WO2017119407A1 - 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
- WO2017119407A1 WO2017119407A1 PCT/JP2017/000005 JP2017000005W WO2017119407A1 WO 2017119407 A1 WO2017119407 A1 WO 2017119407A1 JP 2017000005 W JP2017000005 W JP 2017000005W WO 2017119407 A1 WO2017119407 A1 WO 2017119407A1
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- WIPO (PCT)
- Prior art keywords
- liquid crystal
- meth
- crystal display
- acrylate
- display element
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- 0 C*(CCCC1OC1)CCOc(cc1)ccc1S(c(cc1)ccc1OCCOCC(CC(C)(C)Oc(cc1)ccc1S(c(cc1)ccc1O)(=O)=O)O)(=O)=O Chemical compound C*(CCCC1OC1)CCOc(cc1)ccc1S(c(cc1)ccc1OCCOCC(CC(C)(C)Oc(cc1)ccc1S(c(cc1)ccc1O)(=O)=O)O)(=O)=O 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G59/20—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 epoxy compounds used
- C08G59/22—Di-epoxy compounds
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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
Definitions
- the present invention relates to a sealing agent for liquid crystal display elements that is excellent in 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.
- This invention is the sealing compound for liquid crystal display elements containing curable resin containing the compound represented by following formula (1), and a thermosetting agent.
- l, m, and n are each 0 to 6, and Y is 1 to 20.
- Y is 1 to 20.
- This inventor examined using bisphenol S diglycidyl ether excellent in adhesiveness and low liquid-contamination property as curable resin mix
- bisphenol S diglycidyl ether excellent in adhesiveness and low liquid-contamination property as curable resin mix
- the present inventors can obtain a sealing agent for liquid crystal display elements that is excellent in adhesiveness and can suppress liquid crystal contamination by using a bisphenol S type epoxy resin having a specific structure. As a result, the present invention has been completed.
- 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.
- l, m, and n are each 0 to 6. Each of l, m and n is preferably 1 to 6, more preferably 1 to 3, respectively.
- Y is 1-20. Y is preferably from 1 to 10, and more preferably from 1 to 4.
- the value of l, m, n, and Y in the said Formula (1) is an average value.
- the case where l, m, or n is 0 means that the ethylene oxide structure part to which l, m, or n is attached becomes a bond.
- Examples of the method for producing the compound represented by the above formula (1) include a method in which bisphenol S or ethylene oxide-modified bisphenol S and epichlorohydrin are subjected to a condensation polymerization reaction.
- the content of the compound represented by the above formula (1) in the sealant for liquid crystal display elements of the present invention is preferably 1% by weight or more and less than 30% by weight.
- the content of the compound represented by the formula (1) is within this range, the obtained sealing agent for liquid crystal display elements suppresses adhesion and liquid crystal contamination without deteriorating applicability and moisture permeation prevention. It will be superior to the effect of doing.
- the more preferable lower limit of the content of the compound represented by the formula (1) is 5% by weight, the more preferable upper limit is 25% by weight, the still more preferable lower limit is 10% by weight, and the still more preferable upper limit is 20% 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).
- Examples of the (meth) acrylic compound include epoxy (meth) acrylate obtained by reacting (meth) acrylic acid and an epoxy compound, and (meth) acrylic acid obtained by reacting a compound having a hydroxyl group.
- examples thereof include urethane (meth) acrylates obtained by reacting (meth) acrylic acid ester compounds and isocyanate compounds with (meth) acrylic acid derivatives having a hydroxyl group.
- epoxy (meth) acrylate is preferable.
- the (meth) acrylic compound preferably has two or more (meth) acryloyl groups in the molecule because of its high reactivity.
- (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 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.
- 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 that is the other curable resin examples include, for example, an epoxy compound that is a raw material for synthesizing the epoxy (meth) acrylate other than the compound represented by the formula (1), and a partial (meth) An acrylic modified 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 in one molecule. It can be obtained by reacting a part of the epoxy group having an 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 50:50 in terms of molar ratio. It is preferable to set it to 95: 5.
- the sealing agent for liquid crystal display elements of this invention contains a thermosetting agent.
- the thermosetting agent preferably contains a trifunctional or higher functional thermosetting agent from the viewpoint of reactivity.
- the “trifunctional or higher functional thermosetting agent” means a thermosetting agent made of a compound having three or more functional groups in one molecule which is activated by heating and acts on the curing reaction of the curable resin.
- thermosetting agent examples include citric acid trihydrazide, cyclohexanetricarboxylic acid trihydrazide, 1,3,5-tris (2-carboxyethyl) isocyanurate, and the like.
- thermosetting agent examples include organic acid dihydrazide, imidazole derivatives, amine compounds, polyhydric phenol compounds, acid anhydrides, and the like. Of these, organic acid dihydrazide is preferably used.
- organic acid dihydrazide examples include sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide, and the like.
- organic acid dihydrazides examples include 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 radical polymerization initiator.
- 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.
- 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.
- 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 compound for liquid crystal display elements which is excellent in adhesiveness and can suppress liquid-crystal contamination can be provided.
- 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 8 and Comparative Examples 1 and 2 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.
- the sealing agents for liquid crystal display elements of 1 to 8 and Comparative Examples 1 and 2 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 " ⁇ ".
- 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 compound for liquid crystal display elements which is excellent in adhesiveness and can suppress liquid-crystal contamination can be provided.
- 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
Description
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.
以下に本発明を詳述する。 In the formula (1), l, m, and n are each 0 to 6, and Y is 1 to 20.
The present invention is described in detail below.
そこで本発明者らは更に鋭意検討した結果、特定の構造を有するビスフェノールS型エポキシ樹脂を用いることにより、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。 This inventor examined using bisphenol S diglycidyl ether excellent in adhesiveness and low liquid-contamination property as curable resin mix | blended with the sealing compound for liquid crystal display elements. However, even when bisphenol S diglycidyl ether was used, the effect of suppressing adhesiveness and liquid crystal contamination was not sufficient.
Thus, as a result of further intensive studies, the present inventors can obtain a sealing agent for liquid crystal display elements that is excellent in adhesiveness and can suppress liquid crystal contamination by using a bisphenol S type epoxy resin having a specific structure. As a result, the present invention has been completed.
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.
また、上記式(1)中、Yは、1~20である。上記Yは、1~10であることが好ましく、1~4であることがより好ましい。
なお、上記式(1)におけるl、m、n、及び、Yの値は、平均値である。また、lやmやnが0である場合とは、lや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), l, m, and n are each 0 to 6. Each of l, m and n is preferably 1 to 6, more preferably 1 to 3, respectively.
In the above formula (1), Y is 1-20. Y is preferably from 1 to 10, and more preferably from 1 to 4.
In addition, the value of l, m, n, and Y in the said Formula (1) is an average value. Moreover, the case where l, m, or n is 0 means that the ethylene oxide structure part to which l, m, or n is attached becomes a bond.
上記その他の硬化性樹脂としては、例えば、(メタ)アクリル化合物や、上記式(1)で表される化合物以外のエポキシ化合物等が挙げられる。 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).
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。 Examples of the (meth) acrylic compound include epoxy (meth) acrylate obtained by reacting (meth) acrylic acid and an epoxy compound, and (meth) acrylic acid obtained by reacting a compound having a hydroxyl group. Examples thereof include urethane (meth) acrylates obtained by reacting (meth) acrylic acid ester compounds and isocyanate compounds with (meth) acrylic acid derivatives having a hydroxyl group. Of these, epoxy (meth) acrylate is preferable. The (meth) acrylic compound preferably has two or more (meth) acryloyl groups in the molecule because of its high reactivity.
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.
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、1分子中に2つ以上のエポキシ基を有する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 that is the other curable resin include, for example, an epoxy compound that is a raw material for synthesizing the epoxy (meth) acrylate other than the compound represented by the formula (1), and a partial (meth) An acrylic modified 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 in one molecule. It can be obtained by reacting a part of the epoxy group having an epoxy group with (meth) acrylic acid.
上記熱硬化剤は、反応性の観点から、3官能以上の熱硬化剤を含有することが好ましい。
なお、上記「3官能以上の熱硬化剤」とは、加熱により活性化して硬化性樹脂の硬化反応に作用する官能基を1分子中に3個以上有する化合物からなる熱硬化剤を意味する。 The sealing agent for liquid crystal display elements of this invention contains a thermosetting agent.
The thermosetting agent preferably contains a trifunctional or higher functional thermosetting agent from the viewpoint of reactivity.
The “trifunctional or higher functional thermosetting agent” means a thermosetting agent made of a compound having three or more functional groups in one molecule which is activated by heating and acts on the curing reaction of the curable resin.
上記有機酸ジ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 dihydrazide include sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide, and the like.
Examples of commercially available organic acid dihydrazides include 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。 The sealing agent for liquid crystal display elements of the present invention may contain a radical polymerization initiator.
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.
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、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.).
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、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.
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.
ビス(4-ヒドロキシフェニル)スルホン200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、水酸化ナトリウム60重量部を分割添加した後、50℃で3時間反応を行った。反応終了後、水洗を行い、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℃にまで昇温した。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。得られた物質をエチルトリフェニルホスホニウムアセテートを触媒に用いて反応させた後、水洗を行い、式(1)で表される化合物(l=m=n=0、Y=2(平均値))を合成した。なお、得られた化合物が式(1)で表される化合物(l=m=n=0、Y=2(平均値))であることは、1H-NMR、13C-NMR、及び、IRにより確認した。 (Preparation of compound represented by formula (1) (l = m = n = 0, Y = 2 (average value))
200 parts by weight of bis (4-hydroxyphenyl) sulfone, 370 parts by weight of epichlorohydrin, 185 parts by weight of dimethyl sulfoxide and 5 parts by weight of tetramethylammonium chloride were added and dissolved with stirring, and the temperature was raised to 50 ° C. Next, 60 parts by weight of sodium hydroxide was added in portions, and then reacted at 50 ° C. for 3 hours. After completion of the reaction, washing with water was performed, and excess epichlorohydrin and the like were distilled off from the oil layer at 130 ° C. under reduced pressure using an 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. The obtained substance was reacted using ethyltriphenylphosphonium acetate as a catalyst, then washed with water, and the compound represented by formula (1) (l = m = n = 0, Y = 2 (average value)) Was synthesized. Note that the obtained compound is a compound represented by the formula (1) (l = m = n = 0, Y = 2 (average value)), 1 H-NMR, 13 C-NMR, and Confirmed by IR.
ビス[4-(2-ヒドロキシエトキシ)フェニル]スルホン170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、水酸化ナトリウム60重量部を分割添加した後、50℃で3時間反応を行った。反応終了後、水洗を行い、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。得られた物質をエチルトリフェニルホスホニウムアセテートを触媒に用いて反応させた後、水洗を行い、式(1)で表される化合物(l=m=n=1(平均値)、Y=3(平均値))を合成した。なお、得られた化合物が式(1)で表される化合物(l=m=n=1(平均値)、Y=3(平均値))であることは、1H-NMR、13C-NMR、及び、IRにより確認した。 (Compound represented by formula (1) (production of l = m = n = 1 (average value), Y = 3 (average value))
170 parts by weight of bis [4- (2-hydroxyethoxy) phenyl] sulfone, 370 parts by weight of epichlorohydrin, 185 parts by weight of dimethyl sulfoxide and 5 parts by weight of tetramethylammonium chloride were added and dissolved under stirring, and the temperature was raised to 50 ° C. Warm up. Next, 60 parts by weight of sodium hydroxide was added in portions, and then reacted at 50 ° C. for 3 hours. After completion of the reaction, washing with water was performed, and excess epichlorohydrin and the like were distilled off from the oil layer at 130 ° C. under reduced pressure using an 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. The obtained substance was reacted using ethyltriphenylphosphonium acetate as a catalyst, then washed with water, and the compound represented by formula (1) (l = m = n = 1 (average value), Y = 3 ( An average value)) was synthesized. Note that the obtained compound is a compound represented by the formula (1) (l = m = n = 1 (average value), Y = 3 (average value)). 1 H-NMR, 13 C— Confirmed by NMR and IR.
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1~8、及び、比較例1、2の液晶表示素子用シール剤を調製した。 (Examples 1 to 8 and Comparative Examples 1 and 2)
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. The sealing agents for liquid crystal display elements of 1 to 8 and Comparative Examples 1 and 2 were prepared.
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.
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.
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、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.
Claims (6)
- 下記式(1)で表される化合物を含有する硬化性樹脂と、熱硬化剤とを含有することを特徴とする液晶表示素子用シール剤。
- 式(1)中のYが1~10であ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 Y in the formula (1) is 1 to 10.
- 式(1)中のl、m、及び、nがそれぞれ1~6であることを特徴とする請求項1又は2記載の液晶表示素子用シール剤。 3. The sealant for a liquid crystal display element according to claim 1, wherein l, m and n in the formula (1) are 1 to 6, respectively.
- 熱硬化剤は、3官能以上の熱硬化剤を含有することを特徴とする請求項1、2又は3記載の液晶表示素子用シール剤。 4. The sealing agent for a liquid crystal display element according to claim 1, wherein the thermosetting agent contains a tri- or higher functional thermosetting agent.
- 請求項1、2、3又は4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 liquid crystal display elements according to claim 1, and conductive fine particles.
- 請求項1、2、3若しくは4記載の液晶表示素子用シール剤又は請求項5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, 2, 3, or 4, or the vertical conduction material according to claim 5.
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