WO2016167305A1 - 硬化体、電子部品、表示素子、及び、光湿気硬化型樹脂組成物 - Google Patents
硬化体、電子部品、表示素子、及び、光湿気硬化型樹脂組成物 Download PDFInfo
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- WO2016167305A1 WO2016167305A1 PCT/JP2016/061958 JP2016061958W WO2016167305A1 WO 2016167305 A1 WO2016167305 A1 WO 2016167305A1 JP 2016061958 W JP2016061958 W JP 2016061958W WO 2016167305 A1 WO2016167305 A1 WO 2016167305A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/302—Water
- C08G18/307—Atmospheric humidity
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J201/00—Adhesives based on unspecified macromolecular compounds
- C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
- H10W72/00—Interconnections or connectors in packages
- H10W72/071—Connecting or disconnecting
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
Definitions
- the present invention relates to a cured product having excellent flexibility and reliability. Moreover, this invention relates to the electronic component and display element which use this hardening body. Furthermore, the present invention relates to a light moisture curable resin composition that is suitable for production of the cured product and is excellent in coating property, shape retention property, and adhesiveness.
- liquid crystal display elements In recent years, liquid crystal display elements, organic EL display elements, and the like are widely used as display elements having features such as thinness, light weight, and low power consumption.
- a photocurable resin composition is usually used for sealing a liquid crystal or a light emitting layer, adhering various members such as a substrate, an optical film, and a protective film.
- a frame is being made (hereinafter also referred to as 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.
- 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 photocuring and thermosetting are also used in combination. There was a possibility of adversely affecting the elements and the like by heating.
- Patent Document 1 discloses a thermosetting adhesive containing an epoxy compound having a number average molecular weight of 600 to 1,000.
- the thermosetting adhesive as disclosed in Patent Document 1 is not suitable for bonding electronic components that may be damaged by heat.
- 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.
- a method of using both photocuring and moisture curing using a photomoisture curable resin composition is disclosed.
- the optical moisture curable resin composition as disclosed in Patent Documents 2 and 3 is used, the resin composition after application cannot be maintained in shape and spreads or adheres to an adherend such as a substrate. There has been a problem that the adhesiveness is insufficient.
- An object of this invention is to provide the hardening body excellent in a softness
- the present invention is a cured product of an optical moisture curable resin composition containing a radical polymerizable compound and a moisture curable resin, and has a tensile strength at 400% elongation at 25 ° C. of 3 kgf / cm 2 or more, 20 kgf. It is a cured body that is / cm 2 or less.
- the present invention is described in detail below.
- the inventors of the present invention provide a light moisture curable resin composition containing a radical polymerizable compound and a moisture curable resin, and a cured product obtained by light moisture curing the composition at 25 ° C.
- a light moisture curable resin composition containing a radical polymerizable compound and a moisture curable resin
- a cured product obtained by light moisture curing the composition at 25 ° C.
- the cured product of the present invention has a lower limit of tensile strength at 400% elongation at 25 ° C. of 3 kgf / cm 2 and an upper limit of 20 kgf / cm 2 .
- the cured product of the present invention is heated by a change in temperature when a force is applied to the adherend in the shear direction or the bending direction. Even when stress is generated, excellent adhesion 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.
- the tensile strength at 400% elongation at 25 ° C. means a force when the tensile strength is extended to 4 times that before the tensile test.
- an optical moisture curable resin composition is photocured by irradiating ultraviolet light with a wavelength of 365 nm using an ultraviolet LED (UV-LED) or the like at 1000 mJ / cm 2 , and then 25 ° C., 50% RH.
- UV-LED ultraviolet LED
- a tensile tester for example, “EZ-Graph” manufactured by Shimadzu Corporation
- EZ-Graph manufactured by Shimadzu Corporation
- the measurement of the tensile strength and the tensile elongation at break described later is the state in which the bonded substrates are peeled off. Do. Even when it does not become a dumbbell shape, it can be obtained in the same manner by converting the thickness and width of the cured body in the peeled state.
- the preferred lower limit of the tensile elongation at break at 25 ° C. is 500%.
- the cured product of the present invention generates thermal stress due to temperature change when force is applied to the adherend in the shearing direction or bending direction. In such a case, the effect of maintaining excellent adhesiveness and flexibility is superior.
- a more preferable lower limit of the tensile elongation at break at 25 ° C. is 600%. The tensile elongation at break at 25 ° C.
- the light moisture curable resin composition was specifically obtained by photocuring the light moisture curable resin composition by, for example, irradiating ultraviolet light having a wavelength of 365 nm with 1000 mJ / cm 2 using an ultraviolet LED lamp or the like. After that, it is cured by dampening by allowing it to stand for 72 hours or more at 25 ° C. and 50% RH, and the resulting cured product is punched into a dumbbell shape (No. 6 as defined in “JIS K 6251”). The elongation at break when the test piece was pulled at a rate of 5 mm / min using a tensile tester (eg, “EZ-Graph” manufactured by Shimadzu Corporation) at 25 ° C. can be obtained.
- a tensile tester eg, “EZ-Graph” manufactured by Shimadzu Corporation
- 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 .
- the cured product of the present invention is subjected to a temperature change when a force is applied to the adherend in the shear direction or the bending direction. In the case where thermal stress is generated, the effect of maintaining excellent adhesiveness is improved.
- a more preferred lower limit of the tensile shear bond strength to the polycarbonate and glass is 15 kgf / cm 2 .
- the tensile shear bond strength to the polycarbonate and glass is specifically, for example, by applying a light moisture curable resin composition on a polycarbonate substrate with a width of about 1 mm, and using an ultraviolet LED lamp or the like at a wavelength of 365 nm. After photocuring the light moisture curable resin composition by irradiating with 1000 mJ / cm 2 of ultraviolet rays, the glass substrate is overlaid, a 20 g weight is placed, and it is allowed to stand for 72 hours or more at 25 ° C. and 50% RH.
- the test piece obtained by moisture-curing the optical moisture-curable resin composition was 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 rate of / min.
- the cured product of the present invention has a preferred lower limit of storage modulus at 80 ° C. of 1 ⁇ 10 5 Pa and a preferred upper limit of 1 ⁇ 10 7 Pa.
- 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 is 5 ⁇ 10 6 Pa.
- the storage elastic modulus at 80 ° C. can be measured by using a dynamic viscoelasticity measuring apparatus (for example, “DVA-200” manufactured by IT Measurement Control Co., Ltd.).
- the cured product of the present invention is a cured product of an optical moisture curable resin composition containing a radical polymerizable compound and a moisture curable resin.
- a light moisture curable resin composition that becomes a cured product of the present invention by light moisture curing that is, a light moisture curable resin composition containing a radical polymerizable compound and a moisture curable resin.
- An optical moisture curable resin composition having a tensile strength at 400% elongation at 25 ° C. of 3 to 20 kgf / cm 2 is also one aspect of the present invention.
- the radical polymerizable compound has a high flexibility of the cured product (low tensile strength), weak adhesive strength, and tends to stretch well (high elongation at break).
- the moisture curable resin has a low flexibility of the cured product, a strong adhesive force, and tends to grow well. Therefore, the tensile strength and the like of the cured product can be adjusted to the above-described range by adjusting the types of compounds used as these components, the blending ratio thereof, the glass transition temperature, the crosslinking density, and the like. Moreover, if it is the range which does not inhibit the objective of this invention, the tensile strength of a hardening body etc. can be adjusted to the range mentioned above also by adjusting the kind and compounding quantity of a filler etc. which are mentioned later.
- the light 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 radical polymerizable compound having photopolymerizability, and is a compound having a radical reactive functional group in the molecule.
- a compound having a heavy bond is preferable, and a compound having a (meth) acryloyl group (hereinafter also referred to as “(meth) acrylic compound”) is particularly preferable from the viewpoint of reactivity.
- the “(meth) acryloyl” means acryloyl or methacryloyl
- the “(meth) acryl” means acryl or methacryl.
- (meth) acrylic compound for example, (meth) acrylic acid ester compound obtained by reacting (meth) acrylic acid with a compound having a hydroxyl group, (meth) acrylic acid and epoxy compound are reacted.
- examples include epoxy (meth) acrylates obtained, urethane (meth) acrylates obtained by reacting an isocyanate compound with a (meth) acrylic acid derivative having a hydroxyl group.
- the “(meth) acrylate” means acrylate or methacrylate.
- all the isocyanate groups of the isocyanate compound used as the raw material of the said urethane (meth) acrylate are used for formation of a urethane bond, and the said urethane (meth) acrylate does not have a residual isocyanate group.
- monofunctional ones include, for example, phthalimide acrylates such as N-acryloyloxyethyl hexahydrophthalimide, 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 (
- Examples of the bifunctional compound among the (meth) acrylic acid ester compounds include 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexane.
- those having three or more functions include, for example, trimethylolpropane tri (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) acrylate, 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, glycerol tri (meth) acrylate, propylene oxide-added glycerol tri (meth) acrylate, Tris (meth) acryloyloxyethyl phosphate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra Meth) acrylate, dipentaerythritol pen
- Examples of the epoxy (meth) acrylate include those obtained by reacting an epoxy compound and (meth) acrylic acid in the presence of a basic catalyst according to a conventional method.
- Examples of the epoxy compound as a raw material for synthesizing the epoxy (meth) acrylate include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and 2,2′-diallyl bisphenol A type epoxy resin. , Hydrogenated bisphenol type epoxy resin, propylene oxide added bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, sulfide type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol Novolac epoxy resin, orthocresol novolac epoxy resin, dicyclopentadiene novolac epoxy resin, biphenyl novolac epoxy resin, naphtha Ren phenol novolak 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.
- 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.
- As what is marketed among the said bisphenol F-type epoxy resins jER806, jER4004 (all are the Mitsubishi Chemical company make) etc. are mentioned, for example.
- As what is marketed among the said bisphenol S-type epoxy resins, Epicron EXA1514 (made by DIC Corporation) etc. are mentioned, for example.
- Examples of commercially available 2,2′-diallylbisphenol A type epoxy resins include RE-810NM (manufactured by Nippon Kayaku Co., Ltd.).
- Examples of commercially available diphenyl ether type epoxy resins include YSLV-80DE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
- Examples of commercially available dicyclopentadiene type epoxy resins include EP-4088S (manufactured by ADEKA).
- Examples of commercially available naphthalene type epoxy resins include Epicron HP4032, Epicron EXA-4700 (both manufactured by DIC) and the like.
- Examples of commercially available phenol novolac epoxy resins include Epicron N-770 (manufactured by DIC).
- Examples of the ortho-cresol novolac type epoxy resin that are commercially available include epiclone N-670-EXP-S (manufactured by DIC).
- Examples of commercially available glycidylamine type epoxy resins include jER630 (manufactured by Mitsubishi Chemical), Epicron 430 (manufactured by DIC), and TETRAD-X (manufactured by Mitsubishi Gas Chemical).
- Examples of commercially available alkyl polyol type epoxy resins include ZX-1542 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Epiklon 726 (manufactured by DIC), Epolite 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), Denacol EX-611. (Manufactured by Nagase ChemteX Corporation).
- Examples of commercially available rubber-modified epoxy resins include YR-450, YR-207 (both manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Epolide PB (manufactured by Daicel Corporation), and the like.
- Examples of commercially available glycidyl ester compounds include Denacol EX-147 (manufactured by Nagase ChemteX Corporation).
- Examples of commercially available bisphenol A type episulfide resins include jER YL-7000 (manufactured by Mitsubishi Chemical Corporation).
- 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 Co., Ltd.), jER1031, jER1032 (all Also, Mitsubishi Chemical Corporation), EXA-7120 (DIC Corporation), TEPIC (Nissan Chemical Corporation) and the like.
- Examples of commercially available epoxy (meth) acrylates include EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRY370R ), 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 80MF 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-3
- the urethane (meth) acrylate can be obtained, for example, by reacting a (meth) acrylic acid derivative having a hydroxyl group with an isocyanate compound in the presence of a catalytic amount of a tin-based compound.
- isocyanate compound used as the raw material for the urethane (meth) acrylate examples include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and diphenylmethane-4,4.
- MDI '-Diisocyanate
- 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, tetramethylxylylene diisocyanate, 1,6,11-undecantrie Cyanate, and the like.
- MDI '-Diisocyanate
- XDI xylylene diisocyanate
- XDI hydrogenated XDI
- lysine diisocyanate triphenylmethane triisocyanate
- tris (isocyanate) Phenyl) thiophosphate tetramethylxylylene diisocyanate, 1,6,11-und
- the isocyanate compound is obtained by, for example, reacting a polyol such as ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, polycaprolactone diol and an excess isocyanate compound. It is also possible to use chain-extended isocyanate compounds.
- Examples of the (meth) acrylic acid derivative having a hydroxyl group, which is a raw material of the urethane (meth) acrylate include, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, and 1,4-butane.
- Mono (meth) acrylates of dihydric alcohols such as diol and polyethylene glycol mono (meth) acrylates or di (meth) acrylates of trivalent alcohols such as trimethylolethane, trimethylolpropane and glycerin, bisphenol A type epoxy ( Examples include epoxy (meth) acrylates such as (meth) acrylate.
- Examples of commercially available urethane (meth) acrylates include 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 (both manufactured by Daicel Orunekusu, Inc.
- radical polymerizable compounds other than those described above can be used as appropriate.
- the other radical polymerizable compounds 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, ⁇ -methylstyrene, N-vinylpyrrolidone, N-vinyl- ⁇ -caprolactam, etc. Is mentioned.
- the radical polymerizable compound preferably contains a monofunctional radical polymerizable compound and a polyfunctional radical polymerizable compound from the viewpoint of adjusting curability.
- the monofunctional radical polymerizable compound and the polyfunctional radical polymerizable compound By containing the monofunctional radical polymerizable compound and the polyfunctional radical polymerizable compound, the resulting optical moisture curable resin composition becomes more excellent in curability and tackiness.
- the polyfunctional radically polymerizable compound is preferably bifunctional or trifunctional, and more preferably bifunctional.
- 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 same as the monofunctional radical polymerizable compound and the polyfunctional radical polymerizable compound.
- a preferable lower limit is 2 parts by weight and a preferable upper limit is 45 parts by weight with respect to a total of 100 parts by weight with the functional radical polymerizable compound.
- the content of the polyfunctional radical polymerizable compound is within this range, the resulting optical moisture curable resin composition is more excellent in curability and tackiness.
- the minimum with more preferable content of the said polyfunctional radically polymerizable compound is 5 weight part, and a more preferable upper limit is 35 weight part.
- the content of the radical polymerizable compound is such that a preferred lower limit is 10 parts by weight and a preferred upper limit is 80 parts by weight with respect to a total of 100 parts by weight of the radical polymerizable compound and the moisture curable resin.
- a preferred lower limit of the content of the radical polymerizable compound is 25 parts by weight
- a more preferred upper limit is 70 parts by weight
- a still more preferred lower limit is 30 parts by weight
- a still more preferred upper limit is 59 parts by weight.
- the optical moisture curable resin composition of the present invention contains a moisture curable resin.
- the moisture curable resin include a moisture curable urethane resin and a resin having a crosslinkable silyl group.
- a moisture hardening type urethane resin is preferable.
- the moisture curable urethane resin has a urethane bond and an isocyanate group, and the isocyanate group in the molecule is cured by reacting with moisture in the air or the adherend.
- the moisture curable urethane resin preferably has the isocyanate group at the end of the molecule.
- the moisture curable urethane resin may have only one isocyanate group in one molecule, or may have two or more. Especially, 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 range is 2.5.
- polyol compound the well-known polyol compound normally used for manufacture of a polyurethane can be used, For example, polyester polyol, polyether polyol, polyalkylene polyol, polycarbonate polyol etc. are mentioned. These polyol compounds may be used alone or in combination of two or more.
- polyester polyol examples include a polyester polyol obtained by a reaction between a polyvalent carboxylic acid and a polyol compound, a poly- ⁇ -caprolactone polyol obtained by ring-opening polymerization of ⁇ -caprolactone, and the like.
- polyvalent carboxylic acid used as a raw material for the polyester polyol examples include terephthalic acid, isophthalic acid, 1,5-naphthalic acid, 2,6-naphthalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, and suberin.
- examples include acid, azelaic acid, sebacic acid, decamethylene dicarboxylic acid, dodecamethylene dicarboxylic acid and the like.
- polyol compound used as a raw material for the polyester polyol examples include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6- Examples include hexanediol, diethylene glycol, and cyclohexanediol.
- polyether polyol examples include ethylene glycol, propylene glycol, ring-opening polymer of tetrahydrofuran, ring-opening polymer of 3-methyltetrahydrofuran, and random copolymers or block copolymers of these or derivatives thereof, bisphenol Type polyoxyalkylene modified products.
- the modified bisphenol-type polyoxyalkylene is a polyether polyol obtained by addition reaction of alkylene oxide (for example, ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, etc.) to the active hydrogen portion of the bisphenol-type molecular skeleton, A random copolymer or a block copolymer may be used.
- the modified bisphenol-type polyoxyalkylene preferably has one or more alkylene oxides added to both ends of the bisphenol-type molecular skeleton. It does not specifically limit as a bisphenol type, A type, F type, S type etc. are mentioned, Preferably it is bisphenol A type.
- polyalkylene polyol examples include polybutadiene polyol, hydrogenated polybutadiene polyol, and hydrogenated polyisoprene polyol.
- polycarbonate polyol examples include polyhexamethylene carbonate polyol and polycyclohexane dimethylene carbonate polyol.
- polyisocyanate compound examples include diphenylmethane-4,4′-diisocyanate (MDI), a liquid modified product of MDI, polymeric MDI, tolylene diisocyanate, naphthalene-1,5-diisocyanate, and the like.
- MDI diphenylmethane-4,4′-diisocyanate
- polymeric MDI polymeric MDI
- tolylene diisocyanate polymeric MDI
- naphthalene-1,5-diisocyanate and the like.
- diphenylmethane diisocyanate and its modified products are preferred from the viewpoints of low vapor pressure and toxicity, and ease of handling.
- the said polyisocyanate compound may be used independently and 2 or more types may be used in combination.
- the said moisture hardening type urethane resin is obtained using the polyol compound which has a structure represented by following formula (1).
- a polyol compound having a structure represented by the following formula (1) it is possible to obtain a composition excellent in adhesiveness and a cured product that is flexible and has good elongation, and is compatible with the radical polymerizable compound. It will be excellent.
- a polyether polyol composed of a ring-opening polymerization compound of propylene glycol, a tetrahydrofuran (THF) compound, or a ring-opening polymerization compound of a tetrahydrofuran compound having a substituent such as a methyl group are preferable.
- 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
- m is an integer of 1 to 500.
- n is preferably 1 to 5
- L is preferably 0 to 4
- m is preferably 50 to 200.
- L is 0 means the case where carbon bonded to R is directly bonded to oxygen.
- the moisture curable urethane resin may have a radical 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.
- the moisture curable urethane resin having a radical polymerizable functional group is not included in the radical polymerizable compound and is treated as a moisture curable urethane resin.
- the weight average molecular weight of the moisture curable urethane resin is not particularly limited, but a preferable lower limit is 800 and a preferable 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 obtained cured product is more excellent in flexibility, and the resulting optical moisture curable resin composition has applicability. It 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 8000, the still more preferable lower limit is 2500, and the further preferable upper limit is 6000.
- the said weight average molecular weight is a value calculated
- GPC gel permeation chromatography
- Examples of the column for measuring the weight average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko KK). 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 Corp.), and the like.
- 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.
- the content of the moisture curable resin is within this range, the obtained light moisture curable resin composition is more excellent in moisture curable property and photo curable property.
- a more preferred lower limit of the content of the moisture curable resin is 30 parts by weight, a more preferred upper limit is 75 parts by weight, a still more preferred lower limit is 41 parts by weight, and a still more preferred upper limit is 70 parts by weight.
- the light moisture curable resin composition of the present invention usually contains a radical photopolymerization initiator.
- a radical photopolymerization initiator examples include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, thioxanthones, and the like.
- photo radical polymerization initiators examples include IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 784, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACUREO BASF), benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether (all manufactured by Tokyo Chemical Industry Co., Ltd.) and the like.
- the content of the photo radical polymerization initiator is preferably 0.01 parts by weight and preferably 10 parts by weight with respect to 100 parts by weight of the radical polymerizable compound.
- the minimum with more preferable content of the said radical photopolymerization initiator is 0.1 weight part, and a more preferable upper limit is 5 weight part.
- the light moisture curable resin composition of the present invention preferably contains a filler.
- the light moisture curable resin composition of the present invention has suitable thixotropy and can sufficiently retain the shape after coating.
- the filler preferably has a primary particle diameter with a preferred lower limit of 1 nm and a preferred upper limit of 50 nm.
- the more preferable lower limit of the primary particle diameter of the filler is 5 nm
- the more preferable upper limit is 30 nm
- the still more preferable lower limit is 10 nm
- the still more preferable upper limit is 20 nm.
- the primary particle size of the filler may 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 PARTICS SIZING SYSTEMS). it can.
- the filler may be present as secondary particles (a collection of a plurality of primary particles) in the light moisture curable resin composition of the present invention, and the preferred 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 diameter of the secondary particles of the filler can be measured by observing the optical moisture curable resin composition of the present invention or a cured product thereof using a transmission electron microscope (TEM).
- TEM transmission electron microscope
- an inorganic filler is preferable, and examples thereof include silica, talc, titanium oxide, zinc oxide, calcium carbonate and the like. Among these, silica is preferable because the resulting light moisture curable resin composition is excellent in ultraviolet transmittance. These fillers may be used alone or in combination of two or more.
- the filler is preferably subjected to a hydrophobic surface treatment.
- a hydrophobic surface treatment By the hydrophobic surface treatment, the resulting optical moisture curable resin composition is more excellent in shape retention after application.
- the hydrophobic surface treatment include silylation treatment, alkylation treatment, and epoxidation treatment. Especially, since it is excellent in the effect which improves shape retainability, a silylation process is preferable and a trimethylsilylation process is more preferable.
- Examples of the method for treating the filler with a hydrophobic surface include a method for treating the surface of the filler with a surface treatment agent such as a silane coupling agent.
- a surface treatment agent such as a silane coupling agent.
- the trimethylsilylated silica is prepared by, for example, synthesizing silica by a method such as a sol-gel method and spraying hexamethyldisilazane in a state where the silica is fluidized, in an organic solvent such as alcohol or toluene. Silica is added to the mixture, and further, hexamethyldisilazane and water are added, and then water and an organic solvent are evaporated and dried with an evaporator.
- the content of the filler is such that the preferred lower limit is 1 part by weight and the preferred upper limit is 20 parts by weight with respect to a total of 100 parts by weight of the radical polymerizable compound and the moisture curable resin.
- the content of the filler is within this range, the obtained light moisture curable resin composition is more excellent in coating properties and shape retention after coating.
- the more preferred lower limit of the filler content is 2 parts by weight, the more preferred upper limit is 15 parts by weight, the still more preferred lower limit is 3 parts by weight, the still more preferred upper limit is 10 parts by weight, and the particularly preferred upper limit is 5 parts by weight. .
- the light 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 group selected from the group consisting of the isocyanate group, isothiocyanate group, and carbodiimide group is highly reactive with moisture, and reacts with moisture-curable resin and moisture during storage. It has a role to prevent.
- the compound which has a urethane bond and an isocyanate group is handled as the said moisture hardening type 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 needs to move through the system and rapidly react with moisture, and therefore has a low molecular weight.
- the preferable upper limit of the molecular weight is 500, and the more preferable upper limit is 300.
- a compound having an isocyanate group having an aromatic ring and a compound having an isothiocyanate group having an aromatic ring are suitable.
- the compound which has a carbodiimide group there is no restriction
- a compound having at least one group selected from the group consisting of an isocyanate group, an isothiocyanate group, and a carbodiimide group that did not react with moisture contributes to the curing of the moisture curable resin, and the crosslinking density is improved. By doing so, the cured product of the obtained light moisture curable resin composition is excellent in adhesiveness.
- the compound having at least one group selected from the group consisting of the isocyanate group, isothiocyanate group, and carbodiimide group may be monofunctional or polyfunctional, It is preferable that it is bifunctional because it has moderate reactivity.
- the compound having at least one group selected from the group consisting of the isocyanate group, the isothiocyanate group, and the carbodiimide group is for chemically removing moisture, but the light moisture curable type of the present invention.
- the crosslink density is improved, and the cured product of the resulting light moisture curable resin composition is obtained.
- a compound having an isocyanate group is preferred because it is excellent in the effect of having excellent adhesiveness.
- the compound having an isocyanate group may be the same as or different from the polyisocyanate compound that is a raw material for the moisture-curable resin.
- the compound having an isocyanate group include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and diphenylmethane-4,4′-.
- MDI Diisocyanate
- NDI 1,5-naphthalene diisocyanate
- NDI norbornane diisocyanate
- tolidine diisocyanate xylylene diisocyanate
- XDI hydrogenated XDI
- lysine diisocyanate triphenylmethane triisocyanate
- tris Isocyanatophenyl) thiophosphate, tetramethylxylene diisocyanate, 1,6,11-undecane triisocyanate, etc. Is mentioned.
- the compound having an isothiocyanate group include benzyl isothiocyanate, phenyl isothiocyanate, 4-phenylbutyl isothiocyanate, and 3-phenylpropyl isothiocyanate.
- the compound having a carbodiimide group examples include N, N-dicyclohexylcarbodiimide, N, N-diisopropylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, bis (2 , 6-diisopropylphenyl) carbodiimide, and examples of commercially available products include carbodilite LA-1 (manufactured by Nisshinbo Co., Ltd.). 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, isothiocyanate group, and carbodiimide group is preferable in 100 parts by weight of the entire optical moisture-curable resin composition of the present invention.
- the lower limit is 0.05 parts by weight, and the preferred upper limit is 10 parts by weight.
- the degree of crosslinking during curing of the moisture curable resin is increased.
- the resulting light 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 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.
- the light moisture curable resin composition of the present invention has excellent light-shielding properties. For example, when used in a display element, light leakage can be prevented.
- the display element manufactured using the light moisture curable resin composition of the present invention containing the above light shielding agent is high because the light moisture curable resin composition has sufficient light shielding properties, and does not leak light. It has contrast and has excellent image display quality.
- the “light-shielding agent” means a material having an ability of hardly transmitting light in the visible light region.
- the light-shielding agent examples include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. Further, the light-shielding agent does not have to be black, and materials such as silica, talc, titanium oxide, and the like mentioned as fillers can be used as long as they have the ability to hardly transmit light in the visible light region. Included in the light shielding agent. Of these, titanium black is preferable.
- Titanium black is a substance having a higher transmittance in the vicinity of the ultraviolet region, particularly for light having a wavelength of 370 to 450 nm, compared to the average transmittance for light having a wavelength of 300 to 800 nm. That is, the above-described titanium black sufficiently shields light having a wavelength in the visible light region, thereby imparting light shielding properties to the light moisture curable resin composition of the present invention, while transmitting light having a wavelength in the vicinity of the ultraviolet region. Is a light-shielding agent.
- the light of the photo moisture curable resin composition of the present invention can be used. Curability can be further increased.
- the light-shielding agent contained in the light moisture curable resin composition of the present invention is preferably a highly insulating material, and titanium black is also preferable as the highly insulating light-shielding agent.
- the titanium black preferably has an optical density (OD value) of 3 or more, and more preferably 4 or more.
- 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. There is no particular upper limit to the OD value of the titanium black, but it is usually 5 or less.
- the above-mentioned titanium black exhibits a sufficient effect even if it is not surface-treated, but the surface is treated with an organic component such as a coupling agent, silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide
- an organic component such as a coupling agent, silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide
- Surface-treated titanium black such as those coated with an inorganic component such as magnesium oxide can also be used.
- what is processed with the organic component is preferable at the point which can improve insulation more.
- titanium black examples include 12S, 13M, 13M-C, 13R-N (all manufactured by Mitsubishi Materials Corporation), Tilak D (manufactured by Ako Kasei Co., Ltd.), and the like.
- the preferable lower limit of the specific surface area of the titanium black is 5 m 2 / g
- the preferable upper limit is 40 m 2 / g
- the more preferable lower limit is 10 m 2 / g
- the more preferable upper limit is 25 m 2 / g.
- the preferable lower limit of the sheet resistance of the titanium black is 10 9 ⁇ / ⁇ when mixed with a resin (70% blending), and the more preferable lower limit is 10 11 ⁇ / ⁇ .
- the primary particle diameter of the light-shielding agent is appropriately selected depending on the application, such as the distance between the substrates of the display element, but the preferable lower limit is 30 nm and the preferable upper limit is 500 nm. It is. When the primary particle diameter of the light-shielding agent is within this range, the resulting optical moisture-curable resin composition is more excellent in coating properties and workability 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 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 PARTICS SIZING SYSTEMS).
- the minimum with preferable content of the said light shielding agent in the whole optical moisture hardening type resin composition of this invention is 0.05 weight%, and a preferable upper limit is 10 weight%.
- the content of the light-shielding agent is within this range, the resulting light moisture-curable resin composition has excellent light-drawing properties, adhesion to a substrate, etc., and light-shielding properties while maintaining strength after curing. It will be excellent.
- a more preferable lower limit of the content of the light shielding agent is 0.1% by weight, a more preferable upper limit is 2% by weight, and a still more preferable upper limit 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 as necessary.
- additives such as a colorant, an ionic liquid, a solvent, metal-containing particles, and a reactive diluent as necessary.
- a method for producing the light moisture curable resin composition of the present invention for example, using a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, a three roll, And a method of mixing a moisture curable resin, a radical photopolymerization initiator, and an additive to be added as necessary.
- a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, a three roll, And a method of mixing a moisture curable resin, a radical photopolymerization initiator, and an additive to be added as necessary.
- the moisture content of the light moisture curable resin composition of the present invention is 100 ppm or less.
- the water content is 100 ppm or less, the reaction between the moisture curable resin and moisture during storage is suppressed, and the optical moisture curable resin composition is more excellent in storage stability.
- the water content is more preferably 80 ppm or less.
- the water content can be measured by a Karl Fischer moisture measuring device.
- the preferable lower limit of the viscosity measured at 25 ° C. and 1 rpm using a cone plate viscometer is 50 Pa ⁇ s, and the preferable upper limit is 500 Pa ⁇ s.
- the viscosity is within this range, when the light moisture curable resin composition is used as an adhesive for electronic components or an adhesive for display elements, it is more excellent in workability when applied to an adherend such as a substrate.
- a more preferred lower limit of the viscosity is 80 Pa ⁇ s
- a more preferred upper limit is 300 Pa ⁇ s
- a still more preferred upper limit is 200 Pa ⁇ s.
- paintability can be improved by heating at the time of application
- 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 is 5.0.
- the more preferable lower limit of the thixotropic index is 1.5, and the more preferable upper limit is 4.0.
- the thixotropic index is a viscosity measured at 25 ° C. and 1 rpm using a cone plate viscometer, and measured at 25 ° C. and 10 rpm using a cone plate viscometer. It means the value divided by the viscosity.
- Examples of adherends that can be bonded 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-like body) 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 polyolefin resins such as high density polyethylene, ultra high molecular weight polyethylene, isotactic polypropylene, syndiotactic polypropylene, and ethylene propylene copolymer resin, nylon 6 (N6), nylon 66 (N66), Nylon 46 (N46), Nylon 11 (N11), Nylon 12 (N12), Nylon 610 (N610), Nylon 612 (N612), Nylon 6/66 copolymer (N6 / 66), Nylon 6/66/610 Polymer (N6 / 66/610), nylon MXD6 (MXD6), nylon 6T, nylon 6 / 6T copolymer, nylon 66 / PP copolymer, polyamide 66 resin such as nylon 66 / PPS copo
- Aromatic polyester resins polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile / styrene copolymer (AS), methacrylonitrile / styrene copolymer, methacrylonitrile / styrene / butadiene copolymer, etc.
- polycarbonate polymethacrylate resin such as polymethyl methacrylate (PMMA), polyethyl methacrylate, ethylene / vinyl acetate copolymer (EVA), polyvinyl alcohol (PVA), vinyl alcohol And polyvinyl resins such as vinyl / ethylene copolymer (EVOH), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), vinyl chloride / vinylidene chloride copolymer, vinylidene chloride / methyl acrylate copolymer, and the like.
- PMMA polymethyl methacrylate
- EVA polyvinyl alcohol
- PVDC polyvinylidene chloride
- PVDC polyvinyl chloride
- PVDC polyvinyl chloride
- PVDC polyvinyl chloride
- PVDC polyvinyl chloride
- vinyl chloride / vinylidene chloride copolymer vinylidene chloride / methyl acrylate copolymer
- Examples of the adherend include a composite material having a metal plating layer on the surface, and examples of the base material for plating the composite material include the metal, glass, and plastic described above. Furthermore, examples of the adherend include materials in which a passivation film is formed by passivating a metal surface. Examples of the passivating treatment include heat treatment and anodizing treatment. . In particular, in the case of an aluminum alloy or the like whose material is an international aluminum alloy name in the 6000 series, the adhesiveness can be improved by performing a sulfuric acid alumite treatment or a phosphoric acid alumite treatment as the passivation treatment.
- a step of applying the light moisture curable resin composition of the present invention to a first member a step of applying the light moisture curable resin composition of the present invention to a first member
- the step of irradiating the light moisture curable resin composition of the present invention applied to the member with light to cure the radical polymerizable compound in the light moisture curable resin composition of the present invention first curing step
- first curing step a step of bonding the first member and the second member via the light moisture curable resin composition after the first curing step
- bonding step the light moisture curing of the present invention after the bonding step.
- the first member and / or the second member is made of a material that transmits light, it is preferable to irradiate light through the first member and / or the second member that transmits light.
- the first member and / or the second member is a material that does not easily transmit light, the first member and the second member are interposed via the light moisture curable resin composition. It is preferable to irradiate the side surface of the bonded structure, that is, the portion where the light moisture curable resin composition is exposed.
- 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.
- a method for producing the cured product of the present invention by curing the light moisture curable resin composition of the present invention with light moisture for example, light of 500 to 3000 mJ / cm 2 is applied to the light moisture curable resin composition of the present invention.
- the cured body of the present invention preferably has an optical density (OD value) of 1 or more when the thickness is 1 mm.
- OD value optical density
- the OD value is more preferably 1.5 or more. The higher the OD value, the better.
- the preferable upper limit of the OD value of the cured product is 4.
- the OD value after hardening of the said optical moisture curable resin composition can be measured using an optical densitometer.
- the cured body of the present invention can be particularly suitably used for electronic parts and display element applications.
- An electronic component having the substrate and the cured body of the present invention and a display element having the substrate and the cured body of the present invention are also one aspect of the present invention.
- flexibility and reliability can be provided.
- the electronic component and display element which use this hardening body can be provided.
- it is suitable for manufacture of this hardening body and can provide the optical moisture hardening type resin composition which is excellent in applicability
- FIG.1 (a) is a schematic diagram which shows the case where a test piece is seen from the top
- FIG.1 (b) is a schematic diagram which shows the case where a test piece is seen from the side.
- Examples 1 to 7, Comparative Examples 1 to 3 In accordance with the blending ratio described in Table 1, each material was stirred with a planetary stirrer (“Shinky Co., Ltd.,“ Awatori Netaro ”), and then uniformly mixed with a ceramic three roll. To 7 and 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 having a width of 3 mm, a length of 50 mm, and a height of 1 mm.
- Teflon registered trademark
- UV-LED microwave 365 nm
- Each of the light moisture curable resin compositions obtained in Examples and Comparative Examples is applied on a polycarbonate substrate with a width of about 1 mm, and irradiated with UV light at 1000 mJ / cm 2 using a UV-LED (wavelength 365 nm).
- Each photo-moisture curable resin composition is photocured, and then a glass substrate is stacked, a 20 g weight is placed, and light is left by standing at 25 ° C. and 50% RH for 3 days (72 hours or more).
- the moisture curable resin composition was moisture cured to obtain a test piece.
- the schematic diagram (FIG. 1 (a)) which shows the case where a test piece is seen from the top in FIG.
- FIG. 1 (b) the schematic diagram which shows the case where a test piece is seen from the side were shown.
- Tensile shear strength was measured by pulling the obtained test piece at 25 ° C. using a tensile tester (“EZ-Graph” manufactured by Shimadzu Corporation) at a rate of 10 mm / min in the shear direction.
- flexibility and reliability can be provided.
- the electronic component and display element which use this hardening body can be provided.
- it is suitable for manufacture of this hardening body and can provide the optical moisture hardening type resin composition which is excellent in applicability
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Abstract
Description
ところで、携帯電話、携帯ゲーム機等、各種表示素子付きモバイル機器が普及している現代において、表示素子の小型化は最も求められている課題であり、小型化の手法として、画像表示部を狭額縁化することが行われている(以下、狭額縁設計ともいう)。しかしながら、狭額縁設計においては、充分に光の届かない部分に光硬化型樹脂組成物が塗布されることがあり、その結果、光の届かない部分に塗布された光硬化型樹脂組成物は硬化が不充分となるという問題があった。そこで、光の届かない部分に塗布された場合でも充分に硬化できる樹脂組成物として光熱硬化型樹脂組成物を用い、光硬化と熱硬化とを併用することも行われているが、高温での加熱により素子等に悪影響を与えるおそれがあった。
このような電子部品の接着に用いられる接着剤として、例えば、特許文献1には、数平均分子量が600~1000であるエポキシ化合物を含有する熱硬化型の接着剤が開示されている。しかしながら、特許文献1に開示されているような熱硬化型の接着剤は、熱により損傷する可能性のある電子部品の接着には適さないものであった。
また、電子機器、表示素子等においては、せん断方向又は曲げ方向に力が加えられた場合、温度変化によって熱応力が発生した場合等でも不具合を生じないことが必要とされており、このような条件下でも応力緩和できる柔軟性を持ちながら、高い接着性を維持し、信頼性に優れる電子部品用接着剤及び表示素子用接着剤が求められていた。
以下に本発明を詳述する。
なお、上記25℃における400%伸長時の引張強さは、引張試験において引張る前の4倍にまで伸長した時の力を意味する。具体的には例えば、紫外線LED(UV-LED)等を用いて波長365nmの紫外線を1000mJ/cm2照射することによって光湿気硬化型樹脂組成物を光硬化させた後、25℃、50%RHの条件で72時間以上静置することにより湿気硬化させ、得られた硬化体をダンベル状(「JIS K 6251」で規定される6号形)に打ち抜いて得られた試験片を、25℃において引張試験機(例えば、島津製作所社製、「EZ-Graph」等)を用いて5mm/minの速度で引張り、引張る前の4倍にまで伸長した時の力として求めることができる。
また、硬化体が電子部品等において基板等の接着に用いられている場合は、上記引張強さ及び後述する引張破断伸度等の測定は、接着している基板等を剥がした状態のもので行う。ダンベル状にならない場合でも、剥がした状態での硬化体の厚み及び幅を換算することにより、同様にして求める事ができる。
なお、上記25℃における引張破断伸度は、具体的には例えば、紫外線LEDランプ等を用いて波長365nmの紫外線を1000mJ/cm2照射することによって光湿気硬化型樹脂組成物を光硬化させた後、25℃、50%RHの条件で72時間以上静置することにより湿気硬化させ、得られた硬化体をダンベル状(「JIS K 6251」で規定される6号形)に打ち抜いて得られた試験片を、25℃において引張試験機(例えば、島津製作所社製、「EZ-Graph」等)を用いて5mm/minの速度で引張った際の破断点における伸度として求めることができる。
なお、上記ポリカーボネート及びガラスに対する引張せん断接着強さは、具体的には例えば、光湿気硬化型樹脂組成物をポリカーボネート基板上に約1mmの幅で塗布し、紫外線LEDランプ等を用いて波長365nmの紫外線を1000mJ/cm2照射することによって、光湿気硬化型樹脂組成物を光硬化させた後、ガラス基板を重ね、20gの重りを置き、25℃、50%RHの条件で72時間以上静置することにより光湿気硬化型樹脂組成物を湿気硬化させて得られた試験片を、25℃において引張試験機(例えば、島津製作所社製、「EZ-Graph」等)を用いてせん断方向に10mm/minの速度で引張ることにより測定することができる。
なお、上記80℃における貯蔵弾性率は、動的粘弾性測定装置(例えば、IT計測制御社製、「DVA-200」等)を用いることで測定できる。
上記ラジカル重合性化合物は、硬化物の柔軟性が高く(引張強さが低く)、接着力が弱く、かつ、よく伸びる(破断伸度が高い)傾向にある。一方、上記湿気硬化型樹脂は、硬化物の柔軟性が低く、接着力が強く、かつ、よく伸びる傾向にある。そのため、これらの成分として用いる化合物の種類及びその配合比、ガラス転移温度、架橋密度等を調整することにより、硬化体の引張強さ等を上述した範囲に調整できる。また、本発明の目的を阻害しない範囲であれば、後述する充填剤等の種類及び配合量を調整することによっても、硬化体の引張強さ等を上述した範囲に調整できる。
上記ラジカル重合性化合物としては、光重合性を有するラジカル重合性化合物であればよく、分子中にラジカル反応性官能基を有する化合物であれば特に限定されないが、ラジカル反応性官能基として不飽和二重結合を有する化合物が好適であり、特に反応性の面から(メタ)アクリロイル基を有する化合物(以下、「(メタ)アクリル化合物」ともいう)が好適である。
なお、本明細書において、上記「(メタ)アクリロイル」は、アクリロイル又はメタクリロイルを意味し、上記「(メタ)アクリル」は、アクリル又はメタクリルを意味する。
なお、本明細書において、上記「(メタ)アクリレート」とは、アクリレート又はメタクリレートを意味する。また、上記ウレタン(メタ)アクリレートの原料となるイソシアネート化合物のイソシアネート基は、全てウレタン結合の形成に用いられ、上記ウレタン(メタ)アクリレートは、残存イソシアネート基を有さない。
上記ビスフェノールF型エポキシ樹脂のうち市販されているものとしては、例えば、jER806、jER4004(いずれも三菱化学社製)等が挙げられる。
上記ビスフェノールS型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンEXA1514(DIC社製)等が挙げられる。
上記2,2’-ジアリルビスフェノールA型エポキシ樹脂のうち市販されているものとしては、例えば、RE-810NM(日本化薬社製)等が挙げられる。
上記水添ビスフェノール型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンEXA7015(DIC社製)等が挙げられる。
上記プロピレンオキシド付加ビスフェノールA型エポキシ樹脂のうち市販されているものとしては、例えば、EP-4000S(ADEKA社製)等が挙げられる。
上記レゾルシノール型エポキシ樹脂のうち市販されているものとしては、例えば、EX-201(ナガセケムテックス社製)等が挙げられる。
上記ビフェニル型エポキシ樹脂のうち市販されているものとしては、例えば、jER YX-4000H(三菱化学社製)等が挙げられる。
上記スルフィド型エポキシ樹脂のうち市販されているものとしては、例えば、YSLV-50TE(新日鉄住金化学社製)等が挙げられる。
上記ジフェニルエーテル型エポキシ樹脂のうち市販されているものとしては、例えば、YSLV-80DE(新日鉄住金化学社製)等が挙げられる。
上記ジシクロペンタジエン型エポキシ樹脂のうち市販されているものとしては、例えば、EP-4088S(ADEKA社製)等が挙げられる。
上記ナフタレン型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンHP4032、エピクロンEXA-4700(いずれもDIC社製)等が挙げられる。
上記フェノールノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンN-770(DIC社製)等が挙げられる。
上記オルトクレゾールノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンN-670-EXP-S(DIC社製)等が挙げられる。
上記ジシクロペンタジエンノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンHP7200(DIC社製)等が挙げられる。
上記ビフェニルノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、NC-3000P(日本化薬社製)等が挙げられる。
上記ナフタレンフェノールノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、ESN-165S(新日鉄住金化学社製)等が挙げられる。
上記グリシジルアミン型エポキシ樹脂のうち市販されているものとしては、例えば、jER630(三菱化学社製)、エピクロン430(DIC社製)、TETRAD-X(三菱ガス化学社製)等が挙げられる。
上記アルキルポリオール型エポキシ樹脂のうち市販されているものとしては、例えば、ZX-1542(新日鉄住金化学社製)、エピクロン726(DIC社製)、エポライト80MFA(共栄社化学社製)、デナコールEX-611(ナガセケムテックス社製)等が挙げられる。
上記ゴム変性型エポキシ樹脂のうち市販されているものとしては、例えば、YR-450、YR-207(いずれも新日鉄住金化学社製)、エポリードPB(ダイセル社製)等が挙げられる。
上記グリシジルエステル化合物のうち市販されているものとしては、例えば、デナコールEX-147(ナガセケムテックス社製)等が挙げられる。
上記ビスフェノールA型エピスルフィド樹脂のうち市販されているものとしては、例えば、jER YL-7000(三菱化学社製)等が挙げられる。
上記エポキシ化合物のうちその他に市販されているものとしては、例えば、YDC-1312、YSLV-80XY、YSLV-90CR(いずれも新日鉄住金化学社製)、XAC4151(旭化成社製)、jER1031、jER1032(いずれも三菱化学社製)、EXA-7120(DIC社製)、TEPIC(日産化学社製)等が挙げられる。
上記その他のラジカル重合性化合物としては、例えば、N,N-ジメチル(メタ)アクリルアミド、N-(メタ)アクリロイルモルホリン、N-ヒドロキシエチル(メタ)アクリルアミド、N,N-ジエチル(メタ)アクリルアミド、N-イソプロピル(メタ)アクリルアミド、N,N-ジメチルアミノプロピル(メタ)アクリルアミド等の(メタ)アクリルアミド化合物、スチレン、α-メチルスチレン、N-ビニルピロリドン、N-ビニル-ε-カプロラクタム等のビニル化合物等が挙げられる。
上記湿気硬化型樹脂としては、湿気硬化型ウレタン樹脂及び架橋性シリル基を有する樹脂等が挙げられる。なかでも、湿気硬化時の速硬化性に優れることから、湿気硬化型ウレタン樹脂が好ましい。上記湿気硬化型ウレタン樹脂は、ウレタン結合とイソシアネート基とを有し、分子内のイソシアネート基が空気中又は被着体中の水分と反応して硬化する。
上記湿気硬化型ウレタン樹脂は、上記イソシアネート基を分子の末端に有することが好ましい。
上記湿気硬化型ウレタン樹脂は、1分子中に2個以上の水酸基を有するポリオール化合物と、1分子中に2個以上のイソシアネート基を有するポリイソシアネート化合物とを反応させることにより、得ることができる。
上記ビスフェノール型のポリオキシアルキレン変性体は、ビスフェノール型分子骨格の両末端に、1種又は2種以上のアルキレンオキシドが付加されていることが好ましい。ビスフェノール型としては特に限定されず、A型、F型、S型等が挙げられ、好ましくはビスフェノールA型である。
なかでも、プロピレングリコール、テトラヒドロフラン(THF)化合物の開環重合化合物、又は、メチル基等の置換基を有するテトラヒドロフラン化合物の開環重合化合物からなるポリエーテルポリオールを用いたものが好ましい。
なお、Lが0の場合とは、Rと結合した炭素が直接酸素と結合している場合を意味する。
上記湿気硬化型ウレタン樹脂が有していてもよいラジカル重合性官能基としては、不飽和二重結合を有する基が好ましく、特に反応性の面から(メタ)アクリロイル基がより好ましい。
なお、ラジカル重合性官能基を有する湿気硬化型ウレタン樹脂は、ラジカル重合性化合物には含まず、湿気硬化型ウレタン樹脂として扱う。
なお、本明細書において上記重量平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)で測定を行い、ポリスチレン換算により求められる値である。GPCによってポリスチレン換算による重量平均分子量を測定する際のカラムとしては、例えば、Shodex LF-804(昭和電工社製)等が挙げられる。また、GPCで用いる溶媒としては、テトラヒドロフラン等が挙げられる。
上記架橋性シリル基を有する樹脂のうち市販されているものとしては、例えば、エクスターS2410、S2420、S3430(いずれも旭硝子社製)、XMAP SA-100S(カネカ社製)等が挙げられる。
上記光ラジカル重合開始剤としては、例えば、ベンゾフェノン系化合物、アセトフェノン系化合物、アシルフォスフィンオキサイド系化合物、チタノセン系化合物、オキシムエステル系化合物、ベンゾインエーテル系化合物、チオキサントン等が挙げられる。
なお、上記充填剤の一次粒子径は、NICOMP 380ZLS(PARTICLE SIZING SYSTEMS社製)等の粒度分布測定装置を用いて、上記充填剤を溶媒(水、有機溶媒等)に分散させて測定することができる。
また、上記充填剤は、本発明の光湿気硬化型樹脂組成物中において二次粒子(一次粒子が複数集まったもの)として存在する場合があり、このような二次粒子の粒子径の好ましい下限は5nm、好ましい上限は500nm、より好ましい下限は10nm、より好ましい上限は100nmである。上記充填剤の二次粒子の粒子径は、本発明の光湿気硬化型樹脂組成物又はその硬化体を、透過型電子顕微鏡(TEM)を用いて観察することにより測定することができる。
上記疎水性表面処理としては、シリル化処理、アルキル化処理、エポキシ化処理等が挙げられる。なかでも、形状保持性を向上させる効果に優れることから、シリル化処理が好ましく、トリメチルシリル化処理がより好ましい。
具体的には例えば、上記トリメチルシリル化処理シリカは、例えば、シリカをゾルゲル法等の方法で合成し、シリカを流動させた状態でヘキサメチルジシラザンを噴霧する方法、アルコール、トルエン等の有機溶媒中にシリカを加え、更に、ヘキサメチルジシラザンと水とを加えた後、水と有機溶媒とをエバポレーターで蒸発乾燥させる方法等により作製することができる。
なお、上記イソシアネート基、イソチオシアネート基、及び、カルボジイミド基からなる群より選択される少なくとも1種の基を有する化合物は、化学的に水分を除去するものであるが、本発明の光湿気硬化型樹脂組成物に使用する各材料を配合する前に、予め、必要に応じて、各材料に物理的な処理(ゼオライトのような水分吸着剤による水分の除去)を行っておいてもよい。
上記イソシアネート基を有する化合物は、上記湿気硬化型樹脂の原料となるポリイソシアネート化合物と同様の化合物であってもよいし、異なっていてもよい。
また、イソチオシアネート基を有する化合物としては、具体的には例えば、ベンジルイソチオシアネート、フェニルイソチオシアネート、4-フェニルブチルイソチオシアネート、3-フェニルプロピルイソチオシアネート等が挙げられる。
また、カルボジイミド基を有する化合物としては、具体的には例えば、N,N-ジシクロヘキシルカルボジイミド、N,N-ジイソプロピルカルボジイミド、1-エチル-3-(3-ジメチルアミノプロピル)カルボジイミド塩酸塩、ビス(2,6-ジイソプロピルフェニル)カルボジイミド等が挙げられ、市販されているものとしては、例えば、カルボジライトLA-1(日清紡社製)等が挙げられる。
これらは、単独で用いられてもよいし、2種以上が組み合わせて用いられてもよい。
なお、本明細書において、上記「遮光剤」は、可視光領域の光を透過させ難い能力を有する材料を意味する。
また、上記遮光剤は、黒色を呈するものでなくてもよく、可視光領域の光を透過させ難い能力を有する材料であれば、シリカ、タルク、酸化チタン等、充填剤として挙げた材料等も上記遮光剤に含まれる。なかでも、チタンブラックが好ましい。
即ち、上記チタンブラックは、可視光領域の波長の光を充分に遮蔽することで本発明の光湿気硬化型樹脂組成物に遮光性を付与する一方、紫外線領域付近の波長の光は透過させる性質を有する遮光剤である。従って、光ラジカル重合開始剤として、上記チタンブラックの透過率の高くなる波長(370~450nm)の光によって反応を開始可能なものを用いることで、本発明の光湿気硬化型樹脂組成物の光硬化性をより増大させることができる。また一方で、本発明の光湿気硬化型樹脂組成物に含有される遮光剤としては、絶縁性の高い物質が好ましく、絶縁性の高い遮光剤としてもチタンブラックが好適である。
上記チタンブラックは、光学濃度(OD値)が、3以上であることが好ましく、4以上であることがより好ましい。また、上記チタンブラックは、黒色度(L値)が9以上であることが好ましく、11以上であることがより好ましい。上記チタンブラックの遮光性は高ければ高いほど良く、上記チタンブラックのOD値に好ましい上限は特に無いが、通常は5以下となる。
また、上記チタンブラックのシート抵抗の好ましい下限は、樹脂と混合された場合(70%配合)において、109Ω/□であり、より好ましい下限は1011Ω/□である。
なお、上記遮光剤の粒子径は、NICOMP 380ZLS(PARTICLE SIZING SYSTEMS社製)を用いて、上記遮光剤を溶媒(水、有機溶媒等)に分散させて測定することができる。
なお、上記水分量は、カールフィッシャー水分測定装置により測定することができる。
なお、本発明の光湿気硬化型樹脂組成物の粘度が高すぎる場合は、塗布時に加温することで塗布性を向上させることができる。
なお、本明細書において上記チクソトロピックインデックスとは、コーンプレート型粘度計を用いて25℃、1rpmの条件で測定した粘度を、コーンプレート型粘度計を用いて25℃、10rpmの条件で測定した粘度で除した値を意味する。
上記被着体の形状としては、例えば、フィルム状、シート状、板状、パネル状、トレイ状、ロッド(棒状体)状、箱体状、筐体状等が挙げられる。
上記ガラスとしては、例えば、アルカリガラス、無アルカリガラス、石英ガラス等が挙げられる。
上記プラスチックとしては、例えば、高密度ポリエチレン、超高分子量ポリエチレン、アイソタクチックポリプロピレン、シンジオタクチックポリプロピレン、エチレンプロピレン共重合体樹脂等のポリオレフィン系樹脂、ナイロン6(N6)、ナイロン66(N66)、ナイロン46(N46)、ナイロン11(N11)、ナイロン12(N12)、ナイロン610(N610)、ナイロン612(N612)、ナイロン6/66共重合体(N6/66)、ナイロン6/66/610共重合体(N6/66/610)、ナイロンMXD6(MXD6)、ナイロン6T、ナイロン6/6T共重合体、ナイロン66/PP共重合体、ナイロン66/PPS共重合体等のポリアミド系樹脂、ポリブチレンテレフタレート(PBT)、ポリエチレンテレフタレート(PET)、ポリエチレンイソフタレート(PEI)、PET/PEI共重合体、ポリアリレート(PAR)、ポリブチレンナフタレート(PBN)、液晶ポリエステル、ポリオキシアルキレンジイミドジ酸/ポリブチレンテレフタレート共重合体等の芳香族ポリエステル系樹脂、ポリアクリロニトリル(PAN)、ポリメタクリロニトリル、アクリロニトリル/スチレン共重合体(AS)、メタクリロニトリル/スチレン共重合体、メタクリロニトリル/スチレン/ブタジエン共重合体等のポリニトリル系樹脂、ポリカーボネート、ポリメタクリル酸メチル(PMMA)、ポリメタクリル酸エチル等のポリメタクリレート系樹脂、エチレン/酢酸ビニル共重合体(EVA)、ポリビニルアルコール(PVA)、ビニルアルコール/エチレン共重合体(EVOH)、ポリ塩化ビニリデン(PVDC)、ポリ塩化ビニル(PVC)、塩化ビニル/塩化ビニリデン共重合体、塩化ビニリデン/メチルアクリレート共重合体等のポリビニル系樹脂等が挙げられる。
更に、上記被着体としては、金属表面を不動態化処理することにより不動態皮膜を形成した材料も挙げられ、該不動態化処理としては、例えば、加熱処理、陽極酸化処理等が挙げられる。特に、国際アルミニウム合金名が6000番台の材質であるアルミニウム合金等の場合は、上記不動態化処理として硫酸アルマイト処理又はリン酸アルマイト処理を行うことで、接着性を向上させることができる。
上記OD値は高いほど良いが、上記OD値を高くするために遮光剤を多く配合しすぎると、増粘による作業性の低下等が生じることから、遮光剤の配合量とのバランスをとるため、上記硬化体のOD値の好ましい上限は4である。
なお、上記光湿気硬化型樹脂組成物の硬化後のOD値は、光学濃度計を用いて測定することができる。
ポリオールとして100重量部のポリテトラメチレンエーテルグリコール(三菱化学社製、「PTMG-2000」)と、0.01重量部のジブチル錫ジラウレートとを500mL容のセパラブルフラスコに入れ、真空下(20mmHg以下)、100℃で30分間撹拌し、混合した。その後常圧とし、ジイソシアネートとして26.5重量部のPure MDI(日曹商事社製)を入れ、80℃で3時間撹拌し、反応させ、湿気硬化型ウレタン樹脂A(重量平均分子量2700)を得た。
ポリオールとして100重量部のポリテトラメチレンエーテルグリコール(三菱化学社製、「PTMG-2000」)と、0.01重量部のジブチル錫ジラウレートとを500mL容のセパラブルフラスコに入れ、真空下(20mmHg以下)、100℃で30分間撹拌し、混合した。その後常圧とし、ジイソシアネートとして26.5重量部のPure MDI(日曹商事社製)を入れ、80℃で3時間撹拌し、反応させ、湿気硬化型ウレタン樹脂B(重量平均分子量2900)を得た。
合成例1と同様にして得られた湿気硬化型ウレタン樹脂A100重量部の入った反応容器に、3-メルカプトプロピルトリメトキシシラン(信越化学工業社製、「KBM-803」)9.8重量部を添加し、80℃で1時間撹拌混合し、有機シリル基含有ウレタン樹脂として、分子末端にイソシアネート基とトリメトキシシリル基とを有する湿気硬化型ウレタン樹脂C(重量平均分子量3100)を得た。
表1に記載された配合比に従い、各材料を、遊星式撹拌装置(シンキー社製、「あわとり練太郎」)にて撹拌した後、セラミック3本ロールにて均一に混合して実施例1~7、比較例1~3の光湿気硬化型樹脂組成物を得た。
得られた光湿気硬化型樹脂組成物の一部を、幅3mm、長さ50mm、高さ1mmのテフロン(登録商標)製の型枠に埋めた。その後、UV-LED(波長365nm)を用いて、紫外線を1000mJ/cm2照射することによって、光湿気硬化型樹脂組成物を光硬化させた後、25℃、50%RHの条件で3日(72時間以上)静置することにより湿気硬化させ、硬化体を得た。
実施例及び比較例で得られた各光湿気硬化型樹脂組成物及び各硬化体について以下の評価を行った。結果を表1に示した。
実施例及び比較例で得られた各硬化体をダンベル状(「JIS K 6251」で規定される6号形)に打ち抜いて得られた試験片を、25℃において引張試験機(島津製作所社製、「EZ-Graph」)を用いて5mm/minの速度で引張り、引張る前の4倍にまで伸長した時の力として硬化体の400%伸長時の引張強さを求めた。
実施例及び比較例で得られた各硬化体をダンベル状(「JIS K 6251」で規定される6号形)に打ち抜いて得られた試験片を、25℃において引張試験機(島津製作所社製、「EZ-Graph」)を用いて5mm/minの速度で引張った際の破断点における伸度として硬化体の引張破断伸度を求めた。
実施例及び比較例で得られた各光湿気硬化型樹脂組成物をポリカーボネート基板上に約1mmの幅で塗布し、UV-LED(波長365nm)を用いて、紫外線を1000mJ/cm2照射することによって、各光湿気硬化型樹脂組成物を光硬化させた後、ガラス基板を重ね、20gの重りを置き、25℃、50%RHの条件で3日(72時間以上)静置することにより光湿気硬化型樹脂組成物を湿気硬化させて試験片を得た。図1に試験片を上から見た場合を示す模式図(図1(a))、及び、試験片を横から見た場合を示す模式図(図1(b))を示した。得られた試験片を、25℃において引張試験機(島津製作所社製、「EZ-Graph」)を用いてせん断方向に10mm/minの速度で引張ることにより引張せん断接着強さを測定した。
実施例及び比較例で得られた各光湿気硬化型樹脂組成物30gを、口径4cmの濾過装置に150メッシュのフィルターを敷いて、0.2MPaの圧力で加圧濾過を行い、その通過時間を評価した。通過に必要な時間が30秒未満であった場合を「○」、通過に必要な時間が30秒以上5分未満であった場合を「△」、通過に必要な時間が5分以上であった場合を「×」として、光湿気硬化型樹脂組成物の塗布性(細孔通過性)を評価した。
実施例及び比較例で得られた各光湿気硬化型樹脂組成物を、ディスペンス装置を用いて、ポリカーボネート基板上に約1mmの幅で30mmの長さとなるように塗布した。次いで、UV-LED(波長365nm)を用いて、紫外線を3000mJ/cm2照射することによって、光湿気硬化型樹脂組成物を光硬化させ、線幅(t0)、高さ(t1)を測定した。t1/t0が0.3以上であった場合を「○」、t1/t0が0.3未満であった場合を「×」として、光湿気硬化型樹脂組成物の形状保持性を評価した。
上記「(接着性(引張せん断接着強さ))」と同様にして得られた各試験片を50℃、85%RHの恒温恒湿オーブンに入れ、試験片を地面に対して垂直にぶら下げ、ポリカーボネート基板の端に100gの重りを吊るし、24時間静置した。24時間静置後のガラス基板とポリカーボネート基板との初期位置(重りを吊るす前の位置)からのズレが1mm以下であった場合を「○」、1mmを超え3mm以下であった場合を「△」、3mmを超えた場合を「×」として、光湿気硬化型樹脂組成物の耐クリープ性を評価した。
2 ガラス基板
3 光湿気硬化型樹脂組成物硬化体
Claims (9)
- ラジカル重合性化合物と湿気硬化型樹脂とを含有する光湿気硬化型樹脂組成物の硬化体であって、
25℃における400%伸長時の引張強さが3kgf/cm2以上、20kgf/cm2以下である
ことを特徴とする硬化体。 - 25℃における引張破断伸度が500%以上であることを特徴とする請求項1記載の硬化体。
- 25℃においてJIS K 6850に準拠して測定されるポリカーボネート及びガラスに対する引張せん断接着強さが10kgf/cm2以上であることを特徴とする請求項1又は2記載の硬化体。
- 湿気硬化型樹脂は、湿気硬化型ウレタン樹脂であることを特徴とする請求項1、2又は3記載の硬化体。
- 充填剤を含有することを特徴とする請求項1、2、3又は4記載の硬化体。
- 遮光剤を含有することを特徴とする請求項1、2、3、4又は5記載の硬化体。
- 基板と請求項1、2、3、4、5又は6記載の硬化体とを有することを特徴とする電子部品。
- 基板と請求項1、2、3、4、5又は6記載の硬化体とを有することを特徴とする表示素子。
- ラジカル重合性化合物と湿気硬化型樹脂とを含有する光湿気硬化型樹脂組成物であって、硬化体の25℃における400%伸張時の引張強さが3~20kgf/cm2となることを特徴とする光湿気硬化型樹脂組成物。
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170335144A1 (en) * | 2016-03-07 | 2017-11-23 | Nitto Denko Corporation | Optical adhesive sheet, polarizing film with adhesive layer and liquid crystal display device |
| JP2018173613A (ja) * | 2017-03-31 | 2018-11-08 | シチズンファインデバイス株式会社 | 画像表示装置及びその製造方法 |
| WO2019203277A1 (ja) * | 2018-04-19 | 2019-10-24 | 積水化学工業株式会社 | 硬化性樹脂組成物、硬化体、電子部品及び組立部品 |
| WO2020241803A1 (ja) * | 2019-05-30 | 2020-12-03 | 積水化学工業株式会社 | 硬化性樹脂組成物、硬化体、及び電子部品 |
| JPWO2022004416A1 (ja) * | 2020-06-29 | 2022-01-06 | ||
| WO2022114186A1 (ja) * | 2020-11-30 | 2022-06-02 | 積水化学工業株式会社 | 湿気硬化性樹脂組成物、及び電子機器用接着剤 |
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| KR102574109B1 (ko) * | 2022-10-18 | 2023-09-06 | (주)중앙종합안전기술연구원 | 구조물 안전 점검 및 진단용 균열 폭 측정기 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013016133A2 (en) * | 2011-07-22 | 2013-01-31 | H.B. Fuller Company | A one-component, dual-cure adhesive for use on electronics |
| JP5844504B1 (ja) * | 2014-05-13 | 2016-01-20 | 積水化学工業株式会社 | 光湿気硬化型樹脂組成物、電子部品用接着剤、及び、表示素子用接着剤 |
| JP2016074783A (ja) * | 2014-10-03 | 2016-05-12 | 積水化学工業株式会社 | 光湿気硬化型樹脂組成物 |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19800676A1 (de) * | 1998-01-10 | 1999-07-15 | Henkel Kgaa | Verwendung ausgewählter Klebstoffgemische für die Überlappungsverklebung von Rundumetiketten bei ihrem Auftrag auf Kunststoff-Flaschen |
| JP2000178342A (ja) | 1998-12-17 | 2000-06-27 | Sumitomo Bakelite Co Ltd | 絶縁ペースト |
| US6828355B1 (en) | 1999-07-19 | 2004-12-07 | Henkel Corporation | Resin-reinforced UV, moisture and UV/moisture dual curable silicone compositions |
| JP2001064543A (ja) * | 1999-08-27 | 2001-03-13 | Nippon Shokubai Co Ltd | 硬化型被覆材用樹脂組成物 |
| JP2001220569A (ja) * | 2000-02-09 | 2001-08-14 | Sekisui Chem Co Ltd | 反応性接着剤組成物 |
| JP2001240811A (ja) * | 2000-03-01 | 2001-09-04 | Sekisui Chem Co Ltd | 反応性接着剤組成物及び部材の接合方法 |
| JP2004047415A (ja) * | 2002-05-24 | 2004-02-12 | Sekisui Chem Co Ltd | フレキシブルフラットケーブル、接着剤及びその接合体 |
| JP2004018621A (ja) * | 2002-06-14 | 2004-01-22 | Nippon Shokubai Co Ltd | ラジカル硬化性ウレタン樹脂組成物 |
| US7189781B2 (en) | 2003-03-13 | 2007-03-13 | H.B. Fuller Licensing & Finance Inc. | Moisture curable, radiation curable sealant composition |
| JP5013585B2 (ja) | 2006-09-06 | 2012-08-29 | 日立化成ポリマー株式会社 | 反応性ホットメルト接着剤組成物及びそれを用いた接着方法 |
| JP5228370B2 (ja) | 2007-04-27 | 2013-07-03 | 東亞合成株式会社 | 一液湿気硬化型ウレタン系ホットメルト接着剤組成物及びその使用方法 |
| KR101414090B1 (ko) * | 2008-02-27 | 2014-07-02 | 디아이씨 가부시끼가이샤 | 투습 필름, 그 제조 방법 및 그것을 사용한 적층체 |
| JP5488386B2 (ja) * | 2010-10-14 | 2014-05-14 | Dic株式会社 | 活性エネルギー線硬化性ホットメルトウレタン樹脂組成物、それを用いた電子機器用部材、及びパッキン |
| CN104031598A (zh) * | 2014-06-30 | 2014-09-10 | 江苏华程光电科技有限公司 | 高导热性led密封胶 |
-
2016
- 2016-04-14 TW TW105111579A patent/TWI701310B/zh active
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-
2020
- 2020-04-28 JP JP2020079262A patent/JP2020111764A/ja active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013016133A2 (en) * | 2011-07-22 | 2013-01-31 | H.B. Fuller Company | A one-component, dual-cure adhesive for use on electronics |
| JP5844504B1 (ja) * | 2014-05-13 | 2016-01-20 | 積水化学工業株式会社 | 光湿気硬化型樹脂組成物、電子部品用接着剤、及び、表示素子用接着剤 |
| JP2016074783A (ja) * | 2014-10-03 | 2016-05-12 | 積水化学工業株式会社 | 光湿気硬化型樹脂組成物 |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170335144A1 (en) * | 2016-03-07 | 2017-11-23 | Nitto Denko Corporation | Optical adhesive sheet, polarizing film with adhesive layer and liquid crystal display device |
| JP2018173613A (ja) * | 2017-03-31 | 2018-11-08 | シチズンファインデバイス株式会社 | 画像表示装置及びその製造方法 |
| WO2019203277A1 (ja) * | 2018-04-19 | 2019-10-24 | 積水化学工業株式会社 | 硬化性樹脂組成物、硬化体、電子部品及び組立部品 |
| WO2020241803A1 (ja) * | 2019-05-30 | 2020-12-03 | 積水化学工業株式会社 | 硬化性樹脂組成物、硬化体、及び電子部品 |
| JPWO2020241803A1 (ja) * | 2019-05-30 | 2020-12-03 | ||
| JP7557461B2 (ja) | 2019-05-30 | 2024-09-27 | 積水化学工業株式会社 | 硬化性樹脂組成物、硬化体、及び電子部品 |
| JPWO2022004416A1 (ja) * | 2020-06-29 | 2022-01-06 | ||
| WO2022004416A1 (ja) * | 2020-06-29 | 2022-01-06 | 積水化学工業株式会社 | 光湿気硬化型樹脂組成物、及び硬化体 |
| JP7765287B2 (ja) | 2020-06-29 | 2025-11-06 | 積水化学工業株式会社 | 光湿気硬化型樹脂組成物、及び硬化体 |
| WO2022114186A1 (ja) * | 2020-11-30 | 2022-06-02 | 積水化学工業株式会社 | 湿気硬化性樹脂組成物、及び電子機器用接着剤 |
| JPWO2022114186A1 (ja) * | 2020-11-30 | 2022-06-02 | ||
| JP7835494B2 (ja) | 2020-11-30 | 2026-03-25 | 積水化学工業株式会社 | 湿気硬化性樹脂組成物、及び電子機器用接着剤 |
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| JP6698524B2 (ja) | 2020-05-27 |
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| TW201704394A (zh) | 2017-02-01 |
| KR20170137691A (ko) | 2017-12-13 |
| KR102260532B1 (ko) | 2021-06-03 |
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| CN107108772A (zh) | 2017-08-29 |
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