Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
  • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
  • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
  • C08F299/022—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polycondensates with side or terminal unsaturations
  • C08F299/024—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polycondensates with side or terminal unsaturations the unsaturation being in acrylic or methacrylic groups
• • 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
  • C08G59/14—Polycondensates modified by chemical after-treatment
  • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
  • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
  • C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
  • C08G59/1461—Unsaturated monoacids
  • C08G59/1466—Acrylic or methacrylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/15—Heterocyclic compounds having oxygen in the ring
  • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
  • C08K5/1515—Three-membered rings
• • 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

Definitions

• the present invention relates to a sealant for a liquid crystal display element that can achieve both adhesiveness and moisture permeation preventive property of a cured product. 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 liquid crystal dropping method called a dropping method using a photothermal combined curing type sealing agent containing a polymerization initiator and a thermosetting agent is used.
• a rectangular seal pattern is formed on one of the two substrates with electrodes by dispensing.
• liquid crystal microdrops are dropped into the sealing frame of the substrate in a state where the sealing agent is uncured, the other substrate is superposed under vacuum, and the sealing portion is irradiated with light such as ultraviolet rays to perform temporary curing. Thereafter, heating is performed to perform main curing, and a liquid crystal display element is manufactured.
• this dripping method has become the mainstream method for manufacturing liquid crystal display elements.
• liquid crystal display elements are increasingly required to have moisture resistance reliability when driving in high-temperature and high-humidity environments, and the sealant prevents water from entering from the outside.
• the sealant prevents water from entering from the outside.
• the adhesion of the sealing agent to the substrate, etc. is improved, and the moisture permeability of the sealing agent is prevented. It is necessary to improve the performance.
• a method for improving the moisture permeation preventive property of the sealing agent for example, a method of blending a filler such as talc can be considered.
• a filler such as talc is added in this way, when a strict moisture resistance reliability test is performed, there is a problem that display unevenness occurs in the liquid crystal display element.
• the present invention is a liquid crystal display element sealing agent containing a curable resin and a polymerization initiator and / or a thermosetting agent, wherein the curable resin contains a compound represented by the following formula (1).
• a liquid crystal display element sealing agent wherein the content of the compound represented by the formula (1) in 100 parts by weight of the curable resin is 1 to 90 parts by weight.
• R 1 represents a hydrogen atom or a methyl group
• R 2 represents a group represented by the following formula (2-1), (2-2), or (2-3)
• Ar represents an optionally substituted arylene group
• X represents a ring-opening structure of a cyclic lactone
• n is 0 to 0.5 (average value)
• Ep is a structure derived from an epoxy compound Represents.
• the present inventor surprisingly uses a specific amount of a compound having a specific structure as the curable resin, thereby making it possible to achieve both adhesiveness and moisture permeation preventive property of the cured product. Has been found, and 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 can achieve both adhesiveness and moisture permeation preventive property of the cured product.
• R 1 represents a hydrogen atom or a methyl group. Among them, from the viewpoint of moisture proof property of the cured product of the liquid crystal display element sealing agent obtained, the R 1 is preferably a methyl group.
• R 2 represents a group represented by the above formula (2-1), (2-2), or (2-3).
• R 2 is preferably a group represented by the above formula (2-2).
• 2-2 a group in which a is 2 (ethylene group) is more preferable.
• Ar represents the arylene group which may be substituted.
• the arylene group include 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 1,4-naphthylene group, 1,5-naphthylene group, 1,8-naphthylene group, Examples include 2,6-naphthylene group and 2,7-naphthylene group. Of these, a 1,2-phenylene group and a 1,8-naphthylene group are preferable, and a 1,2-phenylene group is more preferable.
• X represents a ring-opening structure of a cyclic lactone.
• the cyclic lactone include ⁇ -undecalactone, ⁇ -caprolactone, ⁇ -decalactone, ⁇ -dodecalactone, ⁇ -nonalactone, ⁇ -nonanolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -butyrolactone, ⁇ -Butyrolactone, ⁇ -propiolactone, ⁇ -hexanolactone, 7-butyl-2-oxepanone and the like.
• those in which the straight chain portion of the main skeleton has 5 to 7 carbon atoms when ring-opened are preferable.
• Ep represents a structure derived from an epoxy compound.
• the epoxy compound from which Ep is derived include, for example, bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol E type epoxy compounds, bisphenol S type epoxy compounds, resorcinol type epoxy compounds, dicyclopentadiene type epoxy compounds, and naphthalene.
• the compound represented by the above formula (1) has a structure where n is 0 and Ep is derived from a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, or a bisphenol E type epoxy compound. Is preferred.
• Examples of the method for producing the compound represented by the above formula (1) include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl acrylate and aromatic carboxylic acid anhydrides such as phthalic anhydride and naphthalic anhydride. And a step of reacting by heating and stirring in the presence of a polymerization inhibitor such as hydroquinone and p-methoxyphenol, and a step of adding an epoxy resin to the obtained reaction product and reacting by heating and stirring. And the like.
• the hydroxyalkyl (meth) acrylate may be partially reacted with a cyclic lactone such as ⁇ -caprolactone before reacting with the aromatic carboxylic acid anhydride.
• the “(meth) acrylate” means acrylate or methacrylate.
• the lower limit of the content of the compound represented by the formula (1) in 100 parts by weight of the curable resin is 1 part by weight, and the upper limit is 90 parts by weight.
• the content of the compound represented by the formula (1) is 1 part by weight or more, the obtained sealing agent for liquid crystal display elements is excellent in adhesiveness.
• the content of the compound represented by the above formula (1) is 90 parts by weight or less, the obtained sealing agent for liquid crystal display elements has excellent workability in each process during liquid crystal display element production, such as applicability. It becomes.
• the preferred lower limit of the content of the compound represented by the formula (1) is 5 parts by weight, the preferred upper limit is 85 parts by weight, the more preferred lower limit is 10 parts by weight, the more preferred upper limit is 80 parts by weight, and the still more preferred lower limit is 12 parts by weight. Parts, and a more preferred upper limit is 75 parts by weight.
• the said curable resin contains an epoxy compound from a viewpoint of improving adhesiveness more.
• the epoxy compound include bisphenol A type epoxy resin, bisphenol S type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, sulfide type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, and naphthalene type epoxy.
• Resin phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, dicyclopentadiene novolac type epoxy resin, biphenyl novolac type epoxy resin, naphthalenephenol novolac type epoxy resin, glycidylamine type epoxy resin, alkyl polyol type epoxy resin, rubber modified Type epoxy resin, glycidyl ester compound and the like.
• Examples of commercially available bisphenol A type epoxy resins include jER828 and jER1001 (both manufactured by Mitsubishi Chemical Corporation). 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 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).
• 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).
• epoxy resins include, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Co., Ltd.), jER1031, jER1032 (all Also, Mitsubishi Chemical Corporation), EXA-7120 (DIC Corporation), TEPIC (Nissan Chemical Corporation) and the like.
• the said curable resin may contain a partial (meth) acryl modified epoxy resin as said epoxy compound.
• the partial (meth) acryl-modified epoxy resin means a compound having one or more epoxy groups and one or more (meth) acryloyl groups in one molecule. It can be obtained by reacting an epoxy group of a part of an epoxy compound having two or more epoxy groups therein with (meth) acrylic acid.
• the preferable lower limit of the content of the epoxy compound in 100 parts by weight of the curable resin is 1 part by weight, and the preferable upper limit is 80 parts by weight.
• the content of the epoxy compound is within this range, the obtained sealing agent for a liquid crystal display element is more excellent in adhesiveness while suppressing the occurrence of liquid crystal contamination.
• the more preferable lower limit of the content of the epoxy compound is 5 parts by weight, and the more preferable upper limit is 70 parts by weight.
• the said curable resin may contain another curable resin in the range which does not inhibit the objective of this invention.
• other curable resin other (meth) acrylic compounds other than the compound represented by Formula (1) etc. are mentioned, for example.
• the “(meth) acryl” means acryl or methacryl
• the “(meth) acryl compound” means a compound having a (meth) acryloyl group.
• “Meth) acryloyl” means acryloyl or methacryloyl.
• (meth) acrylic acid ester compound obtained by making the compound which has a hydroxyl group react with (meth) acrylic acid for example, and (meth) acrylic acid and an epoxy compound are made to react.
• Epoxy (meth) acrylate obtained by this, urethane (meth) acrylate obtained by making the isocyanate compound react with the (meth) acrylic acid derivative which has a hydroxyl group, etc. are mentioned.
• 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 said "epoxy (meth) acrylate" represents the compound which made all the epoxy groups in an epoxy compound react with (meth) acrylic acid.
• 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, caprolactone-modified trimethylolpropane tri (meth) acrylate, ethylene oxide-added isocyanuric acid tri (meth) acrylate, glycerin tri (meth) acrylate, propylene oxide-added glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, Tris (meth) acryloyloxyethyl phosphate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra Meth) acrylate, dipentaerythritol pen
• Examples of the epoxy (meth) acrylate include those obtained by reacting an epoxy compound and (meth) acrylic acid in the presence of a basic catalyst according to a conventional method.
• Examples of commercially available epoxy (meth) acrylates include EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRY370R ), EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (all manufactured by Shin-Nakamura Chemical Co., Ltd.), epoxy ester M-600A, epoxy ester 40EM, epoxy ester 70PA, Epoxy ester 200PA, Epoxy ester 80MF Epoxy ester 3002M, Epoxy ester 3002A, Epoxy ester 1600A, Epoxy ester 3000M, Epoxy ester 3000A, Epoxy ester 200EA, Epoxy ester 400EA (all manufactured by Kyoeisha Chemical Co., Ltd.), Denacol acrylate DA-141, Denacol acrylate DA-3
• urethane (meth) acrylate for example, 1 equivalent of an isocyanate compound having two isocyanate groups is reacted with 2 equivalents of a (meth) acrylic acid derivative having a hydroxyl group in the presence of a catalytic amount of a tin compound.
• 1 equivalent of an isocyanate compound having two isocyanate groups is reacted with 2 equivalents of a (meth) acrylic acid derivative having a hydroxyl group in the presence of a catalytic amount of a tin compound.
• isocyanate compound examples include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4′-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate, tetramethylxylylene diene Isocyanate, 1,6,11-undecane triisocyanate and the like.
• MDI diphenylmethane-4,4′-diisocyanate
• XDI
• the isocyanate compound is obtained by, for example, reacting a polyol such as ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, polycaprolactone diol and an excess isocyanate compound. It is also possible to use chain-extended isocyanate compounds.
• Examples of the (meth) acrylic acid derivative having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.
• hydroxyalkyl mono (meth) acrylates such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, polyethylene glycol and the like mono (meta) )
• Epoxy (meth) acrylates such as acrylate, mono (meth) acrylate or di (meth) acrylate of trivalent alcohols such as trimethylolethane, trimethylolpropane and glycerin, and bisphenol A type epoxy acrylate Etc. The.
• 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 other curable resin preferably has a hydrogen bonding unit such as —OH group, —NH— group, and —NH 2 group from the viewpoint of suppressing liquid crystal contamination.
• the sealing agent for liquid crystal display elements of this invention contains a polymerization initiator and / or a thermosetting agent.
• a polymerization initiator a radical polymerization initiator is preferably used.
• radical polymerization initiator examples include a photo radical polymerization initiator that generates radicals by light irradiation, a thermal radical polymerization initiator that generates radicals by heating, and the like.
• photo radical polymerization initiator examples include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, thioxanthones, 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 ), 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.
• a polymer azo initiator composed of a polymer azo compound is preferable.
• the polymer azo compound means a compound having an azo group and generating a radical capable of curing a (meth) acryloyloxy 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 polymerization initiator is preferably 0.1 parts by weight and preferably 30 parts by weight with respect to 100 parts by weight of the entire curable resin. When the content of the polymerization initiator is within this range, the resulting sealing agent for liquid crystal display elements is more excellent in curability while maintaining excellent storage stability.
• a more preferable lower limit of the content of the polymerization initiator is 1 part by weight, a more preferable upper limit is 10 parts by weight, and a still more preferable upper limit is 5 parts by weight.
• thermosetting agent examples include organic acid hydrazides, imidazole derivatives, amine compounds, polyhydric phenol compounds, acid anhydrides, and the like. Among these, solid organic acid hydrazide is preferably used.
• Examples of the solid organic acid hydrazide include 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin, sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide, and the like.
• Examples thereof include SDH, ADH (manufactured by Otsuka Chemical Co., Ltd.), MDH (manufactured by Nippon Finechem Co., Ltd.), Amicure VDH, Amicure VDH-J, Amicure UDH (all manufactured by Ajinomoto Fine Techno Co., Ltd.) and the like.
• thermosetting agent As for content of the said thermosetting agent, a preferable minimum is 1 weight part and a preferable upper limit is 50 weight part with respect to 100 weight part of whole curable resin. When the content of the thermosetting agent is within this range, the obtained sealing agent for a liquid crystal display element is more excellent in curability while maintaining excellent coating properties and storage stability.
• the upper limit with more preferable content of the said thermosetting agent is 30 weight part.
• the sealing agent for liquid crystal display elements of the present invention may contain a filler for the purpose of improving the viscosity, further improving the adhesion due to the stress dispersion effect, improving the linear expansion coefficient, improving the moisture resistance of the cured product, 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 preferable lower limit of the content of the filler in 100 parts by weight of the sealant for liquid crystal display elements of the present invention is 10 parts by weight, and the preferable upper limit is 70 parts by weight.
• content of the said filler is this range, effects, such as an adhesive improvement, can be exhibited more, suppressing deterioration, such as applicability
• the minimum with more preferable content of the said filler is 20 weight part, and a more preferable upper limit is 60 weight part.
• the sealing agent for liquid crystal display elements of the present invention preferably contains a silane coupling agent for the purpose of further improving the adhesiveness.
• the silane coupling agent mainly has a role as an adhesion assistant for favorably bonding the sealing agent and the substrate.
• the silane coupling agent for example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane and the like are preferably used.
• the minimum with preferable content of the said silane coupling agent in 100 weight part of sealing compounds for liquid crystal display elements of this invention is 0.1 weight part, and a preferable upper limit is 10 weight part.
• a preferable upper limit is 10 weight part.
• the minimum with more preferable content of the said silane coupling agent is 0.3 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 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 light-shielding agent is not particularly limited as long as it is not more than the distance between the substrates of the liquid crystal display element, but the preferred lower limit is 1 nm and the preferred upper limit is 5 ⁇ m. When the primary particle diameter of the light-shielding agent is within this range, the viscosity and thixotropy of the obtained sealing agent for liquid crystal display elements are not greatly increased, and the coating property is excellent.
• 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 using a particle size distribution meter (for example, “NICOMP 380ZLS” manufactured by PARTICLE SIZING SYSTEMS).
• the preferable lower limit of the content of the light-shielding agent in 100 parts by weight of the sealant for liquid crystal display elements of the present invention is 5 parts by weight, and the preferable upper limit is 80 parts by weight.
• the content of the light-shielding agent is within this range, the effect of improving the light-shielding property is exhibited without lowering the adhesiveness, strength after curing, and drawing property of the obtained sealing agent for liquid crystal display elements. it can.
• the more preferable lower limit of the content of the light shielding agent is 10 parts by weight, the more preferable upper limit is 70 parts by weight, the still more preferable lower limit is 30 parts by weight, and the still more preferable upper limit is 60 parts by weight.
• the sealing agent for liquid crystal display elements of the present invention is further added with a stress relaxation agent, reactive diluent, thixotropic agent, spacer, curing accelerator, antifoaming agent, leveling agent, polymerization inhibitor, etc., if necessary.
• An agent 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.
• a vertical conducting material can be produced by blending conductive fine particles with the liquid crystal display element sealant of the present invention.
• the 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.
• the sealing agent for liquid crystal display elements of this invention can be used suitably for manufacture of the liquid crystal display element by a liquid crystal dropping method.
• a method for producing the liquid crystal display element of the present invention by the liquid crystal dropping method specifically, for example, a rectangular seal pattern is formed on the substrate by screen printing, dispenser application, etc. of the liquid crystal display element sealant of the present invention.
• Examples of the method include a step of irradiating a seal pattern portion such as a sealing agent for liquid crystal display elements with light such as ultraviolet rays to temporarily cure the sealing agent, and a step of heating and temporarily curing the temporarily cured sealing agent. It is done.
• the sealing compound for liquid crystal display elements which can make adhesiveness and moisture permeability prevention property of hardened
• the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal display elements can be provided.
• Examples 1 to 7, Comparative Examples 1 to 3 In accordance with the blending ratio described in Table 1, each material was stirred with a planetary stirrer (“Shinky Co., Ltd.,“ Awatori Netaro ”), and then uniformly mixed with a ceramic three roll. To 7 and Comparative Examples 1 to 3 were obtained.
• a planetary stirrer (“Shinky Co., Ltd.,“ Awatori Netaro ”)
• strength in case panel peeling occurred was measured.
• the value obtained by dividing the obtained measured value (kgf) by the seal diameter (cm) was 3.5 kgf / cm or more, “ ⁇ ”, 3.0 kgf / cm or more and less than 3.5 kgf / cm
• the case was evaluated as “ ⁇ ”, the case where it was 2.5 kgf / cm or more and less than 3.0 kgf / cm as “ ⁇ ”, and the case where it was less than 2.5 kgf / cm as “x”.
• TN liquid crystal manufactured by Chisso Corp., “JC-5001LA”
• JC-5001LA fine droplets of TN liquid crystal
• the two substrates were bonded together under a reduced pressure of 5 Pa.
• the cell after pasting was irradiated with 3000 mJ / cm 2 ultraviolet rays with a metal halide lamp, and then the sealing agent was thermally cured by heating at 120 ° C. for 60 minutes, thereby producing a liquid crystal display element.
• the obtained liquid crystal display element was stored for 72 hours in an environment of a temperature of 80 ° C.
• the sealing compound for liquid crystal display elements which can make adhesiveness and moisture permeability prevention property of hardened
• 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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