WO2017119260A1 - Sealing agent for liquid crystal display elements, vertically conducting material and liquid crystal display element - Google Patents
Sealing agent for liquid crystal display elements, vertically conducting material and liquid crystal display element Download PDFInfo
- Publication number
- WO2017119260A1 WO2017119260A1 PCT/JP2016/087472 JP2016087472W WO2017119260A1 WO 2017119260 A1 WO2017119260 A1 WO 2017119260A1 JP 2016087472 W JP2016087472 W JP 2016087472W WO 2017119260 A1 WO2017119260 A1 WO 2017119260A1
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- WIPO (PCT)
- Prior art keywords
- liquid crystal
- crystal display
- compound
- meth
- formula
- Prior art date
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 97
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 90
- 238000007789 sealing Methods 0.000 title claims abstract description 65
- 239000004020 conductor Substances 0.000 title abstract 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 82
- 229920005989 resin Polymers 0.000 claims abstract description 20
- 239000011347 resin Substances 0.000 claims abstract description 20
- 125000003118 aryl group Chemical group 0.000 claims abstract description 3
- 239000000565 sealant Substances 0.000 claims description 16
- 238000002844 melting Methods 0.000 claims description 15
- 230000008018 melting Effects 0.000 claims description 15
- 229920001187 thermosetting polymer Polymers 0.000 claims description 14
- 239000010419 fine particle Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 238000001723 curing Methods 0.000 abstract description 22
- 238000003860 storage Methods 0.000 abstract description 14
- 238000001029 thermal curing Methods 0.000 abstract 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 93
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- 125000002541 furyl group Chemical group 0.000 description 1
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- 230000000977 initiatory effect Effects 0.000 description 1
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- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
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- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
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- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 238000007650 screen-printing Methods 0.000 description 1
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- 239000000600 sorbitol Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
-
- 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 device that can achieve both storage stability and quick curing at low temperatures. 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.
- a narrow frame of the liquid crystal display unit can be cited.
- the position of the seal portion is arranged under the black matrix (hereinafter also referred to as a narrow frame design).
- the sealing agent is arranged directly under the black matrix, when the dripping method is performed, the light irradiated when photocuring the sealing agent is blocked, and it is difficult for the light to reach the inside of the sealing agent.
- the conventional sealant is insufficiently cured. As described above, when the sealant is insufficiently cured, there is a problem in that the uncured sealant component is eluted in the liquid crystal and easily causes liquid crystal contamination.
- thermosetting agent having a low melting point As a method for curing the sealant by heating at a low temperature for a short time, it is conceivable to use a thermosetting agent having a low melting point, but when a thermosetting agent having a low melting point is used, the obtained sealing agent is stable in storage. It may become inferior.
- the present invention is a liquid crystal display element sealing agent containing a curable resin and a thermosetting agent, wherein the thermosetting agent contains a compound having a structure represented by the following formula (1). Sealing agent.
- X is a structure having an aromatic ring
- n is an integer of 1 or more
- * is a bonding position.
- thermosetting agent a sealing agent for a liquid crystal display element that can achieve both storage stability and quick curing at low temperature can be obtained. It came to complete.
- the sealing agent for liquid crystal display elements of this invention contains a thermosetting agent.
- the said thermosetting agent contains the compound which has a structure represented by the said Formula (1).
- the sealing agent for liquid crystal display elements of the present invention can achieve both storage stability and quick curing at low temperatures.
- n is preferably an integer of 1 to 10, more preferably an integer of 1 to 5.
- X is a structure represented by the following formula (2-1), (2-2), (2-3), (2-4), or (2-5) And more preferably a structure represented by the following formula (2-1), and further a structure in which R 1 and R 2 in the following formula (2-1) are methyl groups. preferable.
- R 1 and R 2 are each independently hydrogen or a methyl group, and in formulas (2-1) to (2-5), * is a bonding position.
- the compound having the structure represented by the above formula (1) preferably has a structure derived from a primary diamine compound having a divalent aliphatic hydrocarbon group, and has a divalent alicyclic hydrocarbon group. More preferably, it has a structure derived from a primary diamine compound having, and more preferably a structure derived from a primary diamine compound having a cyclohexylene group, and has a structure represented by the following formula (3).
- a compound or a compound having a structure represented by the following formula (4) is particularly preferable.
- X has the same structure as X in formula (1), n is the same number as n in formula (1), and * is a bonding position.
- X has the same structure as X in Formula (1), n is the same number as n in Formula (1), and * is a bonding position.
- the compound having the structure represented by the formula (1) preferably has an epoxy group or a primary amino group at the end of the main chain, and more preferably has a primary amino group at the end of the main chain. It is more preferable to have a primary amino group at both ends of the main chain.
- fusing point of the compound which has a structure represented by the said Formula (1) is 60 degreeC, and a preferable upper limit is 100 degreeC.
- the melting point of the compound having the structure represented by the above formula (1) is within this range, the obtained sealing agent for liquid crystal display elements is excellent in the effect of achieving both storage stability and quick curing at low temperature. It becomes.
- fusing point of the compound which has a structure represented by the said Formula (1) is 65 degreeC, and a preferable upper limit is 95 degreeC.
- Specific examples of the method for producing the compound having the structure represented by the above formula (1) include aliphatic primary diamines such as 1,4-bis (aminomethyl) cyclohexane and bisphenol A diglycidyl. Ether, bisphenol F diglycidyl ether, bisphenol E diglycidyl ether, bisphenol S diglycidyl ether, bis (4-glycidyloxyphenyl) ether, resorcinol diglycidyl ether, biphenyl-4,4′-diylbis (glycidyl ether), etc. The method of making it react is mentioned.
- the content of the compound having the structure represented by the formula (1) is preferably 5 parts by weight with respect to 100 parts by weight of the curable resin, and 120 parts by weight with respect to the preferable upper limit.
- the content of the compound having the structure represented by the above formula (1) is within this range, the obtained sealing agent for liquid crystal display elements is more excellent in the effect of achieving both storage stability and quick curing at low temperature. It will be a thing.
- the more preferred lower limit of the content of the compound having the structure represented by the formula (1) is 10 parts by weight, the more preferred upper limit is 100 parts by weight, the still more preferred lower limit is 20 parts by weight, and the still more preferred upper limit is 60 parts by weight. .
- the said thermosetting agent may contain another thermosetting agent in the range which does not inhibit the objective of this invention in addition to the compound which has a structure represented by the said Formula (1).
- curing agent an imidazole type hardening
- hydrazide-based curing agents are preferably used.
- hydrazide-based curing agent examples 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 Amicure VDH, Amicure UDH (all manufactured by Ajinomoto Fine Techno Co.), SDH, IDH, ADH (all manufactured by Otsuka Chemical Co., Ltd.), MDH (manufactured by Nippon Finechem Co., Ltd.), and the like.
- the sealing agent for liquid crystal display elements of this invention contains curable resin.
- the curable resin preferably contains an epoxy compound.
- the epoxy compound include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, 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 novolak type epoxy resin, orthocresol Novolac epoxy resin, dicyclopentadiene novolac epoxy resin, biphenyl novolac epoxy resin, naphthalenephenol novolac And a glycidyl amine type epoxy resin, an alkyl polyol type epoxy resin, a rubber-modified epoxy resin, and a glycidyl ester compound.
- 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.
- the epoxy compound a partial (meth) acryl-modified epoxy resin is also preferably used.
- the partial (meth) acryl-modified epoxy resin means a compound having one or more epoxy groups and (meth) acryloyl groups in one molecule, for example, two or more epoxy groups. It can be obtained by reacting a part of the epoxy group of the epoxy compound having a methacrylic acid with (meth) acrylic acid.
- UVACURE1561 made by Daicel Ornex
- the said curable resin contains a (meth) acryl compound.
- the (meth) acrylic compound for example, (meth) acrylic acid ester compound obtained by reacting (meth) acrylic acid with a compound having a hydroxyl group, (meth) acrylic acid and epoxy compound are reacted.
- examples include epoxy (meth) acrylates obtained, urethane (meth) acrylates obtained by reacting an isocyanate compound with a (meth) acrylic acid derivative having a hydroxyl group. 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.
- the “(meth) acryl” means acryl or methacryl
- the “(meth) acryl compound” means an acryloyl group or a methacryloyl group (hereinafter, “(meth) acryloyl”).
- the “(meth) acrylate” means acrylate or methacrylate
- the “epoxy (meth) acrylate” is a compound obtained by reacting all epoxy groups in the epoxy compound with (meth) acrylic acid. Represents that.
- 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, 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, tetramethylxylylene diisocyanate, 1,6,11-undecantrie Cyanate, and the like.
- MDI '-Diisocyanate
- XDI xylylene diisocyanate
- XDI hydrogenated XDI
- lysine diisocyanate triphenylmethane triisocyanate
- tris (isocyanate) Phenyl) thiophosphate tetramethylxylylene diisocyanate, 1,6,11-und
- 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 mono (meth) acrylates such as acrylate, 4-hydroxybutyl (meth) acrylate, ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, polyethylene glycol Mono (meth) acrylates of dihydric alcohols such as mono (meth) acrylates or di (meth) acrylates of trivalent alcohols such as trimethylolethane, trimethylolpropane and glycerin, and bisphenol A type epoxy Epoxy (meth) acrylates such as acrylate 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 sealing agent for liquid crystal display elements of the present invention contains the epoxy compound and the (meth) acrylic compound
- the ratio of the epoxy group to the (meth) acryloyl group is 5:95 to 70:30. It is preferable to mix an epoxy compound and the (meth) acrylic compound.
- the ratio of the epoxy group 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 curable resin preferably has a hydrogen bondable unit such as —OH group, —NH— group, —NH 2 group, etc. from the viewpoint of suppressing liquid crystal contamination.
- the sealing agent for liquid crystal display elements of the present invention preferably contains a radical polymerization initiator.
- the radical polymerization initiator include a photo radical polymerization initiator that generates radicals by light irradiation and a thermal radical polymerization initiator that generates radicals by heating.
- photo radical polymerization initiator examples include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, benzyl, thioxanthone, and the like.
- Examples of commercially available radical photopolymerization initiators include IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, and Lucin TPO (both BASF-IN, Ether)
- Examples include benzoin ethyl ether and benzoin isopropyl ether (both manufactured by Tokyo Chemical Industry Co., Ltd.).
- thermal radical polymerization initiator what consists of an azo compound, an organic peroxide, etc. is mentioned, for example.
- an initiator composed of an azo compound (hereinafter also referred to as “azo initiator”) is preferable, and an initiator composed of a polymer azo compound (hereinafter referred to as “polymer azo initiator”). More preferred).
- 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. To do.
- 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 the azo initiator other than the polymer azo initiator 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 0.1 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 0.2 weight part, and a more preferable upper limit is 8 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, improving the adhesiveness due to the stress dispersion effect, improving the linear expansion coefficient, and further improving the moisture resistance of the cured product. Good.
- 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.
- 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 may contain 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
- N for example.
- the minimum with preferable content of the said silane coupling agent in 100 weight part of sealing agents for liquid crystal display elements of this invention is 0.1 weight part, and a preferable upper limit is 20 weight part.
- a preferable upper limit is 20 weight part.
- the minimum with more preferable content of the said silane coupling agent is 0.5 weight part, and a more preferable upper limit is 10 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.
- a shading agent is a substance having a higher transmittance in the vicinity of the ultraviolet region, particularly for light having a wavelength of 370 to 450 nm, compared to the average transmittance for light having a wavelength of 300 to 800 nm. That is, the above-described titanium black sufficiently shields light having a wavelength in the visible light region, thereby providing a light shielding property to the sealing agent for liquid crystal display elements of the present invention, while transmitting light having a wavelength in the vicinity of the ultraviolet region.
- a photocatalyst for the sealing agent for liquid crystal display elements of the present invention can be used by using a photo initiator capable of initiating the reaction with light having a wavelength (370 to 450 nm) at which the transmittance of titanium black is high. Curability can be further increased.
- 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 titanium black preferably has an optical density (OD value) per ⁇ m of 3 or more, more preferably 4 or more. The higher the light-shielding property of the titanium black, the better.
- the OD value of the titanium black is not particularly limited, but is usually 5 or less.
- the above-mentioned titanium black exhibits a sufficient effect even if it is not surface-treated, but the surface is treated with an organic component such as a coupling agent, silicon oxide, titanium oxide, germanium oxide, aluminum oxide, 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 (all manufactured by Mitsubishi Materials Corporation), Tilak D (manufactured by Ako Kasei Co., Ltd.), and the like.
- the preferable lower limit of the specific surface area of the titanium black is 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 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 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 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 further comprises a reactive diluent for adjusting the viscosity, a spacer such as polymer beads for adjusting the panel gap, 3-P-chlorophenyl-1,1- You may contain additives, such as hardening accelerators, such as a dimethyl urea, an antifoamer, a leveling agent, a polymerization inhibitor, and another coupling agent.
- a reactive diluent for adjusting the viscosity
- a spacer such as polymer beads for adjusting the panel gap
- 3-P-chlorophenyl-1,1- You may contain additives, such as hardening accelerators, such as a dimethyl urea, an antifoamer, a leveling agent, a polymerization inhibitor, and another coupling agent.
- 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, or a three roll, a curable resin and a heat
- a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, or a three roll, a curable resin and a heat
- a method for mixing a curing agent with a radical polymerization initiator, a filler and the like for example, using a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, or a three roll, a curable resin and a heat
- examples thereof include a method of mixing a curing agent with a radical polymerization initiator, a filler and the like.
- a vertical conduction material can be produced by blending conductive fine particles with the sealing agent for liquid crystal display elements 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.
- electroconductive fine particles what formed the conductive metal layer on the surface of a metal ball, resin microparticles
- 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 method for producing the liquid crystal display element of the present invention a liquid crystal dropping method is preferably used.
- the liquid crystal display element of the present invention is provided on one of two transparent substrates having electrodes such as an ITO thin film.
- the method etc. which have the process of heating and hardening a sealing compound are mentioned.
- the sealing compound for liquid crystal display elements which can make storage stability and quick-curing property in low temperature compatible 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 15, Comparative Examples 1 and 2 According to the mixing ratios described in Tables 1 and 2, after mixing each material using a planetary stirrer (“Shinky Co., Ltd.,“ Awatori Netaro ”), by further mixing using three rolls The sealing agents for liquid crystal display elements of Examples 1 to 15 and Comparative Examples 1 and 2 were prepared.
- the agent part was irradiated with 100 mW / cm 2 ultraviolet rays (wavelength 365 nm) for 30 seconds using a metal halide lamp, and then heated at 100 ° C. for 40 minutes to obtain a liquid crystal display element.
- the liquid crystal alignment disorder of the sealant vicinity after making it into a voltage application state at 80 degreeC for 1000 hours was confirmed visually.
- the alignment disorder is determined by the color unevenness of the display part. Depending on the degree of color unevenness, “ ⁇ ” indicates that there is no color unevenness, “ ⁇ ” indicates that the color unevenness is slight, and “color unevenness”.
- the low liquid crystal contamination property was evaluated with “ ⁇ ” when there was a little, and “ ⁇ ” when there was considerable color unevenness.
- the liquid crystal display elements with the evaluations “ ⁇ ” and “O” are at a level where there is no problem in practical use, and “ ⁇ ” is a level that may cause a problem depending on the display design of the liquid crystal display element.
- "X” is a level that cannot be practically used.
- the sealing compound for liquid crystal display elements which can make storage stability and quick-curing property in low temperature compatible 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
One purpose of the present invention is to provide a sealing agent for liquid crystal display elements, which is capable of achieving a good balance between fast curing properties at low temperatures and storage stability. Another purpose of the present invention is to provide: a vertically conducting material which is obtained using this sealing agent for liquid crystal display elements; and a liquid crystal display element.
The present invention is a sealing agent for liquid crystal display elements, which contains a curable resin and a thermal curing agent, and wherein the thermal curing agent contains a compound that has a structure represented by formula (1).
In formula (1), X represents a structure having an aromatic ring; n represents an integer of 1 or more; and * represents a bonding position.
Description
本発明は、保存安定性と低温での速硬化性とを両立できる液晶表示素子用シール剤に関する。また、本発明は、該液晶表示素子用シール剤を用いてなる上下導通材料及び液晶表示素子に関する。
The present invention relates to a sealant for a liquid crystal display device that can achieve both storage stability and quick curing at low temperatures. Moreover, this invention relates to the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal display elements.
近年、液晶表示セル等の液晶表示素子の製造方法としては、タクトタイム短縮、使用液晶量の最適化といった観点から、特許文献１、特許文献２に開示されているような、硬化性樹脂と光重合開始剤と熱硬化剤とを含有する光熱併用硬化型のシール剤を用いた滴下工法と呼ばれる液晶滴下方式が用いられている。
滴下工法では、まず、２枚の電極付き基板の一方に、ディスペンスにより長方形状のシールパターンを形成する。次いで、シール剤が未硬化の状態で液晶の微小滴を基板のシール枠内に滴下し、真空下で他方の基板を重ね合わせ、シール部に紫外線等の光を照射して仮硬化を行う。その後、加熱して本硬化を行い、液晶表示素子を作製する。現在この滴下工法が液晶表示素子の製造方法の主流となっている。 In recent years, as a method of manufacturing a liquid crystal display element such as a liquid crystal display cell, a curable resin and a light as disclosed in Patent Document 1 and Patent Document 2 from the viewpoint of shortening tact time and optimizing the amount of liquid crystal used. A liquid crystal dropping method called a dropping method using a photothermal combined curing type sealing agent containing a polymerization initiator and a thermosetting agent is used.
In the dropping method, first, a rectangular seal pattern is formed on one of the two substrates with electrodes by dispensing. Next, 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. At present, this dripping method has become the mainstream method for manufacturing liquid crystal display elements.
滴下工法では、まず、２枚の電極付き基板の一方に、ディスペンスにより長方形状のシールパターンを形成する。次いで、シール剤が未硬化の状態で液晶の微小滴を基板のシール枠内に滴下し、真空下で他方の基板を重ね合わせ、シール部に紫外線等の光を照射して仮硬化を行う。その後、加熱して本硬化を行い、液晶表示素子を作製する。現在この滴下工法が液晶表示素子の製造方法の主流となっている。 In recent years, as a method of manufacturing a liquid crystal display element such as a liquid crystal display cell, a curable resin and a light as disclosed in Patent Document 1 and Patent Document 2 from the viewpoint of shortening tact time and optimizing the amount of liquid crystal used. A liquid crystal dropping method called a dropping method using a photothermal combined curing type sealing agent containing a polymerization initiator and a thermosetting agent is used.
In the dropping method, first, a rectangular seal pattern is formed on one of the two substrates with electrodes by dispensing. Next, 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. At present, this dripping method has become the mainstream method for manufacturing liquid crystal display elements.
ところで、携帯電話、携帯ゲーム機等、各種液晶パネル付きモバイル機器が普及している現代において、機器の小型化は最も求められている課題である。機器の小型化の手法としては、液晶表示部の狭額縁化が挙げられ、例えば、シール部の位置をブラックマトリックス下に配置することが行われている（以下、狭額縁設計ともいう）。
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 technique for downsizing the device, a narrow frame of the liquid crystal display unit can be cited. For example, the position of the seal portion is arranged under the black matrix (hereinafter also referred to as a narrow frame design).
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、シール剤の内部に光が到達し難く、従来のシール剤では硬化が不充分となる。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て液晶汚染を発生させやすくなるという問題があった。
However, in the narrow frame design, since the sealing agent is arranged directly under the black matrix, when the dripping method is performed, the light irradiated when photocuring the sealing agent is blocked, and it is difficult for the light to reach the inside of the sealing agent. However, the conventional sealant is insufficiently cured. As described above, when the sealant is insufficiently cured, there is a problem in that the uncured sealant component is eluted in the liquid crystal and easily causes liquid crystal contamination.
そこで、シール剤を加熱によって硬化させることが検討されており、省エネルギー化や液晶の安定性の観点から、シール剤を低温かつ短時間の加熱で熱硬化させることが望まれている。シール剤を低温かつ短時間の加熱で硬化させるための方法としては、融点の低い熱硬化剤を用いることが考えられるが、融点の低い熱硬化剤を用いた場合、得られるシール剤が保存安定性に劣るものとなることがあった。
Therefore, it has been studied to cure the sealing agent by heating. From the viewpoint of energy saving and liquid crystal stability, it is desired to thermally cure the sealing agent by low temperature and short time heating. As a method for curing the sealant by heating at a low temperature for a short time, it is conceivable to use a thermosetting agent having a low melting point, but when a thermosetting agent having a low melting point is used, the obtained sealing agent is stable in storage. It may become inferior.
本発明は、保存安定性と低温での速硬化性とを両立できる液晶表示素子用シール剤を提供することを目的とする。また、本発明は、該液晶表示素子用シール剤を用いてなる上下導通材料及び液晶表示素子を提供することを目的とする。
An object of this invention is to provide the sealing compound for liquid crystal display elements which can make storage stability and quick-curing property at low temperature compatible. Another object of the present invention is to provide a vertical conduction material and a liquid crystal display element using the sealing agent for a liquid crystal display element.
本発明は、硬化性樹脂と熱硬化剤とを含有する液晶表示素子用シール剤であって、上記熱硬化剤は、下記式（１）で表される構造を有する化合物を含有する液晶表示素子用シール剤である。
The present invention is a liquid crystal display element sealing agent containing a curable resin and a thermosetting agent, wherein the thermosetting agent contains a compound having a structure represented by the following formula (1). Sealing agent.
式（１）中、Ｘは、芳香環を有する構造であり、ｎは、１以上の整数であり、＊は、結合位置である。
以下に本発明を詳述する。 In formula (1), X is a structure having an aromatic ring, n is an integer of 1 or more, and * is a bonding position.
The present invention is described in detail below.
以下に本発明を詳述する。 In formula (1), X is a structure having an aromatic ring, n is an integer of 1 or more, and * is a bonding position.
The present invention is described in detail below.
本発明者らは、熱硬化剤として特定の構造を有する化合物を用いることにより、保存安定性と低温での速硬化性とを両立できる液晶表示素子用シール剤が得られることを見出し、本発明を完成させるに至った。
The present inventors have found that by using a compound having a specific structure as a thermosetting agent, a sealing agent for a liquid crystal display element that can achieve both storage stability and quick curing at low temperature can be obtained. It came to complete.
本発明の液晶表示素子用シール剤は、熱硬化剤を含有する。
上記熱硬化剤は、上記式（１）で表される構造を有する化合物を含有する。上記熱硬化剤として上記式（１）で表される構造を有す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、保存安定性と低温での速硬化性とを両立できる。 The sealing agent for liquid crystal display elements of this invention contains a thermosetting agent.
The said thermosetting agent contains the compound which has a structure represented by the said Formula (1). By containing the compound having the structure represented by the above formula (1) as the thermosetting agent, the sealing agent for liquid crystal display elements of the present invention can achieve both storage stability and quick curing at low temperatures.
上記熱硬化剤は、上記式（１）で表される構造を有する化合物を含有する。上記熱硬化剤として上記式（１）で表される構造を有す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、保存安定性と低温での速硬化性とを両立できる。 The sealing agent for liquid crystal display elements of this invention contains a thermosetting agent.
The said thermosetting agent contains the compound which has a structure represented by the said Formula (1). By containing the compound having the structure represented by the above formula (1) as the thermosetting agent, the sealing agent for liquid crystal display elements of the present invention can achieve both storage stability and quick curing at low temperatures.
上記式（１）中、ｎは、１～１０の整数であることが好ましく、１～５の整数であることがより好ましい。
また、上記式（１）中、Ｘは、下記式（２－１）、（２－２）、（２－３）、（２－４）、又は、（２－５）で表される構造であることが好ましく、下記式（２－１）で表される構造であることがより好ましく、下記式（２－１）中のＲ１及びＲ２がメチル基である構造であることが更に好ましい。 In the above formula (1), n is preferably an integer of 1 to 10, more preferably an integer of 1 to 5.
In the above formula (1), X is a structure represented by the following formula (2-1), (2-2), (2-3), (2-4), or (2-5) And more preferably a structure represented by the following formula (2-1), and further a structure in which R 1 and R 2 in the following formula (2-1) are methyl groups. preferable.
また、上記式（１）中、Ｘは、下記式（２－１）、（２－２）、（２－３）、（２－４）、又は、（２－５）で表される構造であることが好ましく、下記式（２－１）で表される構造であることがより好ましく、下記式（２－１）中のＲ１及びＲ２がメチル基である構造であることが更に好ましい。 In the above formula (1), n is preferably an integer of 1 to 10, more preferably an integer of 1 to 5.
In the above formula (1), X is a structure represented by the following formula (2-1), (2-2), (2-3), (2-4), or (2-5) And more preferably a structure represented by the following formula (2-1), and further a structure in which R 1 and R 2 in the following formula (2-1) are methyl groups. preferable.
式（２－１）中、Ｒ１及びＲ２は、それぞれ独立して水素又はメチル基であり、式（２－１）～（２－５）中、＊は、結合位置である。
In formula (2-1), R 1 and R 2 are each independently hydrogen or a methyl group, and in formulas (2-1) to (2-5), * is a bonding position.
上記式（１）で表される構造を有する化合物は、２価の脂肪族炭化水素基を有する第１級ジアミン化合物に由来する構造を有することが好ましく、２価の脂環式炭化水素基を有する第１級ジアミン化合物に由来する構造を有することがより好ましく、シクロヘキシレン基を有する第１級ジアミン化合物に由来する構造を有することが更に好ましく、下記式（３）で表される構造を有する化合物又は下記式（４）で表される構造を有する化合物であることが特に好ましい。
The compound having the structure represented by the above formula (1) preferably has a structure derived from a primary diamine compound having a divalent aliphatic hydrocarbon group, and has a divalent alicyclic hydrocarbon group. More preferably, it has a structure derived from a primary diamine compound having, and more preferably a structure derived from a primary diamine compound having a cyclohexylene group, and has a structure represented by the following formula (3). A compound or a compound having a structure represented by the following formula (4) is particularly preferable.
式（３）中、Ｘは、式（１）中のＸと同じ構造であり、ｎは、式（１）中のｎと同じ数であり、＊は、結合位置である。
In formula (3), X has the same structure as X in formula (1), n is the same number as n in formula (1), and * is a bonding position.
式（４）中、Ｘは、式（１）中のＸと同じ構造であり、ｎは、式（１）中のｎと同じ数であり、＊は、結合位置である。
In Formula (4), X has the same structure as X in Formula (1), n is the same number as n in Formula (1), and * is a bonding position.
上記式（１）で表される構造を有する化合物は、主鎖の末端にエポキシ基又は第１級アミノ基を有することが好ましく、主鎖の末端に第１級アミノ基を有することがより好ましく、主鎖の両末端に第１級アミノ基を有することが更に好ましい。
The compound having the structure represented by the formula (1) preferably has an epoxy group or a primary amino group at the end of the main chain, and more preferably has a primary amino group at the end of the main chain. It is more preferable to have a primary amino group at both ends of the main chain.
上記式（１）で表される構造を有する化合物の融点の好ましい下限は６０℃、好ましい上限は１００℃である。上記式（１）で表される構造を有する化合物の融点がこの範囲であることにより、得られる液晶表示素子用シール剤が保存安定性と低温での速硬化性とを両立する効果により優れるものとなる。上記式（１）で表される構造を有する化合物の融点のより好ましい下限は６５℃、好ましい上限は９５℃である。
The minimum with preferable melting | fusing point of the compound which has a structure represented by the said Formula (1) is 60 degreeC, and a preferable upper limit is 100 degreeC. When the melting point of the compound having the structure represented by the above formula (1) is within this range, the obtained sealing agent for liquid crystal display elements is excellent in the effect of achieving both storage stability and quick curing at low temperature. It becomes. The minimum with more preferable melting | fusing point of the compound which has a structure represented by the said Formula (1) is 65 degreeC, and a preferable upper limit is 95 degreeC.
上記式（１）で表される構造を有する化合物を製造する方法としては、具体的には例えば、１，４－ビス（アミノメチル）シクロヘキサン等の脂肪族第１級ジアミンと、ビスフェノールＡジグリシジルエーテル、ビスフェノールＦジグリシジルエーテル、ビスフェノールＥジグリシジルエーテル、ビスフェノールＳジグリシジルエーテル、ビス（４－グリシジルオキシフェニル）エーテル、レゾルシノールジグリシジルエーテル、ビフェニル－４，４’－ジイルビス（グリシジルエーテル）等とを反応させる方法等が挙げられる。
Specific examples of the method for producing the compound having the structure represented by the above formula (1) include aliphatic primary diamines such as 1,4-bis (aminomethyl) cyclohexane and bisphenol A diglycidyl. Ether, bisphenol F diglycidyl ether, bisphenol E diglycidyl ether, bisphenol S diglycidyl ether, bis (4-glycidyloxyphenyl) ether, resorcinol diglycidyl ether, biphenyl-4,4′-diylbis (glycidyl ether), etc. The method of making it react is mentioned.
上記式（１）で表される構造を有する化合物の含有量は、上記硬化性樹脂１００重量部に対して、好ましい下限が５重量部、好ましい上限が１２０重量部である。上記式（１）で表される構造を有する化合物の含有量がこの範囲であることにより、得られる液晶表示素子用シール剤が保存安定性と低温での速硬化性とを両立する効果により優れるものとなる。上記式（１）で表される構造を有する化合物の含有量のより好ましい下限は１０重量部、より好ましい上限は１００重量部、更に好ましい下限は２０重量部、更に好ましい上限は６０重量部である。
The content of the compound having the structure represented by the formula (1) is preferably 5 parts by weight with respect to 100 parts by weight of the curable resin, and 120 parts by weight with respect to the preferable upper limit. When the content of the compound having the structure represented by the above formula (1) is within this range, the obtained sealing agent for liquid crystal display elements is more excellent in the effect of achieving both storage stability and quick curing at low temperature. It will be a thing. The more preferred lower limit of the content of the compound having the structure represented by the formula (1) is 10 parts by weight, the more preferred upper limit is 100 parts by weight, the still more preferred lower limit is 20 parts by weight, and the still more preferred upper limit is 60 parts by weight. .
上記熱硬化剤は、上記式（１）で表される構造を有する化合物に加えて、本発明の目的を阻害しない範囲で、その他の熱硬化剤を含有してもよい。
上記その他の熱硬化剤としては、例えば、ヒドラジド系硬化剤、イミダゾール系硬化剤、多価フェノール系硬化剤、酸無水物系硬化剤等が挙げられる。なかでも、ヒドラジド系硬化剤が好適に用いられる。 The said thermosetting agent may contain another thermosetting agent in the range which does not inhibit the objective of this invention in addition to the compound which has a structure represented by the said Formula (1).
As said other thermosetting agent, a hydrazide type hardening | curing agent, an imidazole type hardening | curing agent, a polyhydric phenol type hardening | curing agent, an acid anhydride type hardening | curing agent etc. are mentioned, for example. Of these, hydrazide-based curing agents are preferably used.
上記その他の熱硬化剤としては、例えば、ヒドラジド系硬化剤、イミダゾール系硬化剤、多価フェノール系硬化剤、酸無水物系硬化剤等が挙げられる。なかでも、ヒドラジド系硬化剤が好適に用いられる。 The said thermosetting agent may contain another thermosetting agent in the range which does not inhibit the objective of this invention in addition to the compound which has a structure represented by the said Formula (1).
As said other thermosetting agent, a hydrazide type hardening | curing agent, an imidazole type hardening | curing agent, a polyhydric phenol type hardening | curing agent, an acid anhydride type hardening | curing agent etc. are mentioned, for example. Of these, hydrazide-based curing agents are preferably used.
上記ヒドラジド系硬化剤としては、例えば、１，３－ビス（ヒドラジノカルボエチル－５－イソプロピルヒダントイン）、セバシン酸ジヒドラジド、イソフタル酸ジヒドラジド、アジピン酸ジヒドラジド、マロン酸ジヒドラジド等が挙げられ、市販されているものとしては、例えば、アミキュアＶＤＨ、アミキュアＵＤＨ（いずれも味の素ファインテクノ社製）、ＳＤＨ、ＩＤＨ、ＡＤＨ（いずれも大塚化学社製）、ＭＤＨ（日本ファインケム社製）等が挙げられる。
Examples of the hydrazide-based curing agent 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 Amicure VDH, Amicure UDH (all manufactured by Ajinomoto Fine Techno Co.), SDH, IDH, ADH (all manufactured by Otsuka Chemical Co., Ltd.), MDH (manufactured by Nippon Finechem Co., Ltd.), and the like.
本発明の液晶表示素子用シール剤は、硬化性樹脂を含有する。
上記硬化性樹脂は、エポキシ化合物を含有することが好ましい。
上記エポキシ化合物としては、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＥ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、２，２’－ジアリルビスフェノールＡ型エポキシ樹脂、水添ビスフェノール型エポキシ樹脂、プロピレンオキシド付加ビスフェノールＡ型エポキシ樹脂、レゾルシノール型エポキシ樹脂、ビフェニル型エポキシ樹脂、スルフィド型エポキシ樹脂、ジフェニルエーテル型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、ナフタレン型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、オルトクレゾールノボラック型エポキシ樹脂、ジシクロペンタジエンノボラック型エポキシ樹脂、ビフェニルノボラック型エポキシ樹脂、ナフタレンフェノールノボラック型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、アルキルポリオール型エポキシ樹脂、ゴム変性型エポキシ樹脂、グリシジルエステル化合物等が挙げられる。 The sealing agent for liquid crystal display elements of this invention contains curable resin.
The curable resin preferably contains an epoxy compound.
Examples of the epoxy compound include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, 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 novolak type epoxy resin, orthocresol Novolac epoxy resin, dicyclopentadiene novolac epoxy resin, biphenyl novolac epoxy resin, naphthalenephenol novolac And a glycidyl amine type epoxy resin, an alkyl polyol type epoxy resin, a rubber-modified epoxy resin, and a glycidyl ester compound.
上記硬化性樹脂は、エポキシ化合物を含有することが好ましい。
上記エポキシ化合物としては、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＥ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、２，２’－ジアリルビスフェノールＡ型エポキシ樹脂、水添ビスフェノール型エポキシ樹脂、プロピレンオキシド付加ビスフェノールＡ型エポキシ樹脂、レゾルシノール型エポキシ樹脂、ビフェニル型エポキシ樹脂、スルフィド型エポキシ樹脂、ジフェニルエーテル型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、ナフタレン型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、オルトクレゾールノボラック型エポキシ樹脂、ジシクロペンタジエンノボラック型エポキシ樹脂、ビフェニルノボラック型エポキシ樹脂、ナフタレンフェノールノボラック型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、アルキルポリオール型エポキシ樹脂、ゴム変性型エポキシ樹脂、グリシジルエステル化合物等が挙げられる。 The sealing agent for liquid crystal display elements of this invention contains curable resin.
The curable resin preferably contains an epoxy compound.
Examples of the epoxy compound include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, 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 novolak type epoxy resin, orthocresol Novolac epoxy resin, dicyclopentadiene novolac epoxy resin, biphenyl novolac epoxy resin, naphthalenephenol novolac And a glycidyl amine type epoxy resin, an alkyl polyol type epoxy resin, a rubber-modified epoxy resin, and a glycidyl ester compound.
上記ビスフェノールＡ型エポキシ樹脂のうち市販されているものとしては、例えば、ｊＥＲ８２８ＥＬ、ｊＥＲ１００４（いずれも三菱化学社製）、エピクロン８５０（ＤＩＣ社製）等が挙げられる。
上記ビスフェノールＦ型エポキシ樹脂のうち市販されているものとしては、例えば、ｊＥＲ８０６、ｊＥＲ４００４（いずれも三菱化学社製）等が挙げられる。
上記ビスフェノールＥ型エポキシ樹脂のうち市販されているものとしては、例えば、エポミックＲ７１０（三井化学社製）等が挙げられる。
上記ビスフェノールＳ型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンＥＸＡ１５１４（ＤＩＣ社製）等が挙げられる。
上記２，２’－ジアリルビスフェノールＡ型エポキシ樹脂のうち市販されているものとしては、例えば、ＲＥ－８１０ＮＭ（日本化薬社製）等が挙げられる。
上記水添ビスフェノール型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンＥＸＡ７０１５（ＤＩＣ社製）等が挙げられる。
上記プロピレンオキシド付加ビスフェノールＡ型エポキシ樹脂のうち市販されているものとしては、例えば、ＥＰ－４０００Ｓ（ＡＤＥＫＡ社製）等が挙げられる。
上記レゾルシノール型エポキシ樹脂のうち市販されているものとしては、例えば、ＥＸ－２０１（ナガセケムテックス社製）等が挙げられる。
上記ビフェニル型エポキシ樹脂のうち市販されているものとしては、例えば、ｊＥＲ ＹＸ－４０００Ｈ（三菱化学社製）等が挙げられる。
上記スルフィド型エポキシ樹脂のうち市販されているものとしては、例えば、ＹＳＬＶ－５０ＴＥ（新日鉄住金化学社製）等が挙げられる。
上記ジフェニルエーテル型エポキシ樹脂のうち市販されているものとしては、例えば、ＹＳＬＶ－８０ＤＥ（新日鉄住金化学社製）等が挙げられる。
上記ジシクロペンタジエン型エポキシ樹脂のうち市販されているものとしては、例えば、ＥＰ－４０８８Ｓ（ＡＤＥＫＡ社製）等が挙げられる。
上記ナフタレン型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンＨＰ４０３２、エピクロンＥＸＡ－４７００（いずれもＤＩＣ社製）等が挙げられる。
上記フェノールノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンＮ－７７０（ＤＩＣ社製）等が挙げられる。
上記オルトクレゾールノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンＮ－６７０－ＥＸＰ－Ｓ（ＤＩＣ社製）等が挙げられる。
上記ジシクロペンタジエンノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンＨＰ７２００（ＤＩＣ社製）等が挙げられる。
上記ビフェニルノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、ＮＣ－３０００Ｐ（日本化薬社製）等が挙げられる。
上記ナフタレンフェノールノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、ＥＳＮ－１６５Ｓ（新日鉄住金化学社製）等が挙げられる。
上記グリシジルアミン型エポキシ樹脂のうち市販されているものとしては、例えば、ｊＥＲ６３０（三菱化学社製）、エピクロン４３０（ＤＩＣ社製）、ＴＥＴＲＡＤ－Ｘ（三菱ガス化学社製）等が挙げられる。
上記アルキルポリオール型エポキシ樹脂のうち市販されているものとしては、例えば、ＺＸ－１５４２（新日鉄住金化学社製）、エピクロン７２６（ＤＩＣ社製）、エポライト８０ＭＦＡ（共栄社化学社製）、デナコールＥＸ－６１１（ナガセケムテックス社製）等が挙げられる。
上記ゴム変性型エポキシ樹脂のうち市販されているものとしては、例えば、ＹＲ－４５０、ＹＲ－２０７（いずれも新日鉄住金化学社製）、エポリードＰＢ（ダイセル社製）等が挙げられる。
上記グリシジルエステル化合物のうち市販されているものとしては、例えば、デナコールＥＸ－１４７（ナガセケムテックス社製）等が挙げられる。
上記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), Epicron 850 (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, Epomic R710 (made by Mitsui Chemicals) etc. is mentioned, for example.
As what is marketed among the said bisphenol S-type epoxy resins, Epicron EXA1514 (made by DIC Corporation) etc. are mentioned, for example.
Examples of commercially available 2,2′-diallylbisphenol A type epoxy resins include RE-810NM (manufactured by Nippon Kayaku Co., Ltd.).
As what is marketed among the said hydrogenated bisphenol type | mold epoxy resins, Epicron EXA7015 (made by DIC Corporation) etc. are mentioned, for example.
Examples of commercially available propylene oxide-added bisphenol A type epoxy resins include EP-4000S (manufactured by ADEKA).
Examples of commercially available resorcinol type epoxy resins include EX-201 (manufactured by Nagase ChemteX Corporation).
Examples of commercially available biphenyl type epoxy resins include jER YX-4000H (manufactured by Mitsubishi Chemical Corporation).
Examples of commercially available sulfide type epoxy resins include YSLV-50TE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
Examples of commercially available diphenyl ether type epoxy resins include YSLV-80DE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
Examples of commercially available dicyclopentadiene type epoxy resins include EP-4088S (manufactured by ADEKA).
Examples of commercially available naphthalene type epoxy resins include Epicron HP4032, Epicron EXA-4700 (both manufactured by DIC) and the like.
Examples of commercially available phenol novolac epoxy resins include Epicron N-770 (manufactured by DIC).
Examples of the ortho-cresol novolac type epoxy resin that are commercially available include epiclone N-670-EXP-S (manufactured by DIC).
As what is marketed among the said dicyclopentadiene novolak-type epoxy resins, epiclone HP7200 (made by DIC) etc. are mentioned, for example.
Examples of commercially available biphenyl novolac epoxy resins include NC-3000P (manufactured by Nippon Kayaku Co., Ltd.).
Examples of commercially available naphthalene phenol novolac type epoxy resins include ESN-165S (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
Examples of commercially available glycidylamine type epoxy resins include jER630 (manufactured by Mitsubishi Chemical), Epicron 430 (manufactured by DIC), and TETRAD-X (manufactured by Mitsubishi Gas Chemical).
Examples of commercially available alkyl polyol type epoxy resins include ZX-1542 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Epiklon 726 (manufactured by DIC), Epolite 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), Denacol EX-611. (Manufactured by Nagase ChemteX Corporation).
Examples of commercially available rubber-modified epoxy resins include YR-450, YR-207 (both manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Epolide PB (manufactured by Daicel Corporation), and the like.
Examples of commercially available glycidyl ester compounds include Denacol EX-147 (manufactured by Nagase ChemteX Corporation).
Other commercially available epoxy compounds include, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by NS Also, Mitsubishi Chemical Corporation), EXA-7120 (DIC Corporation), TEPIC (Nissan Chemical Corporation) and the like.
上記ビスフェノールＦ型エポキシ樹脂のうち市販されているものとしては、例えば、ｊＥＲ８０６、ｊＥＲ４００４（いずれも三菱化学社製）等が挙げられる。
上記ビスフェノールＥ型エポキシ樹脂のうち市販されているものとしては、例えば、エポミックＲ７１０（三井化学社製）等が挙げられる。
上記ビスフェノールＳ型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンＥＸＡ１５１４（ＤＩＣ社製）等が挙げられる。
上記２，２’－ジアリルビスフェノールＡ型エポキシ樹脂のうち市販されているものとしては、例えば、ＲＥ－８１０ＮＭ（日本化薬社製）等が挙げられる。
上記水添ビスフェノール型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンＥＸＡ７０１５（ＤＩＣ社製）等が挙げられる。
上記プロピレンオキシド付加ビスフェノールＡ型エポキシ樹脂のうち市販されているものとしては、例えば、ＥＰ－４０００Ｓ（ＡＤＥＫＡ社製）等が挙げられる。
上記レゾルシノール型エポキシ樹脂のうち市販されているものとしては、例えば、ＥＸ－２０１（ナガセケムテックス社製）等が挙げられる。
上記ビフェニル型エポキシ樹脂のうち市販されているものとしては、例えば、ｊＥＲ ＹＸ－４０００Ｈ（三菱化学社製）等が挙げられる。
上記スルフィド型エポキシ樹脂のうち市販されているものとしては、例えば、ＹＳＬＶ－５０ＴＥ（新日鉄住金化学社製）等が挙げられる。
上記ジフェニルエーテル型エポキシ樹脂のうち市販されているものとしては、例えば、ＹＳＬＶ－８０ＤＥ（新日鉄住金化学社製）等が挙げられる。
上記ジシクロペンタジエン型エポキシ樹脂のうち市販されているものとしては、例えば、ＥＰ－４０８８Ｓ（ＡＤＥＫＡ社製）等が挙げられる。
上記ナフタレン型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンＨＰ４０３２、エピクロンＥＸＡ－４７００（いずれもＤＩＣ社製）等が挙げられる。
上記フェノールノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンＮ－７７０（ＤＩＣ社製）等が挙げられる。
上記オルトクレゾールノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンＮ－６７０－ＥＸＰ－Ｓ（ＤＩＣ社製）等が挙げられる。
上記ジシクロペンタジエンノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンＨＰ７２００（ＤＩＣ社製）等が挙げられる。
上記ビフェニルノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、ＮＣ－３０００Ｐ（日本化薬社製）等が挙げられる。
上記ナフタレンフェノールノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、ＥＳＮ－１６５Ｓ（新日鉄住金化学社製）等が挙げられる。
上記グリシジルアミン型エポキシ樹脂のうち市販されているものとしては、例えば、ｊＥＲ６３０（三菱化学社製）、エピクロン４３０（ＤＩＣ社製）、ＴＥＴＲＡＤ－Ｘ（三菱ガス化学社製）等が挙げられる。
上記アルキルポリオール型エポキシ樹脂のうち市販されているものとしては、例えば、ＺＸ－１５４２（新日鉄住金化学社製）、エピクロン７２６（ＤＩＣ社製）、エポライト８０ＭＦＡ（共栄社化学社製）、デナコールＥＸ－６１１（ナガセケムテックス社製）等が挙げられる。
上記ゴム変性型エポキシ樹脂のうち市販されているものとしては、例えば、ＹＲ－４５０、ＹＲ－２０７（いずれも新日鉄住金化学社製）、エポリードＰＢ（ダイセル社製）等が挙げられる。
上記グリシジルエステル化合物のうち市販されているものとしては、例えば、デナコールＥＸ－１４７（ナガセケムテックス社製）等が挙げられる。
上記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), Epicron 850 (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, Epomic R710 (made by Mitsui Chemicals) etc. is mentioned, for example.
As what is marketed among the said bisphenol S-type epoxy resins, Epicron EXA1514 (made by DIC Corporation) etc. are mentioned, for example.
Examples of commercially available 2,2′-diallylbisphenol A type epoxy resins include RE-810NM (manufactured by Nippon Kayaku Co., Ltd.).
As what is marketed among the said hydrogenated bisphenol type | mold epoxy resins, Epicron EXA7015 (made by DIC Corporation) etc. are mentioned, for example.
Examples of commercially available propylene oxide-added bisphenol A type epoxy resins include EP-4000S (manufactured by ADEKA).
Examples of commercially available resorcinol type epoxy resins include EX-201 (manufactured by Nagase ChemteX Corporation).
Examples of commercially available biphenyl type epoxy resins include jER YX-4000H (manufactured by Mitsubishi Chemical Corporation).
Examples of commercially available sulfide type epoxy resins include YSLV-50TE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
Examples of commercially available diphenyl ether type epoxy resins include YSLV-80DE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
Examples of commercially available dicyclopentadiene type epoxy resins include EP-4088S (manufactured by ADEKA).
Examples of commercially available naphthalene type epoxy resins include Epicron HP4032, Epicron EXA-4700 (both manufactured by DIC) and the like.
Examples of commercially available phenol novolac epoxy resins include Epicron N-770 (manufactured by DIC).
Examples of the ortho-cresol novolac type epoxy resin that are commercially available include epiclone N-670-EXP-S (manufactured by DIC).
As what is marketed among the said dicyclopentadiene novolak-type epoxy resins, epiclone HP7200 (made by DIC) etc. are mentioned, for example.
Examples of commercially available biphenyl novolac epoxy resins include NC-3000P (manufactured by Nippon Kayaku Co., Ltd.).
Examples of commercially available naphthalene phenol novolac type epoxy resins include ESN-165S (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
Examples of commercially available glycidylamine type epoxy resins include jER630 (manufactured by Mitsubishi Chemical), Epicron 430 (manufactured by DIC), and TETRAD-X (manufactured by Mitsubishi Gas Chemical).
Examples of commercially available alkyl polyol type epoxy resins include ZX-1542 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Epiklon 726 (manufactured by DIC), Epolite 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), Denacol EX-611. (Manufactured by Nagase ChemteX Corporation).
Examples of commercially available rubber-modified epoxy resins include YR-450, YR-207 (both manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Epolide PB (manufactured by Daicel Corporation), and the like.
Examples of commercially available glycidyl ester compounds include Denacol EX-147 (manufactured by Nagase ChemteX Corporation).
Other commercially available epoxy compounds include, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by NS Also, Mitsubishi Chemical Corporation), EXA-7120 (DIC Corporation), TEPIC (Nissan Chemical Corporation) and the like.
上記エポキシ化合物としては、部分（メタ）アクリル変性エポキシ樹脂も好適に用いられる。
なお、本明細書において上記部分（メタ）アクリル変性エポキシ樹脂とは、１分子中にエポキシ基と（メタ）アクリロイル基とをそれぞれ１つ以上有する化合物を意味し、例えば、２つ以上のエポキシ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。 As the epoxy compound, a partial (meth) acryl-modified epoxy resin is also preferably used.
In the present specification, the partial (meth) acryl-modified epoxy resin means a compound having one or more epoxy groups and (meth) acryloyl groups in one molecule, for example, two or more epoxy groups. It can be obtained by reacting a part of the epoxy group of the epoxy compound having a methacrylic acid with (meth) acrylic acid.
なお、本明細書において上記部分（メタ）アクリル変性エポキシ樹脂とは、１分子中にエポキシ基と（メタ）アクリロイル基とをそれぞれ１つ以上有する化合物を意味し、例えば、２つ以上のエポキシ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。 As the epoxy compound, a partial (meth) acryl-modified epoxy resin is also preferably used.
In the present specification, the partial (meth) acryl-modified epoxy resin means a compound having one or more epoxy groups and (meth) acryloyl groups in one molecule, for example, two or more epoxy groups. It can be obtained by reacting a part of the epoxy group of the epoxy compound having a methacrylic acid with (meth) acrylic acid.
上記部分（メタ）アクリル変性エポキシ樹脂のうち市販されているものとしては、例えば、ＵＶＡＣＵＲＥ１５６１（ダイセル・オルネクス社製）等が挙げられる。
As what is marketed among the said partial (meth) acryl modified epoxy resins, UVACURE1561 (made by Daicel Ornex) etc. are mentioned, for example.
また、上記硬化性樹脂は、（メタ）アクリル化合物を含有することが好ましい。
上記（メタ）アクリル化合物としては、例えば、（メタ）アクリル酸に水酸基を有する化合物を反応させることにより得られる（メタ）アクリル酸エステル化合物、（メタ）アクリル酸とエポキシ化合物とを反応させることにより得られるエポキシ（メタ）アクリレート、イソシアネート化合物に水酸基を有する（メタ）アクリル酸誘導体を反応させることにより得られるウレタン（メタ）アクリレート等が挙げられる。なかでも、エポキシ（メタ）アクリレートが好ましい。また、上記（メタ）アクリル化合物は、反応性の高さから分子中に（メタ）アクリロイル基を２個以上有するものが好ましい。
なお、本明細書において、上記「（メタ）アクリル」とは、アクリル又はメタクリルを意味し、上記「（メタ）アクリル化合物」とは、アクリロイル基又はメタクリロイル基（以下、併せて「（メタ）アクリロイル基」ともいう）を有する化合物を意味する。また、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、上記「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。 Moreover, it is preferable that the said curable resin contains a (meth) acryl compound.
As the (meth) acrylic compound, for example, (meth) acrylic acid ester compound obtained by reacting (meth) acrylic acid with a compound having a hydroxyl group, (meth) acrylic acid and epoxy compound are reacted. Examples include epoxy (meth) acrylates obtained, urethane (meth) acrylates obtained by reacting an isocyanate compound with a (meth) acrylic acid derivative having a hydroxyl group. 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 “(meth) acryl” means acryl or methacryl, and the “(meth) acryl compound” means an acryloyl group or a methacryloyl group (hereinafter, “(meth) acryloyl”). A compound having a group). The “(meth) acrylate” means acrylate or methacrylate, and the “epoxy (meth) acrylate” is a compound obtained by reacting all epoxy groups in the epoxy compound with (meth) acrylic acid. Represents that.
上記（メタ）アクリル化合物としては、例えば、（メタ）アクリル酸に水酸基を有する化合物を反応させることにより得られる（メタ）アクリル酸エステル化合物、（メタ）アクリル酸とエポキシ化合物とを反応させることにより得られるエポキシ（メタ）アクリレート、イソシアネート化合物に水酸基を有する（メタ）アクリル酸誘導体を反応させることにより得られるウレタン（メタ）アクリレート等が挙げられる。なかでも、エポキシ（メタ）アクリレートが好ましい。また、上記（メタ）アクリル化合物は、反応性の高さから分子中に（メタ）アクリロイル基を２個以上有するものが好ましい。
なお、本明細書において、上記「（メタ）アクリル」とは、アクリル又はメタクリルを意味し、上記「（メタ）アクリル化合物」とは、アクリロイル基又はメタクリロイル基（以下、併せて「（メタ）アクリロイル基」ともいう）を有する化合物を意味する。また、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、上記「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。 Moreover, it is preferable that the said curable resin contains a (meth) acryl compound.
As the (meth) acrylic compound, for example, (meth) acrylic acid ester compound obtained by reacting (meth) acrylic acid with a compound having a hydroxyl group, (meth) acrylic acid and epoxy compound are reacted. Examples include epoxy (meth) acrylates obtained, urethane (meth) acrylates obtained by reacting an isocyanate compound with a (meth) acrylic acid derivative having a hydroxyl group. 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 “(meth) acryl” means acryl or methacryl, and the “(meth) acryl compound” means an acryloyl group or a methacryloyl group (hereinafter, “(meth) acryloyl”). A compound having a group). The “(meth) acrylate” means acrylate or methacrylate, and the “epoxy (meth) acrylate” is a compound obtained by reacting all epoxy groups in the epoxy compound with (meth) acrylic acid. Represents that.
上記（メタ）アクリル酸エステル化合物のうち単官能のものとしては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ｎ－オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、イソノニル（メタ）アクリレート、イソデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、イソミリスチル（メタ）アクリレート、ステアリル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ビシクロペンテニル（メタ）アクリレート、ベンジル（メタ）アクリレート、２－メトキシエチル（メタ）アクリレート、２－エトキシエチル（メタ）アクリレート、２－ブトキシエチル（メタ）アクリレート、２－フェノキシエチル（メタ）アクリレート、メトキシエチレングリコール（メタ）アクリレート、メトキシポリエチレングリコール（メタ）アクリレート、フェノキシジエチレングリコール（メタ）アクリレート、フェノキシポリエチレングリコール（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、エチルカルビトール（メタ）アクリレート、２，２，２－トリフルオロエチル（メタ）アクリレート、２，２，３，３－テトラフルオロプロピル（メタ）アクリレート、１Ｈ，１Ｈ，５Ｈ－オクタフルオロペンチル（メタ）アクリレート、イミド（メタ）アクリレート、ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート、２－（メタ）アクリロイロキシエチルコハク酸、２－（メタ）アクリロイロキシエチルヘキサヒドロフタル酸、２－（メタ）アクリロイロキシエチル２－ヒドロキシプロピルフタレート、２－（メタ）アクリロイロキシエチルホスフェート、グリシジル（メタ）アクリレート等が挙げられる。
Examples of the monofunctional compounds among the (meth) acrylic acid ester compounds include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. , T-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, iso Myristyl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxy Til (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, bicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2 -Butoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, methoxyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, tetrahydrofur Furyl (meth) acrylate, ethyl carbitol (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, imide (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) ) Acrylate, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl 2-hydroxypropyl phthalate, 2- (meth) acrylic Examples include leuoxyethyl phosphate and glycidyl (meth) acrylate.
また、上記（メタ）アクリル酸エステル化合物のうち２官能のものとしては、例えば、１，３－ブタンジオールジ（メタ）アクリレート、１，４－ブタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、１，９－ノナンジオールジ（メタ）アクリレート、１，１０－デカンジオールジ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、２－ｎ－ブチル－２－エチル－１，３－プロパンジオールジ（メタ）アクリレート、ジプロピレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、エチレンオキシド付加ビスフェノールＡジ（メタ）アクリレート、プロピレンオキシド付加ビスフェノールＡジ（メタ）アクリレート、エチレンオキシド付加ビスフェノールＦジ（メタ）アクリレート、ジメチロールジシクロペンタジエニルジ（メタ）アクリレート、エチレンオキシド変性イソシアヌル酸ジ（メタ）アクリレート、２－ヒドロキシ－３－（メタ）アクリロイロキシプロピル（メタ）アクリレート、カーボネートジオールジ（メタ）アクリレート、ポリエーテルジオールジ（メタ）アクリレート、ポリエステルジオールジ（メタ）アクリレート、ポリカプロラクトンジオールジ（メタ）アクリレート、ポリブタジエンジオールジ（メタ）アクリレート等が挙げられる。
Examples of the bifunctional compound among the (meth) acrylic acid ester compounds include 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexane. Diol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (Meth) acrylate, polyethylene glycol di (meth) acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) ) Acrylate, poly Lopylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide-added bisphenol A di (meth) acrylate, propylene oxide-added bisphenol A di (meth) acrylate, ethylene oxide-added bisphenol F di (meth) acrylate, dimethylol Dicyclopentadienyl di (meth) acrylate, ethylene oxide modified isocyanuric acid di (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, carbonate diol di (meth) acrylate, polyether diol Di (meth) acrylate, polyester diol di (meth) acrylate, polycaprolactone diol di (meth) acrylate, polybutadiene diol (Meth) acrylate.
また、上記（メタ）アクリル酸エステル化合物のうち３官能以上のものとしては、例えば、トリメチロールプロパントリ（メタ）アクリレート、エチレンオキシド付加トリメチロールプロパントリ（メタ）アクリレート、プロピレンオキシド付加トリメチロールプロパントリ（メタ）アクリレート、カプロラクトン変性トリメチロールプロパントリ（メタ）アクリレート、エチレンオキシド付加イソシアヌル酸トリ（メタ）アクリレート、グリセリントリ（メタ）アクリレート、プロピレンオキシド付加グリセリントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、トリス（メタ）アクリロイルオキシエチルフォスフェート、ジトリメチロールプロパンテトラ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート等が挙げられる。
Further, among the above (meth) acrylic acid ester compounds, those having three or more functions include, for example, trimethylolpropane tri (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) acrylate, propylene oxide-added trimethylolpropane tri ( (Meth) acrylate, 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 penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate.
上記エポキシ（メタ）アクリレートとしては、例えば、エポキシ化合物と（メタ）アクリル酸とを、常法に従って塩基性触媒の存在下で反応させることにより得られるもの等が挙げられる。
Examples of the epoxy (meth) acrylate include those obtained by reacting an epoxy compound and (meth) acrylic acid in the presence of a basic catalyst according to a conventional method.
上記エポキシ（メタ）アクリレートを合成するための原料となるエポキシ化合物としては、本発明の液晶表示素子用シール剤の含有する硬化性樹脂として上述したエポキシ化合物と同様のものを用いることができる。
As an epoxy compound used as a raw material for synthesize | combining the said epoxy (meth) acrylate, the thing similar to the epoxy compound mentioned above as a curable resin which the sealing compound for liquid crystal display elements of this invention contains can be used.
上記エポキシ（メタ）アクリレートのうち市販されているものとしては、例えば、ＥＢＥＣＲＹＬ８６０、ＥＢＥＣＲＹＬ３２００、ＥＢＥＣＲＹＬ３２０１、ＥＢＥＣＲＹＬ３４１２、ＥＢＥＣＲＹＬ３６００、ＥＢＥＣＲＹＬ３７００、ＥＢＥＣＲＹＬ３７０１、ＥＢＥＣＲＹＬ３７０２、ＥＢＥＣＲＹＬ３７０３、ＥＢＥＣＲＹＬ３８００、ＥＢＥＣＲＹＬ６０４０、ＥＢＥＣＲＹＬ ＲＤＸ６３１８２（いずれもダイセル・オルネクス社製）、ＥＡ－１０１０、ＥＡ－１０２０、ＥＡ－５３２３、ＥＡ－５５２０、ＥＡ－ＣＨＤ、ＥＭＡ－１０２０（いずれも新中村化学工業社製）、エポキシエステルＭ－６００Ａ、エポキシエステル４０ＥＭ、エポキシエステル７０ＰＡ、エポキシエステル２００ＰＡ、エポキシエステル８０ＭＦＡ、エポキシエステル３００２Ｍ、エポキシエステル３００２Ａ、エポキシエステル１６００Ａ、エポキシエステル３０００Ｍ、エポキシエステル３０００Ａ、エポキシエステル２００ＥＡ、エポキシエステル４００ＥＡ（いずれも共栄社化学社製）、デナコールアクリレートＤＡ－１４１、デナコールアクリレートＤＡ－３１４、デナコールアクリレートＤＡ－９１１（いずれもナガセケムテックス社製）等が挙げられる。
Examples of commercially available epoxy (meth) acrylates include EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, 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-314 And Denacol acrylate DA-911 (all manufactured by Nagase ChemteX Corporation).
上記ウレタン（メタ）アクリレートとしては、例えば、２つのイソシアネート基を有するイソシアネート化合物１当量に対して水酸基を有する（メタ）アクリル酸誘導体２当量を、触媒量のスズ系化合物存在下で反応させることによって得ることができる。
As the urethane (meth) acrylate, for example, by reacting 2 equivalents of a (meth) acrylic acid derivative having a hydroxyl group with 1 equivalent of an isocyanate compound having two isocyanate groups in the presence of a catalytic amount of a tin-based compound. Obtainable.
上記ウレタン（メタ）アクリレートの原料となるイソシアネート化合物としては、例えば、イソホロンジイソシアネート、２，４－トリレンジイソシアネート、２，６－トリレンジイソシアネート、ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、ジフェニルメタン－４，４’－ジイソシアネート（ＭＤＩ）、水添ＭＤＩ、ポリメリックＭＤＩ、１，５－ナフタレンジイソシアネート、ノルボルナンジイソシアネート、トリジンジイソシアネート、キシリレンジイソシアネート（ＸＤＩ）、水添ＸＤＩ、リジンジイソシアネート、トリフェニルメタントリイソシアネート、トリス（イソシアネートフェニル）チオフォスフェート、テトラメチルキシリレンジイソシアネート、１，６，１１－ウンデカントリイソシアネート等が挙げられる。
Examples of the isocyanate compound used as the raw material for the urethane (meth) acrylate include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and diphenylmethane-4,4. '-Diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanate) Phenyl) thiophosphate, tetramethylxylylene diisocyanate, 1,6,11-undecantrie Cyanate, and the like.
また、上記ウレタン（メタ）アクリレートの原料となるイソシアネート化合物としては、例えば、エチレングリコール、プロピレングリコール、グリセリン、ソルビトール、トリメチロールプロパン、カーボネートジオール、ポリエーテルジオール、ポリエステルジオール、ポリカプロラクトンジオール等のポリオールと過剰のイソシアネート化合物との反応により得られる鎖延長されたイソシアネート化合物も使用することができる。
Examples of the isocyanate compound that is a raw material for the urethane (meth) acrylate include, for example, polyols such as ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, and polycaprolactone diol. Chain-extended isocyanate compounds obtained by reaction with excess isocyanate compounds can also be used.
上記ウレタン（メタ）アクリレートの原料となる、水酸基を有する（メタ）アクリル酸誘導体としては、例えば、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート等のヒドロキシアルキルモノ（メタ）アクリレートや、エチレングリコール、プロピレングリコール、１，３－プロパンジオール、１，３－ブタンジオール、１，４－ブタンジオール、ポリエチレングリコール等の二価のアルコールのモノ（メタ）アクリレートや、トリメチロールエタン、トリメチロールプロパン、グリセリン等の三価のアルコールのモノ（メタ）アクリレート又はジ（メタ）アクリレートや、ビスフェノールＡ型エポキシアクリレート等のエポキシ（メタ）アクリレート等が挙げられる。
Examples of the (meth) acrylic acid derivative having a hydroxyl group as a raw material for the urethane (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth). Hydroxyalkyl mono (meth) acrylates such as acrylate, 4-hydroxybutyl (meth) acrylate, ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, polyethylene glycol Mono (meth) acrylates of dihydric alcohols such as mono (meth) acrylates or di (meth) acrylates of trivalent alcohols such as trimethylolethane, trimethylolpropane and glycerin, and bisphenol A type epoxy Epoxy (meth) acrylates such as acrylate and the like.
上記ウレタン（メタ）アクリレートのうち市販されているものとしては、例えば、Ｍ－１１００、Ｍ－１２００、Ｍ－１２１０、Ｍ－１６００（いずれも東亞合成社製）、ＥＢＥＣＲＹＬ２１０、ＥＢＥＣＲＹＬ２２０、ＥＢＥＣＲＹＬ２３０、ＥＢＥＣＲＹＬ２７０、ＥＢＥＣＲＹＬ１２９０、ＥＢＥＣＲＹＬ２２２０、ＥＢＥＣＲＹＬ４８２７、ＥＢＥＣＲＹＬ４８４２、ＥＢＥＣＲＹＬ４８５８、ＥＢＥＣＲＹＬ５１２９、ＥＢＥＣＲＹＬ６７００、ＥＢＥＣＲＹＬ８４０２、ＥＢＥＣＲＹＬ８８０３、ＥＢＥＣＲＹＬ８８０４、ＥＢＥＣＲＹＬ８８０７、ＥＢＥＣＲＹＬ９２６０（いずれもダイセル・オルネクス社製）、アートレジンＵＮ－３３０、アートレジンＳＨ－５００Ｂ、アートレジンＵＮ－１２００ＴＰＫ、アートレジンＵＮ－１２５５、アートレジンＵＮ－３３２０ＨＢ、アートレジンＵＮ－７１００、アートレジンＵＮ－９０００Ａ、アートレジンＵＮ－９０００Ｈ（いずれも根上工業社製）、Ｕ－２ＨＡ、Ｕ－２ＰＨＡ、Ｕ－３ＨＡ、Ｕ－４ＨＡ、Ｕ－６Ｈ、Ｕ－６ＨＡ、Ｕ－６ＬＰＡ、Ｕ－１０Ｈ、Ｕ－１５ＨＡ、Ｕ－１０８、Ｕ－１０８Ａ、Ｕ－１２２Ａ、Ｕ－１２２Ｐ、Ｕ－３２４Ａ、Ｕ－３４０Ａ、Ｕ－３４０Ｐ、Ｕ－１０８４Ａ、Ｕ－２０６１ＢＡ、ＵＡ－３４０Ｐ、ＵＡ－４０００、ＵＡ－４１００、ＵＡ－４２００、ＵＡ－４４００、ＵＡ－５２０１Ｐ、ＵＡ－７１００、ＵＡ－７２００、ＵＡ－Ｗ２Ａ（いずれも新中村化学工業社製）、ＡＨ－６００、ＡＩ－６００、ＡＴ－６００、ＵＡ－１０１Ｉ、ＵＡ－１０１Ｔ、ＵＡ－３０６Ｈ、ＵＡ－３０６Ｉ、ＵＡ－３０６Ｔ（いずれも共栄社化学社製）等が挙げられる。
Examples of commercially available urethane (meth) acrylates include M-1100, M-1200, M-1210, M-1600 (all manufactured by Toagosei Co., Ltd.), EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, EBECRYL1290, EBECRYL2220, EBECRYL4827, EBECRYL4842, EBECRYL4858, EBECRYL5129, EBECRYL6700, EBECRYL8402, EBECRYL8803, EBECRYL8804, EBECRYL8804 , Art resin N-1255, Art Resin UN-3320HB, Art Resin UN-7100, Art Resin UN-9000A, Art Resin UN-9000H (all manufactured by Negami Industrial Co., Ltd.), U-2HA, U-2PHA, U-3HA, U- 4HA, U-6H, U-6HA, U-6LPA, U-10H, U-15HA, U-108, U-108A, U-122A, U-122P, U-324A, U-340A, U-340P, U-1084A, U-2061BA, UA-340P, UA-4000, UA-4100, UA-4200, UA-4400, UA-5201P, UA-7100, UA-7200, UA-W2A (all Shin-Nakamura Chemical Industries AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, A-306I, UA-306T (all manufactured by Kyoeisha Chemical Co., Ltd.).
本発明の液晶表示素子用シール剤が上記エポキシ化合物と上記（メタ）アクリル化合物とを含有する場合、エポキシ基と（メタ）アクリロイル基との比が５：９５～７０：３０になるように上記エポキシ化合物と上記（メタ）アクリル化合物とを配合することが好ましい。エポキシ基の比率がこの範囲であることにより、得られる液晶表示素子用シール剤が液晶汚染の発生を抑制しつつ、接着性により優れるものとなる。
When the sealing agent for liquid crystal display elements of the present invention contains the epoxy compound and the (meth) acrylic compound, the ratio of the epoxy group to the (meth) acryloyl group is 5:95 to 70:30. It is preferable to mix an epoxy compound and the (meth) acrylic compound. When the ratio of the epoxy group 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.
上記硬化性樹脂は、液晶汚染を抑える点で、－ＯＨ基、－ＮＨ－基、－ＮＨ２基等の水素結合性のユニットを有するものが好ましい。
The curable resin preferably has a hydrogen bondable unit such as —OH group, —NH— group, —NH 2 group, etc. from the viewpoint of suppressing liquid crystal contamination.
本発明の液晶表示素子用シール剤は、ラジカル重合開始剤を含有することが好ましい。
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が挙げられる。 The sealing agent for liquid crystal display elements of the present invention preferably contains a radical polymerization initiator.
Examples of the radical polymerization initiator include a photo radical polymerization initiator that generates radicals by light irradiation and a thermal radical polymerization initiator that generates radicals by heating.
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が挙げられる。 The sealing agent for liquid crystal display elements of the present invention preferably contains a radical polymerization initiator.
Examples of the radical polymerization initiator include a photo radical polymerization initiator that generates radicals by light irradiation and a thermal radical polymerization initiator that generates radicals by heating.
上記光ラジカル重合開始剤としては、例えば、ベンゾフェノン系化合物、アセトフェノン系化合物、アシルフォスフィンオキサイド系化合物、チタノセン系化合物、オキシムエステル系化合物、ベンゾインエーテル系化合物、ベンジル、チオキサントン等が挙げられる。
Examples of the photo radical polymerization initiator include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, benzyl, thioxanthone, and the like.
上記光ラジカル重合開始剤のうち市販されているものとしては、例えば、ＩＲＧＡＣＵＲＥ１８４、ＩＲＧＡＣＵＲＥ３６９、ＩＲＧＡＣＵＲＥ３７９、ＩＲＧＡＣＵＲＥ６５１、ＩＲＧＡＣＵＲＥ８１９、ＩＲＧＡＣＵＲＥ９０７、ＩＲＧＡＣＵＲＥ２９５９、ＩＲＧＡＣＵＲＥ ＯＸＥ０１、ルシリンＴＰＯ（いずれもＢＡＳＦ社製）、ベンソインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル（いずれも東京化成工業社製）等が挙げられる。
Examples of commercially available radical photopolymerization initiators include IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, and Lucin TPO (both BASF-IN, Ether) Examples include benzoin ethyl ether and benzoin isopropyl ether (both manufactured by Tokyo Chemical Industry Co., Ltd.).
上記熱ラジカル重合開始剤としては、例えば、アゾ化合物や有機過酸化物等からなるものが挙げられる。なかでも、液晶汚染を抑制する観点から、アゾ化合物からなる開始剤（以下、「アゾ開始剤」ともいう）が好ましく、高分子アゾ化合物からなる開始剤（以下、「高分子アゾ開始剤」ともいう）がより好ましい。
なお、本明細書において上記「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 them, from the viewpoint of suppressing liquid crystal contamination, an initiator composed of an azo compound (hereinafter also referred to as “azo initiator”) is preferable, and an initiator composed of a polymer azo compound (hereinafter referred to as “polymer azo initiator”). More preferred).
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. To do.
なお、本明細書において上記「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 them, from the viewpoint of suppressing liquid crystal contamination, an initiator composed of an azo compound (hereinafter also referred to as “azo initiator”) is preferable, and an initiator composed of a polymer azo compound (hereinafter referred to as “polymer azo initiator”). More preferred).
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. To do.
上記高分子アゾ開始剤の数平均分子量の好ましい下限は１０００、好ましい上限は３０万である。上記高分子アゾ開始剤の数平均分子量がこの範囲であることにより、液晶汚染を抑制しつつ、硬化性樹脂と容易に混合することができる。上記高分子アゾ開始剤の数平均分子量のより好ましい下限は５０００、より好ましい上限は１０万であり、更に好ましい下限は１万、更に好ましい上限は９万である。
なお、本明細書において、上記数平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定を行い、ポリスチレン換算により求められる値である。ＧＰＣによってポリスチレン換算による数平均分子量を測定する際のカラムとしては、例えば、Ｓｈｏｄｅｘ ＬＦ－８０４（昭和電工社製）等が挙げられる。 The preferable lower limit of the number average molecular weight of the polymeric azo initiator is 1000, and the preferable upper limit is 300,000. When the number average molecular weight of the polymeric azo initiator is within this range, it can be easily mixed with a curable resin while suppressing liquid crystal contamination. The more preferable lower limit of the number average molecular weight of the polymeric azo initiator is 5000, the more preferable upper limit is 100,000, the still more preferable lower limit is 10,000, and the still more preferable upper limit is 90,000.
In addition, in this specification, the said number average molecular weight is a value calculated | required by polystyrene conversion by measuring with gel permeation chromatography (GPC). Examples of the column for measuring the number average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko KK).
なお、本明細書において、上記数平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定を行い、ポリスチレン換算により求められる値である。ＧＰＣによってポリスチレン換算による数平均分子量を測定する際のカラムとしては、例えば、Ｓｈｏｄｅｘ ＬＦ－８０４（昭和電工社製）等が挙げられる。 The preferable lower limit of the number average molecular weight of the polymeric azo initiator is 1000, and the preferable upper limit is 300,000. When the number average molecular weight of the polymeric azo initiator is within this range, it can be easily mixed with a curable resin while suppressing liquid crystal contamination. The more preferable lower limit of the number average molecular weight of the polymeric azo initiator is 5000, the more preferable upper limit is 100,000, the still more preferable lower limit is 10,000, and the still more preferable upper limit is 90,000.
In addition, in this specification, the said number average molecular weight is a value calculated | required by polystyrene conversion by measuring with gel permeation chromatography (GPC). Examples of the column for measuring the number average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko KK).
上記高分子アゾ開始剤としては、例えば、アゾ基を介してポリアルキレンオキサイドやポリジメチルシロキサン等のユニットが複数結合した構造を有するものが挙げられる。
上記アゾ基を介してポリアルキレンオキサイド等のユニットが複数結合した構造を有する高分子アゾ開始剤としては、ポリエチレンオキサイド構造を有するものが好ましい。このような高分子アゾ開始剤としては、例えば、４，４’－アゾビス（４－シアノペンタン酸）とポリアルキレングリコールの重縮合物や、４，４’－アゾビス（４－シアノペンタン酸）と末端アミノ基を有するポリジメチルシロキサンの重縮合物等が挙げられ、具体的には例えば、ＶＰＥ－０２０１、ＶＰＥ－０４０１、ＶＰＥ－０６０１、ＶＰＳ－０５０１、ＶＰＳ－１００１（いずれも和光純薬工業社製）等が挙げられる。
また、高分子アゾ開始剤以外のアゾ開始剤としては、例えば、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 the azo initiator other than the polymer azo initiator include V-65 and V-501 (both manufactured by Wako Pure Chemical Industries, Ltd.).
上記アゾ基を介してポリアルキレンオキサイド等のユニットが複数結合した構造を有する高分子アゾ開始剤としては、ポリエチレンオキサイド構造を有するものが好ましい。このような高分子アゾ開始剤としては、例えば、４，４’－アゾビス（４－シアノペンタン酸）とポリアルキレングリコールの重縮合物や、４，４’－アゾビス（４－シアノペンタン酸）と末端アミノ基を有するポリジメチルシロキサンの重縮合物等が挙げられ、具体的には例えば、ＶＰＥ－０２０１、ＶＰＥ－０４０１、ＶＰＥ－０６０１、ＶＰＳ－０５０１、ＶＰＳ－１００１（いずれも和光純薬工業社製）等が挙げられる。
また、高分子アゾ開始剤以外のアゾ開始剤としては、例えば、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 the azo initiator other than the polymer azo initiator include V-65 and V-501 (both manufactured by Wako Pure Chemical Industries, Ltd.).
上記有機過酸化物としては、例えば、ケトンパーオキサイド、パーオキシケタール、ハイドロパーオキサイド、ジアルキルパーオキサイド、パーオキシエステル、ジアシルパーオキサイド、パーオキシジカーボネート等が挙げられる。
Examples of the organic peroxide include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, peroxyester, diacyl peroxide, and peroxydicarbonate.
上記ラジカル重合開始剤の含有量は、上記硬化性樹脂１００重量部に対して、好ましい下限が０．１重量部、好ましい上限が１０重量部である。上記ラジカル重合開始剤の含有量がこの範囲であることにより、得られる液晶表示素子用シール剤が液晶汚染を抑制しつつ、保存安定性や硬化性により優れるものとなる。上記ラジカル重合開始剤の含有量のより好ましい下限は０．２重量部、より好ましい上限は８重量部である。
The content of the radical polymerization initiator is preferably 0.1 parts by weight and preferably 10 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the radical polymerization initiator is within this range, the obtained sealing agent for liquid crystal display elements is excellent in storage stability and curability while suppressing liquid crystal contamination. The minimum with more preferable content of the said radical polymerization initiator is 0.2 weight part, and a more preferable upper limit is 8 weight part.
本発明の液晶表示素子用シール剤は、粘度の向上、応力分散効果による接着性の改善、線膨張率の改善、硬化物の耐湿性の更なる向上等を目的として充填剤を含有してもよい。
The sealing agent for liquid crystal display elements of the present invention may contain a filler for the purpose of improving the viscosity, improving the adhesiveness due to the stress dispersion effect, improving the linear expansion coefficient, and further improving the moisture resistance of the cured product. Good.
上記充填剤としては、例えば、シリカ、タルク、ガラスビーズ、石綿、石膏、珪藻土、スメクタイト、ベントナイト、モンモリロナイト、セリサイト、活性白土、アルミナ、酸化亜鉛、酸化鉄、酸化マグネシウム、酸化錫、酸化チタン、炭酸カルシウム、炭酸マグネシウム、水酸化マグネシウム、水酸化アルミニウム、窒化アルミニウム、窒化珪素、硫酸バリウム、珪酸カルシウム等の無機充填剤や、ポリエステル微粒子、ポリウレタン微粒子、ビニル重合体微粒子、アクリル重合体微粒子等の有機充填剤が挙げられる。
Examples of the filler include silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, smectite, bentonite, montmorillonite, sericite, activated clay, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, Organic fillers such as calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate, and calcium silicate, and organic materials such as polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, and acrylic polymer fine particles A filler is mentioned.
本発明の液晶表示素子用シール剤１００重量部中における上記充填剤の含有量の好ましい下限は１０重量部、好ましい上限は７０重量部である。上記充填剤の含有量がこの範囲であることにより、塗布性等を悪化させることなく、接着性の改善等の効果により優れるものとなる。上記充填剤の含有量のより好ましい下限は２０重量部、より好ましい上限は６０重量部である。
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. When the content of the filler is within this range, the effect of improving adhesiveness and the like is improved without deteriorating applicability and the like. The minimum with more preferable content of the said filler is 20 weight part, and a more preferable upper limit is 60 weight part.
本発明の液晶表示素子用シール剤は、シランカップリング剤を含有してもよい。上記シランカップリング剤は、主にシール剤と基板等とを良好に接着するための接着助剤としての役割を有する。
The sealing agent for liquid crystal display elements of the present invention may contain a silane coupling agent. The silane coupling agent mainly has a role as an adhesion assistant for favorably bonding the sealing agent and the substrate.
上記シランカップリング剤としては、基板等との接着性を向上させる効果に優れ、硬化性樹脂と化学結合することにより液晶中への硬化性樹脂の流出を抑制することができることから、例えば、Ｎ－フェニル－３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリメトキシシラン、３－メルカプトプロピルトリメトキシシラン、３－グリシドキシプロピルトリメトキシシラン、３－イソシアネートプロピルトリメトキシシラン等が挙げられる。
As said silane coupling agent, since it is excellent in the effect which improves adhesiveness with a board | substrate etc. and it can suppress the outflow of curable resin in a liquid crystal by chemically bonding with curable resin, it is N, for example. -Phenyl-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane and the like.
本発明の液晶表示素子用シール剤１００重量部中における上記シランカップリング剤の含有量の好ましい下限は０．１重量部、好ましい上限は２０重量部である。上記シランカップリング剤の含有量がこの範囲であることにより、液晶汚染の発生を抑制しつつ、接着性を向上させる効果により優れるものとなる。上記シランカップリング剤の含有量のより好ましい下限は０．５重量部、より好ましい上限は１０重量部である。
The minimum with preferable content of the said silane coupling agent in 100 weight part of sealing agents for liquid crystal display elements of this invention is 0.1 weight part, and a preferable upper limit is 20 weight part. When the content of the silane coupling agent is within this range, the effect of improving the adhesiveness is suppressed while suppressing the occurrence of liquid crystal contamination. The minimum with more preferable content of the said silane coupling agent is 0.5 weight part, and a more preferable upper limit is 10 weight part.
本発明の液晶表示素子用シール剤は、遮光剤を含有してもよい。上記遮光剤を含有することにより、本発明の液晶表示素子用シール剤は、遮光シール剤として好適に用いることができる。
The sealing agent for liquid crystal display elements of the present invention may contain a light shielding agent. By containing the said light shielding agent, the sealing compound for liquid crystal display elements of this invention can be used suitably as a light shielding sealing agent.
上記遮光剤としては、例えば、酸化鉄、チタンブラック、アニリンブラック、シアニンブラック、フラーレン、カーボンブラック、樹脂被覆型カーボンブラック等が挙げられる。なかでも、チタンブラックが好ましい。
Examples of the light-shielding agent include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. Of these, titanium black is preferable.
上記チタンブラックは、波長３００～８００ｎｍの光に対する平均透過率と比較して、紫外線領域付近、特に波長３７０～４５０ｎｍの光に対する透過率が高くなる物質である。即ち、上記チタンブラックは、可視光領域の波長の光を充分に遮蔽することで本発明の液晶表示素子用シール剤に遮光性を付与する一方、紫外線領域付近の波長の光は透過させる性質を有する遮光剤である。従って、上記光ラジカル重合開始剤として、上記チタンブラックの透過率の高くなる波長（３７０～４５０ｎｍ）の光によって反応を開始可能なものを用いることで、本発明の液晶表示素子用シール剤の光硬化性をより増大させることができる。また一方で、本発明の液晶表示素子用シール剤に含有される遮光剤としては、絶縁性の高い物質が好ましく、絶縁性の高い遮光剤としてもチタンブラックが好適である。
上記チタンブラックは、１μｍあたりの光学濃度（ＯＤ値）が、３以上であることが好ましく、４以上であることがより好ましい。上記チタンブラックの遮光性は高ければ高いほどよく、上記チタンブラックのＯＤ値に好ましい上限は特にないが、通常は５以下となる。 Titanium black is a substance having a higher transmittance in the vicinity of the ultraviolet region, particularly for light having a wavelength of 370 to 450 nm, compared to the average transmittance for light having a wavelength of 300 to 800 nm. That is, the above-described titanium black sufficiently shields light having a wavelength in the visible light region, thereby providing a light shielding property to the sealing agent for liquid crystal display elements of the present invention, while transmitting light having a wavelength in the vicinity of the ultraviolet region. A shading agent. Accordingly, as the photo radical polymerization initiator, a photocatalyst for the sealing agent for liquid crystal display elements of the present invention can be used by using a photo initiator capable of initiating the reaction with light having a wavelength (370 to 450 nm) at which the transmittance of titanium black is high. Curability can be further increased. On the other hand, 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 titanium black preferably has an optical density (OD value) per μm of 3 or more, more preferably 4 or more. The higher the light-shielding property of the titanium black, the better. The OD value of the titanium black is not particularly limited, but is usually 5 or less.
上記チタンブラックは、１μｍあたりの光学濃度（ＯＤ値）が、３以上であることが好ましく、４以上であることがより好ましい。上記チタンブラックの遮光性は高ければ高いほどよく、上記チタンブラックのＯＤ値に好ましい上限は特にないが、通常は５以下となる。 Titanium black is a substance having a higher transmittance in the vicinity of the ultraviolet region, particularly for light having a wavelength of 370 to 450 nm, compared to the average transmittance for light having a wavelength of 300 to 800 nm. That is, the above-described titanium black sufficiently shields light having a wavelength in the visible light region, thereby providing a light shielding property to the sealing agent for liquid crystal display elements of the present invention, while transmitting light having a wavelength in the vicinity of the ultraviolet region. A shading agent. Accordingly, as the photo radical polymerization initiator, a photocatalyst for the sealing agent for liquid crystal display elements of the present invention can be used by using a photo initiator capable of initiating the reaction with light having a wavelength (370 to 450 nm) at which the transmittance of titanium black is high. Curability can be further increased. On the other hand, 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 titanium black preferably has an optical density (OD value) per μm of 3 or more, more preferably 4 or more. The higher the light-shielding property of the titanium black, the better. The OD value of the titanium black is not particularly limited, but is usually 5 or less.
上記チタンブラックは、表面処理されていないものでも充分な効果を発揮するが、表面がカップリング剤等の有機成分で処理されているものや、酸化ケイ素、酸化チタン、酸化ゲルマニウム、酸化アルミニウム、酸化ジルコニウム、酸化マグネシウム等の無機成分で被覆されているもの等、表面処理されたチタンブラックを用いることもできる。なかでも、有機成分で処理されているものは、より絶縁性を向上できる点で好ましい。
また、遮光剤として上記チタンブラックを配合した本発明の液晶表示素子用シール剤を用いて製造した液晶表示素子は、充分な遮光性を有するため、光の漏れ出しがなく高いコントラストを有し、優れた画像表示品質を有する液晶表示素子を実現することができる。 The above-mentioned titanium black exhibits a sufficient effect even if it is not surface-treated, but the surface is treated with an organic component such as a coupling agent, silicon oxide, titanium oxide, germanium oxide, aluminum oxide, oxidized Surface-treated titanium black such as those coated with an inorganic component such as zirconium or magnesium oxide can also be used. Especially, what is processed with the organic component is preferable at the point which can improve insulation more.
In addition, the liquid crystal display element produced using the sealing agent for liquid crystal display elements of the present invention containing the above-described titanium black as a light-shielding agent has sufficient light-shielding properties, and therefore has high contrast without light leakage. A liquid crystal display element having excellent image display quality can be realized.
また、遮光剤として上記チタンブラックを配合した本発明の液晶表示素子用シール剤を用いて製造した液晶表示素子は、充分な遮光性を有するため、光の漏れ出しがなく高いコントラストを有し、優れた画像表示品質を有する液晶表示素子を実現することができる。 The above-mentioned titanium black exhibits a sufficient effect even if it is not surface-treated, but the surface is treated with an organic component such as a coupling agent, silicon oxide, titanium oxide, germanium oxide, aluminum oxide, oxidized Surface-treated titanium black such as those coated with an inorganic component such as zirconium or magnesium oxide can also be used. Especially, what is processed with the organic component is preferable at the point which can improve insulation more.
In addition, the liquid crystal display element produced using the sealing agent for liquid crystal display elements of the present invention containing the above-described titanium black as a light-shielding agent has sufficient light-shielding properties, and therefore has high contrast without light leakage. A liquid crystal display element having excellent image display quality can be realized.
上記チタンブラックのうち市販されているものとしては、例えば、１２Ｓ、１３Ｍ、１３Ｍ－Ｃ、１３Ｒ－Ｎ（いずれも三菱マテリアル社製）、ティラックＤ（赤穂化成社製）等が挙げられる。
Examples of commercially available titanium black include 12S, 13M, 13M-C, 13R-N (all manufactured by Mitsubishi Materials Corporation), Tilak D (manufactured by Ako Kasei Co., Ltd.), and the like.
上記チタンブラックの比表面積の好ましい下限は１３ｍ２／ｇ、好ましい上限は３０ｍ２／ｇであり、より好ましい下限は１５ｍ２／ｇ、より好ましい上限は２５ｍ２／ｇである。
また、上記チタンブラックの体積抵抗の好ましい下限は０．５Ω・ｃｍ、好ましい上限は３Ω・ｃｍであり、より好ましい下限は１Ω・ｃｍ、より好ましい上限は２．５Ω・ｃｍである。 The preferable lower limit of the specific surface area of the titanium black is 13 m 2 / g, the preferable upper limit is 30 m 2 / g, the more preferable lower limit is 15 m 2 / g, and the more preferable upper limit is 25 m 2 / g.
Further, the preferred lower limit of the volume resistance of the titanium black is 0.5 Ω · cm, the preferred upper limit is 3 Ω · cm, the more preferred lower limit is 1 Ω · cm, and the more preferred upper limit is 2.5 Ω · cm.
また、上記チタンブラックの体積抵抗の好ましい下限は０．５Ω・ｃｍ、好ましい上限は３Ω・ｃｍであり、より好ましい下限は１Ω・ｃｍ、より好ましい上限は２．５Ω・ｃｍである。 The preferable lower limit of the specific surface area of the titanium black is 13 m 2 / g, the preferable upper limit is 30 m 2 / g, the more preferable lower limit is 15 m 2 / g, and the more preferable upper limit is 25 m 2 / g.
Further, the preferred lower limit of the volume resistance of the titanium black is 0.5 Ω · cm, the preferred upper limit is 3 Ω · cm, the more preferred lower limit is 1 Ω · cm, and the more preferred upper limit is 2.5 Ω · cm.
上記遮光剤の一次粒子径は、液晶表示素子の基板間の距離以下であれば特に限定されないが、好ましい下限は１ｎｍ、好ましい上限は５０００ｎｍである。上記遮光剤の一次粒子径がこの範囲であることにより、得られる液晶表示素子用シール剤の塗布性等を悪化させることなく遮光性により優れるものとすることができる。上記遮光剤の一次粒子径のより好ましい下限は５ｎｍ、より好ましい上限は２００ｎｍ、更に好ましい下限は１０ｎｍ、更に好ましい上限は１００ｎｍである。
なお、上記遮光剤の一次粒子径は、ＮＩＣＯＭＰ ３８０ＺＬＳ（ＰＡＲＴＩＣＬＥ ＳＩＺＩＮＧ ＳＹＳＴＥＭＳ社製）を用いて、上記遮光剤を溶媒（水、有機溶媒等）に分散させて測定することができる。 Although the primary particle diameter of the said light-shielding agent will not be specifically limited if it is below the distance between the board | substrates of a liquid crystal display element, a preferable minimum is 1 nm and a preferable upper limit is 5000 nm. When the primary particle diameter of the light-shielding agent is within this range, the light-shielding property can be improved without deteriorating the applicability of the obtained sealing agent for liquid crystal display elements. The more preferable lower limit of the primary particle diameter of the light shielding agent is 5 nm, the more preferable upper limit is 200 nm, the still more preferable lower limit is 10 nm, and the still more preferable upper limit is 100 nm.
The primary particle size of the light shielding agent can be measured by using NICOMP 380ZLS (manufactured by PARTICS SIZING SYSTEMS) and dispersing the light shielding agent in a solvent (water, organic solvent, etc.).
なお、上記遮光剤の一次粒子径は、ＮＩＣＯＭＰ ３８０ＺＬＳ（ＰＡＲＴＩＣＬＥ ＳＩＺＩＮＧ ＳＹＳＴＥＭＳ社製）を用いて、上記遮光剤を溶媒（水、有機溶媒等）に分散させて測定することができる。 Although the primary particle diameter of the said light-shielding agent will not be specifically limited if it is below the distance between the board | substrates of a liquid crystal display element, a preferable minimum is 1 nm and a preferable upper limit is 5000 nm. When the primary particle diameter of the light-shielding agent is within this range, the light-shielding property can be improved without deteriorating the applicability of the obtained sealing agent for liquid crystal display elements. The more preferable lower limit of the primary particle diameter of the light shielding agent is 5 nm, the more preferable upper limit is 200 nm, the still more preferable lower limit is 10 nm, and the still more preferable upper limit is 100 nm.
The primary particle size of the light shielding agent can be measured by using NICOMP 380ZLS (manufactured by PARTICS SIZING SYSTEMS) and dispersing the light shielding agent in a solvent (water, organic solvent, etc.).
本発明の液晶表示素子用シール剤１００重量部中における上記遮光剤の含有量の好ましい下限は５重量部、好ましい上限は８０重量部である。上記遮光剤の含有量がこの範囲であることにより、得られる液晶表示素子用シール剤の基板に対する密着性や硬化後の強度や描画性を低下させることなくより優れた遮光性を発揮することができる。上記遮光剤の含有量のより好ましい下限は１０重量部、より好ましい上限は７０重量部であり、更に好ましい下限は３０重量部、更に好ましい上限は６０重量部である。
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. When the content of the light-shielding agent is within this range, the liquid crystal display element sealant can exhibit better light-shielding properties without reducing the adhesion to the substrate, the strength after curing, and the drawability. it can. The more preferable lower limit of the content of the light shielding agent is 10 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.
本発明の液晶表示素子用シール剤は、更に、必要に応じて、粘度調整の為の反応性希釈剤、パネルギャップ調整の為のポリマービーズ等のスペーサー、３－Ｐ－クロロフェニル－１，１－ジメチル尿素等の硬化促進剤、消泡剤、レベリング剤、重合禁止剤、その他のカップリング剤等の添加剤を含有してもよい。
The sealing agent for liquid crystal display elements of the present invention further comprises a reactive diluent for adjusting the viscosity, a spacer such as polymer beads for adjusting the panel gap, 3-P-chlorophenyl-1,1- You may contain additives, such as hardening accelerators, such as a dimethyl urea, an antifoamer, a leveling agent, a polymerization inhibitor, and another coupling agent.
本発明の液晶表示素子用シール剤を製造する方法としては、例えば、ホモディスパー、ホモミキサー、万能ミキサー、プラネタリーミキサー、ニーダー、３本ロール等の混合機を用いて、硬化性樹脂と、熱硬化剤と、ラジカル重合開始剤や充填剤等とを混合する方法等が挙げられる。
As a method for producing the sealing agent for liquid crystal display elements of the present invention, for example, using a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, or a three roll, a curable resin and a heat Examples thereof include a method of mixing a curing agent with a radical polymerization initiator, a filler and the like.
本発明の液晶表示素子用シール剤に導電性微粒子を配合することにより、上下導通材料を製造することができる。このような本発明の液晶表示素子用シール剤と導電性微粒子とを含有する上下導通材料もまた、本発明の１つである。
A vertical conduction material can be produced by blending conductive fine particles with the sealing agent for liquid crystal display elements of the present invention. Such a vertical conduction material containing the sealing agent for liquid crystal display elements of the present invention and conductive fine particles is also one aspect of the present invention.
上記導電性微粒子としては、例えば、金属ボール、樹脂微粒子の表面に導電金属層を形成したもの等を用いることができる。なかでも、樹脂微粒子の表面に導電金属層を形成したものは、樹脂微粒子の優れた弾性により、透明基板等を損傷することなく導電接続が可能であることから好適である。
As said electroconductive fine particles, what formed the conductive metal layer on the surface of a metal ball, resin microparticles | fine-particles etc. can be used, for example. Among them, the one in which the conductive metal layer is formed on the surface of the resin fine particles is preferable because the conductive connection is possible without damaging the transparent substrate due to the excellent elasticity of the resin fine particles.
本発明の液晶表示素子用シール剤又は本発明の上下導通材料を用いてなる液晶表示素子もまた、本発明の１つである。
本発明の液晶表示素子を製造する方法としては、液晶滴下工法が好適に用いられ、具体的には例えば、ＩＴＯ薄膜等の電極を有する２枚の透明基板の一方に、本発明の液晶表示素子用シール剤をスクリーン印刷、ディスペンサー塗布等により枠状のシールパターンを形成する工程、液晶の微小滴をシールパターンの枠内全面に滴下塗布し、真空下で他方の基板を重ね合わせる工程、及び、加熱してシール剤を硬化させる工程を有する方法等が挙げられる。また、加熱してシール剤を硬化させる工程の前に、光照射によりシール剤を仮硬化させる工程を行ってもよい。 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.
As a method for producing the liquid crystal display element of the present invention, a liquid crystal dropping method is preferably used. Specifically, for example, the liquid crystal display element of the present invention is provided on one of two transparent substrates having electrodes such as an ITO thin film. A step of forming a frame-shaped seal pattern by screen printing, dispenser application, etc., a step of applying a liquid crystal microdrop on the entire surface of the frame of the seal pattern, and superimposing the other substrate under vacuum, and The method etc. which have the process of heating and hardening a sealing compound are mentioned. Moreover, you may perform the process of temporarily hardening a sealing agent by light irradiation before the process of heating and hardening a sealing agent.
本発明の液晶表示素子を製造する方法としては、液晶滴下工法が好適に用いられ、具体的には例えば、ＩＴＯ薄膜等の電極を有する２枚の透明基板の一方に、本発明の液晶表示素子用シール剤をスクリーン印刷、ディスペンサー塗布等により枠状のシールパターンを形成する工程、液晶の微小滴をシールパターンの枠内全面に滴下塗布し、真空下で他方の基板を重ね合わせる工程、及び、加熱してシール剤を硬化させる工程を有する方法等が挙げられる。また、加熱してシール剤を硬化させる工程の前に、光照射によりシール剤を仮硬化させる工程を行ってもよい。 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.
As a method for producing the liquid crystal display element of the present invention, a liquid crystal dropping method is preferably used. Specifically, for example, the liquid crystal display element of the present invention is provided on one of two transparent substrates having electrodes such as an ITO thin film. A step of forming a frame-shaped seal pattern by screen printing, dispenser application, etc., a step of applying a liquid crystal microdrop on the entire surface of the frame of the seal pattern, and superimposing the other substrate under vacuum, and The method etc. which have the process of heating and hardening a sealing compound are mentioned. Moreover, you may perform the process of temporarily hardening a sealing agent by light irradiation before the process of heating and hardening a sealing agent.
本発明によれば、保存安定性と低温での速硬化性とを両立できる液晶表示素子用シール剤を提供することができる。また、本発明によれば、該液晶表示素子用シール剤を用いてなる上下導通材料及び液晶表示素子を提供することができる。
ADVANTAGE OF THE INVENTION According to this invention, the sealing compound for liquid crystal display elements which can make storage stability and quick-curing property in low temperature compatible can be provided. Moreover, according to this invention, the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal display elements can be provided.
以下に実施例を掲げて本発明を更に詳しく説明するが、本発明はこれら実施例のみに限定されない。
Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
（式（１）で表される構造を有する化合物Ａの作製）
１，４－ビス（アミノメチル）シクロヘキサン７１重量部と、ビスフェノールＡジグリシジルエーテル１９０重量部に、プロピレングリコールモノメチルエーテルアセテート５００重量部と、ｎ－ブチルアルコール５００重量部を加えて混合溶解し、１００℃で３時間加熱撹拌を行った。得られた反応混合物の溶媒除去と乾燥を行い、得られた固形物をジェットミルにて粉砕し、上記式（１）で表される構造を有する化合物Ａ（融点８３℃）を得た。得られた式（１）で表される構造を有する化合物Ａは、１Ｈ－ＮＭＲ、１３Ｃ－ＮＭＲ、及び、ＦＴ－ＩＲ分析により、上記式（３）で表される構造（Ｘが上記式（２－１）で表される基（Ｒ１及びＲ２がメチル基））を有することを確認した。 (Preparation of Compound A having a structure represented by Formula (1))
100 parts by weight of propylene glycol monomethyl ether acetate and 500 parts by weight of n-butyl alcohol were added to 71 parts by weight of 1,4-bis (aminomethyl) cyclohexane, 190 parts by weight of bisphenol A diglycidyl ether, and mixed and dissolved. Stirring was carried out at 3 ° C. for 3 hours. Solvent removal and drying of the obtained reaction mixture were performed, and the obtained solid was pulverized with a jet mill to obtain Compound A (melting point: 83 ° C.) having a structure represented by the above formula (1). The obtained compound A having the structure represented by the formula (1) was analyzed by 1 H-NMR, 13 C-NMR, and FT-IR analysis. It was confirmed to have a group represented by the formula (2-1) (R 1 and R 2 are methyl groups).
１，４－ビス（アミノメチル）シクロヘキサン７１重量部と、ビスフェノールＡジグリシジルエーテル１９０重量部に、プロピレングリコールモノメチルエーテルアセテート５００重量部と、ｎ－ブチルアルコール５００重量部を加えて混合溶解し、１００℃で３時間加熱撹拌を行った。得られた反応混合物の溶媒除去と乾燥を行い、得られた固形物をジェットミルにて粉砕し、上記式（１）で表される構造を有する化合物Ａ（融点８３℃）を得た。得られた式（１）で表される構造を有する化合物Ａは、１Ｈ－ＮＭＲ、１３Ｃ－ＮＭＲ、及び、ＦＴ－ＩＲ分析により、上記式（３）で表される構造（Ｘが上記式（２－１）で表される基（Ｒ１及びＲ２がメチル基））を有することを確認した。 (Preparation of Compound A having a structure represented by Formula (1))
100 parts by weight of propylene glycol monomethyl ether acetate and 500 parts by weight of n-butyl alcohol were added to 71 parts by weight of 1,4-bis (aminomethyl) cyclohexane, 190 parts by weight of bisphenol A diglycidyl ether, and mixed and dissolved. Stirring was carried out at 3 ° C. for 3 hours. Solvent removal and drying of the obtained reaction mixture were performed, and the obtained solid was pulverized with a jet mill to obtain Compound A (melting point: 83 ° C.) having a structure represented by the above formula (1). The obtained compound A having the structure represented by the formula (1) was analyzed by 1 H-NMR, 13 C-NMR, and FT-IR analysis. It was confirmed to have a group represented by the formula (2-1) (R 1 and R 2 are methyl groups).
（式（１）で表される構造を有する化合物Ｂの作製）
ビスフェノールＡジグリシジルエーテル１９０重量部に代えてビスフェノールＦジグリシジルエーテル１７０重量部を用いたこと以外は、上記「（式（１）で表される構造を有する化合物Ａの作製）」と同様にして、上記式（１）で表される構造を有する化合物Ｂ（融点６８℃）を得た。得られた式（１）で表される構造を有する化合物Ｂは、１Ｈ－ＮＭＲ、１３Ｃ－ＮＭＲ、及び、ＦＴ－ＩＲ分析により、上記式（３）で表される構造（Ｘが上記式（２－１）で表される基（Ｒ１及びＲ２が水素））を有することを確認した。 (Preparation of compound B having the structure represented by formula (1))
Except for using 170 parts by weight of bisphenol F diglycidyl ether instead of 190 parts by weight of bisphenol A diglycidyl ether, the same as “(Preparation of compound A having the structure represented by formula (1))” above. Compound B having a structure represented by the above formula (1) (melting point: 68 ° C.) was obtained. The obtained compound B having the structure represented by the formula (1) was analyzed by 1 H-NMR, 13 C-NMR, and FT-IR analysis, and the structure (X is represented by the above formula (3)). It was confirmed to have a group represented by the formula (2-1) (R 1 and R 2 are hydrogen).
ビスフェノールＡジグリシジルエーテル１９０重量部に代えてビスフェノールＦジグリシジルエーテル１７０重量部を用いたこと以外は、上記「（式（１）で表される構造を有する化合物Ａの作製）」と同様にして、上記式（１）で表される構造を有する化合物Ｂ（融点６８℃）を得た。得られた式（１）で表される構造を有する化合物Ｂは、１Ｈ－ＮＭＲ、１３Ｃ－ＮＭＲ、及び、ＦＴ－ＩＲ分析により、上記式（３）で表される構造（Ｘが上記式（２－１）で表される基（Ｒ１及びＲ２が水素））を有することを確認した。 (Preparation of compound B having the structure represented by formula (1))
Except for using 170 parts by weight of bisphenol F diglycidyl ether instead of 190 parts by weight of bisphenol A diglycidyl ether, the same as “(Preparation of compound A having the structure represented by formula (1))” above. Compound B having a structure represented by the above formula (1) (melting point: 68 ° C.) was obtained. The obtained compound B having the structure represented by the formula (1) was analyzed by 1 H-NMR, 13 C-NMR, and FT-IR analysis, and the structure (X is represented by the above formula (3)). It was confirmed to have a group represented by the formula (2-1) (R 1 and R 2 are hydrogen).
（式（１）で表される構造を有する化合物Ｃの作製）
ビスフェノールＡジグリシジルエーテル１９０重量部に代えてビスフェノールＥジグリシジルエーテル１８０重量部を用いたこと以外は、上記「（式（１）で表される構造を有する化合物Ａの作製）」と同様にして、上記式（１）で表される構造を有する化合物Ｃ（融点７８℃）を得た。得られた式（１）で表される構造を有する化合物Ｃは、１Ｈ－ＮＭＲ、１３Ｃ－ＮＭＲ、及び、ＦＴ－ＩＲ分析により、上記式（３）で表される構造（Ｘが上記式（２－１）で表される基（Ｒ１及びＲ２の一方がメチル基、もう一方が水素））を有することを確認した。 (Preparation of Compound C having the structure represented by Formula (1))
Except that 180 parts by weight of bisphenol E diglycidyl ether was used instead of 190 parts by weight of bisphenol A diglycidyl ether, the same as “(Preparation of compound A having the structure represented by formula (1))” above. Compound C having a structure represented by the above formula (1) (melting point: 78 ° C.) was obtained. The obtained compound C having the structure represented by the formula (1) was analyzed by 1 H-NMR, 13 C-NMR, and FT-IR analysis (the structure represented by the above formula (3) (X is the above) It was confirmed to have a group represented by the formula (2-1) ( one of R 1 and R 2 is a methyl group and the other is hydrogen).
ビスフェノールＡジグリシジルエーテル１９０重量部に代えてビスフェノールＥジグリシジルエーテル１８０重量部を用いたこと以外は、上記「（式（１）で表される構造を有する化合物Ａの作製）」と同様にして、上記式（１）で表される構造を有する化合物Ｃ（融点７８℃）を得た。得られた式（１）で表される構造を有する化合物Ｃは、１Ｈ－ＮＭＲ、１３Ｃ－ＮＭＲ、及び、ＦＴ－ＩＲ分析により、上記式（３）で表される構造（Ｘが上記式（２－１）で表される基（Ｒ１及びＲ２の一方がメチル基、もう一方が水素））を有することを確認した。 (Preparation of Compound C having the structure represented by Formula (1))
Except that 180 parts by weight of bisphenol E diglycidyl ether was used instead of 190 parts by weight of bisphenol A diglycidyl ether, the same as “(Preparation of compound A having the structure represented by formula (1))” above. Compound C having a structure represented by the above formula (1) (melting point: 78 ° C.) was obtained. The obtained compound C having the structure represented by the formula (1) was analyzed by 1 H-NMR, 13 C-NMR, and FT-IR analysis (the structure represented by the above formula (3) (X is the above) It was confirmed to have a group represented by the formula (2-1) ( one of R 1 and R 2 is a methyl group and the other is hydrogen).
（式（１）で表される構造を有する化合物Ｄの作製）
ビスフェノールＡジグリシジルエーテル１９０重量部に代えてレゾルシノールジグリシジルエーテル１３０重量部を用いたこと以外は、上記「（式（１）で表される構造を有する化合物Ａの作製）」と同様にして、上記式（１）で表される構造を有する化合物Ｄ（融点９４℃）を得た。得られた式（１）で表される構造を有する化合物Ｄは、１Ｈ－ＮＭＲ、１３Ｃ－ＮＭＲ、及び、ＦＴ－ＩＲ分析により、上記式（３）で表される構造（Ｘが上記式（２－４）で表される基）を有することを確認した。 (Preparation of compound D having the structure represented by formula (1))
Except for using 130 parts by weight of resorcinol diglycidyl ether in place of 190 parts by weight of bisphenol A diglycidyl ether, the same as “(Preparation of compound A having the structure represented by formula (1))” above, Compound D (melting point 94 ° C.) having the structure represented by the above formula (1) was obtained. The obtained compound D having the structure represented by the formula (1) was analyzed by 1 H-NMR, 13 C-NMR, and FT-IR analysis. Having a group represented by formula (2-4)).
ビスフェノールＡジグリシジルエーテル１９０重量部に代えてレゾルシノールジグリシジルエーテル１３０重量部を用いたこと以外は、上記「（式（１）で表される構造を有する化合物Ａの作製）」と同様にして、上記式（１）で表される構造を有する化合物Ｄ（融点９４℃）を得た。得られた式（１）で表される構造を有する化合物Ｄは、１Ｈ－ＮＭＲ、１３Ｃ－ＮＭＲ、及び、ＦＴ－ＩＲ分析により、上記式（３）で表される構造（Ｘが上記式（２－４）で表される基）を有することを確認した。 (Preparation of compound D having the structure represented by formula (1))
Except for using 130 parts by weight of resorcinol diglycidyl ether in place of 190 parts by weight of bisphenol A diglycidyl ether, the same as “(Preparation of compound A having the structure represented by formula (1))” above, Compound D (melting point 94 ° C.) having the structure represented by the above formula (1) was obtained. The obtained compound D having the structure represented by the formula (1) was analyzed by 1 H-NMR, 13 C-NMR, and FT-IR analysis. Having a group represented by formula (2-4)).
（式（１）で表される構造を有する化合物Ｅの作製）
ビスフェノールＡジグリシジルエーテル１９０重量部に代えてビフェニル－４，４’－ジイルビス（グリシジルエーテル）１８０重量部を用いたこと以外は、上記「（式（１）で表される構造を有する化合物Ａの作製）」と同様にして、上記式（１）で表される構造を有する化合物Ｅ（融点９８℃）を得た。得られた式（１）で表される構造を有する化合物Ｅは、１Ｈ－ＮＭＲ、１３Ｃ－ＮＭＲ、及び、ＦＴ－ＩＲ分析により、上記式（３）で表される構造（Ｘが上記式（２－３）で表される基）を有することを確認した。 (Preparation of Compound E having the structure represented by Formula (1))
Except that 180 parts by weight of biphenyl-4,4′-diylbis (glycidyl ether) was used instead of 190 parts by weight of bisphenol A diglycidyl ether, the above-mentioned “(Compound A having the structure represented by the formula (1)” In the same manner as in “Preparation”, Compound E (melting point: 98 ° C.) having the structure represented by the above formula (1) was obtained. The obtained compound E having the structure represented by the formula (1) was analyzed by 1 H-NMR, 13 C-NMR, and FT-IR analysis. Group having a formula (2-3)).
ビスフェノールＡジグリシジルエーテル１９０重量部に代えてビフェニル－４，４’－ジイルビス（グリシジルエーテル）１８０重量部を用いたこと以外は、上記「（式（１）で表される構造を有する化合物Ａの作製）」と同様にして、上記式（１）で表される構造を有する化合物Ｅ（融点９８℃）を得た。得られた式（１）で表される構造を有する化合物Ｅは、１Ｈ－ＮＭＲ、１３Ｃ－ＮＭＲ、及び、ＦＴ－ＩＲ分析により、上記式（３）で表される構造（Ｘが上記式（２－３）で表される基）を有することを確認した。 (Preparation of Compound E having the structure represented by Formula (1))
Except that 180 parts by weight of biphenyl-4,4′-diylbis (glycidyl ether) was used instead of 190 parts by weight of bisphenol A diglycidyl ether, the above-mentioned “(Compound A having the structure represented by the formula (1)” In the same manner as in “Preparation”, Compound E (melting point: 98 ° C.) having the structure represented by the above formula (1) was obtained. The obtained compound E having the structure represented by the formula (1) was analyzed by 1 H-NMR, 13 C-NMR, and FT-IR analysis. Group having a formula (2-3)).
（式（１）で表される構造を有する化合物Ｆの作製）
ビスフェノールＡジグリシジルエーテル１９０重量部に代えてビスフェノールＡ型エポキシ樹脂２４７重量部を用いたこと以外は、上記「（式（１）で表される構造を有する化合物Ａの作製）」と同様にして、上記式（１）で表される構造を有する化合物Ｆ（融点１０９℃）を得た。得られた式（１）で表される構造を有する化合物Ｆは、１Ｈ－ＮＭＲ、１３Ｃ－ＮＭＲ、及び、ＦＴ－ＩＲ分析により、上記式（３）で表される構造（Ｘが上記式（２－１）で表される基（Ｒ１及びＲ２がメチル基））を有することを確認した。 (Preparation of Compound F having the structure represented by Formula (1))
Except for using 247 parts by weight of bisphenol A type epoxy resin instead of 190 parts by weight of bisphenol A diglycidyl ether, the same as “(Preparation of compound A having the structure represented by formula (1))” above. Compound F having a structure represented by the above formula (1) (melting point: 109 ° C.) was obtained. The obtained compound F having the structure represented by the formula (1) was analyzed by 1 H-NMR, 13 C-NMR, and FT-IR analysis. It was confirmed to have a group represented by the formula (2-1) (R 1 and R 2 are methyl groups).
ビスフェノールＡジグリシジルエーテル１９０重量部に代えてビスフェノールＡ型エポキシ樹脂２４７重量部を用いたこと以外は、上記「（式（１）で表される構造を有する化合物Ａの作製）」と同様にして、上記式（１）で表される構造を有する化合物Ｆ（融点１０９℃）を得た。得られた式（１）で表される構造を有する化合物Ｆは、１Ｈ－ＮＭＲ、１３Ｃ－ＮＭＲ、及び、ＦＴ－ＩＲ分析により、上記式（３）で表される構造（Ｘが上記式（２－１）で表される基（Ｒ１及びＲ２がメチル基））を有することを確認した。 (Preparation of Compound F having the structure represented by Formula (1))
Except for using 247 parts by weight of bisphenol A type epoxy resin instead of 190 parts by weight of bisphenol A diglycidyl ether, the same as “(Preparation of compound A having the structure represented by formula (1))” above. Compound F having a structure represented by the above formula (1) (melting point: 109 ° C.) was obtained. The obtained compound F having the structure represented by the formula (1) was analyzed by 1 H-NMR, 13 C-NMR, and FT-IR analysis. It was confirmed to have a group represented by the formula (2-1) (R 1 and R 2 are methyl groups).
（式（１）で表される構造を有する化合物Ｇの作製）
１，４－ビス（アミノメチル）シクロヘキサン７１重量部に代えてジアミノジフェニルメタン９９重量部を用いたこと以外は、上記「（式（１）で表される構造を有する化合物Ａの作製）」と同様にして、上記式（１）で表される構造を有する化合物Ｇ（融点９７℃）を得た。得られた式（１）で表される構造を有する化合物Ｇは、１Ｈ－ＮＭＲ、１３Ｃ－ＮＭＲ、及び、ＦＴ－ＩＲ分析により、上記式（１）におけるＸが上記式（２－１）で表される基（Ｒ１及びＲ２がメチル基）である構造を有することを確認した。 (Preparation of compound G having the structure represented by formula (1))
Same as “(Preparation of compound A having the structure represented by formula (1))” except that 99 parts by weight of diaminodiphenylmethane was used instead of 71 parts by weight of 1,4-bis (aminomethyl) cyclohexane. Thus, a compound G (melting point: 97 ° C.) having a structure represented by the above formula (1) was obtained. The obtained compound G having the structure represented by formula (1) was analyzed by 1 H-NMR, 13 C-NMR, and FT-IR analysis, and X in formula (1) was converted to formula (2-1). ) (R 1 and R 2 are methyl groups).
１，４－ビス（アミノメチル）シクロヘキサン７１重量部に代えてジアミノジフェニルメタン９９重量部を用いたこと以外は、上記「（式（１）で表される構造を有する化合物Ａの作製）」と同様にして、上記式（１）で表される構造を有する化合物Ｇ（融点９７℃）を得た。得られた式（１）で表される構造を有する化合物Ｇは、１Ｈ－ＮＭＲ、１３Ｃ－ＮＭＲ、及び、ＦＴ－ＩＲ分析により、上記式（１）におけるＸが上記式（２－１）で表される基（Ｒ１及びＲ２がメチル基）である構造を有することを確認した。 (Preparation of compound G having the structure represented by formula (1))
Same as “(Preparation of compound A having the structure represented by formula (1))” except that 99 parts by weight of diaminodiphenylmethane was used instead of 71 parts by weight of 1,4-bis (aminomethyl) cyclohexane. Thus, a compound G (melting point: 97 ° C.) having a structure represented by the above formula (1) was obtained. The obtained compound G having the structure represented by formula (1) was analyzed by 1 H-NMR, 13 C-NMR, and FT-IR analysis, and X in formula (1) was converted to formula (2-1). ) (R 1 and R 2 are methyl groups).
（式（１）で表される構造を有する化合物Ｈの作製）
１，４－ビス（アミノメチル）シクロヘキサン７１重量部に代えて１，３－ビス（アミノメチル）シクロヘキサン７１重量部を用いたこと以外は、上記「（式（１）で表される構造を有する化合物Ａの作製）」と同様にして、上記式（１）で表される構造を有する化合物Ｈ（融点８１℃）を得た。得られた式（１）で表される構造を有する化合物Ｈは、１Ｈ－ＮＭＲ、１３Ｃ－ＮＭＲ、及び、ＦＴ－ＩＲ分析により、上記式（４）で表される構造（Ｘが上記式（２－１）で表される基（Ｒ１及びＲ２がメチル基））を有することを確認した。 (Preparation of Compound H having a structure represented by Formula (1))
Except that 71 parts by weight of 1,3-bis (aminomethyl) cyclohexane was used instead of 71 parts by weight of 1,4-bis (aminomethyl) cyclohexane, it has the structure represented by the above “(formula (1)”. Compound H (melting point: 81 ° C.) having the structure represented by the above formula (1) was obtained in the same manner as in “Preparation of Compound A”. The resulting compound H having the structure represented by the formula (1) was analyzed by 1 H-NMR, 13 C-NMR, and FT-IR analysis (the structure represented by the above formula (4) (X is the above). It was confirmed to have a group represented by the formula (2-1) (R 1 and R 2 are methyl groups).
１，４－ビス（アミノメチル）シクロヘキサン７１重量部に代えて１，３－ビス（アミノメチル）シクロヘキサン７１重量部を用いたこと以外は、上記「（式（１）で表される構造を有する化合物Ａの作製）」と同様にして、上記式（１）で表される構造を有する化合物Ｈ（融点８１℃）を得た。得られた式（１）で表される構造を有する化合物Ｈは、１Ｈ－ＮＭＲ、１３Ｃ－ＮＭＲ、及び、ＦＴ－ＩＲ分析により、上記式（４）で表される構造（Ｘが上記式（２－１）で表される基（Ｒ１及びＲ２がメチル基））を有することを確認した。 (Preparation of Compound H having a structure represented by Formula (1))
Except that 71 parts by weight of 1,3-bis (aminomethyl) cyclohexane was used instead of 71 parts by weight of 1,4-bis (aminomethyl) cyclohexane, it has the structure represented by the above “(formula (1)”. Compound H (melting point: 81 ° C.) having the structure represented by the above formula (1) was obtained in the same manner as in “Preparation of Compound A”. The resulting compound H having the structure represented by the formula (1) was analyzed by 1 H-NMR, 13 C-NMR, and FT-IR analysis (the structure represented by the above formula (4) (X is the above). It was confirmed to have a group represented by the formula (2-1) (R 1 and R 2 are methyl groups).
（式（１）で表される構造を有する化合物Ｉ作製）
１，４－ビス（アミノメチル）シクロヘキサン７１重量部に代えて１，３－ビス（アミノメチル）シクロヘキサン７１重量部を用いたこと以外は、上記「（式（１）で表される構造を有する化合物Ｂの作製）」と同様にして、上記式（１）で表される構造を有する化合物Ｉ（融点６７℃）を得た。得られた式（１）で表される構造を有する化合物Ｉは、１Ｈ－ＮＭＲ、１３Ｃ－ＮＭＲ、及び、ＦＴ－ＩＲ分析により、上記式（４）で表される構造（Ｘが上記式（２－１）で表される基（Ｒ１及びＲ２が水素））を有することを確認した。 (Production of Compound I having the structure represented by Formula (1))
Except that 71 parts by weight of 1,3-bis (aminomethyl) cyclohexane was used instead of 71 parts by weight of 1,4-bis (aminomethyl) cyclohexane, it has the structure represented by the above “(formula (1)”. In the same manner as in “Preparation of Compound B)”, Compound I having a structure represented by the above formula (1) (melting point: 67 ° C.) was obtained. The obtained compound I having the structure represented by the formula (1) was analyzed by 1 H-NMR, 13 C-NMR, and FT-IR analysis (the structure represented by the above formula (4) (X is the above). It was confirmed to have a group represented by the formula (2-1) (R 1 and R 2 are hydrogen).
１，４－ビス（アミノメチル）シクロヘキサン７１重量部に代えて１，３－ビス（アミノメチル）シクロヘキサン７１重量部を用いたこと以外は、上記「（式（１）で表される構造を有する化合物Ｂの作製）」と同様にして、上記式（１）で表される構造を有する化合物Ｉ（融点６７℃）を得た。得られた式（１）で表される構造を有する化合物Ｉは、１Ｈ－ＮＭＲ、１３Ｃ－ＮＭＲ、及び、ＦＴ－ＩＲ分析により、上記式（４）で表される構造（Ｘが上記式（２－１）で表される基（Ｒ１及びＲ２が水素））を有することを確認した。 (Production of Compound I having the structure represented by Formula (1))
Except that 71 parts by weight of 1,3-bis (aminomethyl) cyclohexane was used instead of 71 parts by weight of 1,4-bis (aminomethyl) cyclohexane, it has the structure represented by the above “(formula (1)”. In the same manner as in “Preparation of Compound B)”, Compound I having a structure represented by the above formula (1) (melting point: 67 ° C.) was obtained. The obtained compound I having the structure represented by the formula (1) was analyzed by 1 H-NMR, 13 C-NMR, and FT-IR analysis (the structure represented by the above formula (4) (X is the above). It was confirmed to have a group represented by the formula (2-1) (R 1 and R 2 are hydrogen).
（エポキシ－イミダゾールアダクト化合物の作製）
２－メチルイミダゾール２０重量部と、ビスフェノールＡジグリシジルエーテル１９０重量部に、トルエン５００重量部と、ｎ－ブチルアルコール５００重量部を加えて混合溶解し、７０℃で２時間加熱撹拌を行った。得られた反応混合物の溶媒除去と乾燥を行い、得られた固形物をジェットミルにて粉砕し、エポキシ－イミダゾールアダクト化合物を得た。 (Preparation of epoxy-imidazole adduct compound)
To 200 parts by weight of 2-methylimidazole and 190 parts by weight of bisphenol A diglycidyl ether, 500 parts by weight of toluene and 500 parts by weight of n-butyl alcohol were added, mixed and dissolved, and heated and stirred at 70 ° C. for 2 hours. The resulting reaction mixture was subjected to solvent removal and drying, and the resulting solid was pulverized with a jet mill to obtain an epoxy-imidazole adduct compound.
２－メチルイミダゾール２０重量部と、ビスフェノールＡジグリシジルエーテル１９０重量部に、トルエン５００重量部と、ｎ－ブチルアルコール５００重量部を加えて混合溶解し、７０℃で２時間加熱撹拌を行った。得られた反応混合物の溶媒除去と乾燥を行い、得られた固形物をジェットミルにて粉砕し、エポキシ－イミダゾールアダクト化合物を得た。 (Preparation of epoxy-imidazole adduct compound)
To 200 parts by weight of 2-methylimidazole and 190 parts by weight of bisphenol A diglycidyl ether, 500 parts by weight of toluene and 500 parts by weight of n-butyl alcohol were added, mixed and dissolved, and heated and stirred at 70 ° C. for 2 hours. The resulting reaction mixture was subjected to solvent removal and drying, and the resulting solid was pulverized with a jet mill to obtain an epoxy-imidazole adduct compound.
（実施例１～１５、比較例１、２）
表１、２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１～１５、比較例１、２の各液晶表示素子用シール剤を調製した。 (Examples 1 to 15, Comparative Examples 1 and 2)
According to the mixing ratios described in Tables 1 and 2, after mixing each material using a planetary stirrer (“Shinky Co., Ltd.,“ Awatori Netaro ”), by further mixing using three rolls The sealing agents for liquid crystal display elements of Examples 1 to 15 and Comparative Examples 1 and 2 were prepared.
表１、２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１～１５、比較例１、２の各液晶表示素子用シール剤を調製した。 (Examples 1 to 15, Comparative Examples 1 and 2)
According to the mixing ratios described in Tables 1 and 2, after mixing each material using a planetary stirrer (“Shinky Co., Ltd.,“ Awatori Netaro ”), by further mixing using three rolls The sealing agents for liquid crystal display elements of Examples 1 to 15 and Comparative Examples 1 and 2 were prepared.
＜評価＞
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について以下の評価を行った。結果を表１、２に示した。 <Evaluation>
The following evaluation was performed about each sealing compound for liquid crystal display elements obtained by the Example and the comparative example. The results are shown in Tables 1 and 2.
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について以下の評価を行った。結果を表１、２に示した。 <Evaluation>
The following evaluation was performed about each sealing compound for liquid crystal display elements obtained by the Example and the comparative example. The results are shown in Tables 1 and 2.
（保存安定性）
実施例及び比較例で得られた各液晶表示素子用シール剤について、製造直後の初期粘度と、２５℃で３日間保管したときの粘度とを測定した。（２５℃、３日間保管後の粘度）／（初期粘度）を粘度変化率とし、粘度変化率が１．２未満であったものを「○」、１．２以上１．５未満であったものを「△」、１．５以上であったものを「×」として保存安定性を評価した。
なお、シール剤の粘度は、Ｅ型粘度計（ＢＲＯＯＫ ＦＩＥＬＤ社製、「ＤＶ－ＩＩＩ」）を用い、２５℃において回転速度１．０ｒｐｍの条件で測定した。 (Storage stability)
About each sealing agent for liquid crystal display elements obtained by the Example and the comparative example, the initial viscosity immediately after manufacture and the viscosity when stored at 25 degreeC for 3 days were measured. (Viscosity after storage at 25 ° C. for 3 days) / (initial viscosity) is defined as the rate of change in viscosity. The storage stability was evaluated by assigning “△” for the product and “×” for the product having a value of 1.5 or more.
The viscosity of the sealing agent was measured using an E-type viscometer (manufactured by BROOK FIELD, “DV-III”) at 25 ° C. and a rotation speed of 1.0 rpm.
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について、製造直後の初期粘度と、２５℃で３日間保管したときの粘度とを測定した。（２５℃、３日間保管後の粘度）／（初期粘度）を粘度変化率とし、粘度変化率が１．２未満であったものを「○」、１．２以上１．５未満であったものを「△」、１．５以上であったものを「×」として保存安定性を評価した。
なお、シール剤の粘度は、Ｅ型粘度計（ＢＲＯＯＫ ＦＩＥＬＤ社製、「ＤＶ－ＩＩＩ」）を用い、２５℃において回転速度１．０ｒｐｍの条件で測定した。 (Storage stability)
About each sealing agent for liquid crystal display elements obtained by the Example and the comparative example, the initial viscosity immediately after manufacture and the viscosity when stored at 25 degreeC for 3 days were measured. (Viscosity after storage at 25 ° C. for 3 days) / (initial viscosity) is defined as the rate of change in viscosity. The storage stability was evaluated by assigning “△” for the product and “×” for the product having a value of 1.5 or more.
The viscosity of the sealing agent was measured using an E-type viscometer (manufactured by BROOK FIELD, “DV-III”) at 25 ° C. and a rotation speed of 1.0 rpm.
（低温硬化性）
実施例及び比較例で得られた各液晶表示素子用シール剤について、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、１００℃で４０分間加熱した時のエポキシ基の反応率（エポキシ基由来のピークの減少率）をＦＴ－ＩＲ測定器（Ａｇｉｌｅｎｔ Ｔｅｃｈｎｏｌｏｇｉｅｓ社製、「ＵＭＡ６００」）を用いて測定した。エポキシ基の反応率が９０％以上であったものを「○」、９０％未満７０％以上であったものを「△」、７０％未満であったものを「×」として低温硬化性を評価した。 (Low temperature curability)
About each liquid crystal display element sealing agent obtained in the examples and comparative examples, the reaction rate of epoxy groups when irradiated with 100 mW / cm 2 ultraviolet rays for 30 seconds using a metal halide lamp and then heated at 100 ° C. for 40 minutes (Decrease rate of the peak derived from the epoxy group) was measured using an FT-IR measuring instrument (manufactured by Agilent Technologies, “UMA600”). Low-temperature curability was evaluated by assuming that the reaction rate of the epoxy group was 90% or more as “◯”, the case where it was less than 90% as 70% or more as “Δ”, and the case where it was less than 70% as “X”. did.
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について、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、１００℃で４０分間加熱した時のエポキシ基の反応率（エポキシ基由来のピークの減少率）をＦＴ－ＩＲ測定器（Ａｇｉｌｅｎｔ Ｔｅｃｈｎｏｌｏｇｉｅｓ社製、「ＵＭＡ６００」）を用いて測定した。エポキシ基の反応率が９０％以上であったものを「○」、９０％未満７０％以上であったものを「△」、７０％未満であったものを「×」として低温硬化性を評価した。 (Low temperature curability)
About each liquid crystal display element sealing agent obtained in the examples and comparative examples, the reaction rate of epoxy groups when irradiated with 100 mW / cm 2 ultraviolet rays for 30 seconds using a metal halide lamp and then heated at 100 ° C. for 40 minutes (Decrease rate of the peak derived from the epoxy group) was measured using an FT-IR measuring instrument (manufactured by Agilent Technologies, “UMA600”). Low-temperature curability was evaluated by assuming that the reaction rate of the epoxy group was 90% or more as “◯”, the case where it was less than 90% as 70% or more as “Δ”, and the case where it was less than 70% as “X”. did.
（液晶表示素子の表示性能）
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重量部にスペーサー微粒子（積水化学工業社製、「ミクロパールＳＩ－Ｈ０５０」）１重量部を分散させ、液晶表示素子用シール剤として、２枚のラビング済み配向膜及び透明電極付き基板の一方にシール剤の線幅が１ｍｍになるようにディスペンサーで塗布した。
続いて液晶（チッソ社製、「ＪＣ－５００４ＬＡ」）の微小滴を透明電極付き基板のシール剤の枠内全面に滴下塗布し、すぐにもう一方の透明電極付きカラーフィルター基板を貼り合わせ、シール剤部分にメタルハライドランプを用いて１００ｍＷ／ｃｍ２の紫外線（波長３６５ｎｍ）を３０秒照射した後、１００℃で４０分間加熱して液晶表示素子を得た。
得られた液晶表示素子について、１００時間動作試験を行った後、８０℃で１０００時間電圧印加状態とした後のシール剤付近の液晶配向乱れを目視によって確認した。
配向乱れは表示部の色むらにより判断しており、色むらの程度に応じて、色むらが全くなかった場合を「◎」、色むらが微かにあった場合を「○」、色むらが少しあった場合を「△」、色むらがかなりあった場合を「×」として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り、「△」は液晶表示素子の表示設計によって問題になる可能性があるレベルであり、「×」は実用に耐えないレベルである。 (Display performance of liquid crystal display elements)
1 part by weight of spacer fine particles (“Micropearl SI-H050” manufactured by Sekisui Chemical Co., Ltd.) is dispersed in 100 parts by weight of the sealant for each liquid crystal display element obtained in Examples and Comparative Examples, and the sealant for liquid crystal display element As an example, the sealant was applied to one of the two rubbed alignment films and the substrate with a transparent electrode with a dispenser so that the line width of the sealant was 1 mm.
Subsequently, liquid droplets (manufactured by Chisso Corp., “JC-5004LA”) are dropped onto the entire surface of the sealing agent frame of the substrate with the transparent electrode, and the other color filter substrate with the transparent electrode is immediately bonded to the seal. The agent part was irradiated with 100 mW / cm 2 ultraviolet rays (wavelength 365 nm) for 30 seconds using a metal halide lamp, and then heated at 100 ° C. for 40 minutes to obtain a liquid crystal display element.
About the obtained liquid crystal display element, after performing the operation test for 100 hours, the liquid crystal alignment disorder of the sealant vicinity after making it into a voltage application state at 80 degreeC for 1000 hours was confirmed visually.
The alignment disorder is determined by the color unevenness of the display part. Depending on the degree of color unevenness, “◎” indicates that there is no color unevenness, “○” indicates that the color unevenness is slight, and “color unevenness”. The low liquid crystal contamination property was evaluated with “△” when there was a little, and “×” when there was considerable color unevenness.
In addition, the liquid crystal display elements with the evaluations “◎” and “O” are at a level where there is no problem in practical use, and “Δ” is a level that may cause a problem depending on the display design of the liquid crystal display element. "X" is a level that cannot be practically used.
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重量部にスペーサー微粒子（積水化学工業社製、「ミクロパールＳＩ－Ｈ０５０」）１重量部を分散させ、液晶表示素子用シール剤として、２枚のラビング済み配向膜及び透明電極付き基板の一方にシール剤の線幅が１ｍｍになるようにディスペンサーで塗布した。
続いて液晶（チッソ社製、「ＪＣ－５００４ＬＡ」）の微小滴を透明電極付き基板のシール剤の枠内全面に滴下塗布し、すぐにもう一方の透明電極付きカラーフィルター基板を貼り合わせ、シール剤部分にメタルハライドランプを用いて１００ｍＷ／ｃｍ２の紫外線（波長３６５ｎｍ）を３０秒照射した後、１００℃で４０分間加熱して液晶表示素子を得た。
得られた液晶表示素子について、１００時間動作試験を行った後、８０℃で１０００時間電圧印加状態とした後のシール剤付近の液晶配向乱れを目視によって確認した。
配向乱れは表示部の色むらにより判断しており、色むらの程度に応じて、色むらが全くなかった場合を「◎」、色むらが微かにあった場合を「○」、色むらが少しあった場合を「△」、色むらがかなりあった場合を「×」として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り、「△」は液晶表示素子の表示設計によって問題になる可能性があるレベルであり、「×」は実用に耐えないレベルである。 (Display performance of liquid crystal display elements)
1 part by weight of spacer fine particles (“Micropearl SI-H050” manufactured by Sekisui Chemical Co., Ltd.) is dispersed in 100 parts by weight of the sealant for each liquid crystal display element obtained in Examples and Comparative Examples, and the sealant for liquid crystal display element As an example, the sealant was applied to one of the two rubbed alignment films and the substrate with a transparent electrode with a dispenser so that the line width of the sealant was 1 mm.
Subsequently, liquid droplets (manufactured by Chisso Corp., “JC-5004LA”) are dropped onto the entire surface of the sealing agent frame of the substrate with the transparent electrode, and the other color filter substrate with the transparent electrode is immediately bonded to the seal. The agent part was irradiated with 100 mW / cm 2 ultraviolet rays (wavelength 365 nm) for 30 seconds using a metal halide lamp, and then heated at 100 ° C. for 40 minutes to obtain a liquid crystal display element.
About the obtained liquid crystal display element, after performing the operation test for 100 hours, the liquid crystal alignment disorder of the sealant vicinity after making it into a voltage application state at 80 degreeC for 1000 hours was confirmed visually.
The alignment disorder is determined by the color unevenness of the display part. Depending on the degree of color unevenness, “◎” indicates that there is no color unevenness, “○” indicates that the color unevenness is slight, and “color unevenness”. The low liquid crystal contamination property was evaluated with “△” when there was a little, and “×” when there was considerable color unevenness.
In addition, the liquid crystal display elements with the evaluations “◎” and “O” are at a level where there is no problem in practical use, and “Δ” is a level that may cause a problem depending on the display design of the liquid crystal display element. "X" is a level that cannot be practically used.
本発明によれば、保存安定性と低温での速硬化性とを両立できる液晶表示素子用シール剤を提供することができる。また、本発明によれば、該液晶表示素子用シール剤を用いてなる上下導通材料及び液晶表示素子を提供することができる。
ADVANTAGE OF THE INVENTION According to this invention, the sealing compound for liquid crystal display elements which can make storage stability and quick-curing property in low temperature compatible can be provided. Moreover, according to this invention, the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal display elements can be provided.
Claims (7)
- 硬化性樹脂と熱硬化剤とを含有する液晶表示素子用シール剤であって、
前記熱硬化剤は、下記式（１）で表される構造を有する化合物を含有することを特徴とする液晶表示素子用シール剤。
The said thermosetting agent contains the compound which has a structure represented by following formula (1), The sealing compound for liquid crystal display elements characterized by the above-mentioned.
- 式（１）中のＸが、下記式（２－１）、（２－２）、（２－３）、（２－４）、又は、（２－５）で表される構造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。
- 式（１）で表される構造を有する化合物として、下記式（３）で表される構造を有する化合物を含有す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。
- 式（１）で表される構造を有する化合物として、下記式（４）で表される構造を有する化合物を含有す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。
- 式（１）で表される構造を有する化合物は、融点が６０℃～１００℃であることを特徴とする請求項１、２、３又は４記載の液晶表示素子用シール剤。 5. The sealing agent for a liquid crystal display element according to claim 1, wherein the compound having the structure represented by the formula (1) has a melting point of 60 ° C. to 100 ° C.
- 請求項１、２、３、４又は５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 liquid crystal display element sealant according to claim 1, and conductive fine particles.
- 請求項１、２、３、４若しくは５記載の液晶表示素子用シール剤又は請求項６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, 4, or 5, or the vertical conduction material according to claim 6.
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| JP2010169833A (en) * | 2009-01-21 | 2010-08-05 | Adeka Corp | Sealing agent for liquid crystal dropping method, which contains photocurable resin and thermosetting resin |
| JP2013018810A (en) * | 2011-07-07 | 2013-01-31 | Adeka Corp | Curable resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6802147B2 (en) | 2020-12-16 |
| TW201736562A (en) | 2017-10-16 |
| TWI747862B (en) | 2021-12-01 |
| JPWO2017119260A1 (en) | 2018-11-08 |
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