WO2009128470A1 - 液晶滴下工法用シール剤、液晶パネル用封口剤、上下導通材料及び液晶表示素子 - Google Patents

液晶滴下工法用シール剤、液晶パネル用封口剤、上下導通材料及び液晶表示素子 Download PDF

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WO2009128470A1
WO2009128470A1 PCT/JP2009/057568 JP2009057568W WO2009128470A1 WO 2009128470 A1 WO2009128470 A1 WO 2009128470A1 JP 2009057568 W JP2009057568 W JP 2009057568W WO 2009128470 A1 WO2009128470 A1 WO 2009128470A1
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Prior art keywords
liquid crystal
meth
sealing agent
acrylate
dropping method
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PCT/JP2009/057568
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English (en)
French (fr)
Japanese (ja)
Inventor
尾山雄一
松田正則
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積水化学工業株式会社
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Application filed by 積水化学工業株式会社 filed Critical 積水化学工業株式会社
Priority to CN200980112979.9A priority Critical patent/CN102007447B/zh
Priority to KR1020107018271A priority patent/KR101194202B1/ko
Priority to JP2009516789A priority patent/JP4616404B2/ja
Publication of WO2009128470A1 publication Critical patent/WO2009128470A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/04—Azo-compounds
    • 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
    • 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
    • G02F2202/00—Materials and properties
    • G02F2202/02—Materials and properties organic material
    • G02F2202/022—Materials and properties organic material polymeric
    • G02F2202/023—Materials and properties organic material polymeric curable
    • G02F2202/025—Materials and properties organic material polymeric curable thermocurable

Definitions

  • the present invention relates to a sealing agent for liquid crystal dropping method capable of manufacturing a liquid crystal display element of high quality image with little color unevenness even when the liquid crystal display element is manufactured by the dropping method.
  • the present invention relates to a sealing agent for a liquid crystal panel capable of manufacturing a liquid crystal display element of a high quality image with little color unevenness when manufacturing a liquid crystal display device by a vacuum injection method.
  • liquid crystal display element such as a liquid crystal display cell
  • two transparent substrates with electrodes are made to face each other at a predetermined distance, and the periphery is sealed with a sealing agent to form a cell, which is provided in part thereof
  • the liquid crystal is injected into the cell from the liquid crystal injection port, and the liquid crystal injection port is sealed by using a sealing agent or a sealing agent by a method called a vacuum injection method.
  • a seal pattern provided with a liquid crystal injection port using a thermosetting sealing agent is formed by screen printing on one of two transparent substrates with electrodes, and prebaking is performed at 60 to 100 ° C. Do dry the solvent in the sealant. Then, the two substrates are opposed to each other with the spacer interposed therebetween for alignment and bonding, and after heat pressing at 110 to 220 ° C. for 10 to 90 minutes to adjust the gap in the vicinity of the seal, it is heated at 110 to 220 ° C. in an oven. Heat for 10 to 120 minutes to fully cure the sealant. Then, liquid crystal was injected from the liquid crystal injection port, and finally, the liquid crystal injection port was sealed using a sealing agent to produce a liquid crystal display element.
  • Patent Document 1 and Patent Document 2 methods of manufacturing liquid crystal display devices such as liquid crystal display cells are disclosed in, for example, Patent Document 1 and Patent Document 2 from the above-described vacuum injection method from the viewpoint of shortening tact time and optimizing the amount of liquid crystal used.
  • a sealing agent comprising a photocurable and heat-curable resin composition containing a photocurable acrylic resin and a photopolymerization initiator, and a thermosetting epoxy resin and a thermal polymerization initiator It is replacing the liquid crystal dropping method called the method.
  • liquid crystal dropping method first, a seal pattern is formed on one of the two electrode-attached substrates. Then, with the sealant uncured, small droplets of liquid crystal are dropped over the entire surface of the frame of the substrate, the other substrate is superposed under vacuum, and after returning to normal pressure, ultraviolet rays are irradiated to the seal portion to make acrylic resin Cure (provisional curing step). Thereafter, the epoxy resin is cured by heating to manufacture a liquid crystal display element.
  • a method using a sealing agent containing a low molecular weight peroxide or an azo compound as a component for thermally curing an acrylic resin is also used in order to cure the uncured acrylic resin reliably even after light irradiation. Conceivable.
  • the acrylic resin which has not been cured in the temporary curing step can be cured by heating at the time of liquid crystal annealing.
  • color unevenness occurs around the seal portion, and there is a problem that a liquid crystal display element of high quality image can not be obtained.
  • the present invention provides a sealing agent for a liquid crystal dropping method capable of manufacturing a liquid crystal display element of high quality image with little color unevenness even when the liquid crystal display element is manufactured by a dropping method in view of the above-mentioned present situation.
  • the purpose is to Another object of the present invention is to provide a sealing agent for a liquid crystal panel capable of manufacturing a liquid crystal display element of high quality image with little color unevenness when manufacturing a liquid crystal display device by a vacuum injection method.
  • the present invention is a sealing agent for liquid crystal dropping method comprising a resin having a (meth) acrylic group and a polymeric azo initiator.
  • the present invention is a sealant for a liquid crystal panel, which comprises a resin having a (meth) acrylic group and a polymeric azo initiator. The present invention will be described in detail below.
  • a sealing agent for liquid crystal dropping method containing a resin having a (meth) acrylic group and a high molecular weight azo initiator has no adverse effect on the liquid crystal of the azo initiator itself during heat curing. And, by curing a resin having an uncured (meth) acrylic group, it is found that a liquid crystal display element of high quality image with less color unevenness can be manufactured, and the present invention is completed.
  • the sealing agent for liquid crystal dropping method of the present invention contains a polymeric azo initiator.
  • a polymeric azo initiator means a compound having an azo group and having a molecular weight of 300 or more capable of radically curing a (meth) acrylic group by heat.
  • the said polymeric azo initiator is normally decomposed
  • the preferable lower limit of the number average molecular weight of the above-mentioned polymeric azo initiator is 1000, and the preferable upper limit is 300,000.
  • the number average molecular weight of the above-mentioned high molecular weight azo initiator is less than 1000, the high molecular weight azo initiator may adversely affect the liquid crystal, and when it exceeds 300,000, mixing to the resin having (meth) acrylic group is It can be difficult.
  • a more preferable lower limit of the number average molecular weight of the above-mentioned polymer azo initiator is 5,000, a more preferable upper limit is 100,000, a still more preferable lower limit is 10,000, and a still more preferable upper limit is 90,000.
  • the lower limit of the 10-hour half-life temperature is preferably 50 ° C., and the upper limit is preferably 90 ° C.
  • the 10-hour half-life temperature of the above-mentioned high molecular weight azo compound is less than 50 ° C., the storage stability of the obtained sealing agent for liquid crystal dropping method may be deteriorated.
  • the 10-hour half-life temperature of the above-mentioned high molecular weight azo compound exceeds 90 ° C., curing of the sealing agent for a liquid crystal dropping method of the present invention takes a high temperature and a long time, which may affect the productivity of the panel.
  • Examples of the above-mentioned high molecular weight azo initiator include those having a structure in which a plurality of units such as polydimethylsiloxane and polyalkylene oxide are bonded via an azo group. As a structure which multiple units, such as a polyalkylene oxide, couple
  • a polymeric azo initiator for example, a polycondensate of 4,4'-azobis (4-cyanopentanoic acid) and a polyalkylene glycol, or 4,4'-azobis (4-cyanopentanoic acid) and an end thereof
  • the polycondensate of the polydimethylsiloxane which has an amino group etc. are mentioned, For example, VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 (all are Wako Pure Chemical Industries Ltd. make) Etc.
  • R 12 , R 13 , R 22 and R 23 each independently represent an alkyl group having 1 to 10 carbon atoms or a cyano group, and a and b each independently represent 0 to 4 A 11 and A 12 are polymer chains, and Y 11 and Y 12 are each independently —CO—O—, —O—CO—, —NH—CO— or —CO— NH-, -O- or -S-.
  • the alkyl group having 1 to 10 carbon atoms represented by R 12 , R 13 , R 22 and R 23 is methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl Isobutyl, amyl, isoamyl, t-amyl, hexyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl, heptyl, isoheptyl, t-heptyl, n-octyl, isooctyl, t-octyl, 2-ethylhexyl, n-nonyl, n-decyl Etc.
  • the polymer chains represented by A 11 and A 12 are not particularly limited.
  • compounds in which Y 11 is —O—CO— and Y 12 is —CO—O— are preferable, and the polymer chains represented by A 11 and A 12 are polyether chains and polyester chains. Are more preferable because they are particularly inexpensive and easy to manufacture.
  • the compound represented by the following general formula (II) has good solubility and the molecular weight of the polymerization initiator It is more preferable because it gives a grafted pigment which is easy to control and has high dispersibility.
  • R 12 , R 13 , R 22 , R 23 , a and b are the same as in the above general formula (I), and R 11 and R 21 each independently have 1 to carbon atoms Z 11 , Z 12 , Z 21 and Z 22 each independently represent an alkylene group having 1 to 4 carbon atoms, and m, n, s and t each independently represent 0. The sum of m + n and the sum of s + t are each independently 2 or more. )
  • the alkylene group having 1 to 4 carbon atoms represented by Z 11 , Z 12 , Z 21 and Z 22 is methylene, ethylene, trimethylene, propylene, propylidene, isopropylidene, tetramethylene, butylene And isobutylene, ethylethylene, dimethylethylene and the like
  • the alkyl group having 1 to 24 carbon atoms represented by R 11 and R 21 is methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, Isobutyl, amyl, isoamyl, t-amyl, hexyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl, heptyl, isoheptyl, t-heptyl, n-octyl, isooctyl, t-
  • the alkyl group having 1 to 24 carbon atoms represented by R 11 and R 21 gives a highly dispersible grafted pigment having 1 to 4 carbon atoms, and one end of a chain polymer
  • the compound is preferable because the reactivity of the esterification reaction of the compound having a hydroxyl group with the azodicarboxylic acid compound is high.
  • R 12 , R 13 , R 22 , R 23 , a and b are the same as in the above general formula (I), and Z 13 and Z 23 each independently have 1 to carbon atoms R 31 and R 41 each independently represent a hydrogen atom or an alkyl group having 1 to 24 carbon atoms, and p and u each independently represent a number of 1 to 1000. )
  • the alkylene group having 1 to 18 carbon atoms represented by Z 13 and Z 23 is methylene, ethylene, trimethylene, propylene, propylidene, isopropylidene, tetramethylene, butylene, isobutylene, ethylethylene, Dimethylethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, 1,4-pentanediyl, decamethylene, undecamethylene, 1,4-undecanediyl, dodecamethylene, 1,11-heptadecanediyl, octadecamethylene etc.
  • Examples of the alkyl group having 1 to 24 carbon atoms represented by R 31 and R 41 include those exemplified as R 11 and R 21 in the above general formula (II).
  • the alkyl group having 1 to 24 carbon atoms represented by R 31 and R 41 gives a highly dispersible grafted pigment having 1 to 4 carbon atoms, and one end of the chain polymer The compound is preferable because the reactivity of the esterification reaction of the compound having a hydroxyl group with the azodicarboxylic acid compound is high.
  • the content of the above-mentioned high molecular weight azo initiator in the sealing agent for liquid crystal dropping method of the present invention is not particularly limited, but the preferable lower limit is 0.1 parts by weight with respect to 100 parts by weight of the resin having the (meth) acrylic group.
  • the upper limit is 30 parts by weight. If the content of the high molecular weight azo initiator is less than 0.1 parts by weight, the polymerization of the resin having the (meth) acrylic group may not proceed sufficiently. When the content of the above-mentioned high molecular weight azo initiator exceeds 30 parts by weight, the viscosity of the obtained sealing agent for liquid crystal dropping method becomes high, which may adversely affect the coating workability and the like.
  • the more preferable lower limit of the content of the above-mentioned polymeric azo initiator is 0.5 parts by weight, and the more preferable upper limit is 10 parts by weight.
  • the sealing agent for liquid crystal dropping method of the present invention contains a resin having a (meth) acrylic group.
  • the resin having the above (meth) acrylic group is not particularly limited, and for example, an ester compound obtained by reacting a compound having a hydroxyl group with (meth) acrylic acid, a reaction of (meth) acrylic acid and an epoxy compound Epoxy (meth) acrylates obtained by the above, and urethane (meth) acrylates obtained by reacting an isocyanate with a (meth) acrylic acid derivative having a hydroxyl group.
  • the ester compound obtained by reacting the compound having a hydroxyl group with the above (meth) acrylic acid is not particularly limited, and the monofunctional ester compound is, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) ) Acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) ) Acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, methoxy ethylene glycol (meth) acrylate, 2-ethoxyethyl (meth) acrylate Tetrahydrofurfuryl (meth) acrylate
  • the difunctional ester compound is, for example, 1,4-butanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9 -Nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate 2-n-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate , Tripropylene glycol di (meth) acrylate, polypropylene glycol (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate Propylene oxide-added bisphenol A di (me)
  • the trifunctional or higher ester compound is, for example, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, propylene oxide-added trimethylolpropane tri (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) Acrylate, caprolactone modified trimethylolpropane tri (meth) acrylate, ethylene oxide adducted isocyanuric acid tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, Pentaerythritol tetra (meth) acrylate, glycerin tri (meth) acrylate, propylene oxide addition glycerol Entry (meth) acrylate, tris
  • the epoxy (meth) acrylate obtained by reacting the above (meth) acrylic acid and the epoxy compound is not particularly limited, and, for example, an epoxy resin and (meth) acrylic acid in the presence of a basic catalyst according to a conventional method And the like.
  • combining the said epoxy (meth) acrylate is not specifically limited, For example, what is marketed is bisphenol A type
  • molds such as Epicoat 828EL and Epicoat 1004 (all are Japan epoxy resin company make) Epoxy resin, bisphenol F type epoxy resin such as Epi
  • Propylene oxide addition bis fe Type A epoxy resin resorcinol type epoxy resin such as EX-201 (made by Nagase ChemteX Corp.), biphenyl type epoxy resin such as Epicoat YX-4000H (made by Japan Epoxy Resins Co., Ltd.), YSLV-50TE Sulfide-type epoxy resins such as those manufactured by Kasei Chemical Co., Ltd., ether-type epoxy resins such as YSLV-80DE (manufactured by Toto Kasei Co., Ltd.), dicyclopentadiene-type epoxy resins such as EP-4088S (manufactured by Asahi Denka Co., Ltd.), Epiclon HP4032 And naphthalene type epoxy resins such as Epiclon EXA-4700 (all manufactured by Dainippon Ink Co., Ltd.), phenol novolac epoxy resins such as Epiclon N-770 (manufactured by Dainippon Ink Co., Ltd.),
  • Alkyl polyol type epoxy resins such as ZX-1542 (made by Tohto Kasei Co., Ltd.), Epiclon 726 (made by Dainippon Ink Co., Ltd.), Epolight 80 MFA (made by Kyoeisha Chemical Co., Ltd.), Denacol EX-611, (made by Nagase ChemteX Corp.) , YR-450, YR-207 (All are Rubber-modified epoxy resin such as Kasei Chemical Co., Ltd., EPIDEL PB (made by Daicel Chemical Industries, Ltd.), glycidyl ester compounds such as DENACOAL EX-147 (made by Nagase ChemteX Co., Ltd.), Epicoat YL-7000 (manufactured by Japan Epoxy Resins Co., Ltd.) Etc., YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Tohto Kasei Co., Ltd.), XAC
  • the epoxy (meth) acrylate obtained by reacting the above (meth) acrylic acid and the epoxy compound is, for example, 360 parts by weight of resorcinol type epoxy resin (EX-201, manufactured by Nagase ChemteX Corp.),
  • the reaction can be obtained by reacting 2 parts by weight of p-methoxyphenol as a polymerization inhibitor, 2 parts by weight of triethylamine as a reaction catalyst, and 210 parts by weight of acrylic acid for 5 hours with reflux stirring at 90 ° C. while introducing air.
  • the urethane (meth) acrylate obtained by reacting the above-mentioned isocyanate with a (meth) acrylic acid derivative having a hydroxyl group is, for example, a (meth) acrylic acid derivative 2 having a hydroxyl group with respect to one equivalent of a compound having two isocyanate groups.
  • An equivalent amount can be obtained by reacting in the presence of a catalytic amount of a tin-based compound.
  • the isocyanate used as a raw material of urethane (meth) acrylate obtained by reacting the above-mentioned isocyanate with a (meth) acrylic acid derivative having a hydroxyl group is not particularly limited.
  • the isocyanate as a raw material of urethane (meth) acrylate obtained by reacting the above-mentioned isocyanate with a (meth) acrylic acid derivative having a hydroxyl group is not particularly limited.
  • ethylene glycol, glycerin, sorbitol, trimethylolpropane It is also possible to use chain-extended isocyanate compounds obtained by the reaction of a polyol such as (poly) propylene glycol, carbonate diol, polyether diol, polyester diol, polycaprolactone diol and the like with an excess of isocyanate.
  • the (meth) acrylic acid derivative having a hydroxyl group which is a raw material of urethane (meth) acrylate obtained by reacting a (meth) acrylic acid derivative having a hydroxyl group with the above-mentioned isocyanate, is not particularly limited, for example, 2-hydroxyethyl
  • Commercial products such as (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, ethylene glycol, propylene glycol, 1,3-propanediol, 1
  • Mono- (meth) acrylates of dihydric alcohols such as 3-butanediol, 1,4-butanediol and polyethylene glycol
  • mono (meth) acrylates of trihydric alcohols such as trimethylolethane, trimethylolpropane and glycerin or (Meth) acrylates, epoxy acrylates such as bisphenol
  • urethane (meth) acrylate obtained by reacting the above-mentioned isocyanate with a (meth) acrylic acid derivative having a hydroxyl group is, for example, 134 parts by weight of trimethylolpropane, 0.2 parts by weight of BHT as a polymerization inhibitor, As a reaction catalyst, 0.01 part by weight of dibutyltin dilaurate and 666 parts by weight of isophorone diisocyanate are added and reacted for 2 hours while stirring under reflux at 60 ° C. Then, 51 parts by weight of 2-hydroxyethyl acrylate is added and air is fed in It can be obtained by reacting for 2 hours with reflux stirring at 90 ° C.
  • urethane (meth) acrylates include, for example, M-1100, M-1200, M-1210 and M-1600 (all from Toagosei Co., Ltd.), Ebecryl 230, Ebecryl 270, Ebecryl 4858, Ebecryl 8402, Ebecryl 8804, Ebecryl 8803, Ebecryl 8260, Ebecryl 9260, Ebecryl 1290, Ebecryl 5129, Ebecryl 4842, Ebecryl 210, Ebecryl 4700, Ebecryl 6700, Ebecryl 220, Ebecryl 2202 (all manufactured by Daicel-Citech Inc.) 9000H, Art resin UN-9000A, Art resin UN-7100, Art resin UN-1255, Art resin UN-330, Art resin UN-3320HB, A Toresin UN-1200TPK, Art Resin SH-500B (all from Negami Industries), U-122P, U-108A, U-340P, U
  • the resin having a (meth) acrylic group is preferably one having a hydrogen bonding unit such as -OH group, -NH- group or -NH 2 group from the viewpoint of suppressing an adverse effect on liquid crystal, and easiness of synthesis Particularly preferred is epoxy (meth) acrylate.
  • the resin having a (meth) acrylic group is preferably one having 2 to 3 (meth) acrylic groups in the molecule from the viewpoint of reactivity.
  • the sealing agent for a liquid crystal dropping method of the present invention preferably further contains a resin having an epoxy group in order to improve adhesion.
  • the resin having the above epoxy group is not particularly limited, and commercially available resins include, for example, bisphenol A epoxy resin such as Epicoat 828EL, Epicoat 1004 (all manufactured by Japan Epoxy Resins Co., Ltd.), Epicoat 806, Epicoat 4004 ( All are bisphenol F-type epoxy resins such as those manufactured by Japan Epoxy Resins, bisphenol S-type epoxy resins such as Epiclon EXA 1514 (manufactured by Dainippon Ink), and 2 such as RE-810NM (manufactured by Nippon Kayaku Co., Ltd.) '-Diallyl bisphenol A epoxy resin, hydrogenated bisphenol epoxy resin such as Epiclon EXA 7015 (manufactured by Dainippon Ink), propylene oxide added bisphenol A epoxy resin such as EP-4000S (manufactured by Asahi Denka Co.), EX-201 (Nagase Resorcinol type epoxy resin such as Mutex Co., Ltd., biphenyl type epoxy resin such
  • the resin having an epoxy group may be, for example, a compound having a (meth) acrylic group and an epoxy group in one molecule.
  • Such compounds include, for example, compounds obtained by reacting an epoxy group of a part of a compound having two or more epoxy groups with (meth) acrylic acid.
  • the compound obtained by reacting the epoxy group of a part of the compound having two or more epoxy groups with (meth) acrylic acid is, for example, an epoxy resin and (meth) acrylic acid in a basic catalyst according to a conventional method. It is obtained by reacting in the presence. Specifically, for example, 190 g of a phenol novolac epoxy resin N-770 (manufactured by Dainippon Ink and Chemicals, Inc.) is dissolved in 500 mL of toluene, 0.1 g of triphenylphosphine is added to this solution, and a uniform solution is obtained.
  • a phenol novolac epoxy resin N-770 manufactured by Dainippon Ink and Chemicals, Inc.
  • the (meth) acrylic group is selected so that the ratio of (meth) acrylic group to epoxy group is 50:50 to 95: 5. It is preferable to blend the resin having and the resin having an epoxy group.
  • the proportion of the (meth) acrylic group is 50% or less, a large amount of uncured epoxy resin component may be present even when the thermal polymerization by the azo initiator is completed, which may contaminate the liquid crystal. If the proportion of (meth) acrylic group is 95% or more, sufficient adhesion may not be obtained.
  • the sealing agent for a liquid crystal dropping method of the present invention contains a resin having the above-mentioned epoxy group, it is preferable to further contain an epoxy thermosetting agent.
  • the said epoxy thermosetting agent is not specifically limited, For example, organic acid hydrazide, an imidazole derivative, an amine compound, a polyhydric phenol type compound, an acid anhydride etc. are mentioned. Among them, solid organic acid hydrazide is suitably used.
  • the solid organic acid hydrazide is not particularly limited, and examples thereof include sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid hydrazide other amicure VDH, amicure UDH (all manufactured by Ajinomoto Fine Techno Co., Ltd.), and the like.
  • the content of the epoxy thermosetting agent is not particularly limited, but a preferable lower limit is 1 part by weight and a preferable upper limit is 50 parts by weight with respect to 100 parts by weight of the resin having an epoxy group. If the content of the epoxy thermosetting agent is less than 1 part by weight, the effect of including the thermosetting agent can hardly be obtained. When the content of the epoxy thermosetting agent exceeds 50 parts by weight, the viscosity of the sealing agent for a liquid crystal dropping method of the present invention may be high, which may impair the coating property and the like. A more preferable upper limit of the content of the epoxy thermosetting agent is 30 parts by weight.
  • the sealing agent for a liquid crystal dropping method of the present invention can be used not only to thermally cure the resin having the (meth) acrylic group but also to photocure it by using the above-described polymer azo initiator. However, if necessary, it may further contain a photopolymerization initiator.
  • the photopolymerization initiator is not particularly limited, and commercially available ones include, for example, IRGACURE 184, IRGACURE 2959, IRGACURE 907, IRGACURE 819, IRGACURE 651, IRGACURE 369, IRGACURE 379, IRGACURE OXE01 (all of which are Ciba specialty) And the like. Bensuin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, Lucillin TPO (manufactured by BASF Japan) and the like can be mentioned.
  • the content of the photopolymerization initiator is not particularly limited, but a preferable lower limit is 0.1 parts by weight and a preferable upper limit is 10 parts by weight with respect to 100 parts by weight of the (meth) acrylic group-containing resin.
  • a preferable lower limit is 0.1 parts by weight
  • a preferable upper limit is 10 parts by weight with respect to 100 parts by weight of the (meth) acrylic group-containing resin.
  • the sealant for a liquid crystal dropping method of the present invention may not be sufficiently photocured.
  • the content of the photopolymerization initiator exceeds 10 parts by weight, the storage stability may be reduced.
  • the sealing agent for liquid crystal dropping method of the present invention may further contain a light-shielding colorant.
  • the sealing agent for liquid crystal dropping method of the present invention is colored by containing the light-shielding coloring agent. Thereby, even when the width of the black mask is narrow and the sealing agent protrudes to the outside from immediately below the black mask, it is possible to prevent the area where the light from the sealing agent or the backlight leaks and the contrast is lowered.
  • the light-shielding coloring agent is added to the conventional sealing agent for liquid crystal dropping method, the light irradiation may be inhibited and the curability may be impaired.
  • the sealing agent for a liquid crystal dropping method of the present invention can be reliably cured by heat by containing the above-described (meth) acrylic group-containing resin and a polymeric azo initiator.
  • “light shielding property” means that light having a wavelength of 370 to 800 nm is shielded by 80% or more.
  • the light-shielding colorant is not particularly limited as long as it imparts a light-shielding property to the sealing agent for a liquid crystal dropping method of the present invention after curing and has few impurities to the liquid crystal.
  • the light-shielding colorant is preferably, for example, a black pigment, or a plurality of pigments and / or dyes which have a complementary color relationship which becomes black when mixed.
  • the black pigment is not particularly limited, and examples thereof include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, resin-coated carbon black and the like.
  • the black pigments may be used alone or in combination of two or more. Among them, titanium black and / or carbon black are preferable in terms of insulation and workability.
  • the carbon black is not particularly limited as long as the elution of impurities into the liquid crystal is small.
  • known carbon blacks such as channel black, lamp black, furnace black and thermal black can be used.
  • grafted carbon black having a grafted surface, coated carbon black having a surface coated with an insulating inorganic substance or an insulating organic substance, and / or acidic carbon black having an oxidized surface preferable. Since such carbon black has lower conductivity than untreated carbon black, when used in the sealing agent for a liquid crystal dropping method of the present invention, a liquid crystal display element with less current leakage and high reliability is obtained. Can.
  • the titanium black is not particularly limited, and specific commercial products include, for example, 12S, 13M, 13MC, 13R-N (all of them are manufactured by Mitsubishi Materials Corporation), Tirac D (manufactured by Akaho Kasei Co., Ltd.), etc. Be
  • a coupling agent or one in which an inorganic component such as silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide or magnesium oxide is coated. it can.
  • organic pigments in a complementary color relationship that turns black when mixed as described above, but, for example, azo pigments such as insoluble azo pigments and soluble azo pigments, copper phthalocyanine blue pigments, halogenated copper phthalocyanine pigments, sulfonated copper Phthalocyanine pigments such as phthalocyanine pigments, metal free phthalocyanine pigments, different metal phthalocyanine pigments, and condensation polycyclic pigments such as aminoanthraquinone pigments, indanthrone pigments, isoindolinone pigments, quinacridones, dioxazine pigments, perinone pigments, perylene pigments, etc. Etc.
  • halogenated copper phthalocyanine pigments and condensation sensitizing pigments are suitably used.
  • These organic pigments can also be used as an auxiliary coloring component of the above-mentioned black pigment.
  • the plurality of dyes in a complementary color relationship that turns black when mixed as described above there are no particular limitations on the plurality of dyes in a complementary color relationship that turns black when mixed as described above, but, for example, cyanine dyes, methacyanine dyes, rhodacyanine dyes, oxonol dyes, styryl dyes, base styryl dyes, benzopyran dyes , Quinolidine dyes, coumarin dyes, thiazole dyes, indanthrone dyes, pyrantron dyes, anthraquinone carbazole dyes, anthraquinone oxazole dyes, indigo, thioindigo, pyrazolone azo dyes, ⁇ -acid azo dyes, H- Acid azo dyes, triallylmethane dyes, oxazine dyes and the like can be mentioned. These dyes can also be used as auxiliary coloring components of the above-menti
  • the particle size of the light-shielding colorant is not particularly limited, but the preferable lower limit of the primary particles is 10 nm, and the preferable upper limit is 500 nm. When the particle size of the light-shielding coloring agent is out of this range, the dispersibility in the sealant for a dropping method of the present invention is deteriorated.
  • the content of the light-shielding coloring agent is not particularly limited, but a preferable lower limit is 5 parts by weight and a preferable upper limit is 50 parts by weight with respect to 100 parts by weight in total of the sealing agent for a dropping method of the present invention.
  • a preferable lower limit is 5 parts by weight
  • a preferable upper limit is 50 parts by weight with respect to 100 parts by weight in total of the sealing agent for a dropping method of the present invention.
  • the more preferable lower limit of the content of the light shielding colorant is 10 parts by weight, and the more preferable upper limit is 40 parts by weight.
  • the sealing agent for a dropping method of the present invention may contain a pigment (organic pigment, inorganic pigment), a dye or the like as an auxiliary coloring component in addition to the light-shielding colorant.
  • a pigment organic pigment, inorganic pigment
  • a dye or the like as an auxiliary coloring component in addition to the light-shielding colorant.
  • the black pigment is reddish black
  • the light-shielding colorant can be made to exhibit a more preferable black color by adding an auxiliary coloring component that exhibits a blue that is a complementary color of red.
  • the sealing agent for liquid crystal dropping method of the present invention preferably further contains a silane coupling agent.
  • the above-mentioned silane coupling agent mainly plays a role as an adhesion aiding agent for favorably bonding the sealing agent for liquid crystal dropping method and the liquid crystal display element substrate.
  • silane coupling agent is not particularly limited, but it is excellent in the adhesive improvement effect with a glass substrate etc. and it can prevent the outflow into the liquid crystal by chemically bonding with a curable resin, for example, ⁇ -amino Propyltrimethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -isocyanatopropyltrimethoxysilane and the like are preferably used.
  • a curable resin for example, ⁇ -amino Propyltrimethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -isocyanatopropyltrimethoxysilane and the like are preferably used.
  • These silane coupling agents may be used alone or in combination of two or more.
  • the sealing agent for a liquid crystal dropping method of the present invention may contain a filler for the purpose of improving adhesion by a stress dispersion effect, improving a linear expansion coefficient, and the like.
  • the filler is not particularly limited.
  • the sealant for a liquid crystal dropping method of the present invention further comprises, if necessary, a reactive diluent for viscosity adjustment, a thixotropic agent for adjusting thixotropy, a spacer such as a polymer bead for panel gap adjustment, 3 -A curing accelerator such as P-chlorophenyl-1,1-dimethylurea, an antifoamer, a leveling agent, a polymerization inhibitor, other additives and the like may be contained.
  • the method for producing the sealing agent for a liquid crystal display element of the present invention is not particularly limited.
  • An up-and-down conduction material can be manufactured by mix
  • the conductive fine particles are not particularly limited, and metal balls, resin fine particles having a conductive metal layer formed on the surface, or the like can be used. Among them, those in which a conductive metal layer is formed on the surface of resin fine particles are preferable because the excellent elasticity of the resin fine particles allows conductive connection without damaging the electrodes and the like.
  • the liquid crystal display element using the sealing agent for liquid crystal dropping method of the present invention and / or the vertical conduction material of the present invention is also one of the present invention.
  • the method for producing the liquid crystal display device of the present invention is, for example, forming a seal pattern by screen printing, dispenser coating, etc. of the sealing agent for liquid crystal dropping method of the present invention on one of two electrode-attached substrates such as ITO thin film.
  • a method including a step of temporarily curing, and a step of main curing a seal pattern comprising the sealing agent for liquid crystal dropping method of the present invention by heating and the like can be mentioned.
  • Such a liquid crystal display element using the sealing agent for liquid crystal dropping method of the present invention and / or the vertical conduction material of the present invention is also one of the present invention.
  • the sealing agent for liquid crystal panels containing resin which has the said (meth) acryl group, and the said polymeric azo initiator is also one of this invention. Also when manufacturing a liquid crystal display device by the vacuum injection method which is the conventional method, as in the case of manufacturing the liquid crystal display device by the above liquid crystal dropping method, the liquid crystal panel sealing agent is not cured when liquid crystal is sealed. Contact with At this time, when sufficient light is not irradiated to the liquid crystal panel sealing agent, color unevenness occurs around the sealing portion as well, and a liquid crystal display element of high quality image can not be obtained.
  • the sealing agent for liquid crystal panels of this invention is used as a sealing agent at the time of manufacturing a liquid crystal display device by a vacuum injection
  • the panel design which is not fully irradiated with an ultraviolet-ray, it is very effective.
  • the sealing agent for a liquid crystal panel of the present invention like the sealing agent for a liquid crystal dropping method of the present invention, comprises a resin having an epoxy group, an epoxy thermosetting agent, a photopolymerization initiator, a light shielding colorant, a silane coupling agent and a filler. And various additives may be contained.
  • the sealing agent for liquid crystal dropping method capable of manufacturing a liquid crystal display element of high quality image with little color unevenness even when the liquid crystal display element is manufactured by the dropping method. it can.
  • the sealing compound for liquid crystal panels which can manufacture the liquid crystal display element of a high quality image with few color nonuniformity can be provided.
  • FIG. 7 is a view schematically showing a procedure for manufacturing a liquid crystal display element by a vacuum injection method in Examples and Comparative Examples.
  • Examples 1 to 10 and Comparative Examples 1 to 3 According to the compounding ratio described in Table 1, Examples 1 to 10 are obtained by mixing each material using a planetary stirrer ("Awatori Neritaro" manufactured by Shinky Co., Ltd.) and then mixing using a 3-roll mill. Then, sealing agents for liquid crystal dropping method of Comparative Examples 1 to 3 were prepared.
  • the obtained sealing agent for liquid crystal dropping method is applied by a dispenser to draw a square frame on a substrate on which a transparent electrode and an alignment film are formed, and inside the square frame
  • the obtained sealing agent for liquid crystal dropping method was spotted.
  • microdroplets of liquid crystal ("JC-5004LA” manufactured by Chisso Corporation) are dropped and applied to the entire surface of the frame of the transparent substrate, and a substrate on which another transparent electrode and an alignment film are formed is superposed in vacuum.
  • the outer frame seal portion was irradiated with ultraviolet light for 30 seconds at 100 mW / cm 2 using a high pressure mercury lamp.
  • Example 11 to 15 and Comparative Examples 4 to 5 For the liquid crystal panels of Examples 11 to 15 and Comparative Examples 4 to 5 by mixing the respective materials using a planetary stirrer ("Awatori Neritaro" manufactured by Shinky Co., Ltd.) according to the compounding ratio described in Table 2 A sealant was prepared.
  • a planetary stirrer (“Awatori Neritaro" manufactured by Shinky Co., Ltd.) according to the compounding ratio described in Table 2
  • a sealant was prepared.
  • the sealing agent for liquid crystal dropping method of Example 1 was applied by a dispenser for breaking a part of the square frame, and then another The substrate on which the transparent electrode and the alignment film were formed was stacked and pressurized until the sealing agent reached a predetermined gap, and heat treatment was performed at 120 ° C. for 1 h to obtain an empty cell before liquid crystal injection.
  • the empty cell is put in vacuum, and then the liquid crystal ("JC-5004LA” manufactured by Chisso Corporation) is brought into contact with the part where the part of the square frame is broken, then returned to normal pressure and left for 2 hours. Got a cell filled with liquid crystal.
  • the sealing agent of Examples 11 to 15 and Comparative Examples 4 to 5 was used to seal a portion where a part of the square frame was interrupted, after sealing using the obtained sealing agent for liquid crystal panel,
  • the sealing agent was irradiated with ultraviolet light at 100 mW / cm 2 for 30 seconds using a high pressure mercury lamp. Thereafter, liquid crystal annealing was performed at 120 ° C. for one hour, and simultaneously the sealing agent was thermally cured to obtain a liquid crystal display element. At this time, a liquid crystal display element was also obtained under the condition that liquid crystal annealing was performed at 120 ° C. for 1 h without irradiating the sealing agent with ultraviolet light.
  • a silica spacer (Micropearl SI, manufactured by Sekisui Chemical Co., Ltd.) having a diameter of 5 ⁇ m was added as a spacer to 100 g of the obtained sealing agent for liquid crystal dropping method, and mixed and stirred.
  • the obtained sealing agent for a spacer-containing liquid crystal dropping method is applied on a 50 mm ⁇ 50 mm glass substrate, a glass substrate of the same size is superposed on the substrate, a load is applied, and the spacer is crushed to a uniform diameter did.
  • irradiation was performed at 100 mW / cm 2 for 30 seconds using a metal halide lamp. Thereafter, curing was performed in an oven at 120 ° C. for 1 hour to obtain a measurement sample of a light-shielding sealant.
  • the optical density (OD value) of the obtained sample was measured using PDA-100 manufactured by Konica Corporation.
  • the sealing agent for liquid crystal dropping method was sandwiched between two polyethylene terephthalate films so that the thickness of the sealing agent was about 5 ⁇ m, and a sample was prepared.
  • the sample was irradiated with ultraviolet light at 100 mW / cm 2 for 30 seconds using a high pressure mercury lamp, and then heat treated at 120 ° C. for 1 hour.
  • the polyethylene terephthalate film was peeled off after the heat treatment, the case where no tack remained on both sides was evaluated as "o", and the case where either one remained tack was evaluated as "x".
  • the sealing agent for liquid crystal dropping method capable of manufacturing a liquid crystal display element of high quality image with little color unevenness even when the liquid crystal display element is manufactured by the dropping method. it can.
  • the sealing compound for liquid crystal panels which can manufacture the liquid crystal display element of a high quality image with few color nonuniformity can be provided.

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PCT/JP2009/057568 2008-04-18 2009-04-15 液晶滴下工法用シール剤、液晶パネル用封口剤、上下導通材料及び液晶表示素子 WO2009128470A1 (ja)

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WO2012077572A1 (ja) * 2010-12-09 2012-06-14 積水化学工業株式会社 液晶滴下工法用シール剤、上下導通材料、及び、液晶表示素子
WO2012137749A1 (ja) * 2011-04-05 2012-10-11 積水化学工業株式会社 液晶表示素子用遮光シール剤、上下導通材料及び液晶表示素子
JP2013011879A (ja) * 2011-06-01 2013-01-17 Sekisui Chem Co Ltd 液晶表示素子用遮光シール剤、上下導通材料及び液晶表示素子
WO2013024844A1 (ja) * 2011-08-18 2013-02-21 積水化学工業株式会社 エポキシ化合物、エポキシ化合物の混合物、硬化性組成物及び接続構造体
JP2013514449A (ja) * 2009-12-15 2013-04-25 チュンホン・リ 液晶配向層のためのハイブリッドポリマー材料
JP2014006325A (ja) * 2012-06-22 2014-01-16 Nippon Kayaku Co Ltd 液晶シール剤及びそれを用いた液晶表示セル
KR20160028404A (ko) 2013-07-03 2016-03-11 세키스이가가쿠 고교가부시키가이샤 액정 적하 공법용 시일제, 상하 도통 재료, 액정 표시 소자, 및, 차광성 유연 실리콘 입자
JP6114893B1 (ja) * 2015-10-26 2017-04-12 積水化学工業株式会社 液晶表示素子用シール剤、上下導通材料及び液晶表示素子

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KR102285528B1 (ko) * 2014-05-23 2021-08-03 세키스이가가쿠 고교가부시키가이샤 액정 적하 공법용 시일제, 상하 도통 재료, 및 액정 표시 소자
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KR102106760B1 (ko) * 2016-12-27 2020-05-06 세키스이가가쿠 고교가부시키가이샤 액정 표시 소자용 시일제, 상하 도통 재료 및 액정 표시 소자
JP7053471B2 (ja) * 2017-07-14 2022-04-12 積水化学工業株式会社 液晶表示素子用シール剤、上下導通材料、及び、液晶表示素子
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JP2013514449A (ja) * 2009-12-15 2013-04-25 チュンホン・リ 液晶配向層のためのハイブリッドポリマー材料
JP2012088412A (ja) * 2010-10-18 2012-05-10 Sekisui Chem Co Ltd 液晶表示素子用遮光シール剤、上下導通材料及び液晶表示素子
WO2012077572A1 (ja) * 2010-12-09 2012-06-14 積水化学工業株式会社 液晶滴下工法用シール剤、上下導通材料、及び、液晶表示素子
JP5049409B2 (ja) * 2010-12-09 2012-10-17 積水化学工業株式会社 液晶滴下工法用シール剤、上下導通材料、及び、液晶表示素子
CN103261957B (zh) * 2010-12-09 2015-04-29 积水化学工业株式会社 液晶滴下工艺用密封剂、上下导通材料以及液晶显示元件
KR101298418B1 (ko) 2010-12-09 2013-08-20 세키스이가가쿠 고교가부시키가이샤 액정 적하 공법용 시일제, 상하 도통 재료, 및 액정 표시 소자
CN103261957A (zh) * 2010-12-09 2013-08-21 积水化学工业株式会社 液晶滴下工艺用密封剂、上下导通材料以及液晶显示元件
KR101321694B1 (ko) 2011-04-05 2013-10-23 세키스이가가쿠 고교가부시키가이샤 액정 표시 소자용 차광 시일제, 상하 도통 재료 및 액정 표시 소자
WO2012137749A1 (ja) * 2011-04-05 2012-10-11 積水化学工業株式会社 液晶表示素子用遮光シール剤、上下導通材料及び液晶表示素子
JP5238909B2 (ja) * 2011-04-05 2013-07-17 積水化学工業株式会社 液晶表示素子用遮光シール剤、上下導通材料及び液晶表示素子
JP2013011879A (ja) * 2011-06-01 2013-01-17 Sekisui Chem Co Ltd 液晶表示素子用遮光シール剤、上下導通材料及び液晶表示素子
JPWO2013024844A1 (ja) * 2011-08-18 2015-03-05 積水化学工業株式会社 エポキシ化合物、エポキシ化合物の混合物、硬化性組成物及び接続構造体
WO2013024844A1 (ja) * 2011-08-18 2013-02-21 積水化学工業株式会社 エポキシ化合物、エポキシ化合物の混合物、硬化性組成物及び接続構造体
JP2014006325A (ja) * 2012-06-22 2014-01-16 Nippon Kayaku Co Ltd 液晶シール剤及びそれを用いた液晶表示セル
KR20160028404A (ko) 2013-07-03 2016-03-11 세키스이가가쿠 고교가부시키가이샤 액정 적하 공법용 시일제, 상하 도통 재료, 액정 표시 소자, 및, 차광성 유연 실리콘 입자
JP6114893B1 (ja) * 2015-10-26 2017-04-12 積水化学工業株式会社 液晶表示素子用シール剤、上下導通材料及び液晶表示素子
WO2017073548A1 (ja) * 2015-10-26 2017-05-04 積水化学工業株式会社 液晶表示素子用シール剤、上下導通材料及び液晶表示素子

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