WO2017119406A1 - Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element - Google Patents
Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element Download PDFInfo
- Publication number
- WO2017119406A1 WO2017119406A1 PCT/JP2017/000004 JP2017000004W WO2017119406A1 WO 2017119406 A1 WO2017119406 A1 WO 2017119406A1 JP 2017000004 W JP2017000004 W JP 2017000004W WO 2017119406 A1 WO2017119406 A1 WO 2017119406A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- liquid crystal
- crystal display
- meth
- acrylate
- display element
- Prior art date
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 111
- 239000000565 sealant Substances 0.000 title claims abstract description 31
- 239000000463 material Substances 0.000 title claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 65
- 150000001875 compounds Chemical class 0.000 claims abstract description 63
- 229920005989 resin Polymers 0.000 claims abstract description 32
- 239000011347 resin Substances 0.000 claims abstract description 32
- 239000007870 radical polymerization initiator Substances 0.000 claims abstract description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 97
- 238000007789 sealing Methods 0.000 claims description 49
- 239000004593 Epoxy Substances 0.000 claims description 29
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- 229920001187 thermosetting polymer Polymers 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 238000011109 contamination Methods 0.000 abstract description 16
- 239000011248 coating agent Substances 0.000 abstract description 10
- 238000000576 coating method Methods 0.000 abstract description 10
- 230000002265 prevention Effects 0.000 abstract description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract 1
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- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 description 3
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
-
- 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
-
- 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
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/378—Thiols containing heterocyclic rings
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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
- C08L101/00—Compositions of unspecified macromolecular compounds
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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
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/062—Copolymers with monomers not covered by C08L33/06
- C08L33/068—Copolymers with monomers not covered by C08L33/06 containing glycidyl 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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1339—Gaskets; Spacers; Sealing of cells
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
- C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
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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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
- C09K2200/0645—Macromolecular organic compounds, e.g. prepolymers obtained otherwise than by reactions involving carbon-to-carbon unsaturated bonds
- C09K2200/0647—Polyepoxides
Definitions
- the present invention relates to a sealing agent for a liquid crystal display element that is excellent in coating properties, moisture permeation prevention properties, and adhesiveness, and can suppress liquid crystal contamination. Moreover, this invention relates to the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal display elements.
- a rectangular seal pattern is formed on one of two transparent substrates with electrodes by dispensing.
- a liquid crystal micro-droplet is dropped on the entire surface of the transparent substrate frame in a state where the sealant is uncured, and the other transparent substrate is immediately overlaid, and the seal portion is irradiated with light such as ultraviolet rays for temporary curing. .
- heating is performed to perform main curing, and a liquid crystal display element is manufactured.
- a liquid crystal display element can be manufactured with extremely high efficiency by bonding the substrates under a reduced pressure, and this dropping method is currently the mainstream method for manufacturing liquid crystal display elements.
- the position of the seal portion is arranged under the black matrix (hereinafter also referred to as a narrow frame design).
- the sealant is placed directly under the black matrix, so when the dripping method is used, the light irradiated when photocuring the sealant is blocked, and the light does not reach the inside of the sealant. There was a problem that the curing was insufficient. If the sealant is insufficiently cured in this manner, the uncured sealant component is eluted in the liquid crystal, and the curing reaction by the eluted sealant component proceeds in the liquid crystal, resulting in liquid crystal contamination. there were.
- An object of this invention is to provide the sealing compound for liquid crystal display elements which is excellent in applicability
- Another object of the present invention is to provide a vertical conduction material and a liquid crystal display element using the sealing agent for a liquid crystal display element.
- the present invention is a sealing agent for a liquid crystal display element containing a curable resin and a radical polymerization initiator and / or a thermosetting agent, wherein the curable resin is a compound represented by the following formula (1). It is a sealing compound for liquid crystal display elements which is contained and the content of the compound represented by the formula (1) in the sealing compound for liquid crystal display elements is 1% by weight or more and less than 30% by weight.
- R 1 is hydrogen or a methyl group
- m and n are each 0 to 6.
- the present inventor has studied the blending of a bisphenol S-type epoxy resin having excellent adhesion and low liquid crystal contamination as a curable resin.
- a bisphenol S-type epoxy resin having excellent adhesion and low liquid crystal contamination as a curable resin.
- the present inventors have a liquid crystal display element that is excellent in coating property, moisture permeation prevention property, and adhesiveness and can suppress liquid crystal contamination by blending a specific amount of a specific compound having a bisphenol S-type structure.
- the present inventors have found that a sealant can be obtained and have completed the present invention.
- the sealing agent for liquid crystal display elements of this invention contains curable resin.
- the said curable resin contains the compound represented by the said Formula (1).
- the sealing agent for liquid crystal display elements of the present invention is excellent in the effect of suppressing adhesiveness and liquid crystal contamination.
- m and n are each 0 to 6.
- M and n are each preferably 1 to 6, and more preferably 1 to 3, respectively.
- the value of m and n in the said Formula (1) and Formula (2) mentioned later is an average value.
- the case where m and n are 0 means that the ethylene oxide structure portion to which m or n is attached becomes a bond.
- a compound represented by the above formula (1) for example, by reacting bisphenol S or ethylene oxide-added bisphenol S with epichlorohydrin, a compound represented by the following formula (2) is produced, Examples thereof include a method of reacting one epoxy group of the obtained compound represented by the formula (2) with (meth) acrylic acid.
- the “(meth) acryl” means acryl or methacryl.
- n and n are each 0 to 6.
- the content of the compound represented by the above formula (1) in the sealant for liquid crystal display elements of the present invention is 1% by weight or more and less than 30% by weight.
- the obtained sealing agent for liquid crystal display elements tends to be inferior in adhesiveness.
- the content of the compound represented by the above formula (1) is 30% by weight or more, the obtained sealant for a display element is inferior in applicability and moisture permeability prevention.
- the preferable lower limit of the content of the compound represented by the formula (1) is 5% by weight, the preferable upper limit is 25% by weight, the more preferable lower limit is 10% by weight, the more preferable upper limit is 20% by weight, and the further preferable upper limit is 15% by weight. %.
- the curable resin preferably contains other curable resin in addition to the compound represented by the formula (1).
- the other curable resin include (meth) acrylic compounds and epoxy compounds other than the compound represented by the above formula (1).
- (meth) acrylate” means acrylate or methacrylate
- epoxy (meth) acrylate” means that all epoxy groups in the epoxy compound are reacted with (meth) acrylic acid. Represents a compound.
- Examples of the (meth) acrylic compound that is the other curable resin include epoxy (meth) acrylate obtained by reacting (meth) acrylic acid and an epoxy compound, and a compound having a hydroxyl group in (meth) acrylic acid.
- (Meth) acrylate is preferred.
- the (meth) acrylic compound preferably has two or more (meth) acryloyl groups in the molecule because of its high reactivity.
- 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 used as a raw material for synthesizing the epoxy (meth) acrylate include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E 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 type epoxy resin, orthocresol novolac type epoxy resin, dicyclopentadiene novolac type epoxy resin, biphenyl Novolak type epoxy resins, naphthalene phenol novolac-type epoxy resin, glycidyl amine type epoxy resin, alkyl polyol type epoxy resin, rubber-modified epoxy resins, glycidyl ester compounds.
- a res
- Examples of commercially available 2,2′-diallylbisphenol A type epoxy resins include RE-810NM (manufactured by Nippon Kayaku Co., Ltd.). As what is marketed among the said hydrogenated bisphenol type
- 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 Corporation). Examples of commercially available biphenyl type epoxy resins include jER YX-4000H (manufactured by Mitsubishi Chemical Corporation).
- Examples of commercially available sulfide type epoxy resins include YSLV-50TE (manufactured by Nippon Steel & Sumikin Chemical 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). As what is marketed among the said dicyclopentadiene novolak-type epoxy resins, epiclone HP7200 (made by DIC) etc. are mentioned, for example.
- Examples of commercially available biphenyl novolac epoxy resins include NC-3000P (manufactured by Nippon Kayaku Co., Ltd.). Examples of commercially available naphthalene phenol 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), 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).
- Other commercially available epoxy compounds include, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by NS 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, EBECRY3702, EBECRY3703, EBECRYL3701, EBECRYL3701.
- 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 Xyester 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 Corporation) and the like.
- Examples of the monofunctional compounds among the (meth) acrylic acid ester compounds include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate.
- 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, ethylene oxide-added isocyanuric acid tri (meth) acrylate, glycerin tri (meth) acrylate, propylene oxide-added glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, ditri Methylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate DOO, dipentaerythri
- urethane (meth) acrylate for example, by reacting 2 equivalents of a (meth) acrylic acid derivative having a hydroxyl group with 1 equivalent of an isocyanate compound having two isocyanate groups in the presence of a catalytic amount of a tin-based compound. Obtainable.
- 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, tetramethylxylene diisocyanate, 1,6,11-undecanetriiso Aneto and the like.
- Examples of the isocyanate compound that is a raw material for the urethane (meth) acrylate include, for example, polyols such as ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, and polycaprolactone diol. Chain-extended isocyanate compounds obtained by reaction with excess isocyanate compounds can also be used.
- Examples of the (meth) acrylic acid derivative having a hydroxyl group as a raw material for the urethane (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth). Hydroxyalkyl (meth) acrylates such as acrylate, 4-hydroxybutyl (meth) acrylate, ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, polyethylene glycol, etc.
- Mono (meth) acrylates of dihydric alcohols mono (meth) acrylates or di (meth) acrylates of trivalent alcohols such as trimethylolethane, trimethylolpropane and glycerin, and bisphenol A type epoxy alcohol Epoxy (meth) acrylate of rate, and the like.
- Examples of commercially available urethane (meth) acrylates include M-1100, M-1200, M-1210, M-1600 (all manufactured by Toagosei Co., Ltd.), EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, EBECRYL1290, EBECRYL2220, EBECRYL4827, EBECRYL4842, EBECRYL4858, EBECRYL5129, EBECRYL6700, EBECRYL8402, EBECRYL8803, EBECRYL8804, EBECRYL8804 , Art resin N-1255, Art Resin UN-3320HB, Art Resin UN-7100, Art Resin UN-9000A, Art Resin UN-9000H (all manufactured by Negami Industrial Co., Ltd.), U-2HA, U-2PHA, U-3HA, U- 4HA, U-6H, U-6HA, U-6LPA, U-10H, U-15HA, U
- the epoxy compound which is the other curable resin examples include, for example, an epoxy compound which is a raw material for synthesizing the epoxy (meth) acrylate and a partial (meth) acryl modification other than the compound represented by the formula (1) An epoxy resin etc. are mentioned.
- the partial (meth) acryl-modified epoxy resin means a compound having one or more epoxy groups and (meth) acryloyl groups in one molecule, for example, two or more epoxy compounds. Can be obtained by reacting a part of the epoxy group with (meth) acrylic acid.
- Examples of commercially available partial (meth) acrylic-modified epoxy resins include UVACURE 1561 (manufactured by Daicel Ornex).
- the minimum with preferable content of the compound represented by the said Formula (1) in 100 weight part of curable resin whole is 5 weight part, and a preferable upper limit is 25 weight part.
- the content of the compound represented by the above formula (1) is within this range, the obtained sealing agent for a liquid crystal display element has an effect of suppressing applicability, adhesiveness, moisture permeation prevention, and liquid crystal contamination. It will be better.
- the minimum with more preferable content of the compound represented by said Formula (1) is 10 weight part, and a more preferable upper limit is 20 weight part.
- the content ratio of the (meth) acryloyl group and the epoxy group in the curable resin is preferably 50:50 to 95: 5.
- the sealing agent for liquid crystal display elements of this invention contains a radical polymerization initiator and / or a thermosetting agent.
- radical polymerization initiator examples include a photo radical polymerization initiator that generates radicals by light irradiation, a thermal radical polymerization initiator that generates radicals by heating, and the like.
- photo radical polymerization initiator examples include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, thioxanthone compounds, and the like.
- photo radical polymerization initiators examples include IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, all manufactured by Rusilin TPO ), NCI-930 (manufactured by ADEKA), SPEEDCURE EMK (manufactured by Nippon Sebel Hegner), benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether (all manufactured by Tokyo Chemical Industry Co., Ltd.) and the like.
- thermal radical polymerization initiator what consists of an azo compound, an organic peroxide, etc. is mentioned, for example.
- an initiator made of a polymer azo compound (hereinafter also referred to as “polymer azo initiator”) is preferable.
- the polymer azo compound means a compound having an azo group and generating a radical capable of curing a (meth) acryloyl group by heat and having a number average molecular weight of 300 or more.
- the preferable lower limit of the number average molecular weight of the polymeric azo initiator is 1000, and the preferable upper limit is 300,000.
- the more preferable lower limit of the number average molecular weight of the polymeric azo initiator is 5000, the more preferable upper limit is 100,000, the still more preferable lower limit is 10,000, and the still more preferable upper limit is 90,000.
- the said number average molecular weight is a value calculated
- polymer azo initiator examples include those having a structure in which a plurality of units such as polyalkylene oxide and polydimethylsiloxane are bonded via an azo group.
- polymer azo initiator having a structure in which a plurality of units such as polyalkylene oxide are bonded via the azo group those having a polyethylene oxide structure are preferable.
- Examples of such a polymer azo initiator include polycondensates of 4,4′-azobis (4-cyanopentanoic acid) and polyalkylene glycol, and 4,4′-azobis (4-cyanopentanoic acid) Examples thereof include polycondensates of polydimethylsiloxane having a terminal amino group, such as VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 (all of which are Wako Pure Chemical Industries, Ltd.) Manufactured) and the like.
- Examples of azo compounds that are not polymers include V-65 and V-501 (both manufactured by Wako Pure Chemical Industries, Ltd.).
- organic peroxide examples include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, peroxyester, diacyl peroxide, and peroxydicarbonate.
- the content of the 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 curable resin.
- the content of the radical polymerization initiator is within this range, the obtained sealing agent for liquid crystal display elements is excellent in storage stability and curability while suppressing liquid crystal contamination.
- the minimum with more preferable content of the said radical polymerization initiator is 0.1 weight part, and a more preferable upper limit is 5 weight part.
- thermosetting agent examples include organic acid hydrazides, imidazole derivatives, amine compounds, polyhydric phenol compounds, acid anhydrides, and the like. Of these, organic acid hydrazide is preferably used.
- organic acid hydrazide examples include sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide, and the like.
- organic acid hydrazides examples include, for example, SDH, ADH (all manufactured by Otsuka Chemical Co., Ltd.), Amicure VDH, Amicure VDH-J, Amicure UDH, Amicure UDH-J (all Ajinomoto Fine Techno Co., Ltd.) Manufactured) and the like.
- the content of the thermosetting agent is preferably 1 part by weight with respect to 100 parts by weight of the curable resin, and 50 parts by weight with respect to the preferable upper limit.
- the upper limit with more preferable content of the said thermosetting agent is 30 weight part.
- the sealing agent for liquid crystal display elements of the present invention may contain a filler for the purpose of improving viscosity, improving adhesiveness due to stress dispersion effect, improving linear expansion coefficient, improving moisture permeability of cured products, and the like. preferable.
- the filler examples include silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, smectite, bentonite, montmorillonite, sericite, activated clay, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide,
- Organic fillers such as calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate, and calcium silicate, and organic materials such as polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, and acrylic polymer fine particles A filler is mentioned.
- the minimum with preferable content of the said filler in the sealing compound for liquid crystal display elements of this invention is 10 weight%, and a preferable upper limit is 70 weight%.
- a preferable upper limit is 70 weight%.
- the more preferable lower limit of the content of the filler is 20% by weight, and the more preferable upper limit is 60% by weight.
- the sealing compound for liquid crystal display elements of this invention contains a silane coupling agent.
- the silane coupling agent mainly has a role as an adhesion assistant for favorably bonding the sealing agent and the substrate.
- silane coupling agent since it is excellent in the effect which improves adhesiveness with a board
- -Aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane and the like are preferably used.
- the minimum with preferable content of the said silane coupling agent in the sealing compound for liquid crystal display elements of this invention is 0.1 weight%, and a preferable upper limit is 10 weight%.
- a preferable upper limit is 10 weight%.
- the minimum with more preferable content of the said silane coupling agent is 0.3 weight%, and a more preferable upper limit is 5 weight%.
- the sealing agent for liquid crystal display elements of the present invention may contain a light shielding agent.
- the sealing compound for liquid crystal display elements of this invention can be used suitably as a light shielding sealing agent.
- Examples of the light-shielding agent include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. 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 providing a light shielding property to the sealing agent for liquid crystal display elements of the present invention, while transmitting light having a wavelength in the vicinity of the ultraviolet region.
- the light shielding agent contained in the liquid crystal display element sealant of the present invention is preferably a highly insulating material, and titanium black is also preferred as the highly insulating light shielding agent.
- 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, oxidized Surface-treated titanium black such as those coated with an inorganic component such as zirconium or magnesium oxide can also be used. Especially, what is processed with the organic component is preferable at the point which can improve insulation more.
- the liquid crystal display element produced using the sealing agent for liquid crystal display elements of the present invention containing the above-described titanium black as a light-shielding agent has sufficient light-shielding properties, and therefore has high contrast without light leakage A liquid crystal display element having excellent image display quality can be realized.
- titanium black examples include 12S, 13M, 13M-C, 13R-N, 14M-C (all manufactured by Mitsubishi Materials Corporation), Tilak D (manufactured by Ako Kasei Co., Ltd.), and the like. Can be mentioned.
- the preferable lower limit of the specific surface area of the titanium black is 13 m 2 / g, the preferable upper limit is 30 m 2 / g, the more preferable lower limit is 15 m 2 / g, and the more preferable upper limit is 25 m 2 / g.
- the preferred lower limit of the volume resistance of the titanium black is 0.5 ⁇ ⁇ cm, the preferred upper limit is 3 ⁇ ⁇ cm, the more preferred lower limit is 1 ⁇ ⁇ cm, and the more preferred upper limit is 2.5 ⁇ ⁇ cm.
- the primary particle diameter of the said light-shielding agent will not be specifically limited if it is below the distance between the board
- the more preferable lower limit of the primary particle diameter of the light shielding agent is 5 nm
- the more preferable upper limit is 200 nm
- the still more preferable lower limit is 10 nm
- the still more preferable upper limit is 100 nm.
- the primary particle size of the light shielding agent can be measured by using NICOMP 380ZLS (manufactured by PARTICS SIZING SYSTEMS) and dispersing the light shielding agent in a solvent (water, organic solvent, etc.).
- the minimum with preferable content of the said light-shielding agent in the sealing compound for liquid crystal display elements of this invention is 5 weight%, and a preferable upper limit is 80 weight%.
- the content of the light-shielding agent is within this range, the liquid crystal display element sealant can exhibit better light-shielding properties without reducing the adhesion to the substrate, the strength after curing, and the drawability. it can.
- the more preferable lower limit of the content of the light-shielding agent is 10% by weight, the more preferable upper limit is 70% by weight, the still more preferable lower limit is 30% by weight, and the still more preferable upper limit is 60% by weight.
- the sealing agent for liquid crystal display elements of the present invention is further added as necessary, stress relieving agent, reactive diluent, thixotropic agent, spacer, curing accelerator, antifoaming agent, leveling agent, polymerization inhibitor, etc.
- An agent or the like may be contained.
- a method for producing the sealing agent for liquid crystal display elements 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, a curable resin, and a polymerization
- a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, a three roll, a curable resin, and a polymerization
- examples thereof include a method of mixing an initiator and / or a thermosetting agent and an additive such as a silane coupling agent added as necessary.
- the sealing agent for liquid crystal display elements of the present invention has a preferable lower limit of 50,000 mPa ⁇ s and a preferable upper limit of 700,000 mPa ⁇ s measured using an E-type viscometer at 25 ° C. and 1 rpm. When the viscosity is within this range, the obtained sealing agent for liquid crystal display elements has excellent coating properties.
- a more preferable lower limit of the viscosity is 100,000 mPa ⁇ s, and a more preferable upper limit is 500,000 mPa ⁇ s.
- As the E-type viscometer for example, 5XHBDV-III + CP (manufactured by Brookfield, rotor No. CP-51) can be used.
- a vertical conducting material can be produced by blending conductive fine particles with the liquid crystal display element sealant of the present invention.
- Such a vertical conduction material containing the sealing agent for liquid crystal display elements of the present invention and conductive fine particles is also one aspect of the present invention.
- the conductive fine particles a metal ball, a resin fine particle formed with a conductive metal layer on the surface, or the like can be used.
- the one in which the conductive metal layer is formed on the surface of the resin fine particles is preferable because the conductive connection is possible without damaging the transparent substrate due to the excellent elasticity of the resin fine particles.
- the liquid crystal display element using the sealing agent for liquid crystal display elements of this invention or the vertical conduction material of this invention is also one of this invention.
- a liquid crystal dropping method is preferably used.
- the liquid crystal display element sealant of the present invention is applied to one of two substrates such as a glass substrate with electrodes such as an ITO thin film or a polyethylene terephthalate substrate by screen printing, dispenser application, or the like.
- the sealing agent for liquid crystal display elements which can be excellent in applicability
- the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal display elements can be provided.
- Examples 1 to 7 and Comparative Examples 1 to 4 According to the mixing ratio described in Table 1, each material was mixed using a planetary stirrer (manufactured by Shinky Co., Ltd., “Awatori Nertaro”), and then further mixed using three rolls. To 7 and Comparative Examples 1 to 4 were prepared.
- the adhesive strength was measured using the tension gauge.
- the resulting value obtained by dividing measured values (kgf) in the seal coating cross sectional area (cm 2) is a case was 35 kgf / cm 2 or more " ⁇ " was 30 kgf / cm 2 or more 35 kgf / cm less than 2 where " ⁇ ", the case was 25 kgf / cm 2 or more 30 kgf / cm less than 2 " ⁇ ", and evaluated the adhesiveness of the case was less than 25 kgf / cm 2 as " ⁇ ".
- the moisture permeation preventive property was evaluated by setting “ ⁇ ” when it was 2 ⁇ 24 hr or more and less than 120 g / m 2 ⁇ 24 hr, and “x” when it was 120 g / m 2 ⁇ 24 hr or more.
- TN liquid crystal manufactured by Chisso Corporation, “JC-5001LA”
- JC-5001LA fine droplets of TN liquid crystal
- the other transparent electrode substrate is 5 Pa with a vacuum bonding device. Bonding was performed under vacuum to obtain a cell.
- the obtained cell was irradiated with 100 mW / cm 2 of ultraviolet rays for 30 seconds using a metal halide lamp, and then heated at 120 ° C. for 1 hour to cure the sealant to obtain a liquid crystal display element.
- the display unevenness generated in the liquid crystal (especially the corner portion) around the seal portion was visually observed, and when the display unevenness was not confirmed, “ ⁇ ”, slight display unevenness was confirmed.
- the display performance (low liquid crystal contamination) of the liquid crystal display element was evaluated with “ ⁇ ” as the case, “ ⁇ ” when the display unevenness was clearly confirmed, and “X” when the severe display unevenness was confirmed. Note that the liquid crystal display elements evaluated as “ ⁇ ” and “ ⁇ ” are at a level that causes no problem in practical use.
- the sealing agent for liquid crystal display elements which can be excellent in applicability
- the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal display elements can be provided.
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Abstract
A purpose of the present invention is to provide a sealant for a liquid crystal display element, said sealant demonstrating superior coating properties, moisture permeation prevention, and adhesion, as well as being able to minimize liquid crystal contamination. Another purpose of the present invention is to provide a vertical conduction material and a liquid crystal display element that are obtained using said sealant for a liquid crystal display element. This sealant for a liquid crystal display element includes a curable resin as well as a radical polymerization initiator and/or a thermal curing agent, wherein the curable resin includes a compound expressed in formula (1), and the content of the compound expressed in formula (1) within the sealant for a liquid crystal display element is greater than or equal to 1 wt% and less than 30 wt%. In formula (1), R1 is hydrogen or a methyl group, and m and n are each 0-6.
Description
本発明は、塗布性、透湿防止性、及び、接着性に優れ、かつ、液晶汚染を抑制できる液晶表示素子用シール剤に関する。また、本発明は、該液晶表示素子用シール剤を用いてなる上下導通材料及び液晶表示素子に関する。
The present invention relates to a sealing agent for a liquid crystal display element that is excellent in coating properties, moisture permeation prevention properties, and adhesiveness, and can suppress liquid crystal contamination. Moreover, this invention relates to the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal display elements.
近年、液晶表示素子の製造方法としては、タクトタイム短縮、使用液晶量の最適化といった観点から、特許文献１、特許文献２に開示されているような、硬化性樹脂と光重合開始剤と熱硬化剤とを含有する光熱併用硬化型のシール剤を用いた滴下工法と呼ばれる液晶滴下方式が用いられている。
In recent years, as a method for manufacturing a liquid crystal display element, a curable resin, a photopolymerization initiator, and a heat as disclosed in Patent Document 1 and Patent Document 2 from the viewpoint of shortening tact time and optimizing the amount of liquid crystal used. A liquid crystal dropping method called a dropping method using a photothermal combined curing type sealing agent containing a curing agent is used.
滴下工法では、まず、２枚の電極付き透明基板の一方に、ディスペンスにより長方形状のシールパターンを形成する。次いで、シール剤が未硬化の状態で液晶の微小滴を透明基板の枠内全面に滴下し、すぐに他方の透明基板を重ね合わせ、シール部に紫外線等の光を照射して仮硬化を行う。その後、加熱して本硬化を行い、液晶表示素子を作製する。基板の貼り合わせを減圧下で行うことで極めて高い効率で液晶表示素子を製造することができ、現在この滴下工法が液晶表示素子の製造方法の主流となっている。
In the dropping method, first, a rectangular seal pattern is formed on one of two transparent substrates with electrodes by dispensing. Next, a liquid crystal micro-droplet is dropped on the entire surface of the transparent substrate frame in a state where the sealant is uncured, and the other transparent substrate is immediately overlaid, and the seal portion is irradiated with light such as ultraviolet rays for temporary curing. . Thereafter, heating is performed to perform main curing, and a liquid crystal display element is manufactured. A liquid crystal display element can be manufactured with extremely high efficiency by bonding the substrates under a reduced pressure, and this dropping method is currently the mainstream method for manufacturing liquid crystal display elements.
ところで、携帯電話、携帯ゲーム機等、各種液晶パネル付きモバイル機器が普及している現代において、装置の小型化は最も求められている課題である。装置の小型化の手法としては、液晶表示部の狭額縁化が挙げられ、例えば、シール部の位置をブラックマトリックス下に配置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、狭額縁設計ではシール剤がブラックマトリックスの直下に配置されるため、滴下工法を行うと、シール剤を光硬化させる際に照射した光が遮られ、シール剤の内部まで光が到達せず硬化が不充分となるという問題があった。このようにシール剤の硬化が不充分となると、未硬化のシール剤成分が液晶中に溶出し、溶出したシール剤成分による硬化反応が液晶中において進行することで液晶汚染が発生するという問題があった。 By the way, in the present age when mobile devices with various liquid crystal panels such as mobile phones and portable game machines are widespread, downsizing of devices is the most demanded issue. As a method for reducing the size of the apparatus, there is a narrow frame of the liquid crystal display unit. For example, the position of the seal portion is arranged under the black matrix (hereinafter also referred to as a narrow frame design).
However, in the narrow frame design, the sealant is placed directly under the black matrix, so when the dripping method is used, the light irradiated when photocuring the sealant is blocked, and the light does not reach the inside of the sealant. There was a problem that the curing was insufficient. If the sealant is insufficiently cured in this manner, the uncured sealant component is eluted in the liquid crystal, and the curing reaction by the eluted sealant component proceeds in the liquid crystal, resulting in liquid crystal contamination. there were.
しかしながら、狭額縁設計ではシール剤がブラックマトリックスの直下に配置されるため、滴下工法を行うと、シール剤を光硬化させる際に照射した光が遮られ、シール剤の内部まで光が到達せず硬化が不充分となるという問題があった。このようにシール剤の硬化が不充分となると、未硬化のシール剤成分が液晶中に溶出し、溶出したシール剤成分による硬化反応が液晶中において進行することで液晶汚染が発生するという問題があった。 By the way, in the present age when mobile devices with various liquid crystal panels such as mobile phones and portable game machines are widespread, downsizing of devices is the most demanded issue. As a method for reducing the size of the apparatus, there is a narrow frame of the liquid crystal display unit. For example, the position of the seal portion is arranged under the black matrix (hereinafter also referred to as a narrow frame design).
However, in the narrow frame design, the sealant is placed directly under the black matrix, so when the dripping method is used, the light irradiated when photocuring the sealant is blocked, and the light does not reach the inside of the sealant. There was a problem that the curing was insufficient. If the sealant is insufficiently cured in this manner, the uncured sealant component is eluted in the liquid crystal, and the curing reaction by the eluted sealant component proceeds in the liquid crystal, resulting in liquid crystal contamination. there were.
本発明は、塗布性、透湿防止性、及び、接着性に優れ、かつ、液晶汚染を抑制できる液晶表示素子用シール剤を提供することを目的とする。また、本発明は、該液晶表示素子用シール剤を用いてなる上下導通材料及び液晶表示素子を提供することを目的とする。
An object of this invention is to provide the sealing compound for liquid crystal display elements which is excellent in applicability | paintability, moisture-permeable prevention property, and adhesiveness, and can suppress liquid-crystal contamination. Another object of the present invention is to provide a vertical conduction material and a liquid crystal display element using the sealing agent for a liquid crystal display element.
本発明は、硬化性樹脂と、ラジカル重合開始剤及び／又は熱硬化剤とを含有する液晶表示素子用シール剤であって、上記硬化性樹脂は、下記式（１）で表される化合物を含有し、液晶表示素子用シール剤中における上記式（１）で表される化合物の含有量が１重量％以上３０重量％未満である液晶表示素子用シール剤である。
The present invention is a sealing agent for a liquid crystal display element containing a curable resin and a radical polymerization initiator and / or a thermosetting agent, wherein the curable resin is a compound represented by the following formula (1). It is a sealing compound for liquid crystal display elements which is contained and the content of the compound represented by the formula (1) in the sealing compound for liquid crystal display elements is 1% by weight or more and less than 30% by weight.
式（１）中、Ｒ１は、水素又はメチル基であり、ｍ及びｎは、それぞれ０～６である。
以下に本発明を詳述する。 In the formula (1), R 1 is hydrogen or a methyl group, and m and n are each 0 to 6.
The present invention is described in detail below.
以下に本発明を詳述する。 In the formula (1), R 1 is hydrogen or a methyl group, and m and n are each 0 to 6.
The present invention is described in detail below.
本発明者は、硬化性樹脂として、接着性に優れ、かつ、液晶汚染性の低いビスフェノールＳ型エポキシ樹脂を配合することを検討した。しかしながら、ビスフェノールＳ型エポキシ樹脂を用いた場合でも、液晶汚染を抑制する効果が充分でなかったり、得られる液晶表示素子用シール剤が塗布性や透湿防止性に劣るものとなったりするという問題があった。
そこで本発明者らは、ビスフェノールＳ型構造を有する特定の化合物を特定量配合することにより、塗布性、透湿防止性、及び、接着性に優れ、かつ、液晶汚染を抑制できる液晶表示素子用シール剤を得ることができることを見出し、本発明を完成させるに至った。 The present inventor has studied the blending of a bisphenol S-type epoxy resin having excellent adhesion and low liquid crystal contamination as a curable resin. However, even when a bisphenol S-type epoxy resin is used, the effect of suppressing liquid crystal contamination is not sufficient, and the obtained sealing agent for liquid crystal display elements is inferior in applicability and moisture permeation prevention. was there.
Therefore, the present inventors have a liquid crystal display element that is excellent in coating property, moisture permeation prevention property, and adhesiveness and can suppress liquid crystal contamination by blending a specific amount of a specific compound having a bisphenol S-type structure. The present inventors have found that a sealant can be obtained and have completed the present invention.
そこで本発明者らは、ビスフェノールＳ型構造を有する特定の化合物を特定量配合することにより、塗布性、透湿防止性、及び、接着性に優れ、かつ、液晶汚染を抑制できる液晶表示素子用シール剤を得ることができることを見出し、本発明を完成させるに至った。 The present inventor has studied the blending of a bisphenol S-type epoxy resin having excellent adhesion and low liquid crystal contamination as a curable resin. However, even when a bisphenol S-type epoxy resin is used, the effect of suppressing liquid crystal contamination is not sufficient, and the obtained sealing agent for liquid crystal display elements is inferior in applicability and moisture permeation prevention. was there.
Therefore, the present inventors have a liquid crystal display element that is excellent in coating property, moisture permeation prevention property, and adhesiveness and can suppress liquid crystal contamination by blending a specific amount of a specific compound having a bisphenol S-type structure. The present inventors have found that a sealant can be obtained and have completed the present invention.
本発明の液晶表示素子用シール剤は、硬化性樹脂を含有する。
上記硬化性樹脂は、上記式（１）で表される化合物を含有する。上記式（１）で表される化合物を含有することにより、本発明の液晶表示素子用シール剤は、接着性及び液晶汚染を抑制する効果に優れるものとなる。 The sealing agent for liquid crystal display elements of this invention contains curable resin.
The said curable resin contains the compound represented by the said Formula (1). By containing the compound represented by the above formula (1), the sealing agent for liquid crystal display elements of the present invention is excellent in the effect of suppressing adhesiveness and liquid crystal contamination.
上記硬化性樹脂は、上記式（１）で表される化合物を含有する。上記式（１）で表される化合物を含有することにより、本発明の液晶表示素子用シール剤は、接着性及び液晶汚染を抑制する効果に優れるものとなる。 The sealing agent for liquid crystal display elements of this invention contains curable resin.
The said curable resin contains the compound represented by the said Formula (1). By containing the compound represented by the above formula (1), the sealing agent for liquid crystal display elements of the present invention is excellent in the effect of suppressing adhesiveness and liquid crystal contamination.
上記式（１）中、ｍ及びｎは、それぞれ０～６である。上記ｍ及びｎは、それぞれ１～６であることが好ましく、それぞれ１～３であることがより好ましい。
なお、上記式（１）及び後述する式（２）におけるｍ及びｎの値は、平均値である。また、ｍやｎが０である場合とは、ｍやｎが付されたエチレンオキサイド構造部分が結合手となることを意味する。 In the above formula (1), m and n are each 0 to 6. M and n are each preferably 1 to 6, and more preferably 1 to 3, respectively.
In addition, the value of m and n in the said Formula (1) and Formula (2) mentioned later is an average value. The case where m and n are 0 means that the ethylene oxide structure portion to which m or n is attached becomes a bond.
なお、上記式（１）及び後述する式（２）におけるｍ及びｎの値は、平均値である。また、ｍやｎが０である場合とは、ｍやｎが付されたエチレンオキサイド構造部分が結合手となることを意味する。 In the above formula (1), m and n are each 0 to 6. M and n are each preferably 1 to 6, and more preferably 1 to 3, respectively.
In addition, the value of m and n in the said Formula (1) and Formula (2) mentioned later is an average value. The case where m and n are 0 means that the ethylene oxide structure portion to which m or n is attached becomes a bond.
上記式（１）で表される化合物を製造する方法としては、例えば、ビスフェノールＳ又はエチレンオキサイド付加ビスフェノールＳとエピクロルヒドリンとを反応させることにより、下記式（２）で表される化合物を製造し、得られた式（２）で表される化合物の一方のエポキシ基を（メタ）アクリル酸と反応させる方法等が挙げられる。
なお、本明細書において上記「（メタ）アクリル」とは、アクリル又はメタクリルを意味する。 As a method for producing the compound represented by the above formula (1), for example, by reacting bisphenol S or ethylene oxide-added bisphenol S with epichlorohydrin, a compound represented by the following formula (2) is produced, Examples thereof include a method of reacting one epoxy group of the obtained compound represented by the formula (2) with (meth) acrylic acid.
In the present specification, the “(meth) acryl” means acryl or methacryl.
なお、本明細書において上記「（メタ）アクリル」とは、アクリル又はメタクリルを意味する。 As a method for producing the compound represented by the above formula (1), for example, by reacting bisphenol S or ethylene oxide-added bisphenol S with epichlorohydrin, a compound represented by the following formula (2) is produced, Examples thereof include a method of reacting one epoxy group of the obtained compound represented by the formula (2) with (meth) acrylic acid.
In the present specification, the “(meth) acryl” means acryl or methacryl.
式（２）中、ｍ及びｎは、それぞれ０～６である。
In the formula (2), m and n are each 0 to 6.
本発明の液晶表示素子用シール剤中における上記式（１）で表される化合物の含有量は、１重量％以上３０重量％未満である。上記式（１）で表される化合物の含有量が１重量％未満であると、得られる液晶表示素子用シール剤が接着性に劣るものとなり易くなる。上記式（１）で表される化合物の含有量が３０重量％以上であると、得られる表示素子用封止剤が塗布性や透湿防止性に劣るものとなる。上記式（１）で表される化合物の含有量の好ましい下限は５重量％、好ましい上限は２５重量％、より好ましい下限は１０重量％、より好ましい上限は２０重量％、更に好ましい上限は１５重量％である。
The content of the compound represented by the above formula (1) in the sealant for liquid crystal display elements of the present invention is 1% by weight or more and less than 30% by weight. When the content of the compound represented by the above formula (1) is less than 1% by weight, the obtained sealing agent for liquid crystal display elements tends to be inferior in adhesiveness. When the content of the compound represented by the above formula (1) is 30% by weight or more, the obtained sealant for a display element is inferior in applicability and moisture permeability prevention. The preferable lower limit of the content of the compound represented by the formula (1) is 5% by weight, the preferable upper limit is 25% by weight, the more preferable lower limit is 10% by weight, the more preferable upper limit is 20% by weight, and the further preferable upper limit is 15% by weight. %.
上記硬化性樹脂は、上記式（１）で表される化合物に加えて、その他の硬化性樹脂を含有することが好ましい。
上記その他の硬化性樹脂としては、例えば、上記式（１）で表される化合物以外の、（メタ）アクリル化合物やエポキシ化合物等が挙げられる。なかでも、上記（メタ）アクリル化合物として後述するエポキシ（メタ）アクリレートを含有することが好ましく、レゾルシノール型エポキシ（メタ）アクリレートを含有することがより好ましい。
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し、「エポキシ（メタ）アクリレート」とは、エポキシ化合物中の全てのエポキシ基を（メタ）アクリル酸と反応させた化合物のことを表す。 The curable resin preferably contains other curable resin in addition to the compound represented by the formula (1).
Examples of the other curable resin include (meth) acrylic compounds and epoxy compounds other than the compound represented by the above formula (1). Especially, it is preferable to contain the epoxy (meth) acrylate mentioned later as the said (meth) acrylic compound, and it is more preferable to contain resorcinol type | mold epoxy (meth) acrylate.
In the present specification, the above “(meth) acrylate” means acrylate or methacrylate, and “epoxy (meth) acrylate” means that all epoxy groups in the epoxy compound are reacted with (meth) acrylic acid. Represents a compound.
上記その他の硬化性樹脂としては、例えば、上記式（１）で表される化合物以外の、（メタ）アクリル化合物やエポキシ化合物等が挙げられる。なかでも、上記（メタ）アクリル化合物として後述するエポキシ（メタ）アクリレートを含有することが好ましく、レゾルシノール型エポキシ（メタ）アクリレートを含有することがより好ましい。
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し、「エポキシ（メタ）アクリレート」とは、エポキシ化合物中の全てのエポキシ基を（メタ）アクリル酸と反応させた化合物のことを表す。 The curable resin preferably contains other curable resin in addition to the compound represented by the formula (1).
Examples of the other curable resin include (meth) acrylic compounds and epoxy compounds other than the compound represented by the above formula (1). Especially, it is preferable to contain the epoxy (meth) acrylate mentioned later as the said (meth) acrylic compound, and it is more preferable to contain resorcinol type | mold epoxy (meth) acrylate.
In the present specification, the above “(meth) acrylate” means acrylate or methacrylate, and “epoxy (meth) acrylate” means that all epoxy groups in the epoxy compound are reacted with (meth) acrylic acid. Represents a compound.
上記その他の硬化性樹脂である（メタ）アクリル化合物としては、例えば、（メタ）アクリル酸とエポキシ化合物とを反応させることにより得られるエポキシ（メタ）アクリレート、（メタ）アクリル酸に水酸基を有する化合物を反応させることにより得られる（メタ）アクリル酸エステル化合物、イソシアネート化合物に水酸基を有する（メタ）アクリル酸誘導体を反応させることにより得られるウレタン（メタ）アクリレート等が挙げられ、上述したように、エポキシ（メタ）アクリレートが好ましい。また、上記（メタ）アクリル化合物は、反応性の高さから分子中に（メタ）アクリロイル基を２個以上有するものが好ましい。
Examples of the (meth) acrylic compound that is the other curable resin include epoxy (meth) acrylate obtained by reacting (meth) acrylic acid and an epoxy compound, and a compound having a hydroxyl group in (meth) acrylic acid. (Meth) acrylic acid ester compounds obtained by reacting urethane compounds, urethane (meth) acrylates obtained by reacting isocyanate compounds with (meth) acrylic acid derivatives having a hydroxyl group, etc. (Meth) acrylate is preferred. The (meth) acrylic compound preferably has two or more (meth) acryloyl groups in the molecule because of its high reactivity.
上記エポキシ（メタ）アクリレートとしては、例えば、エポキシ化合物と（メタ）アクリル酸とを、常法に従って塩基性触媒の存在下で反応することにより得られるもの等が挙げられる。
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.
上記エポキシ（メタ）アクリレートを合成するための原料となるエポキシ化合物としては、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＥ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、２，２’－ジアリルビスフェノールＡ型エポキシ樹脂、水添ビスフェノール型エポキシ樹脂、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、レゾルシノール型エポキシ樹脂、ビフェニル型エポキシ樹脂、スルフィド型エポキシ樹脂、ジフェニルエーテル型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、ナフタレン型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、オルトクレゾールノボラック型エポキシ樹脂、ジシクロペンタジエンノボラック型エポキシ樹脂、ビフェニルノボラック型エポキシ樹脂、ナフタレンフェノールノボラック型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、アルキルポリオール型エポキシ樹脂、ゴム変性型エポキシ樹脂、グリシジルエステル化合物等が挙げられる。なかでも、レゾルシノール型エポキシ樹脂が好ましい。
Examples of the epoxy compound used as a raw material for synthesizing the epoxy (meth) acrylate include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E 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 type epoxy resin, orthocresol novolac type epoxy resin, dicyclopentadiene novolac type epoxy resin, biphenyl Novolak type epoxy resins, naphthalene phenol novolac-type epoxy resin, glycidyl amine type epoxy resin, alkyl polyol type epoxy resin, rubber-modified epoxy resins, glycidyl ester compounds. Among these, a resorcinol type epoxy resin is preferable.
上記ビスフェノール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、ｊＥＲ８２８ＥＬ、ｊＥＲ１００４（いずれも三菱化学社製）、エピクロン８５０ＣＲＰ（ＤＩＣ社製）等が挙げられる。
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Ｅ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、Ｒ７１０（プリンテック社製）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。 As what is marketed among the said bisphenol A type epoxy resins, jER828EL, jER1004 (all are the Mitsubishi Chemical company make), Epiklon 850CRP (made by DIC company), etc. are mentioned, for example.
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 E-type epoxy resins, R710 (made by Printec Co., Ltd.) 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.).
As what is marketed among the said hydrogenated bisphenol type | mold epoxy resins, Epicron EXA7015 (made by DIC Corporation) etc. are mentioned, for example.
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 Corporation).
Examples of commercially available biphenyl type epoxy resins include jER YX-4000H (manufactured by Mitsubishi Chemical Corporation).
Examples of commercially available sulfide type epoxy resins include YSLV-50TE (manufactured by Nippon Steel & Sumikin Chemical 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).
As what is marketed among the said dicyclopentadiene novolak-type epoxy resins, epiclone HP7200 (made by DIC) etc. are mentioned, for example.
Examples of commercially available biphenyl novolac epoxy resins include NC-3000P (manufactured by Nippon Kayaku Co., Ltd.).
Examples of commercially available naphthalene phenol 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), 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).
Other commercially available epoxy compounds include, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by NS Also, Mitsubishi Chemical Corporation), EXA-7120 (DIC Corporation), TEPIC (Nissan Chemical Corporation) and the like.
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Ｅ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、Ｒ７１０（プリンテック社製）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。 As what is marketed among the said bisphenol A type epoxy resins, jER828EL, jER1004 (all are the Mitsubishi Chemical company make), Epiklon 850CRP (made by DIC company), etc. are mentioned, for example.
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 E-type epoxy resins, R710 (made by Printec Co., Ltd.) 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.).
As what is marketed among the said hydrogenated bisphenol type | mold epoxy resins, Epicron EXA7015 (made by DIC Corporation) etc. are mentioned, for example.
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 Corporation).
Examples of commercially available biphenyl type epoxy resins include jER YX-4000H (manufactured by Mitsubishi Chemical Corporation).
Examples of commercially available sulfide type epoxy resins include YSLV-50TE (manufactured by Nippon Steel & Sumikin Chemical 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).
As what is marketed among the said dicyclopentadiene novolak-type epoxy resins, epiclone HP7200 (made by DIC) etc. are mentioned, for example.
Examples of commercially available biphenyl novolac epoxy resins include NC-3000P (manufactured by Nippon Kayaku Co., Ltd.).
Examples of commercially available naphthalene phenol 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), 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).
Other commercially available epoxy compounds include, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by NS Also, Mitsubishi Chemical Corporation), EXA-7120 (DIC Corporation), TEPIC (Nissan Chemical Corporation) and the like.
上記エポキシ（メタ）アクリレートのうち市販されているものとしては、例えば、ＥＢＥＣＲＹＬ８６０、ＥＢＥＣＲＹＬ３２００、ＥＢＥＣＲＹＬ３２０１、ＥＢＥＣＲＹＬ３４１２、ＥＢＥＣＲＹＬ３６００、ＥＢＥＣＲＹＬ３７００、ＥＢＥＣＲＹＬ３７０１、ＥＢＥＣＲＹＬ３７０２、ＥＢＥＣＲＹＬ３７０３、ＥＢＥＣＲＹＬ３７０８、ＥＢＥＣＲＹＬ３８００、ＥＢＥＣＲＹＬ６０４０、ＥＢＥＣＲＹＬＲＤＸ６３１８２（いずれもダイセル・オルネクス社製）、ＥＡ－１０１０、ＥＡ－１０２０、ＥＡ－５３２３、ＥＡ－５５２０、ＥＡ－ＣＨＤ、ＥＭＡ－１０２０（いずれも新中村化学工業社製）、エポキシエステルＭ－６００Ａ、エポキシエステル４０ＥＭ、エポキシエステル７０ＰＡ、エポキシエステル２００ＰＡ、エポキシエステル８０ＭＦＡ、エポキシエステル３００２Ｍ、エポキシエステル３００２Ａ、エポキシエステル１６００Ａ、エポキシエステル３０００Ｍ、エポキシエステル３０００Ａ、エポキシエステル２００ＥＡ、エポキシエステル４００ＥＡ（いずれも共栄社化学社製）、デナコールアクリレートＤＡ－１４１、デナコールアクリレートＤＡ－３１４、デナコールアクリレートＤＡ－９１１（いずれもナガセケムテックス社製）等が挙げられる。
Examples of commercially available epoxy (meth) acrylates include EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRY3702, EBECRY3703, EBECRYL3701, EBECRYL3701. 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 Xyester 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 Corporation) and the like.
上記（メタ）アクリル酸エステル化合物のうち単官能のものとしては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ｎ－オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、イソノニル（メタ）アクリレート、イソデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、イソミリスチル（メタ）アクリレート、ステアリル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ビシクロペンテニル（メタ）アクリレート、ベンジル（メタ）アクリレート、２－メトキシエチル（メタ）アクリレート、２－エトキシエチル（メタ）アクリレート、２－ブトキシエチル（メタ）アクリレート、２－フェノキシエチル（メタ）アクリレート、メトキシエチレングリコール（メタ）アクリレート、メトキシポリエチレングリコール（メタ）アクリレート、フェノキシジエチレングリコール（メタ）アクリレート、フェノキシポリエチレングリコール（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、エチルカルビトール（メタ）アクリレート、２，２，２－トリフルオロエチル（メタ）アクリレート、２，２，３，３－テトラフルオロプロピル（メタ）アクリレート、１Ｈ，１Ｈ，５Ｈ－オクタフルオロペンチル（メタ）アクリレート、イミド（メタ）アクリレート、ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート、２－（メタ）アクリロイロキシエチルコハク酸、２－（メタ）アクリロイロキシエチルヘキサヒドロフタル酸、２－（メタ）アクリロイロキシエチル２－ヒドロキシプロピルフタレート、２－（メタ）アクリロイロキシエチルホスフェート、グリシジル（メタ）アクリレート等が挙げられる。
Examples of the monofunctional compounds among the (meth) acrylic acid ester compounds include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. , T-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, iso Myristyl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxy Til (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, bicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2 -Butoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, methoxyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, tetrahydrofur Furyl (meth) acrylate, ethyl carbitol (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, imide (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) ) Acrylate, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl 2-hydroxypropyl phthalate, 2- (meth) acrylic Examples include leuoxyethyl phosphate and glycidyl (meth) acrylate.
また、上記（メタ）アクリル酸エステル化合物のうち２官能のものとしては、例えば、１，３－ブタンジオールジ（メタ）アクリレート、１，４－ブタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、１，９－ノナンジオールジ（メタ）アクリレート、１，１０－デカンジオールジ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、２－ｎ－ブチル－２－エチル－１，３－プロパンジオールジ（メタ）アクリレート、ジプロピレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、エチレンオキシド付加ビスフェノールＡジ（メタ）アクリレート、プロピレンオキシド付加ビスフェノールＡジ（メタ）アクリレート、エチレンオキシド付加ビスフェノールＦジ（メタ）アクリレート、ジメチロールジシクロペンタジエニルジ（メタ）アクリレート、エチレンオキシド変性イソシアヌル酸ジ（メタ）アクリレート、２－ヒドロキシ－３－（メタ）アクリロイロキシプロピル（メタ）アクリレート、カーボネートジオールジ（メタ）アクリレート、ポリエーテルジオールジ（メタ）アクリレート、ポリエステルジオールジ（メタ）アクリレート、ポリカプロラクトンジオールジ（メタ）アクリレート、ポリブタジエンジオールジ（メタ）アクリレート等が挙げられる。
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. Diol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (Meth) acrylate, polyethylene glycol di (meth) acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) ) Acrylate, poly Lopylene glycol di (meth) acrylate, neopentyl 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, dimethylol Dicyclopentadienyl di (meth) acrylate, ethylene oxide modified isocyanuric acid di (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, carbonate diol di (meth) acrylate, polyether diol Di (meth) acrylate, polyester diol di (meth) acrylate, polycaprolactone diol di (meth) acrylate, polybutadiene diol (Meth) acrylate.
また、上記（メタ）アクリル酸エステル化合物のうち３官能以上のものとしては、例えば、トリメチロールプロパントリ（メタ）アクリレート、エチレンオキシド付加トリメチロールプロパントリ（メタ）アクリレート、プロピレンオキシド付加トリメチロールプロパントリ（メタ）アクリレート、エチレンオキシド付加イソシアヌル酸トリ（メタ）アクリレート、グリセリントリ（メタ）アクリレート、プロピレンオキシド付加グリセリントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、トリス（メタ）アクリロイルオキシエチルフォスフェート、ジトリメチロールプロパンテトラ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート等が挙げられる。
Further, among the above (meth) acrylic acid ester compounds, 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, ethylene oxide-added isocyanuric acid tri (meth) acrylate, glycerin tri (meth) acrylate, propylene oxide-added glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, ditri Methylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate DOO, dipentaerythritol hexa (meth) acrylate.
上記ウレタン（メタ）アクリレートとしては、例えば、２つのイソシアネート基を有するイソシアネート化合物１当量に対して水酸基を有する（メタ）アクリル酸誘導体２当量を、触媒量のスズ系化合物存在下で反応させることによって得ることができる。
As the urethane (meth) acrylate, for example, by reacting 2 equivalents of a (meth) acrylic acid derivative having a hydroxyl group with 1 equivalent of an isocyanate compound having two isocyanate groups in the presence of a catalytic amount of a tin-based compound. Obtainable.
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としては、例えば、イソホロンジイソシアネート、２，４－トリレンジイソシアネート、２，６－トリレンジイソシアネート、ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、ジフェニルメタン－４，４’－ジイソシアネート（ＭＤＩ）、水添ＭＤＩ、ポリメリックＭＤＩ、１，５－ナフタレンジイソシアネート、ノルボルナンジイソシアネート、トリジンジイソシアネート、キシリレンジイソシアネート（ＸＤＩ）、水添ＸＤＩ、リジンジイソシアネート、トリフェニルメタントリイソシアネート、トリス（イソシアネートフェニル）チオフォスフェート、テトラメチルキシレンジイソシアネート、１，６，１１－ウンデカントリイソシアネート等が挙げられる。
Examples of the isocyanate compound used as the raw material for the urethane (meth) acrylate include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and 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, tetramethylxylene diisocyanate, 1,6,11-undecanetriiso Aneto and the like.
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としては、例えば、エチレングリコール、プロピレングリコール、グリセリン、ソルビトール、トリメチロールプロパン、カーボネートジオール、ポリエーテルジオール、ポリエステルジオール、ポリカプロラクトンジオール等のポリオールと過剰のイソシアネート化合物との反応により得られる鎖延長されたイソシアネート化合物も使用することができる。
Examples of the isocyanate compound that is a raw material for the urethane (meth) acrylate include, for example, polyols such as ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, and polycaprolactone diol. Chain-extended isocyanate compounds obtained by reaction with excess isocyanate compounds can also be used.
上記ウレタン（メタ）アクリレートの原料となる、水酸基を有する（メタ）アクリル酸誘導体としては、例えば、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート等のヒドロキシアルキル（メタ）アクリレートや、エチレングリコール、プロピレングリコール、１，３－プロパンジオール、１，３－ブタンジオール、１，４－ブタンジオール、ポリエチレングリコール等の二価のアルコールのモノ（メタ）アクリレートや、トリメチロールエタン、トリメチロールプロパン、グリセリン等の三価のアルコールのモノ（メタ）アクリレート又はジ（メタ）アクリレートや、ビスフェノールＡ型エポキシアクリレート等のエポキシ（メタ）アクリレート等が挙げられる。
Examples of the (meth) acrylic acid derivative having a hydroxyl group as a raw material for the urethane (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth). Hydroxyalkyl (meth) acrylates such as acrylate, 4-hydroxybutyl (meth) acrylate, ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, polyethylene glycol, etc. Mono (meth) acrylates of dihydric alcohols, mono (meth) acrylates or di (meth) acrylates of trivalent alcohols such as trimethylolethane, trimethylolpropane and glycerin, and bisphenol A type epoxy alcohol Epoxy (meth) acrylate of rate, and the like.
上記ウレタン（メタ）アクリレートのうち市販されているものとしては、例えば、Ｍ－１１００、Ｍ－１２００、Ｍ－１２１０、Ｍ－１６００（いずれも東亞合成社製）、ＥＢＥＣＲＹＬ２１０、ＥＢＥＣＲＹＬ２２０、ＥＢＥＣＲＹＬ２３０、ＥＢＥＣＲＹＬ２７０、ＥＢＥＣＲＹＬ１２９０、ＥＢＥＣＲＹＬ２２２０、ＥＢＥＣＲＹＬ４８２７、ＥＢＥＣＲＹＬ４８４２、ＥＢＥＣＲＹＬ４８５８、ＥＢＥＣＲＹＬ５１２９、ＥＢＥＣＲＹＬ６７００、ＥＢＥＣＲＹＬ８４０２、ＥＢＥＣＲＹＬ８８０３、ＥＢＥＣＲＹＬ８８０４、ＥＢＥＣＲＹＬ８８０７、ＥＢＥＣＲＹＬ９２６０（いずれもダイセル・オルネクス社製）、アートレジンＵＮ－３３０、アートレジンＳＨ－５００Ｂ、アートレジンＵＮ－１２００ＴＰＫ、アートレジンＵＮ－１２５５、アートレジンＵＮ－３３２０ＨＢ、アートレジンＵＮ－７１００、アートレジンＵＮ－９０００Ａ、アートレジンＵＮ－９０００Ｈ（いずれも根上工業社製）、Ｕ－２ＨＡ、Ｕ－２ＰＨＡ、Ｕ－３ＨＡ、Ｕ－４ＨＡ、Ｕ－６Ｈ、Ｕ－６ＨＡ、Ｕ－６ＬＰＡ、Ｕ－１０Ｈ、Ｕ－１５ＨＡ、Ｕ－１０８、Ｕ－１０８Ａ、Ｕ－１２２Ａ、Ｕ－１２２Ｐ、Ｕ－３２４Ａ、Ｕ－３４０Ａ、Ｕ－３４０Ｐ、Ｕ－１０８４Ａ、Ｕ－２０６１ＢＡ、ＵＡ－３４０Ｐ、ＵＡ－４０００、ＵＡ－４１００、ＵＡ－４２００、ＵＡ－４４００、ＵＡ－５２０１Ｐ、ＵＡ－７１００、ＵＡ－７２００、ＵＡ－Ｗ２Ａ（いずれも新中村化学工業社製）、ＡＨ－６００、ＡＩ－６００、ＡＴ－６００、ＵＡ－１０１Ｉ、ＵＡ－１０１Ｔ、ＵＡ－３０６Ｈ、ＵＡ－３０６Ｉ、ＵＡ－３０６Ｔ（いずれも共栄社化学社製）等が挙げられる。
Examples of commercially available urethane (meth) acrylates include M-1100, M-1200, M-1210, M-1600 (all manufactured by Toagosei Co., Ltd.), EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, EBECRYL1290, EBECRYL2220, EBECRYL4827, EBECRYL4842, EBECRYL4858, EBECRYL5129, EBECRYL6700, EBECRYL8402, EBECRYL8803, EBECRYL8804, EBECRYL8804 , Art resin N-1255, Art Resin UN-3320HB, Art Resin UN-7100, Art Resin UN-9000A, Art Resin UN-9000H (all manufactured by Negami Industrial Co., Ltd.), U-2HA, U-2PHA, U-3HA, U- 4HA, U-6H, U-6HA, U-6LPA, U-10H, U-15HA, U-108, U-108A, U-122A, U-122P, U-324A, U-340A, U-340P, U-1084A, U-2061BA, UA-340P, UA-4000, UA-4100, UA-4200, UA-4400, UA-5201P, UA-7100, UA-7200, UA-W2A (all Shin-Nakamura Chemical Industries AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, A-306I, UA-306T (all manufactured by Kyoeisha Chemical Co., Ltd.).
上記その他の硬化性樹脂であるエポキシ化合物としては、例えば、上記エポキシ（メタ）アクリレートを合成するための原料となるエポキシ化合物や、式（１）で表される化合物以外の部分（メタ）アクリル変性エポキシ樹脂等が挙げられる。
なお、本明細書において上記部分（メタ）アクリル変性エポキシ樹脂とは、１分子中にエポキシ基と（メタ）アクリロイル基とをそれぞれ１つ以上有する化合物を意味し、例えば、２つ以上のエポキシ化合物の一部分のエポキシ基を（メタ）アクリル酸と反応させることによって得ることができる。 Examples of the epoxy compound which is the other curable resin include, for example, an epoxy compound which is a raw material for synthesizing the epoxy (meth) acrylate and a partial (meth) acryl modification other than the compound represented by the formula (1) An epoxy resin etc. are mentioned.
In the present specification, the partial (meth) acryl-modified epoxy resin means a compound having one or more epoxy groups and (meth) acryloyl groups in one molecule, for example, two or more epoxy compounds. Can be obtained by reacting a part of the epoxy group with (meth) acrylic acid.
なお、本明細書において上記部分（メタ）アクリル変性エポキシ樹脂とは、１分子中にエポキシ基と（メタ）アクリロイル基とをそれぞれ１つ以上有する化合物を意味し、例えば、２つ以上のエポキシ化合物の一部分のエポキシ基を（メタ）アクリル酸と反応させることによって得ることができる。 Examples of the epoxy compound which is the other curable resin include, for example, an epoxy compound which is a raw material for synthesizing the epoxy (meth) acrylate and a partial (meth) acryl modification other than the compound represented by the formula (1) An epoxy resin etc. are mentioned.
In the present specification, the partial (meth) acryl-modified epoxy resin means a compound having one or more epoxy groups and (meth) acryloyl groups in one molecule, for example, two or more epoxy compounds. Can be obtained by reacting a part of the epoxy group with (meth) acrylic acid.
上記部分（メタ）アクリル変性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、ＵＶＡＣＵＲＥ１５６１（ダイセル・オルネクス社製）等が挙げられる。
Examples of commercially available partial (meth) acrylic-modified epoxy resins include UVACURE 1561 (manufactured by Daicel Ornex).
上記その他の硬化性樹脂を含有する場合、硬化性樹脂全体１００重量部中における上記式（１）で表される化合物の含有量の好ましい下限は５重量部、好ましい上限は２５重量部である。上記式（１）で表される化合物の含有量がこの範囲であることにより、得られる液晶表示素子用シール剤が、塗布性、接着性、透湿防止性、及び、液晶汚染を抑制する効果により優れるものとなる。上記式（１）で表される化合物の含有量のより好ましい下限は１０重量部、より好ましい上限は２０重量部である。
When it contains the said other curable resin, the minimum with preferable content of the compound represented by the said Formula (1) in 100 weight part of curable resin whole is 5 weight part, and a preferable upper limit is 25 weight part. When the content of the compound represented by the above formula (1) is within this range, the obtained sealing agent for a liquid crystal display element has an effect of suppressing applicability, adhesiveness, moisture permeation prevention, and liquid crystal contamination. It will be better. The minimum with more preferable content of the compound represented by said Formula (1) is 10 weight part, and a more preferable upper limit is 20 weight part.
本発明の液晶表示素子用シール剤は、硬化性樹脂中の（メタ）アクリロイル基とエポキシ基との含有割合をモル比で５０：５０～９５：５とすることが好ましい。
In the sealing agent for liquid crystal display elements of the present invention, the content ratio of the (meth) acryloyl group and the epoxy group in the curable resin is preferably 50:50 to 95: 5.
本発明の液晶表示素子用シール剤は、ラジカル重合開始剤及び／又は熱硬化剤を含有する。
The sealing agent for liquid crystal display elements of this invention contains a radical polymerization initiator and / or a thermosetting agent.
上記ラジカル重合開始剤としては、光照射によりラジカルを発生する光ラジカル重合開始剤や、加熱によりラジカルを発生する熱ラジカル重合開始剤等が挙げられる。
Examples of the radical polymerization initiator include a photo radical polymerization initiator that generates radicals by light irradiation, a thermal radical polymerization initiator that generates radicals by heating, and the like.
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、チオキサントン系化合物等が挙げられる。
Examples of the photo radical polymerization initiator include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, thioxanthone compounds, and the like.
上記光ラジカル重合開始剤のうち市販されているものとしては、例えば、ＩＲＧＡＣＵＲＥ １８４、ＩＲＧＡＣＵＲＥ ３６９、ＩＲＧＡＣＵＲＥ ３７９、ＩＲＧＡＣＵＲＥ ６５１、ＩＲＧＡＣＵＲＥ ８１９、ＩＲＧＡＣＵＲＥ ９０７、ＩＲＧＡＣＵＲＥ ２９５９、ＩＲＧＡＣＵＲＥ ＯＸＥ０１、ルシリンＴＰＯ（いずれもＢＡＳＦ社製）、ＮＣＩ－９３０（ＡＤＥＫＡ社製）、ＳＰＥＥＤＣＵＲＥ ＥＭＫ（日本シーベルヘグナー社製）、ベンソインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル（いずれも東京化成工業社製）等が挙げられる。
Examples of commercially available photo radical polymerization initiators include IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, all manufactured by Rusilin TPO ), NCI-930 (manufactured by ADEKA), SPEEDCURE EMK (manufactured by Nippon Sebel Hegner), benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether (all manufactured by Tokyo Chemical Industry Co., Ltd.) and the like.
上記熱ラジカル重合開始剤としては、例えば、アゾ化合物、有機過酸化物等からなるものが挙げられる。なかでも、高分子アゾ化合物からなる開始剤（以下、「高分子アゾ開始剤」ともいう）が好ましい。
なお、本明細書において高分子アゾ化合物とは、アゾ基を有し、熱によって（メタ）アクリロイル基を硬化させることができるラジカルを生成する、数平均分子量が３００以上の化合物を意味する。 As said thermal radical polymerization initiator, what consists of an azo compound, an organic peroxide, etc. is mentioned, for example. Among these, an initiator made of a polymer azo compound (hereinafter also referred to as “polymer azo initiator”) is preferable.
In the present specification, the polymer azo compound means a compound having an azo group and generating a radical capable of curing a (meth) acryloyl group by heat and having a number average molecular weight of 300 or more.
なお、本明細書において高分子アゾ化合物とは、アゾ基を有し、熱によって（メタ）アクリロイル基を硬化させることができるラジカルを生成する、数平均分子量が３００以上の化合物を意味する。 As said thermal radical polymerization initiator, what consists of an azo compound, an organic peroxide, etc. is mentioned, for example. Among these, an initiator made of a polymer azo compound (hereinafter also referred to as “polymer azo initiator”) is preferable.
In the present specification, the polymer azo compound means a compound having an azo group and generating a radical capable of curing a (meth) acryloyl group by heat and having a number average molecular weight of 300 or more.
上記高分子アゾ開始剤の数平均分子量の好ましい下限は１０００、好ましい上限は３０万である。上記高分子アゾ開始剤の数平均分子量がこの範囲であることにより、液晶汚染を抑制しつつ、硬化性樹脂と容易に混合することができる。上記高分子アゾ開始剤の数平均分子量のより好ましい下限は５０００、より好ましい上限は１０万であり、更に好ましい下限は１万、更に好ましい上限は９万である。
なお、本明細書において、上記数平均分子量は、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数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。 The preferable lower limit of the number average molecular weight of the polymeric azo initiator is 1000, and the preferable upper limit is 300,000. When the number average molecular weight of the polymeric azo initiator is within this range, it can be easily mixed with a curable resin while suppressing liquid crystal contamination. The more preferable lower limit of the number average molecular weight of the polymeric azo initiator is 5000, the more preferable upper limit is 100,000, the still more preferable lower limit is 10,000, and the still more preferable upper limit is 90,000.
In addition, in this specification, the said number average molecular weight is a value calculated | required by polystyrene conversion by measuring with gel permeation chromatography (GPC). Examples of the column for measuring the number average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko KK).
なお、本明細書において、上記数平均分子量は、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数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。 The preferable lower limit of the number average molecular weight of the polymeric azo initiator is 1000, and the preferable upper limit is 300,000. When the number average molecular weight of the polymeric azo initiator is within this range, it can be easily mixed with a curable resin while suppressing liquid crystal contamination. The more preferable lower limit of the number average molecular weight of the polymeric azo initiator is 5000, the more preferable upper limit is 100,000, the still more preferable lower limit is 10,000, and the still more preferable upper limit is 90,000.
In addition, in this specification, the said number average molecular weight is a value calculated | required by polystyrene conversion by measuring with gel permeation chromatography (GPC). Examples of the column for measuring the number average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko KK).
上記高分子アゾ開始剤としては、例えば、アゾ基を介してポリアルキレンオキサイドやポリジメチルシロキサン等のユニットが複数結合した構造を有するものが挙げられる。
上記アゾ基を介してポリアルキレンオキサイド等のユニットが複数結合した構造を有する高分子アゾ開始剤としては、ポリエチレンオキサイド構造を有するものが好ましい。このような高分子アゾ開始剤としては、例えば、４，４’－アゾビス（４－シアノペンタン酸）とポリアルキレングリコールの重縮合物や、４，４’－アゾビス（４－シアノペンタン酸）と末端アミノ基を有するポリジメチルシロキサンの重縮合物等が挙げられ、具体的には例えば、ＶＰＥ－０２０１、ＶＰＥ－０４０１、ＶＰＥ－０６０１、ＶＰＳ－０５０１、ＶＰＳ－１００１（いずれも和光純薬工業社製）等が挙げられる。
また、高分子ではないアゾ化合物の例としては、Ｖ－６５、Ｖ－５０１（いずれも和光純薬工業社製）等が挙げられる。 Examples of the polymer azo initiator include those having a structure in which a plurality of units such as polyalkylene oxide and polydimethylsiloxane are bonded via an azo group.
As the polymer azo initiator having a structure in which a plurality of units such as polyalkylene oxide are bonded via the azo group, those having a polyethylene oxide structure are preferable. Examples of such a polymer azo initiator include polycondensates of 4,4′-azobis (4-cyanopentanoic acid) and polyalkylene glycol, and 4,4′-azobis (4-cyanopentanoic acid) Examples thereof include polycondensates of polydimethylsiloxane having a terminal amino group, such as VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 (all of which are Wako Pure Chemical Industries, Ltd.) Manufactured) and the like.
Examples of azo compounds that are not polymers include V-65 and V-501 (both manufactured by Wako Pure Chemical Industries, Ltd.).
上記アゾ基を介してポリアルキレンオキサイド等のユニットが複数結合した構造を有する高分子アゾ開始剤としては、ポリエチレンオキサイド構造を有するものが好ましい。このような高分子アゾ開始剤としては、例えば、４，４’－アゾビス（４－シアノペンタン酸）とポリアルキレングリコールの重縮合物や、４，４’－アゾビス（４－シアノペンタン酸）と末端アミノ基を有するポリジメチルシロキサンの重縮合物等が挙げられ、具体的には例えば、ＶＰＥ－０２０１、ＶＰＥ－０４０１、ＶＰＥ－０６０１、ＶＰＳ－０５０１、ＶＰＳ－１００１（いずれも和光純薬工業社製）等が挙げられる。
また、高分子ではないアゾ化合物の例としては、Ｖ－６５、Ｖ－５０１（いずれも和光純薬工業社製）等が挙げられる。 Examples of the polymer azo initiator include those having a structure in which a plurality of units such as polyalkylene oxide and polydimethylsiloxane are bonded via an azo group.
As the polymer azo initiator having a structure in which a plurality of units such as polyalkylene oxide are bonded via the azo group, those having a polyethylene oxide structure are preferable. Examples of such a polymer azo initiator include polycondensates of 4,4′-azobis (4-cyanopentanoic acid) and polyalkylene glycol, and 4,4′-azobis (4-cyanopentanoic acid) Examples thereof include polycondensates of polydimethylsiloxane having a terminal amino group, such as VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 (all of which are Wako Pure Chemical Industries, Ltd.) Manufactured) and the like.
Examples of azo compounds that are not polymers include V-65 and V-501 (both manufactured by Wako Pure Chemical Industries, Ltd.).
上記有機過酸化物としては、例えば、ケトンパーオキサイド、パーオキシケタール、ハイドロパーオキサイド、ジアルキルパーオキサイド、パーオキシエステル、ジアシルパーオキサイド、パーオキシジカーボネート等が挙げられる。
Examples of the organic peroxide include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, peroxyester, diacyl peroxide, and peroxydicarbonate.
上記ラジカル重合開始剤の含有量は、硬化性樹脂１００重量部に対して、好ましい下限が０．０１重量部、好ましい上限が１０重量部である。上記ラジカル重合開始剤の含有量がこの範囲であることにより、得られる液晶表示素子用シール剤が液晶汚染を抑制しつつ、保存安定性や硬化性により優れるものとなる。上記ラジカル重合開始剤の含有量のより好ましい下限は０．１重量部、より好ましい上限は５重量部である。
The content of the 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 curable resin. When the content of the radical polymerization initiator is within this range, the obtained sealing agent for liquid crystal display elements is excellent in storage stability and curability while suppressing liquid crystal contamination. The minimum with more preferable content of the said radical polymerization initiator is 0.1 weight part, and a more preferable upper limit is 5 weight part.
上記熱硬化剤としては、例えば、有機酸ヒドラジド、イミダゾール誘導体、アミン化合物、多価フェノール系化合物、酸無水物等が挙げられる。なかでも、有機酸ヒドラジドが好適に用いられる。
Examples of the thermosetting agent include organic acid hydrazides, imidazole derivatives, amine compounds, polyhydric phenol compounds, acid anhydrides, and the like. Of these, organic acid hydrazide is preferably used.
上記有機酸ヒドラジドとしては、例えば、セバシン酸ジヒドラジド、イソフタル酸ジヒドラジド、アジピン酸ジヒドラジド、マロン酸ジヒドラジド等が挙げられる。
上記有機酸ヒドラジドのうち市販されているものとしては、例えば、ＳＤＨ、ＡＤＨ（いずれも大塚化学社製）、アミキュアＶＤＨ、アミキュアＶＤＨ－Ｊ、アミキュアＵＤＨ、アミキュアＵＤＨ－Ｊ（いずれも味の素ファインテクノ社製）等が挙げられる。 Examples of the organic acid hydrazide include sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide, and the like.
Examples of commercially available organic acid hydrazides include, for example, SDH, ADH (all manufactured by Otsuka Chemical Co., Ltd.), Amicure VDH, Amicure VDH-J, Amicure UDH, Amicure UDH-J (all Ajinomoto Fine Techno Co., Ltd.) Manufactured) and the like.
上記有機酸ヒドラジドのうち市販されているものとしては、例えば、ＳＤＨ、ＡＤＨ（いずれも大塚化学社製）、アミキュアＶＤＨ、アミキュアＶＤＨ－Ｊ、アミキュアＵＤＨ、アミキュアＵＤＨ－Ｊ（いずれも味の素ファインテクノ社製）等が挙げられる。 Examples of the organic acid hydrazide include sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide, and the like.
Examples of commercially available organic acid hydrazides include, for example, SDH, ADH (all manufactured by Otsuka Chemical Co., Ltd.), Amicure VDH, Amicure VDH-J, Amicure UDH, Amicure UDH-J (all Ajinomoto Fine Techno Co., Ltd.) Manufactured) and the like.
上記熱硬化剤の含有量は、上記硬化性樹脂１００重量部に対して、好ましい下限が１重量部、好ましい上限が５０重量部である。上記熱硬化剤の含有量がこの範囲であることにより、得られる液晶表示素子用シール剤の塗布性等を悪化させることなく、より熱硬化性に優れるものとすることができる。上記熱硬化剤の含有量のより好ましい上限は３０重量部である。
The content of the thermosetting agent is preferably 1 part by weight with respect to 100 parts by weight of the curable resin, and 50 parts by weight with respect to the preferable upper limit. When the content of the thermosetting agent is within this range, the thermosetting property can be further improved without deteriorating the applicability of the obtained sealing agent for liquid crystal display elements. The upper limit with more preferable content of the said thermosetting agent is 30 weight part.
本発明の液晶表示素子用シール剤は、粘度の向上、応力分散効果による接着性の改善、線膨張率の改善、硬化物の透湿防止性の向上等を目的として充填剤を含有することが好ましい。
The sealing agent for liquid crystal display elements of the present invention may contain a filler for the purpose of improving viscosity, improving adhesiveness due to stress dispersion effect, improving linear expansion coefficient, improving moisture permeability of cured products, and the like. preferable.
上記充填剤としては、例えば、シリカ、タルク、ガラスビーズ、石綿、石膏、珪藻土、スメクタイト、ベントナイト、モンモリロナイト、セリサイト、活性白土、アルミナ、酸化亜鉛、酸化鉄、酸化マグネシウム、酸化錫、酸化チタン、炭酸カルシウム、炭酸マグネシウム、水酸化マグネシウム、水酸化アルミニウム、窒化アルミニウム、窒化珪素、硫酸バリウム、珪酸カルシウム等の無機充填剤や、ポリエステル微粒子、ポリウレタン微粒子、ビニル重合体微粒子、アクリル重合体微粒子等の有機充填剤が挙げられる。
Examples of the filler include silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, smectite, bentonite, montmorillonite, sericite, activated clay, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, Organic fillers such as calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate, and calcium silicate, and organic materials such as polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, and acrylic polymer fine particles A filler is mentioned.
本発明の液晶表示素子用シール剤中における上記充填剤の含有量の好ましい下限は１０重量％、好ましい上限は７０重量％である。上記充填剤の含有量がこの範囲であることにより、塗布性等を悪化させることなく、接着性の改善等の効果により優れるものとなる。上記充填剤の含有量のより好ましい下限は２０重量％、より好ましい上限は６０重量％である。
The minimum with preferable content of the said filler in the sealing compound for liquid crystal display elements of this invention is 10 weight%, and a preferable upper limit is 70 weight%. When the content of the filler is within this range, the effect of improving adhesiveness and the like is improved without deteriorating applicability and the like. The more preferable lower limit of the content of the filler is 20% by weight, and the more preferable upper limit is 60% by weight.
本発明の液晶表示素子用シール剤は、シランカップリング剤を含有することが好ましい。上記シランカップリング剤は、主にシール剤と基板等とを良好に接着するための接着助剤としての役割を有する。
It is preferable that the sealing compound for liquid crystal display elements of this invention contains a silane coupling agent. The silane coupling agent mainly has a role as an adhesion assistant for favorably bonding the sealing agent and the substrate.
上記シランカップリング剤としては、基板等との接着性を向上させる効果に優れ、硬化性樹脂と化学結合することにより液晶中への硬化性樹脂の流出を抑制することができることから、例えば、３－アミノプロピルトリメトキシシラン、３－メルカプトプロピルトリメトキシシラン、３－グリシドキシプロピルトリメトキシシラン、３－イソシアネートプロピルトリメトキシシラン等が好適に用いられる。
As said silane coupling agent, since it is excellent in the effect which improves adhesiveness with a board | substrate etc. and it can suppress the outflow of curable resin in a liquid crystal by chemically bonding with curable resin, it is 3 for example. -Aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane and the like are preferably used.
本発明の液晶表示素子用シール剤中における上記シランカップリング剤の含有量の好ましい下限は０．１重量％、好ましい上限は１０重量％である。上記シランカップリング剤の含有量がこの範囲であることにより、液晶汚染の発生を抑制しつつ、接着性を向上させる効果により優れるものとなる。上記シランカップリング剤の含有量のより好ましい下限は０．３重量％、より好ましい上限は５重量％である。
The minimum with preferable content of the said silane coupling agent in the sealing compound for liquid crystal display elements of this invention is 0.1 weight%, and a preferable upper limit is 10 weight%. When the content of the silane coupling agent is within this range, the effect of improving the adhesiveness is suppressed while suppressing the occurrence of liquid crystal contamination. The minimum with more preferable content of the said silane coupling agent is 0.3 weight%, and a more preferable upper limit is 5 weight%.
本発明の液晶表示素子用シール剤は、遮光剤を含有してもよい。上記遮光剤を含有することにより、本発明の液晶表示素子用シール剤は、遮光シール剤として好適に用いることができる。
The sealing agent for liquid crystal display elements of the present invention may contain a light shielding agent. By containing the said light shielding agent, the sealing compound for liquid crystal display elements of this invention can be used suitably as a light shielding sealing agent.
上記遮光剤としては、例えば、酸化鉄、チタンブラック、アニリンブラック、シアニンブラック、フラーレン、カーボンブラック、樹脂被覆型カーボンブラック等が挙げられる。なかでも、チタンブラックが好ましい。
Examples of the light-shielding agent include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. Of these, titanium black is preferable.
上記チタンブラックは、波長３００～８００ｎｍの光に対する平均透過率と比較して、紫外線領域付近、特に波長３７０～４５０ｎｍの光に対する透過率が高くなる物質である。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液晶表示素子用シール剤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。本発明の液晶表示素子用シール剤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。
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 providing a light shielding property to the sealing agent for liquid crystal display elements of the present invention, while transmitting light having a wavelength in the vicinity of the ultraviolet region. A shading agent. The light shielding agent contained in the liquid crystal display element sealant of the present invention is preferably a highly insulating material, and titanium black is also preferred as the highly insulating light shielding agent.
上記チタンブラックは、表面処理されていないものでも充分な効果を発揮するが、表面がカップリング剤等の有機成分で処理されているものや、酸化ケイ素、酸化チタン、酸化ゲルマニウム、酸化アルミニウム、酸化ジルコニウム、酸化マグネシウム等の無機成分で被覆されているもの等、表面処理されたチタンブラックを用いることもできる。なかでも、有機成分で処理されているものは、より絶縁性を向上できる点で好ましい。
また、遮光剤として上記チタンブラックを含有する本発明の液晶表示素子用シール剤を用いて製造した液晶表示素子は、充分な遮光性を有するため、光の漏れ出しがなく高いコントラストを有し、優れた画像表示品質を有する液晶表示素子を実現することができる。 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, oxidized Surface-treated titanium black such as those coated with an inorganic component such as zirconium or magnesium oxide can also be used. Especially, what is processed with the organic component is preferable at the point which can improve insulation more.
In addition, the liquid crystal display element produced using the sealing agent for liquid crystal display elements of the present invention containing the above-described titanium black as a light-shielding agent has sufficient light-shielding properties, and therefore has high contrast without light leakage A liquid crystal display element having excellent image display quality can be realized.
また、遮光剤として上記チタンブラックを含有する本発明の液晶表示素子用シール剤を用いて製造した液晶表示素子は、充分な遮光性を有するため、光の漏れ出しがなく高いコントラストを有し、優れた画像表示品質を有する液晶表示素子を実現することができる。 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, oxidized Surface-treated titanium black such as those coated with an inorganic component such as zirconium or magnesium oxide can also be used. Especially, what is processed with the organic component is preferable at the point which can improve insulation more.
In addition, the liquid crystal display element produced using the sealing agent for liquid crystal display elements of the present invention containing the above-described titanium black as a light-shielding agent has sufficient light-shielding properties, and therefore has high contrast without light leakage A liquid crystal display element having excellent image display quality can be realized.
上記チタンブラックのうち市販されているものとしては、例えば、１２Ｓ、１３Ｍ、１３Ｍ－Ｃ、１３Ｒ－Ｎ、１４Ｍ－Ｃ（いずれも三菱マテリアル社製）、ティラックＤ（赤穂化成社製）等が挙げられる。
Examples of commercially available titanium black include 12S, 13M, 13M-C, 13R-N, 14M-C (all manufactured by Mitsubishi Materials Corporation), Tilak D (manufactured by Ako Kasei Co., Ltd.), and the like. Can be mentioned.
上記チタンブラックの比表面積の好ましい下限は１３ｍ２／ｇ、好ましい上限は３０ｍ２／ｇであり、より好ましい下限は１５ｍ２／ｇ、より好ましい上限は２５ｍ２／ｇである。
また、上記チタンブラックの体積抵抗の好ましい下限は０．５Ω・ｃｍ、好ましい上限は３Ω・ｃｍであり、より好ましい下限は１Ω・ｃｍ、より好ましい上限は２．５Ω・ｃｍである。 The preferable lower limit of the specific surface area of the titanium black is 13 m 2 / g, the preferable upper limit is 30 m 2 / g, the more preferable lower limit is 15 m 2 / g, and the more preferable upper limit is 25 m 2 / g.
Further, the preferred lower limit of the volume resistance of the titanium black is 0.5 Ω · cm, the preferred upper limit is 3 Ω · cm, the more preferred lower limit is 1 Ω · cm, and the more preferred upper limit is 2.5 Ω · cm.
また、上記チタンブラックの体積抵抗の好ましい下限は０．５Ω・ｃｍ、好ましい上限は３Ω・ｃｍであり、より好ましい下限は１Ω・ｃｍ、より好ましい上限は２．５Ω・ｃｍである。 The preferable lower limit of the specific surface area of the titanium black is 13 m 2 / g, the preferable upper limit is 30 m 2 / g, the more preferable lower limit is 15 m 2 / g, and the more preferable upper limit is 25 m 2 / g.
Further, the preferred lower limit of the volume resistance of the titanium black is 0.5 Ω · cm, the preferred upper limit is 3 Ω · cm, the more preferred lower limit is 1 Ω · cm, and the more preferred upper limit is 2.5 Ω · cm.
上記遮光剤の一次粒子径は、液晶表示素子の基板間の距離以下であれば特に限定されないが、好ましい下限は１ｎｍ、好ましい上限は５０００ｎｍである。上記遮光剤の一次粒子径がこの範囲であることにより、得られる液晶表示素子用シール剤の塗布性等を悪化させることなく遮光性により優れるものとすることができる。上記遮光剤の一次粒子径のより好ましい下限は５ｎｍ、より好ましい上限は２００ｎｍ、更に好ましい下限は１０ｎｍ、更に好ましい上限は１００ｎｍである。
なお、上記遮光剤の一次粒子径は、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。 Although the primary particle diameter of the said light-shielding agent will not be specifically limited if it is below the distance between the board | substrates of a liquid crystal display element, a preferable minimum is 1 nm and a preferable upper limit is 5000 nm. When the primary particle diameter of the light-shielding agent is within this range, the light-shielding property can be improved without deteriorating the applicability of the obtained sealing agent for liquid crystal display elements. The more preferable lower limit of the primary particle diameter of the light shielding agent is 5 nm, the more preferable upper limit is 200 nm, the still more preferable lower limit is 10 nm, and the still more preferable upper limit is 100 nm.
The primary particle size of the light shielding agent can be measured by using NICOMP 380ZLS (manufactured by PARTICS SIZING SYSTEMS) and dispersing the light shielding agent in a solvent (water, organic solvent, etc.).
なお、上記遮光剤の一次粒子径は、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。 Although the primary particle diameter of the said light-shielding agent will not be specifically limited if it is below the distance between the board | substrates of a liquid crystal display element, a preferable minimum is 1 nm and a preferable upper limit is 5000 nm. When the primary particle diameter of the light-shielding agent is within this range, the light-shielding property can be improved without deteriorating the applicability of the obtained sealing agent for liquid crystal display elements. The more preferable lower limit of the primary particle diameter of the light shielding agent is 5 nm, the more preferable upper limit is 200 nm, the still more preferable lower limit is 10 nm, and the still more preferable upper limit is 100 nm.
The primary particle size of the light shielding agent can be measured by using NICOMP 380ZLS (manufactured by PARTICS SIZING SYSTEMS) and dispersing the light shielding agent in a solvent (water, organic solvent, etc.).
本発明の液晶表示素子用シール剤中における上記遮光剤の含有量の好ましい下限は５重量％、好ましい上限は８０重量％である。上記遮光剤の含有量がこの範囲であることにより、得られる液晶表示素子用シール剤の基板に対する密着性や硬化後の強度や描画性を低下させることなくより優れた遮光性を発揮することができる。上記遮光剤の含有量のより好ましい下限は１０重量％、より好ましい上限は７０重量％であり、更に好ましい下限は３０重量％、更に好ましい上限は６０重量％である。
The minimum with preferable content of the said light-shielding agent in the sealing compound for liquid crystal display elements of this invention is 5 weight%, and a preferable upper limit is 80 weight%. When the content of the light-shielding agent is within this range, the liquid crystal display element sealant can exhibit better light-shielding properties without reducing the adhesion to the substrate, the strength after curing, and the drawability. it can. The more preferable lower limit of the content of the light-shielding agent is 10% by weight, the more preferable upper limit is 70% by weight, the still more preferable lower limit is 30% by weight, and the still more preferable upper limit is 60% by weight.
本発明の液晶表示素子用シール剤は、更に、必要に応じて、応力緩和剤、反応性希釈剤、揺変剤、スペーサー、硬化促進剤、消泡剤、レベリング剤、重合禁止剤、その他添加剤等を含有してもよい。
The sealing agent for liquid crystal display elements of the present invention is further added as necessary, stress relieving agent, reactive diluent, thixotropic agent, spacer, curing accelerator, antifoaming agent, leveling agent, polymerization inhibitor, etc. An agent or the like may be contained.
本発明の液晶表示素子用シール剤を製造する方法としては、例えば、ホモディスパー、ホモミキサー、万能ミキサー、プラネタリーミキサー、ニーダー、３本ロール等の混合機を用いて、硬化性樹脂と、重合開始剤及び／又は熱硬化剤と、必要に応じて添加するシランカップリング剤等の添加剤とを混合する方法等が挙げられる。
As a method for producing the sealing agent for liquid crystal display elements 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, a curable resin, and a polymerization Examples thereof include a method of mixing an initiator and / or a thermosetting agent and an additive such as a silane coupling agent added as necessary.
本発明の液晶表示素子用シール剤は、Ｅ型粘度計を用いて２５℃、１ｒｐｍの条件で測定した粘度の好ましい下限が５万ｍＰａ・ｓ、好ましい上限が７０万ｍＰａ・ｓである。上記粘度がこの範囲であることにより、得られる液晶表示素子用シール剤が塗布性に優れるものとなる。上記粘度のより好ましい下限は１０万ｍＰａ・ｓ、より好ましい上限は５０万ｍＰａ・ｓである。
なお、上記Ｅ型粘度計としては、例えば、５ＸＨＢＤＶ－ＩＩＩ＋ＣＰ（ブルックフィールド社製、ローターＮｏ．ＣＰ－５１）等を用いることができる。 The sealing agent for liquid crystal display elements of the present invention has a preferable lower limit of 50,000 mPa · s and a preferable upper limit of 700,000 mPa · s measured using an E-type viscometer at 25 ° C. and 1 rpm. When the viscosity is within this range, the obtained sealing agent for liquid crystal display elements has excellent coating properties. A more preferable lower limit of the viscosity is 100,000 mPa · s, and a more preferable upper limit is 500,000 mPa · s.
As the E-type viscometer, for example, 5XHBDV-III + CP (manufactured by Brookfield, rotor No. CP-51) can be used.
なお、上記Ｅ型粘度計としては、例えば、５ＸＨＢＤＶ－ＩＩＩ＋ＣＰ（ブルックフィールド社製、ローターＮｏ．ＣＰ－５１）等を用いることができる。 The sealing agent for liquid crystal display elements of the present invention has a preferable lower limit of 50,000 mPa · s and a preferable upper limit of 700,000 mPa · s measured using an E-type viscometer at 25 ° C. and 1 rpm. When the viscosity is within this range, the obtained sealing agent for liquid crystal display elements has excellent coating properties. A more preferable lower limit of the viscosity is 100,000 mPa · s, and a more preferable upper limit is 500,000 mPa · s.
As the E-type viscometer, for example, 5XHBDV-III + CP (manufactured by Brookfield, rotor No. CP-51) can be used.
本発明の液晶表示素子用シール剤に、導電性微粒子を配合することにより、上下導通材料を製造することができる。このような本発明の液晶表示素子用シール剤と導電性微粒子とを含有する上下導通材料もまた、本発明の１つである。
A vertical conducting material can be produced by blending conductive fine particles with the liquid crystal display element sealant of the present invention. Such a vertical conduction material containing the sealing agent for liquid crystal display elements of the present invention and conductive fine particles is also one aspect of the present invention.
上記導電性微粒子としては、金属ボール、樹脂微粒子の表面に導電金属層を形成したもの等を用いることができる。なかでも、樹脂微粒子の表面に導電金属層を形成したものは、樹脂微粒子の優れた弾性により、透明基板等を損傷することなく導電接続が可能であることから好適である。
As the conductive fine particles, a metal ball, a resin fine particle formed with a conductive metal layer on the surface, or the like can be used. Among them, the one in which the conductive metal layer is formed on the surface of the resin fine particles is preferable because the conductive connection is possible without damaging the transparent substrate due to the excellent elasticity of the resin fine particles.
本発明の液晶表示素子用シール剤又は本発明の上下導通材料を用いてなる液晶表示素子もまた、本発明の１つである。
The liquid crystal display element using the sealing agent for liquid crystal display elements of this invention or the vertical conduction material of this invention is also one of this invention.
本発明の液晶表示素子を製造する方法としては、液晶滴下工法が好適に用いられる。具体的には例えば、ＩＴＯ薄膜等の電極付きのガラス基板やポリエチレンテレフタレート基板等の２枚の基板の一方に、本発明の液晶表示素子用シール剤を、スクリーン印刷、ディスペンサー塗布等により塗布して枠状のシールパターンを形成する工程、本発明の液晶表示素子用シール剤が未硬化の状態で液晶の微小滴を基板のシールパターンの枠内に滴下塗布し、真空下で別の基板を重ね合わせる工程、及び、本発明の液晶表示素子用シール剤のシールパターン部分に紫外線等の光を照射してシール剤を仮硬化させる工程、及び、仮硬化させたシール剤を加熱して本硬化させる工程を有する方法等が挙げられる。
As a method for producing the liquid crystal display element of the present invention, a liquid crystal dropping method is preferably used. Specifically, for example, the liquid crystal display element sealant of the present invention is applied to one of two substrates such as a glass substrate with electrodes such as an ITO thin film or a polyethylene terephthalate substrate by screen printing, dispenser application, or the like. A step of forming a frame-shaped seal pattern, in which the liquid crystal display element sealant of the present invention is in an uncured state, droplets of liquid crystal are dropped into the frame of the substrate seal pattern, and another substrate is stacked under vacuum. A step of aligning, a step of irradiating the seal pattern portion of the sealant for the liquid crystal display element of the present invention with light such as ultraviolet rays, and temporarily curing the sealant, and heating and temporarily curing the temporarily cured sealant. Examples thereof include a method having a step.
本発明によれば、塗布性、透湿防止性、及び、接着性に優れ、かつ、液晶汚染を抑制できる液晶表示素子用シール剤を提供することができる。また、本発明によれば、該液晶表示素子用シール剤を用いてなる上下導通材料及び液晶表示素子を提供することができる。
ADVANTAGE OF THE INVENTION According to this invention, the sealing agent for liquid crystal display elements which can be excellent in applicability | paintability, moisture-permeability prevention property, and adhesiveness, and can suppress liquid crystal contamination can be provided. Moreover, according to this invention, the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal display elements can be provided.
以下に実施例を掲げて本発明を更に詳しく説明するが、本発明はこれら実施例のみに限定されない。
Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
（式（１）で表される化合物（Ｒ１がＨ、ｍ＝ｎ＝０）の作製）
ビスフェノールＳジグリシジルエーテル１０００重量部、重合禁止剤としてｐ－メトキシフェノール２重量部、反応触媒としてトリエチルアミン２重量部、及び、アクリル酸２００重量部を、空気を送り込みながら９０℃で５時間還流撹拌して反応させた。得られた樹脂１００重量部を、反応物中のイオン性不純物を吸着させる為にクオルツとカオリンの天然結合物（ホフマンミネラル社製、「シリチンＶ８５」）１０重量部が充填されたカラムで濾過し、式（１）で表される化合物（Ｒ１がＨ、ｍ＝ｎ＝０）を得た。なお、得られた化合物が式（１）で表される化合物（Ｒ１がＨ、ｍ＝ｎ＝０）であることは、１Ｈ－ＮＭＲ、１３Ｃ－ＮＭＲ、及び、ＩＲにより確認した。 (Production of compound represented by formula (1) (R 1 is H, m = n = 0))
1000 parts by weight of bisphenol S diglycidyl ether, 2 parts by weight of p-methoxyphenol as a polymerization inhibitor, 2 parts by weight of triethylamine as a reaction catalyst, and 200 parts by weight of acrylic acid were stirred at 90 ° C. for 5 hours while supplying air. And reacted. In order to adsorb ionic impurities in the reaction product, 100 parts by weight of the obtained resin was filtered through a column packed with 10 parts by weight of a natural combination of quartz and kaolin (manufactured by Hoffman Mineral Co., Ltd., “Siritin V85”). Thus, a compound represented by the formula (1) (R 1 is H, m = n = 0) was obtained. Note that it was confirmed by 1 H-NMR, 13 C-NMR, and IR that the obtained compound was a compound represented by the formula (1) (R 1 is H, m = n = 0).
ビスフェノールＳジグリシジルエーテル１０００重量部、重合禁止剤としてｐ－メトキシフェノール２重量部、反応触媒としてトリエチルアミン２重量部、及び、アクリル酸２００重量部を、空気を送り込みながら９０℃で５時間還流撹拌して反応させた。得られた樹脂１００重量部を、反応物中のイオン性不純物を吸着させる為にクオルツとカオリンの天然結合物（ホフマンミネラル社製、「シリチンＶ８５」）１０重量部が充填されたカラムで濾過し、式（１）で表される化合物（Ｒ１がＨ、ｍ＝ｎ＝０）を得た。なお、得られた化合物が式（１）で表される化合物（Ｒ１がＨ、ｍ＝ｎ＝０）であることは、１Ｈ－ＮＭＲ、１３Ｃ－ＮＭＲ、及び、ＩＲにより確認した。 (Production of compound represented by formula (1) (R 1 is H, m = n = 0))
1000 parts by weight of bisphenol S diglycidyl ether, 2 parts by weight of p-methoxyphenol as a polymerization inhibitor, 2 parts by weight of triethylamine as a reaction catalyst, and 200 parts by weight of acrylic acid were stirred at 90 ° C. for 5 hours while supplying air. And reacted. In order to adsorb ionic impurities in the reaction product, 100 parts by weight of the obtained resin was filtered through a column packed with 10 parts by weight of a natural combination of quartz and kaolin (manufactured by Hoffman Mineral Co., Ltd., “Siritin V85”). Thus, a compound represented by the formula (1) (R 1 is H, m = n = 0) was obtained. Note that it was confirmed by 1 H-NMR, 13 C-NMR, and IR that the obtained compound was a compound represented by the formula (1) (R 1 is H, m = n = 0).
（式（１）で表される化合物（Ｒ１がＨ、ｍ＝ｎ＝１（平均値））の作製）
温度計、滴下ロート、冷却管、及び、撹拌器を取り付けたフラスコに４，４’－ビス（２－ヒドロキシエチルオキシ）ジフェニルスルホン１６９重量部、エピクロルヒドリン３７０重量部、ジメチルスルホキシド１８５重量部、及び、テトラメチルアンモニウムクロライド５重量部を加えて撹拌下で溶解し、５０℃まで昇温した。次いで、フレーク状の水酸化ナトリウム６０重量部を１００分かけて分割添加した後、更に５０℃で３時間、後反応を行った。反応終了後、水４００重量部を加えて水洗を行い、ロータリーエバポレーターを用いて、１３０℃、減圧下にて、油層から過剰のエピクロルヒドリン等を留去した。残留物にメチルイソブチルケトン４５０重量部を加えて溶解し、７０℃まで昇温した。撹拌下で３０％の水酸化ナトリウム水溶液１０重量部を加え、１時間反応を行った後、水洗を３回行い、ロータリーエバポレーターを用いて、１８０℃、減圧下にて、メチルイソブチルケトンを留去した。得られた反応物１１００重量部、重合禁止剤としてｐ－メトキシフェノール２重量部、反応触媒としてトリエチルアミン２重量部、及び、アクリル酸２００重量部を、空気を送り込みながら９０℃で５時間還流撹拌して反応させた。得られた樹脂１００重量部を、反応物中のイオン性不純物を吸着させる為にクオルツとカオリンの天然結合物（ホフマンミネラル社製、「シリチンＶ８５」）１０重量部が充填されたカラムで濾過し、式（１）で表される化合物（Ｒ１がＨ、ｍ＝ｎ＝１（平均値））を得た。なお、得られた化合物が式（１）で表される化合物（Ｒ１がＨ、ｍ＝ｎ＝１（平均値））であることは、１Ｈ－ＮＭＲ、１３Ｃ－ＮＭＲ、及び、ＩＲにより確認した。 (Production of the compound represented by the formula (1) (R 1 is H, m = n = 1 (average value))
In a flask equipped with a thermometer, dropping funnel, condenser, and stirrer, 169 parts by weight of 4,4′-bis (2-hydroxyethyloxy) diphenylsulfone, 370 parts by weight of epichlorohydrin, 185 parts by weight of dimethyl sulfoxide, and 5 parts by weight of tetramethylammonium chloride was added and dissolved under stirring, and the temperature was raised to 50 ° C. Subsequently, 60 parts by weight of flaky sodium hydroxide was added in portions over 100 minutes, and then the reaction was further performed at 50 ° C. for 3 hours. After completion of the reaction, 400 parts by weight of water was added for washing with water, and excess epichlorohydrin and the like were distilled off from the oil layer at 130 ° C. under reduced pressure using a rotary evaporator. To the residue, 450 parts by weight of methyl isobutyl ketone was added and dissolved, and the temperature was raised to 70 ° C. Under stirring, 10 parts by weight of a 30% aqueous sodium hydroxide solution was added and the reaction was carried out for 1 hour, followed by washing with water three times. Distilling off methyl isobutyl ketone at 180 ° C. under reduced pressure using a rotary evaporator. did. 1100 parts by weight of the resulting reaction product, 2 parts by weight of p-methoxyphenol as a polymerization inhibitor, 2 parts by weight of triethylamine as a reaction catalyst, and 200 parts by weight of acrylic acid were stirred at 90 ° C. for 5 hours while feeding air. And reacted. In order to adsorb ionic impurities in the reaction product, 100 parts by weight of the obtained resin was filtered through a column packed with 10 parts by weight of a natural combination of quartz and kaolin (manufactured by Hoffman Mineral Co., Ltd., “Siritin V85”). Thus, a compound represented by the formula (1) (R 1 is H, m = n = 1 (average value)) was obtained. Note that the obtained compound is a compound represented by the formula (1) (R 1 is H, m = n = 1 (average value)), which means that 1 H-NMR, 13 C-NMR, and IR Confirmed by
温度計、滴下ロート、冷却管、及び、撹拌器を取り付けたフラスコに４，４’－ビス（２－ヒドロキシエチルオキシ）ジフェニルスルホン１６９重量部、エピクロルヒドリン３７０重量部、ジメチルスルホキシド１８５重量部、及び、テトラメチルアンモニウムクロライド５重量部を加えて撹拌下で溶解し、５０℃まで昇温した。次いで、フレーク状の水酸化ナトリウム６０重量部を１００分かけて分割添加した後、更に５０℃で３時間、後反応を行った。反応終了後、水４００重量部を加えて水洗を行い、ロータリーエバポレーターを用いて、１３０℃、減圧下にて、油層から過剰のエピクロルヒドリン等を留去した。残留物にメチルイソブチルケトン４５０重量部を加えて溶解し、７０℃まで昇温した。撹拌下で３０％の水酸化ナトリウム水溶液１０重量部を加え、１時間反応を行った後、水洗を３回行い、ロータリーエバポレーターを用いて、１８０℃、減圧下にて、メチルイソブチルケトンを留去した。得られた反応物１１００重量部、重合禁止剤としてｐ－メトキシフェノール２重量部、反応触媒としてトリエチルアミン２重量部、及び、アクリル酸２００重量部を、空気を送り込みながら９０℃で５時間還流撹拌して反応させた。得られた樹脂１００重量部を、反応物中のイオン性不純物を吸着させる為にクオルツとカオリンの天然結合物（ホフマンミネラル社製、「シリチンＶ８５」）１０重量部が充填されたカラムで濾過し、式（１）で表される化合物（Ｒ１がＨ、ｍ＝ｎ＝１（平均値））を得た。なお、得られた化合物が式（１）で表される化合物（Ｒ１がＨ、ｍ＝ｎ＝１（平均値））であることは、１Ｈ－ＮＭＲ、１３Ｃ－ＮＭＲ、及び、ＩＲにより確認した。 (Production of the compound represented by the formula (1) (R 1 is H, m = n = 1 (average value))
In a flask equipped with a thermometer, dropping funnel, condenser, and stirrer, 169 parts by weight of 4,4′-bis (2-hydroxyethyloxy) diphenylsulfone, 370 parts by weight of epichlorohydrin, 185 parts by weight of dimethyl sulfoxide, and 5 parts by weight of tetramethylammonium chloride was added and dissolved under stirring, and the temperature was raised to 50 ° C. Subsequently, 60 parts by weight of flaky sodium hydroxide was added in portions over 100 minutes, and then the reaction was further performed at 50 ° C. for 3 hours. After completion of the reaction, 400 parts by weight of water was added for washing with water, and excess epichlorohydrin and the like were distilled off from the oil layer at 130 ° C. under reduced pressure using a rotary evaporator. To the residue, 450 parts by weight of methyl isobutyl ketone was added and dissolved, and the temperature was raised to 70 ° C. Under stirring, 10 parts by weight of a 30% aqueous sodium hydroxide solution was added and the reaction was carried out for 1 hour, followed by washing with water three times. Distilling off methyl isobutyl ketone at 180 ° C. under reduced pressure using a rotary evaporator. did. 1100 parts by weight of the resulting reaction product, 2 parts by weight of p-methoxyphenol as a polymerization inhibitor, 2 parts by weight of triethylamine as a reaction catalyst, and 200 parts by weight of acrylic acid were stirred at 90 ° C. for 5 hours while feeding air. And reacted. In order to adsorb ionic impurities in the reaction product, 100 parts by weight of the obtained resin was filtered through a column packed with 10 parts by weight of a natural combination of quartz and kaolin (manufactured by Hoffman Mineral Co., Ltd., “Siritin V85”). Thus, a compound represented by the formula (1) (R 1 is H, m = n = 1 (average value)) was obtained. Note that the obtained compound is a compound represented by the formula (1) (R 1 is H, m = n = 1 (average value)), which means that 1 H-NMR, 13 C-NMR, and IR Confirmed by
（実施例１～７、及び、比較例１～４）
表１に記載された配合比に従い、各材料を遊星式撹拌機（シンキー社製、「あわとり練太郎」）を用いて混合した後、更に３本ロールを用いて混合することにより実施例１～７、及び、比較例１～４の液晶表示素子用シール剤を調製した。 (Examples 1 to 7 and Comparative Examples 1 to 4)
According to the mixing ratio described in Table 1, each material was mixed using a planetary stirrer (manufactured by Shinky Co., Ltd., “Awatori Nertaro”), and then further mixed using three rolls. To 7 and Comparative Examples 1 to 4 were prepared.
表１に記載された配合比に従い、各材料を遊星式撹拌機（シンキー社製、「あわとり練太郎」）を用いて混合した後、更に３本ロールを用いて混合することにより実施例１～７、及び、比較例１～４の液晶表示素子用シール剤を調製した。 (Examples 1 to 7 and Comparative Examples 1 to 4)
According to the mixing ratio described in Table 1, each material was mixed using a planetary stirrer (manufactured by Shinky Co., Ltd., “Awatori Nertaro”), and then further mixed using three rolls. To 7 and Comparative Examples 1 to 4 were prepared.
＜評価＞
実施例及び比較例で得られた液晶表示素子用シール剤について以下の評価を行った。結果を表１に示した。 <Evaluation>
The following evaluation was performed about the sealing compound for liquid crystal display elements obtained by the Example and the comparative example. The results are shown in Table 1.
実施例及び比較例で得られた液晶表示素子用シール剤について以下の評価を行った。結果を表１に示した。 <Evaluation>
The following evaluation was performed about the sealing compound for liquid crystal display elements obtained by the Example and the comparative example. The results are shown in Table 1.
（塗布性）
ディスペンサー（武蔵エンジニアリング社製、「ＳＨＯＴＭＡＳＴＥＲ３００」）を用いて、実施例及び比較例で得られた各液晶表示素子用シール剤をガラス基板上に塗布した。ディスペンスノズルを４００μｍ、ノズルギャップを３０μｍ、塗出圧を３００ｋＰａに固定して塗布したとき、かすれやダレがなく塗布できた場合を「◎」、わずかにかすれやダレが生じた場合を「○」、塗布切れはないが大きなかすれやダレが生じた場合を「△」、塗布切れが生じたり、全く塗布できなかったりした場合を「×」として塗布性を評価した。 (Applicability)
Using a dispenser (manufactured by Musashi Engineering Co., Ltd., “SHOTMASTER300”), the sealing agents for liquid crystal display elements obtained in Examples and Comparative Examples were applied on a glass substrate. When the dispensing nozzle is 400 μm, the nozzle gap is 30 μm, and the coating pressure is fixed at 300 kPa, “◎” indicates that the coating can be applied without fading or sagging, and “○” indicates that the coating is slightly fading or sagging. The applicability was evaluated as “Δ” when the coating was not cut off but large faint or sagging occurred, and “X” when the coating was cut off or not applied at all.
ディスペンサー（武蔵エンジニアリング社製、「ＳＨＯＴＭＡＳＴＥＲ３００」）を用いて、実施例及び比較例で得られた各液晶表示素子用シール剤をガラス基板上に塗布した。ディスペンスノズルを４００μｍ、ノズルギャップを３０μｍ、塗出圧を３００ｋＰａに固定して塗布したとき、かすれやダレがなく塗布できた場合を「◎」、わずかにかすれやダレが生じた場合を「○」、塗布切れはないが大きなかすれやダレが生じた場合を「△」、塗布切れが生じたり、全く塗布できなかったりした場合を「×」として塗布性を評価した。 (Applicability)
Using a dispenser (manufactured by Musashi Engineering Co., Ltd., “SHOTMASTER300”), the sealing agents for liquid crystal display elements obtained in Examples and Comparative Examples were applied on a glass substrate. When the dispensing nozzle is 400 μm, the nozzle gap is 30 μm, and the coating pressure is fixed at 300 kPa, “◎” indicates that the coating can be applied without fading or sagging, and “○” indicates that the coating is slightly fading or sagging. The applicability was evaluated as “Δ” when the coating was not cut off but large faint or sagging occurred, and “X” when the coating was cut off or not applied at all.
（接着性）
実施例及び比較例で得られた各液晶表示素子用シール剤１００重量部に対して平均粒子径５μｍのスペーサー粒子（積水化学工業社製、「ミクロパールＳＰ－２０５０」）１重量部を遊星式撹拌装置によって均一に分散させ、極微量をコーニングガラス１７３７（２０ｍｍ×５０ｍｍ×厚さ０．７ｍｍ）の中央部に取り、同型のガラスをその上に重ね合わせて液晶表示素子用シール剤を押し広げ、メタルハライドランプを用いて１００ｍＷ／ｃｍ２の紫外線を３０秒照射した後、１２０℃で１時間加熱してシール剤を硬化させ、接着試験片を得た。
得られた接着試験片について、テンションゲージを用いて接着強度を測定した。得られた測定値（ｋｇｆ）をシール塗布断面積（ｃｍ２）で除した値が、３５ｋｇｆ／ｃｍ２以上であった場合を「◎」、３０ｋｇｆ／ｃｍ２以上３５ｋｇｆ／ｃｍ２未満であった場合を「○」、２５ｋｇｆ／ｃｍ２以上３０ｋｇｆ／ｃｍ２未満であった場合を「△」、２５ｋｇｆ／ｃｍ２未満であった場合を「×」として接着性を評価した。 (Adhesiveness)
One part by weight of spacer particles (Sekisui Chemical Co., Ltd., “Micropearl SP-2050”) having an average particle diameter of 5 μm is used for 100 parts by weight of each sealing agent for liquid crystal display elements obtained in Examples and Comparative Examples. Disperse uniformly with a stirrer, take a trace amount in the center of Corning glass 1737 (20 mm x 50 mm x thickness 0.7 mm), and stack the same type of glass on top to spread the sealant for liquid crystal display elements After irradiating with 100 mW / cm 2 ultraviolet rays for 30 seconds using a metal halide lamp, the sealant was cured by heating at 120 ° C. for 1 hour to obtain an adhesion test piece.
About the obtained adhesion test piece, the adhesive strength was measured using the tension gauge. The resulting value obtained by dividing measured values (kgf) in the seal coating cross sectional area (cm 2) is a case was 35 kgf / cm 2 or more "◎" was 30 kgf / cm 2 or more 35 kgf / cm less than 2 where "○", the case was 25 kgf / cm 2 or more 30 kgf / cm less than 2 "△", and evaluated the adhesiveness of the case was less than 25 kgf / cm 2 as "×".
実施例及び比較例で得られた各液晶表示素子用シール剤１００重量部に対して平均粒子径５μｍのスペーサー粒子（積水化学工業社製、「ミクロパールＳＰ－２０５０」）１重量部を遊星式撹拌装置によって均一に分散させ、極微量をコーニングガラス１７３７（２０ｍｍ×５０ｍｍ×厚さ０．７ｍｍ）の中央部に取り、同型のガラスをその上に重ね合わせて液晶表示素子用シール剤を押し広げ、メタルハライドランプを用いて１００ｍＷ／ｃｍ２の紫外線を３０秒照射した後、１２０℃で１時間加熱してシール剤を硬化させ、接着試験片を得た。
得られた接着試験片について、テンションゲージを用いて接着強度を測定した。得られた測定値（ｋｇｆ）をシール塗布断面積（ｃｍ２）で除した値が、３５ｋｇｆ／ｃｍ２以上であった場合を「◎」、３０ｋｇｆ／ｃｍ２以上３５ｋｇｆ／ｃｍ２未満であった場合を「○」、２５ｋｇｆ／ｃｍ２以上３０ｋｇｆ／ｃｍ２未満であった場合を「△」、２５ｋｇｆ／ｃｍ２未満であった場合を「×」として接着性を評価した。 (Adhesiveness)
One part by weight of spacer particles (Sekisui Chemical Co., Ltd., “Micropearl SP-2050”) having an average particle diameter of 5 μm is used for 100 parts by weight of each sealing agent for liquid crystal display elements obtained in Examples and Comparative Examples. Disperse uniformly with a stirrer, take a trace amount in the center of Corning glass 1737 (20 mm x 50 mm x thickness 0.7 mm), and stack the same type of glass on top to spread the sealant for liquid crystal display elements After irradiating with 100 mW / cm 2 ultraviolet rays for 30 seconds using a metal halide lamp, the sealant was cured by heating at 120 ° C. for 1 hour to obtain an adhesion test piece.
About the obtained adhesion test piece, the adhesive strength was measured using the tension gauge. The resulting value obtained by dividing measured values (kgf) in the seal coating cross sectional area (cm 2) is a case was 35 kgf / cm 2 or more "◎" was 30 kgf / cm 2 or more 35 kgf / cm less than 2 where "○", the case was 25 kgf / cm 2 or more 30 kgf / cm less than 2 "△", and evaluated the adhesiveness of the case was less than 25 kgf / cm 2 as "×".
（透湿防止性）
実施例及び比較例で得られた各液晶表示素子用シール剤を、平滑な離型フィルム状にコーターで厚さ２００～３００μｍに塗行した後、メタルハライドランプを用いて１００ｍＷ／ｃｍ２の紫外線を３０秒照射した後、１２０℃で１時間加熱することによって透湿度測定用硬化フィルムを得た。
ＪＩＳ Ｚ ０２０８の防湿包装材料の透湿度試験方法（カップ法）に準じた方法で透湿度試験用カップを作製し、得られた透湿度測定用硬化フィルムを取り付け、温度８０℃湿度９０％ＲＨの恒温恒湿オーブンに投入して透湿度を測定した。得られた透湿度の値が６０ｇ／ｍ２・２４ｈｒ未満であった場合を「◎」、６０ｇ／ｍ２・２４ｈｒ以上１００ｇ／ｍ２・２４ｈｒ未満であった場合を「○」、１００ｇ／ｍ２・２４ｈｒ以上１２０ｇ／ｍ２・２４ｈｒ未満であった場合を「△」、１２０ｇ／ｍ２・２４ｈｒ以上であった場合を「×」として透湿防止性を評価した。 (Moisture permeability prevention)
Each of the liquid crystal display element sealants obtained in the Examples and Comparative Examples was applied to a smooth release film with a coater to a thickness of 200 to 300 μm, and then 100 mW / cm 2 ultraviolet rays were applied using a metal halide lamp. After irradiation for 30 seconds, the cured film for measuring moisture permeability was obtained by heating at 120 ° C. for 1 hour.
A moisture permeability test cup was prepared by a method according to JIS Z 0208 for moisture proof packaging materials (cup method), and the obtained cured film for moisture permeability measurement was attached, and the temperature was 80 ° C. and the humidity was 90% RH. The moisture permeability was measured by putting in a constant temperature and humidity oven. The case where the obtained moisture permeability value is less than 60 g / m 2 · 24 hr is “◎”, and the case where it is 60 g / m 2 · 24 hr or more and less than 100 g / m 2 · 24 hr is “◯”, 100 g / m The moisture permeation preventive property was evaluated by setting “Δ” when it was 2 · 24 hr or more and less than 120 g / m 2 · 24 hr, and “x” when it was 120 g / m 2 · 24 hr or more.
実施例及び比較例で得られた各液晶表示素子用シール剤を、平滑な離型フィルム状にコーターで厚さ２００～３００μｍに塗行した後、メタルハライドランプを用いて１００ｍＷ／ｃｍ２の紫外線を３０秒照射した後、１２０℃で１時間加熱することによって透湿度測定用硬化フィルムを得た。
ＪＩＳ Ｚ ０２０８の防湿包装材料の透湿度試験方法（カップ法）に準じた方法で透湿度試験用カップを作製し、得られた透湿度測定用硬化フィルムを取り付け、温度８０℃湿度９０％ＲＨの恒温恒湿オーブンに投入して透湿度を測定した。得られた透湿度の値が６０ｇ／ｍ２・２４ｈｒ未満であった場合を「◎」、６０ｇ／ｍ２・２４ｈｒ以上１００ｇ／ｍ２・２４ｈｒ未満であった場合を「○」、１００ｇ／ｍ２・２４ｈｒ以上１２０ｇ／ｍ２・２４ｈｒ未満であった場合を「△」、１２０ｇ／ｍ２・２４ｈｒ以上であった場合を「×」として透湿防止性を評価した。 (Moisture permeability prevention)
Each of the liquid crystal display element sealants obtained in the Examples and Comparative Examples was applied to a smooth release film with a coater to a thickness of 200 to 300 μm, and then 100 mW / cm 2 ultraviolet rays were applied using a metal halide lamp. After irradiation for 30 seconds, the cured film for measuring moisture permeability was obtained by heating at 120 ° C. for 1 hour.
A moisture permeability test cup was prepared by a method according to JIS Z 0208 for moisture proof packaging materials (cup method), and the obtained cured film for moisture permeability measurement was attached, and the temperature was 80 ° C. and the humidity was 90% RH. The moisture permeability was measured by putting in a constant temperature and humidity oven. The case where the obtained moisture permeability value is less than 60 g / m 2 · 24 hr is “◎”, and the case where it is 60 g / m 2 · 24 hr or more and less than 100 g / m 2 · 24 hr is “◯”, 100 g / m The moisture permeation preventive property was evaluated by setting “Δ” when it was 2 · 24 hr or more and less than 120 g / m 2 · 24 hr, and “x” when it was 120 g / m 2 · 24 hr or more.
（液晶表示素子の表示性能（低液晶汚染性））
実施例及び比較例で得られた各液晶表示素子用シール剤１００重量部に対して平均粒子径５μｍのスペーサー粒子（積水化学工業社製、「ミクロパールＳＰ－２０５０」）１重量部を遊星式撹拌装置によって均一に分散させ、得られたシール剤をディスペンス用のシリンジ（武蔵エンジニアリング社製、「ＰＳＹ－１０Ｅ」）に充填し、脱泡処理を行ってから、ディスペンサー（武蔵エンジニアリング社製、「ＳＨＯＴＭＡＳＴＥＲ３００」）にて、２枚のＩＴＯ薄膜付きの透明電極基板の一方にシール剤を枠状に塗布した。続いて、ＴＮ液晶（チッソ社製、「ＪＣ－５００１ＬＡ」）の微小滴を液晶滴下装置にてシール剤の枠内に滴下塗布し、他方の透明電極基板を、真空貼り合わせ装置にて５Ｐａの真空下にて貼り合わせ、セルを得た。得られたセルに、メタルハライドランプを用いて１００ｍＷ／ｃｍ２の紫外線を３０秒照射した後、１２０℃で１時間加熱してシール剤を硬化させ、液晶表示素子を得た。
得られた液晶表示素子について、シール部周辺の液晶（特にコーナー部）に生じる表示むらを目視にて観察し、表示むらが確認されなかった場合を「◎」、わずかな表示むらが確認された場合を「○」、はっきりと表示むらが確認された場合を「△」、酷い表示むらが確認された場合を「×」として液晶表示素子の表示性能（低液晶汚染性）を評価した。
なお、評価が「◎」、「○」の液晶表示素子は、実用に全く問題のないレベルである。 (Display performance of liquid crystal display elements (low liquid crystal contamination))
One part by weight of spacer particles (Sekisui Chemical Co., Ltd., “Micropearl SP-2050”) having an average particle diameter of 5 μm is used for 100 parts by weight of each sealing agent for liquid crystal display elements obtained in Examples and Comparative Examples. After uniformly dispersing with a stirrer, the resulting sealant is filled into a dispensing syringe (Musashi Engineering, PSY-10E), defoamed, and dispenser (Musashi Engineering, The sealant was applied in a frame shape to one of the two transparent electrode substrates with an ITO thin film by using SHOTMASTER 300 "). Subsequently, fine droplets of TN liquid crystal (manufactured by Chisso Corporation, “JC-5001LA”) are applied dropwise to the frame of the sealing agent with a liquid crystal dropping device, and the other transparent electrode substrate is 5 Pa with a vacuum bonding device. Bonding was performed under vacuum to obtain a cell. The obtained cell was irradiated with 100 mW / cm 2 of ultraviolet rays for 30 seconds using a metal halide lamp, and then heated at 120 ° C. for 1 hour to cure the sealant to obtain a liquid crystal display element.
Regarding the obtained liquid crystal display element, the display unevenness generated in the liquid crystal (especially the corner portion) around the seal portion was visually observed, and when the display unevenness was not confirmed, “◎”, slight display unevenness was confirmed. The display performance (low liquid crystal contamination) of the liquid crystal display element was evaluated with “◯” as the case, “△” when the display unevenness was clearly confirmed, and “X” when the severe display unevenness was confirmed.
Note that the liquid crystal display elements evaluated as “◎” and “、” are at a level that causes no problem in practical use.
実施例及び比較例で得られた各液晶表示素子用シール剤１００重量部に対して平均粒子径５μｍのスペーサー粒子（積水化学工業社製、「ミクロパールＳＰ－２０５０」）１重量部を遊星式撹拌装置によって均一に分散させ、得られたシール剤をディスペンス用のシリンジ（武蔵エンジニアリング社製、「ＰＳＹ－１０Ｅ」）に充填し、脱泡処理を行ってから、ディスペンサー（武蔵エンジニアリング社製、「ＳＨＯＴＭＡＳＴＥＲ３００」）にて、２枚のＩＴＯ薄膜付きの透明電極基板の一方にシール剤を枠状に塗布した。続いて、ＴＮ液晶（チッソ社製、「ＪＣ－５００１ＬＡ」）の微小滴を液晶滴下装置にてシール剤の枠内に滴下塗布し、他方の透明電極基板を、真空貼り合わせ装置にて５Ｐａの真空下にて貼り合わせ、セルを得た。得られたセルに、メタルハライドランプを用いて１００ｍＷ／ｃｍ２の紫外線を３０秒照射した後、１２０℃で１時間加熱してシール剤を硬化させ、液晶表示素子を得た。
得られた液晶表示素子について、シール部周辺の液晶（特にコーナー部）に生じる表示むらを目視にて観察し、表示むらが確認されなかった場合を「◎」、わずかな表示むらが確認された場合を「○」、はっきりと表示むらが確認された場合を「△」、酷い表示むらが確認された場合を「×」として液晶表示素子の表示性能（低液晶汚染性）を評価した。
なお、評価が「◎」、「○」の液晶表示素子は、実用に全く問題のないレベルである。 (Display performance of liquid crystal display elements (low liquid crystal contamination))
One part by weight of spacer particles (Sekisui Chemical Co., Ltd., “Micropearl SP-2050”) having an average particle diameter of 5 μm is used for 100 parts by weight of each sealing agent for liquid crystal display elements obtained in Examples and Comparative Examples. After uniformly dispersing with a stirrer, the resulting sealant is filled into a dispensing syringe (Musashi Engineering, PSY-10E), defoamed, and dispenser (Musashi Engineering, The sealant was applied in a frame shape to one of the two transparent electrode substrates with an ITO thin film by using SHOTMASTER 300 "). Subsequently, fine droplets of TN liquid crystal (manufactured by Chisso Corporation, “JC-5001LA”) are applied dropwise to the frame of the sealing agent with a liquid crystal dropping device, and the other transparent electrode substrate is 5 Pa with a vacuum bonding device. Bonding was performed under vacuum to obtain a cell. The obtained cell was irradiated with 100 mW / cm 2 of ultraviolet rays for 30 seconds using a metal halide lamp, and then heated at 120 ° C. for 1 hour to cure the sealant to obtain a liquid crystal display element.
Regarding the obtained liquid crystal display element, the display unevenness generated in the liquid crystal (especially the corner portion) around the seal portion was visually observed, and when the display unevenness was not confirmed, “◎”, slight display unevenness was confirmed. The display performance (low liquid crystal contamination) of the liquid crystal display element was evaluated with “◯” as the case, “△” when the display unevenness was clearly confirmed, and “X” when the severe display unevenness was confirmed.
Note that the liquid crystal display elements evaluated as “◎” and “、” are at a level that causes no problem in practical use.
本発明によれば、塗布性、透湿防止性、及び、接着性に優れ、かつ、液晶汚染を抑制できる液晶表示素子用シール剤を提供することができる。また、本発明によれば、該液晶表示素子用シール剤を用いてなる上下導通材料及び液晶表示素子を提供することができる。
ADVANTAGE OF THE INVENTION According to this invention, the sealing agent for liquid crystal display elements which can be excellent in applicability | paintability, moisture-permeability prevention property, and adhesiveness, and can suppress liquid crystal contamination can be provided. Moreover, according to this invention, the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal display elements can be provided.
Claims (4)
- 硬化性樹脂と、ラジカル重合開始剤及び／又は熱硬化剤とを含有する液晶表示素子用シール剤であって、
前記硬化性樹脂は、下記式（１）で表される化合物を含有し、
液晶表示素子用シール剤中における前記式（１）で表される化合物の含有量が１重量％以上３０重量％未満である
ことを特徴とする液晶表示素子用シール剤。
The curable resin contains a compound represented by the following formula (1),
The sealing agent for liquid crystal display elements, wherein the content of the compound represented by the formula (1) in the sealing agent for liquid crystal display elements is 1% by weight or more and less than 30% by weight.
- 硬化性樹脂は、更にエポキシ（メタ）アクリレートを含有することを特徴とする請求項１記載の液晶表示素子用シール剤。 The sealing agent for liquid crystal display elements according to claim 1, wherein the curable resin further contains an epoxy (meth) acrylate.
- 請求項１又は２記載の液晶表示素子用シール剤と導電性微粒子とを含有することを特徴とする上下導通材料。 A vertical conduction material comprising the sealing agent for a liquid crystal display element according to claim 1 or 2 and conductive fine particles.
- 請求項１若しくは２記載の液晶表示素子用シール剤又は請求項３記載の上下導通材料を用いてなることを特徴とする液晶表示素子。 A liquid crystal display element comprising the sealant for a liquid crystal display element according to claim 1 or 2 or the vertical conduction material according to claim 3.
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| JP2017502913A JP6798978B2 (en) | 2016-01-07 | 2017-01-04 | Sealing agent for liquid crystal display element, vertical conduction material, and liquid crystal display element |
| KR1020177035070A KR102709510B1 (en) | 2016-01-07 | 2017-01-04 | Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element |
| CN201780001784.1A CN107636524B (en) | 2016-01-07 | 2017-01-04 | Sealing agent for liquid crystal display element, vertical conduction material, and liquid crystal display element |
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| WO2018159387A1 (en) * | 2017-03-03 | 2018-09-07 | 日本ユピカ株式会社 | Crystalline radical-polymerizable composition for electric/electronic component, molded electric/electronic component obtained using said composition, and production method for said molded electric/electronic component |
| JP2018145280A (en) * | 2017-03-03 | 2018-09-20 | 日本ユピカ株式会社 | Crystalline radically polymerizable composition for sealing electric/electronic component, sealing body for electric/electronic component using the composition, and method of manufacturing the sealing body |
| JP2019089871A (en) * | 2017-11-10 | 2019-06-13 | 日本ユピカ株式会社 | Crystalline radical-polymerizable composition for electric/electronic components, electric/electronic component molding prepared using the composition, and method for producing the electric/electronic component molding |
| EP4119589A1 (en) * | 2021-07-16 | 2023-01-18 | Hilti Aktiengesellschaft | Epoxy resin mixtures comprising epoxide-acrylate hybrid molecules and multicomponent reactive resin compositions therefrom |
| EP4119590A1 (en) * | 2021-07-16 | 2023-01-18 | Hilti Aktiengesellschaft | Epoxide-acrylate hybrid molecules and their use for chemical anchoring |
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| KR20210012994A (en) * | 2018-05-25 | 2021-02-03 | 세키스이가가쿠 고교가부시키가이샤 | Liquid crystal display element sealing agent, upper and lower conduction material and liquid crystal display element |
| KR20210098945A (en) * | 2018-12-07 | 2021-08-11 | 세키스이가가쿠 고교가부시키가이샤 | Sealing agent for display elements, hardened|cured material, vertical conduction material, and display element |
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| WO2011040397A1 (en) * | 2009-10-02 | 2011-04-07 | 積水化学工業株式会社 | Method for manufacturing liquid crystal display device |
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| JP4752131B2 (en) * | 2001-05-16 | 2011-08-17 | 味の素株式会社 | Latent curing agent for epoxy resin and curable epoxy resin composition |
| CN100410782C (en) * | 2004-09-06 | 2008-08-13 | 日本化药株式会社 | Liquid crystal sealing material and liquid crystal display cell using same |
| KR101202370B1 (en) * | 2005-09-02 | 2012-11-16 | 디아이씨 가부시끼가이샤 | Photocurable composition for sealing agent, liquid crystal sealing agent, and liquid crystal panel |
| CN105283803B (en) * | 2013-06-11 | 2017-08-01 | 积水化学工业株式会社 | Sealant for liquid crystal dripping process, up and down conductive material and liquid crystal display cells |
| JP6523167B2 (en) * | 2014-05-23 | 2019-05-29 | 積水化学工業株式会社 | Sealant for liquid crystal dropping method, vertical conduction material, and liquid crystal display element |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018159387A1 (en) * | 2017-03-03 | 2018-09-07 | 日本ユピカ株式会社 | Crystalline radical-polymerizable composition for electric/electronic component, molded electric/electronic component obtained using said composition, and production method for said molded electric/electronic component |
| JP2018145280A (en) * | 2017-03-03 | 2018-09-20 | 日本ユピカ株式会社 | Crystalline radically polymerizable composition for sealing electric/electronic component, sealing body for electric/electronic component using the composition, and method of manufacturing the sealing body |
| US11485801B2 (en) | 2017-03-03 | 2022-11-01 | Japan U-Pica Company, Ltd. | Crystalline radical polymerizable composition for electrical and electronic component, molded article of electrical and electronic component using the composition, and method of the molded article of electrical and electronic component |
| JP2019089871A (en) * | 2017-11-10 | 2019-06-13 | 日本ユピカ株式会社 | Crystalline radical-polymerizable composition for electric/electronic components, electric/electronic component molding prepared using the composition, and method for producing the electric/electronic component molding |
| EP4119589A1 (en) * | 2021-07-16 | 2023-01-18 | Hilti Aktiengesellschaft | Epoxy resin mixtures comprising epoxide-acrylate hybrid molecules and multicomponent reactive resin compositions therefrom |
| EP4119590A1 (en) * | 2021-07-16 | 2023-01-18 | Hilti Aktiengesellschaft | Epoxide-acrylate hybrid molecules and their use for chemical anchoring |
| WO2023285221A1 (en) * | 2021-07-16 | 2023-01-19 | Hilti Aktiengesellschaft | Epoxide-acrylate hybrid molecules and their use for chemical anchoring |
| WO2023285220A1 (en) * | 2021-07-16 | 2023-01-19 | Hilti Aktiengesellschaft | Epoxy resin mixtures comprising epoxide-acrylate hybrid molecules and multicomponent reactive resin compositions therefrom |
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| JPWO2017119406A1 (en) | 2018-10-25 |
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| JP6798978B2 (en) | 2020-12-09 |
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