 parts by weight of the total amount of the radically polymerizable compound and the moisture-curable resin. When the content of the above-mentioned filler is in this range, the obtained photo-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 2 parts by weight, the more preferable upper limit thereof is 15 parts by weight, the still more preferable lower limit thereof is 3 parts by weight, the still more preferable upper limit thereof is 10 parts by weight, and the particularly preferable upper limit thereof is 5 parts by weight. ..

The photo-moisture curable resin composition of the present invention preferably contains a compound having at least one group selected from the group consisting of an isocyanate group, an isothiocyanate group, and a carbodiimide group. The compound having at least one type of group selected from the group consisting of the isocyanate group, the isothiocyanate group, and the carbodiimide group has high reactivity with water and reacts between the moisture-curable resin and water during storage. It has a role to prevent. A compound having a urethane bond and an isocyanate group is treated as the moisture-curable urethane resin.

The compound having at least one group selected from the group consisting of the isocyanate group, the isothiocyanate group, and the carbodiimide group has a small molecular weight because it needs to move through the system to react rapidly with water. In particular, in the case of a compound having an isocyanate group and/or an isothiocyanate group, the preferable upper limit of the molecular weight is 500, and the more preferable upper limit is 300. Further, from the viewpoint of increasing the reaction rate with water and effectively removing water, a compound having an isocyanate group having an aromatic ring and a compound having an isothiocyanate group having an aromatic ring are preferable. The compound having a carbodiimide group is not particularly limited. Further, the compound having at least one kind of group selected from the group consisting of an isocyanate group, an isothiocyanate group, and a carbodiimide group which have not reacted with water contributes to the curing of the moisture-curable resin and improves the crosslink density. By doing so, the obtained cured product of the light moisture curable resin composition has excellent adhesiveness.

The compound having at least one type of group selected from the group consisting of an isocyanate group, an isothiocyanate group, and a carbodiimide group may be monofunctional or polyfunctional, but with respect to moisture. It is preferably bifunctional because it has an appropriate reactivity.
The compound having at least one group selected from the group consisting of the isocyanate group, the isothiocyanate group, and the carbodiimide group described above is one that chemically removes water, but the photo-moisture curing type of the present invention is used. Before blending each material used in the resin composition, each material may be subjected in advance to physical treatment (removal of moisture by a moisture adsorbent such as zeolite), if necessary.

Among the compounds having at least one group selected from the group consisting of the isocyanate group, the isothiocyanate group, and the carbodiimide group, the crosslinking density is improved to obtain a cured product of the photo-moisture curable resin composition obtained. A compound having an isocyanate group is preferable because it is excellent in the effect of providing excellent adhesiveness.
The compound having an isocyanate group may be the same as or different from the polyisocyanate compound used as the raw material of the moisture-curable resin.

Specific examples of the compound having an isocyanate group include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4′-. Diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate (NDI), norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris( Isocyanate phenyl) thiophosphate, tetramethyl xylene diisocyanate, 1,6,11-undecane triisocyanate and the like can be mentioned.
Specific examples of the compound having an isothiocyanate group include benzyl isothiocyanate, phenyl isothiocyanate, 4-phenylbutyl isothiocyanate, and 3-phenylpropyl isothiocyanate.
Specific examples of the compound having a carbodiimide group include N,N-dicyclohexylcarbodiimide, N,N-diisopropylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride and bis(2 , 6-diisopropylphenyl)carbodiimide and the like, and examples of commercially available products include carbodilite LA-1 (manufactured by Nisshinbo Co., Ltd.) and the like.
These may be used alone or in combination of two or more.

The content of the compound having at least one group selected from the group consisting of the isocyanate group, the isothiocyanate group, and the carbodiimide group is preferable in 100 parts by weight of the entire photo-moisture curable resin composition of the present invention. The lower limit is 0.05 parts by weight, and the preferable upper limit is 10 parts by weight. When the content of the compound having at least one group selected from the group consisting of the isocyanate group, the isothiocyanate group, and the carbodiimide group is within this range, the crosslinking degree of the moisture-curable resin at the time of curing increases. The resulting photo-moisture-curable resin composition is more excellent in storage stability and adhesiveness while preventing it from becoming too hard and brittle. The more preferable lower limit of the content of the compound having at least one group selected from the group consisting of the isocyanate group, the isothiocyanate group, and the carbodiimide group is 0.1 parts by weight, and the more preferable upper limit thereof is 3.0 parts by weight. A more preferred lower limit is 0.2 parts by weight, and a more preferred upper limit is 1.5 parts by weight.

The light moisture curable resin composition of the present invention may contain a light shielding agent. By containing the above-mentioned light-shielding agent, the light moisture curable resin composition of the present invention has excellent light-shielding properties, and can prevent light leakage when used in a display element, for example. In addition, the display element produced using the light-moisture-curable resin composition of the present invention containing the above-mentioned light-shielding agent has a high light-moisture-curable resin composition, which has sufficient light-shielding properties and therefore does not leak light. It has a contrast and an excellent image display quality.
In addition, in the present specification, the above-mentioned “light-shielding agent” means a material having a capability of hardly transmitting light in the visible light region.

Examples of the light-shielding agent include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, resin-coated carbon black, and the like.
Further, the above-mentioned light-shielding agent does not have to exhibit a black color, and silica, talc, titanium oxide, etc., such as the materials mentioned as the filler, may be used as long as they have a capability of hardly transmitting light in the visible light region. It is included in the above light-shielding agent. Of these, titanium black is preferable.

The titanium black is a substance having a higher transmittance in the vicinity of the ultraviolet region, particularly in the light having a wavelength of 370 to 450 nm than the average transmittance for light having a wavelength of 300 to 800 nm.
That is, the titanium black imparts a light-shielding property to the light moisture curable resin composition of the present invention by sufficiently shielding light having a wavelength in the visible light region, while allowing light having a wavelength in the ultraviolet region to pass therethrough. Is a light-shielding agent. Therefore, by using, as the photo-radical polymerization initiator, one capable of initiating a reaction by light having a wavelength (370 to 450 nm) at which the above-mentioned titanium black has a high transmittance, the light of the photo-moisture curable resin composition of the present invention can be obtained. The curability can be further increased. On the other hand, as the light-shielding agent contained in the photo-moisture curable resin composition of the present invention, a substance having a high insulating property is preferable, and titanium black is also suitable as a light-shielding agent having a high insulating property.
The optical density (OD value) of the titanium black is preferably 3 or more, more preferably 4 or more. In addition, the titanium black preferably has a blackness (L value) of 9 or more, more preferably 11 or more. The higher the light-shielding property of the titanium black, the better. The OD value of the titanium black has no particular upper limit, but it is usually 5 or less.

The above-mentioned titanium black exhibits sufficient effects even if it is not surface-treated, but its surface is treated with an organic component such as a coupling agent, silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide. It is also possible to use surface-treated titanium black such as those coated with an inorganic component such as magnesium oxide. Among them, those treated with an organic component are preferable because the insulating property can be further improved.

Examples of commercially available titanium blacks include 12S, 13M, 13M-C, 13R-N (all manufactured by Mitsubishi Materials), Tilac D (manufactured by Ako Chemicals), 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.
Further, a preferable lower limit of the sheet resistance of the above titanium black is 10 ⁹ Ω/□ when mixed with a resin (70% blending), and a more preferable lower limit thereof is 10 ¹¹ Ω/□.

In the light moisture curable resin composition of the present invention, the primary particle size of the light shielding agent is appropriately selected according to the application such as the distance between the substrates of the display element or the like, but the preferred lower limit is 30 nm, and the preferred upper limit is 500 nm. Is. When the primary particle size of the light-shielding agent is within this range, the resulting light-moisture-curable resin composition is more excellent in coatability and workability on a substrate without significantly increasing viscosity and thixotropy. The more preferable lower limit of the primary particle diameter of the light shielding agent is 50 nm, and the more preferable upper limit thereof is 200 nm.
The particle size of the light-shielding agent can be measured by dispersing the light-shielding agent in a solvent (water, organic solvent, etc.) using NICOMP 380ZLS (manufactured by PARTICLE SIZING SYSTEMS).

The preferable lower limit of the content of the light-shielding agent in the entire light moisture curable resin composition of the present invention is 0.05% by weight, and the preferable upper limit thereof is 10% by weight. When the content of the light-shielding agent is within this range, the resulting light-moisture-curable resin composition has excellent drawing properties, adhesiveness to a substrate, etc., and light-shielding properties while maintaining strength after curing. It will be excellent. The more preferable lower limit of the content of the light-shielding agent is 0.1% by weight, the more preferable upper limit thereof is 2% by weight, and the still more preferable upper limit thereof is 1% by weight.

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

Examples of the method for producing the photo-moisture curable resin composition of the present invention include a homopolymer, a homomixer, a universal mixer, a planetary mixer, a kneader, and a three-roll mixer. Examples include a method of mixing a moisture-curable resin, a photoradical polymerization initiator, and an additive that is added as necessary.

The light moisture curable resin composition of the present invention preferably has a water content of 100 ppm or less. When the amount of water is 100 ppm or less, the reaction between the moisture-curable resin and moisture during storage is suppressed, and the photohumidity-curable resin composition becomes more excellent in storage stability. The water content is more preferably 80 ppm or less.
The water content can be measured with a Karl Fischer water content measuring device.

In the light moisture curable resin composition of the present invention, the viscosity is preferably 50 Pa·s and 500 Pa·s, respectively, when the viscosity is measured with a cone-plate viscometer at 25° C. and 1 rpm. When the viscosity is in this range, it is more excellent in workability when applied to an adherend such as a substrate when the light moisture curable resin composition is used as an adhesive for electronic parts or an adhesive for display elements. Become. The more preferable lower limit of the viscosity is 80 Pa·s, the more preferable upper limit thereof is 300 Pa·s, and the still more preferable upper limit thereof is 200 Pa·s.
In addition, when the viscosity of the photo-moisture curable resin composition of the present invention is too high, the coating property can be improved by heating at the time of coating.

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

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

Examples of the metal include steel, stainless steel, aluminum, copper, nickel, chromium, and alloys thereof.
Examples of the glass include alkali glass, non-alkali glass, and quartz glass.
Examples of the plastic include high density polyethylene, ultra high molecular weight polyethylene, polyolefin resin such as isotactic polypropylene, syndiotactic polypropylene, 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 Polyamide resins such as polymer (N6/66/610), nylon MXD6 (MXD6), nylon 6T, nylon 6/6T copolymer, nylon 66/PP copolymer, nylon 66/PPS copolymer, polybutylene Terephthalate (PBT), polyethylene terephthalate (PET), polyethylene isophthalate (PEI), PET/PEI copolymer, polyarylate (PAR), polybutylene naphthalate (PBN), liquid crystal polyester, polyoxyalkylene diimide diacid/poly Aromatic polyester resin such as butylene terephthalate copolymer, polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile/styrene copolymer (AS), methacrylonitrile/styrene copolymer, methacrylonitrile/styrene/butadiene Polynitrile resin such as copolymer, polycarbonate, polymethylmethacrylate (PMMA), polymethacrylate resin such as polyethylmethacrylate, ethylene/vinyl acetate copolymer (EVA), polyvinyl alcohol (PVA), vinyl alcohol/ Examples include polyvinyl resins such as ethylene copolymer (EVOH), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), vinyl chloride/vinylidene chloride copolymer, and vinylidene chloride/methyl acrylate copolymer.

The adherend also includes a composite material having a metal plating layer on its surface, and examples of the base material for plating the composite material include the above-mentioned metals, glass, plastics, and the like.
Further, examples of the adherend include materials in which a passivation film is formed by subjecting a metal surface to passivation treatment. Examples of the passivation treatment include heat treatment and anodization treatment. .. In particular, in the case of an aluminum alloy or the like whose international aluminum alloy name is in the 6000 range, the adhesion can be improved by performing the sulfate alumite treatment or phosphoric acid alumite treatment as the passivation treatment.

Examples of the method for adhering an adherend using the light moisture curable resin composition of the present invention include, for example, a step of applying the light moisture curable resin composition of the present invention to a first member, and the above first step. A step of irradiating the light moisture curable resin composition of the present invention applied to a member with light to cure the radically polymerizable compound in the light moisture curable resin composition of the present invention (first curing step); A step of attaching the first member and the second member to each other via the light moisture-curable resin composition after the first curing step (attaching step), and the light moisture curing of the present invention after the attaching step. Examples include a method including a step (second curing step) in which the first member and the second member are bonded to each other by moisture curing of the moisture-curable resin in the mold resin composition, and the bonding step. It is preferable to include a step of irradiating light later. By including the step of irradiating light after the above-mentioned bonding step, it is possible to improve the adhesiveness (initial adhesiveness) immediately after adhering to the adherend. When the first member and/or the second member is made of a material that transmits light, it is preferable to irradiate the light through the first member and/or the second member that transmits light. When the first member and/or the second member are made of a material that does not allow light to easily pass therethrough, the first member and the second member are interposed via the light moisture-curable resin composition. It is preferable to irradiate the side surface of the bonded structure, that is, the portion where the light moisture curable resin composition is exposed, with light.

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

As a method for producing a cured product of the present invention by curing the optical moisture-curable resin composition of the present invention with the optical moisture, for example, the optical moisture-curable resin composition of the present invention is exposed to light of 500 to 3000 mJ/cm ² . It has a process of irradiating and photo-curing, and a process of exposing the photo-cured photo-moisture curable resin composition of the present invention to an environment of 20 to 30° C. and 40 to 60% RH for 72 hours or more to cure the moisture. Methods and the like.

The cured product of the present invention preferably has an optical density (OD value) of 1 or more when it has a thickness of 1 mm. When the OD value is 1 or more, the effect of suppressing the leakage of light when used in a display element or the like becomes more excellent, and high contrast can be obtained. More preferably, the OD value is 1.5 or more.
The higher the OD value, the better, but if too much light-shielding agent is added to increase the above-mentioned OD value, workability may be deteriorated due to thickening. Therefore, the amount of the light-shielding agent should be balanced. The preferable upper limit of the OD value of the cured product is 4.
The OD value after curing of the light moisture curable resin composition can be measured using an optical densitometer.

The cured product of the present invention can be particularly suitably used for electronic parts and display device applications. An electronic component having a substrate and the cured product of the present invention, and a display element having the substrate and the cured product of the present invention are also one aspect of the present invention.

According to the present invention, it is possible to provide a cured product having excellent flexibility and reliability. Further, according to the present invention, it is possible to provide an electronic component and a display element using the cured body. Furthermore, according to the present invention, it is possible to provide a photo-moisture curable resin composition that is suitable for producing the cured product and is excellent in coating properties, shape retention properties, and adhesive properties.

FIG. 1A is a schematic diagram showing a case where the test piece is viewed from above, and FIG. 1B is a schematic diagram showing a case where the test piece is viewed from the side.

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

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

(Synthesis Example 2 (Preparation of Moisture Curable Urethane Resin B))
100 parts by weight of polytetramethylene ether glycol (“PTMG-2000” manufactured by Mitsubishi Chemical Co., Ltd.) as a polyol and 0.01 part by weight of dibutyltin dilaurate were placed in a 500 mL separable flask, and under vacuum (20 mmHg or less). ), stirred at 100° C. for 30 minutes and mixed. Thereafter, the pressure was adjusted to normal pressure, 26.5 parts by weight of Pure MDI (manufactured by Nisso Shoji Co., Ltd.) was added as a diisocyanate, and the mixture was stirred at 80° C. for 3 hours and reacted to obtain a moisture-curable urethane resin B (weight average molecular weight 2900). It was

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

(Examples 1 to 7, Comparative Examples 1 to 3)
According to the compounding ratios shown in Table 1, each material was stirred by a planetary stirring device ("Awatori Kentaro", manufactured by Shinky Co., Ltd.), and then uniformly mixed by a three-roll ceramic roll. 7 and the light moisture curable resin compositions of Comparative Examples 1 to 3 were obtained.
A part of the obtained light moisture curable resin composition was embedded in a Teflon (registered trademark) mold frame having a width of 3 mm, a length of 50 mm and a height of 1 mm. After that, the photo-moisture curable resin composition was photo-cured by irradiating with ultraviolet rays at 1000 mJ/cm ² using a UV-LED (wavelength 365 nm), and then at 25° C. and 50% RH for 3 days ( It was allowed to stand for 72 hours or more) to be moisture-cured to obtain a cured product.

<Evaluation>
The following evaluations were performed on the light moisture curable resin compositions and the cured products obtained in the examples and comparative examples. The results are shown in Table 1.

(Tensile strength of cured product at 400% elongation)
Each of the cured products obtained in the examples and comparative examples was punched into a dumbbell shape (No. 6 specified in "JIS K 6251") to obtain a test piece, which was subjected to a tensile tester (manufactured by Shimadzu Corporation) at 25°C. , "EZ-Graph") was used to pull at a speed of 5 mm/min, and the tensile strength at 400% elongation of the cured product was determined as the force when the material was stretched to 4 times the tension before pulling.

(Tensile rupture elongation of cured product)
Each of the cured products obtained in the examples and comparative examples was punched into a dumbbell shape (No. 6 specified in "JIS K 6251") to obtain a test piece, which was subjected to a tensile tester (manufactured by Shimadzu Corporation) at 25°C. , “EZ-Graph”) was used to determine the tensile elongation at break of the cured product as the elongation at break when the material was pulled at a speed of 5 mm/min.

(Adhesiveness (tensile shear adhesive strength))
Each of the photo-moisture curable resin compositions obtained in Examples and Comparative Examples is applied on a polycarbonate substrate in a width of about 1 mm, and UV rays are irradiated at 1000 mJ/cm ² using a UV-LED (wavelength 365 nm). After each photo-moisture curable resin composition is photo-cured, the glass substrates are stacked, a weight of 20 g is placed, and the glass substrate is allowed to stand for 3 days (72 hours or more) under the conditions of 25°C and 50% RH. A moisture-curable resin composition was moisture-cured to obtain a test piece. FIG. 1 shows a schematic view showing the test piece viewed from above (FIG. 1A) and a schematic view showing the test piece viewed from the side (FIG. 1B). The tensile shear adhesive strength was measured by pulling the obtained test piece at 25° C. in a shear direction at a speed of 10 mm/min using a tensile tester (“EZ-Graph” manufactured by Shimadzu Corporation).

(Applicability (pore permeability))
30 g of each photo-moisture-curable resin composition obtained in Examples and Comparative Examples was laid with a 150-mesh filter in a filtration device having a diameter of 4 cm, and pressure filtration was performed at a pressure of 0.2 MPa, and the passage time was changed. evaluated. If the time required for passing was less than 30 seconds, it was "○", if the time required for passing was 30 seconds or more and less than 5 minutes, it was "△", the time required for passing was 5 minutes or more. When the case was "x", the applicability (pore permeability) of the light moisture curable resin composition was evaluated.

(Shape retention)
Each of the photo-moisture curable resin compositions obtained in Examples and Comparative Examples was applied onto a polycarbonate substrate using a dispensing device so as to have a width of about 1 mm and a length of 30 mm. Then, using a UV-LED (wavelength 365 nm), the photo-moisture-curable resin composition is photo-cured by irradiating it with ultraviolet rays at 3000 mJ/cm ^2, so that the line width (t ₀ ) and the height (t ₁ ) are set. It was measured. The shape retention of the photo-moisture curable resin composition is defined as "○" when t ₁ /t ₀ is 0.3 or more and "x" when t ₁ /t ₀ is less than 0.3. Was evaluated.

(Creep resistance (reliability evaluation))
Each test piece obtained in the same manner as in the above "(Adhesiveness (tensile shear adhesive strength))" was placed in a constant temperature and humidity oven at 50°C and 85% RH, and the test piece was hung vertically to the ground, A 100 g weight was hung on the edge of the polycarbonate substrate and left standing for 24 hours. When the deviation from the initial position (the position before hanging the weight) between the glass substrate and the polycarbonate substrate after standing for 24 hours was 1 mm or less, "○" was given, and when the deviation was more than 1 mm and 3 mm or less, "△" was given. The creep resistance of the light-moisture-curable resin composition was evaluated by setting “x” when it exceeds 3 mm.

According to the present invention, it is possible to provide a cured product having excellent flexibility and reliability. Further, according to the present invention, it is possible to provide an electronic component and a display element using the cured body. Furthermore, according to the present invention, it is possible to provide a photo-moisture curable resin composition that is suitable for producing the cured product and is excellent in coating properties, shape retention properties, and adhesive properties.

1 Polycarbonate substrate 2 Glass substrate 3 Light moisture curable resin composition cured product

Claims (8)

A cured product of a photo-moisture curable resin composition containing a radically polymerizable compound and a moisture curable urethane resin ,
A cured product, which has a tensile strength at 25% of 400% elongation of 3 kgf/cm ² or more and 20 kgf/cm ² or less. The cured product according to claim 1, wherein the tensile elongation at break at 25°C is 500% or more. The cured product according to claim 1 or 2, wherein the tensile shear adhesive strength to polycarbonate and glass measured at 25°C according to JIS K 6850 is 10 kgf/cm ² or more. The cured product according to claim 1, 2 or 3 , which contains a filler. The cured product according to claim 1, 2, 3 or 4, further comprising a light-shielding agent. An electronic component comprising a substrate and the cured product according to claim 1, 2, 3, 4 or 5 . A display device comprising a substrate and the cured product according to claim 1 . A photo-moisture-curable resin composition containing a radically polymerizable compound and a moisture-curable urethane resin , wherein the cured product has a tensile strength of 3 to 20 kgf/cm ² at 400% elongation at 25°C. A light-moisture-curable resin composition characterized by the above.

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