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
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/50—Amines
  • C08G59/56—Amines together with other curing agents
• • 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
• • 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
• • 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 sealant for a liquid crystal display element, which is excellent in storage stability, adhesiveness, and low liquid crystal stain resistance.
• the present invention also relates to a vertically conductive material and a liquid crystal display element using the sealant for a liquid crystal display element.
• a liquid crystal dropping method called a construction method is used.
• the dropping method first, a frame-shaped seal pattern is formed on one of the two substrates with electrodes by dispensing. Next, in a state where the sealant is uncured, fine droplets of liquid crystal are dropped into the frame of the seal pattern, the other substrate is laminated under vacuum, and then the sealant is cured to produce a liquid crystal display element.
• this dropping method is the mainstream method for manufacturing liquid crystal display elements.
• miniaturization of the devices is the most sought after issue.
• a narrowing of the frame of the liquid crystal display unit is mentioned.
• the position of the seal portion is arranged under the black matrix (hereinafter, also referred to as a narrow frame design).
• the sealant In the narrow frame design, the sealant is placed directly under the black matrix, so if the dropping method is used, the light emitted when the sealant is photo-cured is blocked, and it is difficult for the light to reach the inside of the sealant.
• the sealing agent is insufficiently cured. When the curing of the sealing agent is insufficient as described above, there is a problem that the uncured sealing agent component is eluted into the liquid crystal display and the liquid crystal contamination is likely to occur. In particular, in recent years, with the increasing polarity of liquid crystals, liquid crystal contamination may occur even when a sealing agent, which has not been a problem in the past, is used, and the sealing agent is required to have further low liquid crystal contamination.
• thermosetting agent is added to the sealant. ..
• the sealant is also arranged on the alignment film, there is a demand for a sealant for a liquid crystal display element having excellent adhesiveness not only to the substrate but also to the alignment film.
• the obtained sealant may be inferior in storage stability or cause liquid crystal contamination. was there.
• the present invention is a sealant for a liquid crystal display element containing a curable resin and a thermosetting agent
• the thermosetting agent is a sealant for a liquid crystal display element containing an amine adduct body of an epoxy compound and an imidazole compound. ..
• the present invention will be described in detail below.
• the present inventor uses a combination of an amine adduct of an epoxy compound and an imidazole compound as a thermosetting agent to provide a sealant for a liquid crystal display element which is excellent in storage stability, adhesiveness, and low liquid crystal contamination. It was found that the present invention can be obtained, and the present invention has been completed.
• the sealant for a liquid crystal display element of the present invention contains a thermosetting agent.
• the thermosetting agent contains an amine adduct body of an epoxy compound (hereinafter, also simply referred to as “amine adduct body”) and an imidazole compound.
• amine adduct body an epoxy compound
• imidazole compound an imidazole compound
• the amine adduct body has a structure derived from an epoxy compound and a structure derived from an amine compound.
• Examples of the epoxy compound from which the amine adduct is derived include bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol E type epoxy compound, bisphenol S type epoxy compound, and 2,2'-diallyl bisphenol A type epoxy compound. , Hydrogenated bisphenol type epoxy compound, propylene oxide added bisphenol A type epoxy compound, resorcinol type epoxy compound, biphenyl type epoxy compound, sulfide type epoxy compound, diphenyl ether type epoxy compound, dicyclopentadiene type epoxy compound, naphthalene type epoxy compound, phenol Novolak type epoxy compound, orthocresol novolak type epoxy compound, dicyclopentadiene novolak type epoxy compound, biphenylnovolak type epoxy compound, naphthalenephenol novolak type epoxy compound, glycidylamine type epoxy compound, alkylpolypoly type epoxy compound, rubber-modified epoxy compound , Glysidyl ester compound and the like. Of these, bisphenol A type epoxy compounds
• Examples of the amine compound from which the amine adduct is derived include an aliphatic primary monoamine, an alicyclic primary monoamine, an aromatic primary monoamine, an alkylenediamine, and an imidazolyl substituted with a nitrogen atom at the 1-position.
• Examples thereof include primary diamines having a group, polyalkyl polyamines, alicyclic polyamines, aromatic polyamines and the like.
• Examples of the aliphatic primary monoamine include methylamine, ethylamine, propylamine, butylamine, ethanolamine, propanolamine and the like.
• Examples of the alicyclic primary monoamine include cyclohexylamine and the like.
• Examples of the aromatic primary monoamine include aniline and toluidine.
• alkylenediamine examples include ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,3-diaminobutane, 1,4-diaminobutane, cadaverine, hexamethylenediamine and other alkylenediamines. Be done.
• Examples of the primary diamine having an imidazolyl group in which the nitrogen atom at the 1-position is substituted include 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine.
• the polyalkylpolyamine include diethylenetriamine, triethylenetriamine, tetraethylenetriamine, tetraethylenepentamine and the like.
• Examples of the alicyclic polyamine include 1,4-bis (aminomethyl) cyclohexane, 1,3-bis (aminomethyl) cyclohexane, 1,2-bis (aminomethyl) cyclohexane, and 1,4-diamino-3. , 6-diethylcyclohexane, isophoronediamine and the like.
• Examples of the aromatic polyamine include aromatic polyamines such as o-xylylene diamine, m-xylylene diamine, p-xylylene diamine, diaminodiphenylmethane, and diaminodiphenyl sulfone. Of these, 1,4-bis (aminomethyl) cyclohexane is preferable.
• the preferable lower limit of the mass average molecular weight is 500, and the preferable upper limit is 1500.
• the mass average molecular weight of the amine adduct body is 500 or more, the obtained sealant for a liquid crystal display element becomes more excellent in low liquid crystal contamination.
• the mass average molecular weight of the amine adduct body is 1500 or less, the obtained sealant for a liquid crystal display element becomes excellent in handleability.
• the more preferable lower limit of the mass average molecular weight of the amine adduct body is 1000, and the more preferable upper limit is 1200.
• the mass average molecular weight is a value obtained by measuring by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent and converting it into polystyrene.
• GPC gel permeation chromatography
• Examples of the column for measuring the mass average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko KK) and the like.
• the amine adduct body preferably contains a compound represented by the following formula (1).
• R 1 is an independent hydrogen atom or a methyl group
• n is an integer of 1 or more and 10 or less.
• each of R 1 in the above formula (1) is a methyl group.
• the preferable lower limit of the content ratio of the amine adduct body in the entire sealant for a liquid crystal display element of the present invention is 2% by mass, and the preferable upper limit is 5% by mass.
• the content ratio of the amine adduct compound in the entire sealant for a liquid crystal display element of the present invention is 2% by mass or more, the obtained sealant for a liquid crystal display element becomes more excellent in adhesiveness.
• the content ratio of the amine adduct compound in the entire sealant for a liquid crystal display element of the present invention is 5% by mass or less, the obtained sealant for a liquid crystal display element becomes more excellent in low liquid crystal contamination.
• a more preferable lower limit of the content ratio of the amine adduct compound in the entire sealant for a liquid crystal display element of the present invention is 3% by mass, and a more preferable upper limit is 4% by mass.
• the preferable lower limit of the content of the amine adduct body with respect to 100 parts by mass of the curable resin described later is 2 parts by mass, and the preferable upper limit is 5 parts by mass.
• the content of the amine adduct compound with respect to 100 parts by mass of the curable resin is 5 parts by mass or less, the obtained sealing agent for a liquid crystal display element becomes more excellent in low liquid crystal contamination.
• the more preferable lower limit of the content of the amine adduct compound with respect to 100 parts by mass of the curable resin is 3 parts by mass, and the more preferable upper limit is 4 parts by mass.
• the imidazole compound preferably has an alkyl chain having 10 or more carbon atoms, and more preferably has an alkyl chain having 10 or more carbon atoms and 12 or less carbon atoms.
• the preferable upper limit of the melting point of the imidazole compound is 130 ° C.
• the melting point of the imidazole compound is 130 ° C. or lower, the obtained sealant for a liquid crystal display element becomes more excellent in low liquid crystal contamination.
• a more preferable upper limit of the melting point of the imidazole compound is 120 ° C.
• a further preferable upper limit is 110 ° C.
• a further preferable upper limit is 60 ° C.
• a more preferable lower limit of the melting point of the imidazole compound is 30 ° C.
• the melting point of the imidazole compound can be determined by differential scanning calorimetry or a commercially available melting point measuring instrument.
• Examples of the imidazole compound include a compound represented by the following formula (2), a compound represented by the following formula (3), a compound represented by the following formula (4), and the like.
• the compound represented by the following formula (2) is preferable, and the compound (1- (2-cyanoethyl) -2-undecylimidazole) in which m is 10 and l is 2 in the following formula (2) is preferable. Especially preferable.
• m is an integer of 1 or more and 10 or less
• l is an integer of 1 or more and 3 or less.
• m is an integer of 1 or more and 10 or less
• l is an integer of 1 or more and 3 or less.
• l is an integer of 1 or more and 3 or less.
• the preferable lower limit of the content ratio of the imidazole compound in the entire sealant for a liquid crystal display element of the present invention is 0.1% by mass, and the preferable upper limit is 0.7% by mass.
• the content of the imidazole compound in the entire sealant for a liquid crystal display element of the present invention is 0.1% by mass or more, the obtained sealant for a liquid crystal display element becomes more excellent in adhesiveness.
• the content of the imidazole compound in the entire sealant for a liquid crystal display element of the present invention is 0.7% by mass or less, the obtained sealant for a liquid crystal display element is excellent in adhesiveness and storage stability.
• a more preferable upper limit of the content ratio of the imidazole compound in the entire sealant for a liquid crystal display element of the present invention is 0.3% by mass.
• the preferable lower limit of the content of the imidazole compound with respect to 100 parts by mass of the curable resin described later is 0.1 parts by mass, and the preferable upper limit is 0.7 parts by mass.
• the content of the imidazole compound with respect to 100 parts by mass of the curable resin is 0.1 part by mass or more, the obtained sealant for a liquid crystal display element becomes more excellent in adhesiveness.
• the content of the imidazole compound with respect to 100 parts by mass of the curable resin is 0.7 parts by mass or less, the obtained sealant for a liquid crystal display element becomes excellent in adhesiveness and storage stability.
• a more preferable upper limit of the content of the imidazole compound with respect to 100 parts by mass of the curable resin is 0.3 parts by mass.
• the ratio of the content of the amine adduct to the content of the imidazole compound is a mass ratio with a preferable lower limit of 15 and a preferred upper limit of 50.
• the ratio of the content of the amine adduct to the content of the imidazole compound is 15 or more, the obtained sealant for a liquid crystal display element becomes excellent in adhesiveness and storage stability.
• the ratio of the content of the amine adduct to the content of the imidazole compound is 50 or less, the obtained sealing agent for a liquid crystal display element becomes more excellent in low liquid crystal contamination.
• the more preferable lower limit of the ratio of the content of the amine adduct to the content of the imidazole compound is 17.5, and the more preferable upper limit is 35.
• thermosetting agent may contain other thermosetting agents in addition to the amine adduct body and the imidazole compound as long as the object of the present invention is not impaired.
• the other heat-curing agent include organic acid hydrazide, polyhydric phenolic compound, acid anhydride and the like.
• the sealant for a liquid crystal display element of the present invention contains a curable resin.
• the curable resin preferably contains an epoxy compound.
• the epoxy compound include bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol E type epoxy compound, bisphenol S type epoxy compound, 2,2'-diallyl bisphenol A type epoxy compound, hydrogenated bisphenol type epoxy compound.
• Examples of commercially available bisphenol A type epoxy compounds include jER828EL, jER1004 (all manufactured by Mitsubishi Chemical Corporation), EPICLON850 (manufactured by DIC Corporation), and the like.
• Examples of commercially available bisphenol F type epoxy compounds include jER806, jER4004 (all manufactured by Mitsubishi Chemical Corporation), EPICLON EXA-830CRP (manufactured by DIC Corporation), and the like.
• Examples of commercially available bisphenol E-type epoxy compounds include Epomic R710 (manufactured by Mitsui Chemicals, Inc.) and the like.
• Examples of commercially available bisphenol S-type epoxy compounds include EPICLON EXA-1514 (manufactured by DIC Corporation) and the like.
• Examples of commercially available 2,2'-diallyl bisphenol A type epoxy compounds include RE-810NM (manufactured by Nippon Kayaku Co., Ltd.).
• Examples of commercially available hydrogenated bisphenol type epoxy compounds include EPICLON EXA-7015 (manufactured by DIC Corporation) and the like.
• Examples of commercially available propylene oxide-added bisphenol A type epoxy compounds include EP-4000S (manufactured by ADEKA Corporation) and the like.
• Examples of commercially available resorcinol-type epoxy compounds include EX-201 (manufactured by Nagase ChemteX Corporation) and the like.
• Examples of commercially available biphenyl type epoxy compounds include jER YX-4000H (manufactured by Mitsubishi Chemical Corporation) and the like.
• Examples of commercially available sulfide-type epoxy compounds include YSLV-50TE (manufactured by Nittetsu Chemical & Materials Co., Ltd.).
• Examples of commercially available diphenyl ether type epoxy compounds include YSLV-80DE (manufactured by Nittetsu Chemical & Materials Co., Ltd.).
• Examples of commercially available dicyclopentadiene type epoxy compounds include EP-4088S (manufactured by ADEKA Corporation) and the like.
• Examples of commercially available naphthalene-type epoxy compounds include EPICLON HP-4032 and EPICLON EXA-4700 (both manufactured by DIC Corporation).
• Examples of commercially available phenol novolac type epoxy compounds include EPICLON N-770 (manufactured by DIC Corporation) and the like.
• Examples of commercially available orthocresol novolak type epoxy compounds include EPICLON N-670-EXP-S (manufactured by DIC Corporation) and the like.
• Examples of commercially available dicyclopentadiene novolak type epoxy compounds include EPICLON HP-7200 (manufactured by DIC Corporation) and the like.
• Examples of commercially available biphenyl novolac type epoxy compounds include NC-3000P (manufactured by Nippon Kayaku Co., Ltd.) and the like.
• Examples of commercially available naphthalene phenol novolac type epoxy compounds include ESN-165S (manufactured by Nittetsu Chemical & Materials Co., Ltd.).
• Examples of commercially available glycidylamine type epoxy compounds include jER630 (manufactured by Mitsubishi Chemical Corporation), EPICLON430 (manufactured by DIC Corporation), TETRAD-X (manufactured by Mitsubishi Gas Chemical Company, Inc.) and the like.
• alkyl polyol type epoxy compounds for example, ZX-1542 (manufactured by Nittetsu Chemical & Materials Co., Ltd.), EPICLON726 (manufactured by DIC Corporation), Epolite 80MFA (manufactured by Kyoei Co., Ltd.), Denacol EX- 611 (manufactured by Nagase ChemteX Corporation) and the like can be mentioned.
• Examples of commercially available rubber-modified epoxy compounds include YR-450, YR-207 (all manufactured by Nittetsu Chemical & Materials Co., Ltd.), Epolide PB (manufactured by Daicel Co., Ltd.), and the like.
• Examples of commercially available glycidyl ester compounds include Denacol EX-147 (manufactured by Nagase ChemteX Corporation) and the like.
• Other commercially available epoxy compounds include, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nittetsu Chemical & Materials Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Co., Ltd.), jER1031 and jER1032. (All manufactured by Mitsubishi Chemical Corporation), EXA-7120 (manufactured by DIC Corporation), TEPIC (manufactured by Nissan Chemical Industries, Ltd.) and the like can be mentioned.
• the epoxy compound a partially (meth) acrylic-modified epoxy compound is also preferably used.
• the partial (meth) acrylic-modified epoxy compound can be obtained by reacting an epoxy group of a part of an epoxy compound having two or more epoxy groups with (meth) acrylic acid. It means a compound having one or more epoxy groups and one or more (meth) acryloyl groups in the molecule.
• the above-mentioned "(meth) acrylic” means acrylic or methacrylic
• the above-mentioned "(meth) acryloyl” means acryloyl or methacrylic acid.
• Examples of commercially available partial (meth) acrylic-modified epoxy compounds include UVACURE1561, KRM8287 (both manufactured by Dycel Ornex) and the like.
• the curable resin may contain a (meth) acrylic compound.
• the (meth) acrylic compound include (meth) acrylic acid ester compounds, epoxy (meth) acrylates, urethane (meth) acrylates, and the like. Of these, epoxy (meth) acrylate is preferable.
• the (meth) acrylic compound preferably has two or more (meth) acryloyl groups in one molecule from the viewpoint of reactivity.
• the above-mentioned "(meth) acrylic compound” means a compound having a (meth) acryloyl group.
• (meth) acrylate means acrylate or methacrylate
• epoxy (meth) acrylate is a compound obtained by reacting all epoxy groups in an epoxy compound with (meth) acrylic acid. Represents that.
• monofunctional ones include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate.
• bifunctional ones include, for example, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexane.
• Dimethylol dicyclopentadienyldi (meth) acrylate Dimethylol dicyclopentadienyldi (meth) acrylate, ethylene oxide modified isocyanuric acid di (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, carbonate diol di (meth) acrylate, Examples thereof include polyether diol di (meth) acrylate, polyester diol di (meth) acrylate, polycaprolactone diol di (meth) acrylate, and polybutadiene diol di (meth) acrylate.
• those having trifunctionality or higher include, for example, trimethylol propanetri (meth) acrylate, ethylene oxide-added trimethylol propanetri (meth) acrylate, and propylene oxide-added trimethylol propanetri (meth) acrylate.
• 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.
• the same epoxy compound as the above-mentioned epoxy compound can be used as the curable resin contained in the sealant for a liquid crystal display element of the present invention.
• epoxy (meth) acrylates commercially available ones include, for example, epoxy (meth) acrylate manufactured by Dycel Ornex, epoxy (meth) acrylate manufactured by Shin-Nakamura Chemical Industry Co., Ltd., and epoxy manufactured by Kyoei Co., Ltd. Examples thereof include meta) acrylate and epoxy (meth) acrylate manufactured by Nagase ChemteX Corporation.
• Examples of the epoxy (meth) acrylate manufactured by Dycel Ornex include EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3702, EBECRYL3702, EBECRYL3701, EBECRYL3701
• Examples of the epoxy (meth) acrylate manufactured by Shin-Nakamura Chemical Industry Co., Ltd. include EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 and the like.
• Examples of the epoxy (meth) acrylate manufactured by Kyoeisha Chemical Co., Ltd. include epoxy ester M-600A, epoxy ester 40EM, epoxy ester 70PA, epoxy ester 200PA, epoxy ester 80MFA, epoxy ester 3002M, epoxy ester 3002A, and epoxy ester 1600A. Examples thereof include epoxy ester 3000M, epoxy ester 3000A, epoxy ester 200EA, and epoxy ester 400EA. Examples of the epoxy (meth) acrylate manufactured by Nagase ChemteX include Denacol acrylate DA-141, Denacol acrylate DA-314, and Denacol acrylate DA-911.
• the urethane (meth) acrylate can be obtained, for example, by reacting a (meth) acrylic acid derivative having a hydroxyl group with respect to an isocyanate compound in the presence of a catalytic amount of a tin-based compound.
• Examples of the isocyanate compound used as a 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.
• MDI '-Diisocyanate
• XDI xylylene diisocyanate
• XDI hydrogenated XDI
• lysine diisocyanate triphenylmethane triisocyanate
• tris (isocyanate) Phenyl) thiophosphate tetramethylxylylene diisocyanate
• 1,6,11-undecantry isocyanate and the like can be mentioned.
• the isocyanate compound which is a raw material of the urethane (meth) acrylate a chain-extended isocyanate compound obtained by reacting a polyol with an excess isocyanate compound can also be used.
• the polyol include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, and polycaprolactone diol.
• Examples of the (meth) acrylic acid derivative having a hydroxyl group include hydroxyalkyl mono (meth) acrylate, mono (meth) acrylate of dihydric alcohol, mono (meth) acrylate of trihydric alcohol or di (meth) acrylate. , Epoxy (meth) acrylate and the like.
• Examples of the hydroxyalkyl mono (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. Can be mentioned.
• Examples of the divalent alcohol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, polyethylene glycol and the like.
• Examples of the trihydric alcohol include trimethylolethane, trimethylolpropane, and glycerin.
• Examples of the epoxy (meth) acrylate include bisphenol A type epoxy (meth) acrylate.
• urethane (meth) acrylates commercially available ones include, for example, urethane (meth) acrylate manufactured by Toa Synthetic Co., Ltd., urethane (meth) acrylate manufactured by Dycel Ornex, and urethane (meth) manufactured by Negami Kogyo Co., Ltd. Examples thereof include acrylate, urethane (meth) acrylate manufactured by Shin-Nakamura Chemical Industry Co., Ltd., urethane (meth) acrylate manufactured by Kyoeisha Chemical Co., Ltd., and the like. Examples of the urethane (meth) acrylate manufactured by Toagosei Co., Ltd.
• the urethane (meth) acrylate manufactured by the Daicel Orunekusu Inc. for example, EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, EBECRYL1290, EBECRYL2220, EBECRYL4827, EBECRYL4842, EBECRYL4858, EBECRYL5129, EBECRYL6700, EBECRYL8402, EBECRYL8803, EBECRYL8804, EBECRYL8807, EBECRYL9260 etc. Can be mentioned.
• Examples of the urethane (meth) acrylate manufactured by Negami Kogyo Co., Ltd. include Art Resin UN-330, Art Resin SH-500B, Art Resin UN-1200TPK, Art Resin UN-1255, Art Resin UN-3320HB, and Art Resin UN-. 7100, Art Resin UN-9000A, Art Resin UN-9000H and the like can be mentioned.
• Examples of the urethane (meth) acrylate manufactured by Shin Nakamura Chemical Industry Co., Ltd. include U-2HA, U-2PHA, U-3HA, U-4HA, U-6H, U-6HA, U-6LPA, U-10H, and the like.
• Examples of the urethane (meth) acrylate manufactured by Kyoeisha Chemical Co., Ltd. include AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA-306T and the like. Be done.
• the curable resin contains the (meth) acrylic compound in addition to the epoxy compound, or when the partially (meth) acrylic-modified epoxy compound is contained, the epoxy group and the (meth) in the curable resin are contained. It is preferable that the ratio of the (meth) acryloyl group in the total with the acryloyl group is 30 mol% or more and 95 mol% or less. When the ratio of the (meth) acryloyl group is in this range, the sealant for the liquid crystal display element obtained is excellent in adhesiveness while suppressing the occurrence of liquid crystal contamination.
• the curable resin preferably has a hydrogen-bonding unit such as an -OH group, an -NH- group, and an -NH 2 group from the viewpoint of further suppressing liquid crystal contamination.
• the sealant for a liquid crystal display element of the present invention preferably contains a photoradical polymerization initiator.
• the photoradical polymerization initiator include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanosen compounds, oxime ester compounds, benzoin ether compounds, thioxanthone compounds and the like.
• Specific examples of the photoradical polymerization initiator include 1-hydroxycyclohexylphenylketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, and 2- (dimethylamino).
• the content of the photoradical polymerization initiator has a preferable lower limit of 0.5 parts by mass and a preferable upper limit of 10 parts by mass with respect to 100 parts by mass of the curable resin.
• the content of the photoradical polymerization initiator is in this range, the obtained sealing agent for a liquid crystal display element is excellent in storage stability and photocurability while suppressing liquid crystal contamination.
• the more preferable lower limit of the content of the photoradical polymerization initiator is 1 part by mass, and the more preferable upper limit is 7 parts by mass.
• the sealant for a liquid crystal display element of the present invention may contain a thermal radical polymerization initiator.
• the thermal radical polymerization initiator include those composed of an azo compound, an organic peroxide, or the like. Among them, an initiator composed of an azo compound (hereinafter, also referred to as “azo initiator”) is preferable from the viewpoint of suppressing liquid crystal contamination, and an initiator composed of a polymer azo compound (hereinafter, “polymer azo”) is preferable. Also referred to as “initiator”) is more preferred.
• the thermal radical polymerization initiator may be used alone or in combination of two or more.
• polymer azo compound means a compound having an azo group and having a number average molecular weight of 300 or more, which generates a radical capable of reacting a (meth) acryloyl group by heat. do.
• the preferable lower limit of the number average molecular weight of the polymer azo compound is 1000, and the preferable upper limit is 300,000.
• the more preferable lower limit of the number average molecular weight of the polymer azo compound is 5000, the more preferable upper limit is 100,000, the further preferable lower limit is 10,000, and the further preferable upper limit is 90,000.
• the number average molecular weight is a value obtained by measuring by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent and converting it into polystyrene. 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) and the like.
• Examples of the polymer azo compound include those having a structure in which a plurality of units such as polyalkylene oxide and polydimethylsiloxane are bonded via an azo group.
• the polymer azo compound 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.
• Specific examples of the polymer azo compound include a polycondensate of 4,4'-azobis (4-cyanopentanoic acid) and polyalkylene glycol, and 4,4'-azobis (4-cyanopentanoic acid). And a polycondensate of polydimethylsiloxane having a terminal amino group and the like.
• polymer azo initiators include, for example, VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and the like. Can be mentioned.
• examples of the non-polymer azo initiator include V-65 and V-501 (both manufactured by Wako Pure Chemical Industries, Ltd.).
• organic peroxide examples include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, peroxyesters, diacyl peroxides, peroxydicarbonates and the like.
• the content of the thermal radical polymerization initiator has a preferable lower limit of 0.1 parts by mass and a preferable upper limit of 10 parts by mass with respect to 100 parts by mass of the curable resin.
• the content of the thermal radical polymerization initiator is in this range, the obtained sealing agent for a liquid crystal display element is excellent in storage stability and thermosetting property while suppressing liquid crystal contamination.
• the more preferable lower limit of the content of the thermal radical polymerization initiator is 0.3 parts by mass, and the more preferable upper limit is 5 parts by mass.
• the sealant for a liquid crystal display element of the present invention may contain a filler for the purpose of improving the viscosity, improving the adhesiveness by the stress dispersion effect, improving the linear expansion rate, improving the moisture resistance of the cured product, and the like.
• an inorganic filler or an organic filler can be used as the filler.
• the inorganic filler include silica, talc, glass beads, asbestos, gypsum, diatomaceous soil, smectite, bentonite, montmorillonite, sericite, active white clay, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide and titanium oxide. , Calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate, calcium silicate and the like.
• the organic filler include polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, acrylic polymer fine particles, and the like. The filler may be used alone or in combination of two or more.
• the preferable lower limit of the content of the filler in 100 parts by mass of the sealant for a liquid crystal display element of the present invention is 10 parts by mass, and the preferable upper limit is 70 parts by mass.
• the content of the filler is in this range, the effect of improving the adhesiveness and the like is excellent without deteriorating the coatability and the like.
• the more preferable lower limit of the content of the filler is 20 parts by mass, and the more preferable upper limit is 60 parts by mass.
• the sealant for a liquid crystal display element of the present invention may contain a silane coupling agent.
• the silane coupling agent mainly has a role as an adhesive auxiliary for satisfactorily adhering a sealant for a liquid crystal display element and a substrate or the like.
• silane coupling agent for example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane and the like are preferably used. These are excellent in the effect of improving the adhesiveness with the substrate and the like, and can suppress the outflow of the curable resin into the liquid crystal display by chemically bonding with the curable resin. Of these, 3-glycidoxypropyltrimethoxysilane is preferable.
• the silane coupling agent may be used alone or in combination of two or more.
• the preferable lower limit of the content of the silane coupling agent in 100 parts by mass of the sealant for a liquid crystal display element of the present invention is 0.1 parts by mass, and the preferable upper limit is 10 parts by mass.
• the content of the silane coupling agent is within this range, the effect of improving the adhesiveness while suppressing the occurrence of liquid crystal contamination becomes more excellent.
• the more preferable lower limit of the content of the silane coupling agent is 0.3 parts by mass, and the more preferable upper limit is 5 parts by mass.
• the sealant for a liquid crystal display element of the present invention may contain a light-shielding agent.
• the sealant for a liquid crystal display element of the present invention can be suitably used as a light-shielding sealant.
• 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.
• the titanium black is a substance having a higher transmittance in the vicinity of the ultraviolet region, particularly for light having a wavelength of 370 nm or more and 450 nm or less, as compared with the average transmittance for light having a wavelength of 300 nm or more and 800 nm or less. That is, the titanium black has a property of imparting a light-shielding property to the sealant for a liquid crystal display element of the present invention by sufficiently blocking light having a wavelength in the visible light region, while transmitting light having a wavelength in the vicinity of the ultraviolet region. It is a light-shielding agent.
• the photoradical polymerization initiator that can initiate the reaction with light having a wavelength having a high transmittance of the titanium black, the photocurability of the sealant for a liquid crystal display element of the present invention is further improved. Can be made to.
• the light-shielding agent contained in the sealant for a liquid crystal display element of the present invention a substance having a high insulating property is preferable, and as a light-shielding agent having a high insulating property, titanium black is preferable.
• the titanium black has an optical density (OD value) of 3 or more, more preferably 4 or more, per 1 ⁇ m. The higher the light-shielding property of the titanium black, the better, and the OD value of the titanium black has no particular preferable upper limit, but is usually 5 or less.
• the above titanium black exerts 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, and oxidation.
• an organic component such as a coupling agent, silicon oxide, titanium oxide, germanium oxide, aluminum oxide, and oxidation.
• Surface-treated titanium black such as those coated with an inorganic component such as zirconium or magnesium oxide, can also be used. Among them, those treated with an organic component are preferable in that the insulating property can be further improved.
• the liquid crystal display element manufactured by using the sealant for the liquid crystal display element of the present invention containing the above titanium black as a light shielding agent has sufficient light shielding property, so that there is no light leakage and a high contrast is obtained. It is possible to realize a liquid crystal display element having excellent image display quality.
• Examples of commercially available titanium blacks include titanium black manufactured by Mitsubishi Materials Corporation and titanium black manufactured by Ako Kasei Co., Ltd. Examples of the titanium black manufactured by Mitsubishi Materials Corporation include 12S, 13M, 13M-C, 13RN, 14M-C and the like. Examples of the titanium black manufactured by Ako Kasei Co., Ltd. include Tilak D and the like.
• 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 preferable lower limit of the volume resistance of the titanium black is 0.5 ⁇ ⁇ cm, the preferable upper limit is 3 ⁇ ⁇ cm, the more preferable lower limit is 1 ⁇ ⁇ cm, and the more preferable upper limit is 2.5 ⁇ ⁇ cm.
• the primary particle diameter of the light-shielding agent is not particularly limited as long as it is equal to or less than the distance between the substrates of the liquid crystal display element, but the preferable lower limit is 1 nm and the preferable upper limit is 5000 nm.
• the primary particle size of the light-shielding agent is in this range, the light-shielding property can be improved without deteriorating the coatability of the obtained sealant for a liquid crystal display element.
• 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 further preferable lower limit is 10 nm
• the further preferable upper limit is 100 nm.
• the primary particle size of the light-shielding agent can be measured by using NICOMP 380ZLS (manufactured by PARTICLE SIZING SYSTEMS) to disperse the light-shielding agent in a solvent (water, organic solvent, etc.).
• the preferable lower limit of the content of the light-shielding agent in 100 parts by mass of the sealant for a liquid crystal display element of the present invention is 5 parts by mass, and the preferable upper limit is 80 parts by mass.
• the content of the light-shielding agent is within this range, the adhesiveness of the obtained sealant for a liquid crystal display element, the strength after curing, and the drawing property are not significantly deteriorated, and more excellent light-shielding property is exhibited.
• the more preferable lower limit of the content of the light-shielding agent is 10 parts by mass
• the more preferable upper limit is 70 parts by mass
• the further preferable lower limit is 30 parts by mass
• the further preferable upper limit is 60 parts by mass.
• the sealant for a liquid crystal display element of the present invention further contains, if necessary, a stress relaxation agent, a reactive diluent, a rocking agent, a spacer, a curing accelerator, a defoaming agent, a leveling agent, a polymerization inhibitor and the like. It may contain an agent.
• a curable resin, a thermosetting agent, a photoradical polymerization initiator added as necessary, and the like are mixed using a mixer. How to do it, etc.
• the mixer include a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and three rolls.
• a vertically conductive material By blending conductive fine particles with the sealant for a liquid crystal display element of the present invention, a vertically conductive material can be manufactured.
• a vertically conductive material containing a sealing agent for a liquid crystal display element of the present invention and conductive fine particles is also one of the present inventions.
• the conductive fine particles for example, a metal ball, a resin fine particle having a conductive metal layer formed on the surface thereof, 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 excellent elasticity of the resin fine particles enables conductive connection without damaging the transparent substrate or the like.
• a liquid crystal display element having a cured product of a sealant for a liquid crystal display element of the present invention or a cured product of a vertically conductive material of the present invention is also one of the present inventions.
• the liquid crystal display element of the present invention a liquid crystal display element having a narrow frame design is preferable.
• the width of the frame portion around the liquid crystal display unit is preferably 2 mm or less.
• the coating width of the sealant for the liquid crystal display element of the present invention when manufacturing the liquid crystal display element of the present invention is preferably 1 mm or less.
• the sealant for a liquid crystal display element of the present invention can be suitably used for manufacturing a liquid crystal display element by a liquid crystal dropping method.
• Examples of the method for manufacturing the liquid crystal display element of the present invention by the liquid crystal dropping method include the following methods. First, a step of forming a frame-shaped seal pattern on a substrate by screen printing, applying a dispenser, or the like with the sealant for a liquid crystal display element of the present invention is performed. Next, in a state where the sealant for a liquid crystal display element of the present invention is uncured, fine droplets of liquid crystal are dropped and applied to the entire surface of the frame of the seal pattern, and a step of immediately superimposing another substrate is performed.
• a liquid crystal display element can be obtained by a method of heating and curing the sealant. Further, before the step of heating and curing the sealant, a step of irradiating the seal pattern portion with light such as ultraviolet rays to temporarily cure the sealant may be performed.
• the present invention it is possible to provide a sealant for a liquid crystal display element having excellent storage stability, adhesiveness, and low liquid crystal contamination. Further, according to the present invention, it is possible to provide a vertically conductive material and a liquid crystal display element using the sealant for a liquid crystal display element.
• Examples 1 to 16 Comparative Examples 1 to 13
• a planetary stirrer manufactured by Shinky Co., Ltd., "Awatori Rentaro"
• Sealing agents for liquid crystal display elements of Examples 1 to 16 and Comparative Examples 1 to 13 were prepared.
• the sealant for the liquid crystal display element is spread, irradiated with ultraviolet rays (wavelength 365 nm) of 100 mW / cm 2 for 30 seconds using a metal halide lamp, and then heated at 120 ° C. for 1 hour to cure the sealant for the liquid crystal display element.
• An adhesion test piece was obtained.
• An adhesion test piece was obtained in the same manner for a glass substrate having a polyimide alignment film for TN (manufactured by Nissan Chemical Industries, Ltd., "SE6414”) on the surface instead of the glass substrate with an ITO thin film.
• the adhesive strength (adhesive strength) of each of the obtained adhesive test pieces was measured using a tension gauge.
• the sealant for the liquid crystal display element after the defoaming treatment is applied to the two alignment films under the conditions of a nozzle diameter of 0.4 mm ⁇ , a nozzle gap of 42 ⁇ m, a syringe discharge pressure of 100 to 400 kPa, and a coating speed of 60 mm / sec. It was applied in a frame shape to one of the substrates with ITO. At this time, the discharge pressure was adjusted so that the line width of the sealant for the liquid crystal display element was about 1.0 mm.
• liquid crystal 4-pentyl-4-biphenylcarbonitrile manufactured by Tokyo Chemical Industry Co., Ltd.
• the other substrate was bonded under vacuum.
• the sealant for the liquid crystal display element is temporarily irradiated with ultraviolet rays of 100 mW / cm 2 for 30 seconds using a metal halide lamp. It was cured. Then, it was heated at 120 ° C. for 1 hour to perform main curing, and a liquid crystal display element was manufactured.
• orientation disorder display unevenness
• VHX-5000 polarizing microscope
• Orientation disorder is judged from the color unevenness of the display part, and if no display unevenness is seen on the liquid crystal display element, there is " ⁇ ", and there is display unevenness in a part of the seal peripheral part (near the sealant for the liquid crystal display element).
• the low liquid crystal contamination property was evaluated as " ⁇ ” in the case of " ⁇ ” and "x” in the case where uneven display occurred over the entire peripheral part of the seal.
• the present invention it is possible to provide a sealant for a liquid crystal display element having excellent storage stability, adhesiveness, and low liquid crystal contamination. Further, according to the present invention, it is possible to provide a vertically conductive material and a liquid crystal display element using the sealant for a liquid crystal display element.

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• 2021
  • 2021-09-29 WO PCT/JP2021/035891 patent/WO2022071404A1/ja active Application Filing
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