WO2009128470A1 - Sealing agent for use in liquid crystal dropping process, sealing agent for liquid crystal panel, vertical-conduction material, and liquid crystal display element - Google Patents

Sealing agent for use in liquid crystal dropping process, sealing agent for liquid crystal panel, vertical-conduction material, and liquid crystal display element Download PDF

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Publication number
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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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 JP2009516789A priority Critical patent/JP4616404B2/en
Priority to CN200980112979.9A priority patent/CN102007447B/en
Priority to KR1020107018271A priority patent/KR101194202B1/en
Publication of WO2009128470A1 publication Critical patent/WO2009128470A1/en

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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.

Abstract

Disclosed is a sealing agent for use in a liquid crystal dropping process, which enable the production of a liquid crystal display element having reduced unevenness in color and high image quality even when the liquid crystal display element is produced by a dropping process. The sealing agent comprises a resin having a (meth)acryl group and a polymeric azo initiator.

Description

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Sealant for liquid crystal dropping method, sealer for liquid crystal panel, vertical conduction material and liquid crystal display device
本発明は、滴下工法により液晶表示素子を製造した場合であっても、色ムラが少ない高品位な画像の液晶表示素子を製造することができる液晶滴下工法用シール剤に関する。また、真空注入方式により液晶表示装置の製造する場合に、色ムラが少ない高品位な画像の液晶表示素子を製造することができる液晶パネル用封口剤に関する。 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. In addition, 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.
従来、液晶表示セル等の液晶表示素子は、２枚の電極付き透明基板を、所定の間隔をおいて対向させ、その周囲をシール剤で封着してセルを形成し、その一部に設けられた液晶注入口からセル内に液晶を注入し、その液晶注入口をシール剤又は封口剤を用いて封止するという真空注入方式と呼ばれる工法により作製されていた。 Conventionally, in a 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.
真空注入方式では、まず、２枚の電極付き透明基板のいずれか一方に、スクリーン印刷により熱硬化性シール剤を用いた液晶注入口を設けたシールパターンを形成し、６０～１００℃でプリベイクを行いシール剤中の溶剤を乾燥させる。次いで、スペーサーを挟んで２枚の基板を対向させてアライメントを行い貼り合わせ、１１０～２２０℃で１０～９０分間熱プレスを行いシール近傍のギャップを調整した後、オーブン中で１１０～２２０℃で１０～１２０分間加熱しシール剤を本硬化させる。次いで、液晶注入口から液晶を注入し、最後に封口剤を用いて液晶注入口を封止して、液晶表示素子を作製していた。 In the vacuum injection method, first, 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.
しかし近年では、液晶表示セル等の液晶表示装置の製造方法は、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、上記真空注入方式から、例えば、特許文献１、特許文献２に開示されているような光硬化性のアクリル樹脂と光重合開始剤、及び、熱硬化性のエポキシ樹脂と熱重合開始剤を含有する、光、熱併用硬化型の樹脂組成物からなるシール剤を用いた滴下工法と呼ばれる液晶滴下方式にかわりつつある。 However, in recent years, 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. Drop using 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.
液晶滴下方式では、まず、２枚の電極付き基板の一方に、シールパターンを形成する。次いで、シール剤未硬化の状態で液晶の微小滴を基板の枠内全面に滴下し、真空下で他方の基板を重ね合わせ、常圧に戻した後シール部に紫外線を照射してアクリル樹脂の硬化を行う（仮硬化工程）。その後、加熱してエポキシ樹脂の硬化を行い、液晶表示素子を作製する。 In the 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.
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、装置の小型化は最も求められている課題である。小型化の手法として、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 modern world where various liquid crystal panel-equipped mobile devices such as mobile phones and portable game machines are in widespread use, downsizing of the device is the most demanded issue. As a method of downsizing, narrowing the frame of the liquid crystal display unit is mentioned, and for example, the position of the sealing unit is disposed under the black matrix (hereinafter, also referred to as narrow frame design).
しかしながら、滴下工法を狭額縁設計で行うと、ブラックマトリックスによりシール部に光の当たらない箇所が存在するため、充分に光照射されず硬化が進行しないアクリル樹脂の部分が生じ、仮硬化工程後に未硬化のアクリル樹脂が溶出してしまい、液晶が汚染され、液晶表示ムラが起こるという問題があった。
また、確実にブラックマトリックス下のシール部にも光を照射するために、基板の裏面、すなわちアレイ側から光を照射する方法も考えられるが、アレイ基板上にも金属配線、トランジスタ等が存在し、シール部に光の当たらない箇所が存在する。 However, when the dropping method is performed with a narrow frame design, there is a portion where light does not strike the seal portion due to the black matrix, so there is a portion of acrylic resin that is not sufficiently irradiated with light and curing does not proceed. There is a problem that the cured acrylic resin is eluted, the liquid crystal is contaminated, and the liquid crystal display unevenness occurs.
Although it is conceivable to irradiate light from the back side of the substrate, that is, the array side, in order to surely irradiate light to the seal portion under the black matrix, metal wiring, transistors, etc. are present also on the array substrate. , There is a place where the light does not hit the seal part.
このような問題に対し、光照射後にも未硬化のアクリル樹脂を確実に硬化させるために、アクリル樹脂を熱硬化させる成分として低分子量の過酸化物やアゾ化合物を配合したシール剤を用いる方法も考えられる。このようなシール剤を用いると、仮硬化工程で硬化されなかったアクリル樹脂を液晶アニール時の加熱により硬化させることができる。しかしながら、低分子量の過酸化物やアゾ化合物の液晶への溶出によりシール部の周りに色ムラが発生し、高品位な画像の液晶表示素子を得ることができないという問題があった。 To solve such problems, 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. When such a sealing agent is used, 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. However, due to the elution of low molecular weight peroxides and azo compounds into the liquid crystal, 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.
一方、従来工法である真空注入方式により液晶表示装置の製造する場合にも、上記液晶滴下方式の場合と同様の課題がある。即ち、真空注入方式により液晶表示装置の製造する際、液晶封止に用いる液晶パネル用封口剤は未硬化の状態で液晶と接触する。ここで液晶パネル用封口剤に充分な光が照射されない場合には、やはり封口部の周りに色ムラが発生し、高品位な画像の液晶表示素子を得ることができない。 On the other hand, in the case of manufacturing a liquid crystal display device by a vacuum injection method which is a conventional method, there are the same problems as in the case of the liquid crystal dropping method. That is, when manufacturing a liquid crystal display device by a vacuum injection method, the sealing agent for liquid crystal panels used for liquid crystal sealing contacts with a liquid crystal in the unhardened state. Here, when sufficient light is not irradiated to the sealing agent for liquid crystal panels, a color nonuniformity also generate | occur | produces around a sealing part again, and the liquid crystal display element of a high quality image can not be obtained.
特開２００１－１３３７９４号公報JP 2001-133794 A 特開平５－２９５０８７号公報Unexamined-Japanese-Patent No. 5-295087
本発明は、上記現状に鑑み、滴下工法により液晶表示素子を製造した場合であっても、色ムラが少ない高品位な画像の液晶表示素子を製造することができる液晶滴下工法用シール剤を提供することを目的とする。また、真空注入方式により液晶表示装置の製造する場合に、色ムラが少ない高品位な画像の液晶表示素子を製造することができる液晶パネル用封口剤を提供することを目的とする。 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.
本発明は、（メタ）アクリル基を有する樹脂と高分子アゾ開始剤とを含有する液晶滴下工法用シール剤である。
本発明は、（メタ）アクリル基を有する樹脂と高分子アゾ開始剤とを含有する液晶パネル用封口剤である。
以下に本発明を詳述する。 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.
本発明者らは、鋭意検討の結果、（メタ）アクリル基を有する樹脂と高分子アゾ開始剤とを含有する液晶滴下工法用シール剤は、熱硬化時にアゾ開始剤自体の液晶への悪影響なく、かつ、未硬化の（メタ）アクリル基を有する樹脂を硬化させることにより、色ムラが少ない高品位な画像の液晶表示素子を製造することができるということを見出し、本発明を完成させるに至った。 As a result of intensive studies, the inventors of the present invention have found that 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
本発明の液晶滴下工法用シール剤は、高分子アゾ開始剤を含有する。
本発明の液晶滴下工法用シール剤においては、このような開始剤を用いることにより、ブラックマトリックス等により光の当たらない箇所のシール部分であっても熱により確実に硬化させることが可能であるため、液晶汚染を生じることが極めて少ない。
本明細書において高分子アゾ開始剤とは、アゾ基を有し、熱にて（メタ）アクリル基を硬化させることができるラジカル生成する分子量が３００以上の化合物を意味する。
なお、上記高分子アゾ開始剤は通常光照射によっても分解してラジカルを発生することから、光ラジカル開始剤としても機能し得る。 The sealing agent for liquid crystal dropping method of the present invention contains a polymeric azo initiator.
In the sealing agent for a liquid crystal dropping method of the present invention, by using such an initiator, it is possible to reliably cure by heat even a seal portion of a portion not exposed to light by a black matrix or the like. , Very little occurrence of liquid crystal contamination.
In the present specification, 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.
In addition, since the said polymeric azo initiator is normally decomposed | disassembled also by light irradiation and generate | occur | producing a radical, it can function also as an optical radical initiator.
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１０００未満であると、高分子アゾ開始剤が液晶に悪影響を与えることがあり、３０万を超えると、（メタ）アクリル基を有する樹脂への混合が困難になることがある。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。 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. When 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.
上記高分子アゾ開始剤は、１０時間半減期温度の好ましい下限が５０℃、好ましい上限が９０℃である。上記高分子アゾ化合物の１０時間半減期温度が５０℃未満であると、得られる液晶滴下工法用シール剤の貯蔵安定性が悪くなることがある。上記高分子アゾ化合物の１０時間半減期温度が９０℃を超えると、本発明の液晶滴下工法用シール剤の硬化に高温かつ長時間を要し、パネルの生産性に影響を与えることがある。 The lower limit of the 10-hour half-life temperature is preferably 50 ° C., and the upper limit is preferably 90 ° C. When 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. When 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.
上記高分子アゾ開始剤は、例えば、アゾ基を介してポリジメチルシロキサンや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ものが挙げられる。
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。 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 | bonded, what has a polyethylene oxide structure is preferable.
As such 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.
上記高分子アゾ化合物は、その他にも特開２００８－５０５７２号公報や特開２００３－１２７８４号公報に記載された下記一般式（Ｉ）で表される高分子アゾ化合物も好適に用いることができる。 As the above-mentioned high molecular weight azo compound, other high molecular weight azo compounds represented by the following general formula (I) described in JP-A-2008-50572 and JP-A-2003-12784 can also be suitably used. .
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
式（Ｉ）中、Ｒ１２、Ｒ１３、Ｒ２２及びＲ２３は、それぞれ独立に、炭素原子数１～１０のアルキル基又はシアノ基を表し、ａ及びｂは、それぞれ独立に、０～４の数であり、Ａ１１及びＡ１２は、高分子鎖であり、Ｙ１１及びＹ１２は、それぞれ独立に、－ＣＯ－Ｏ－、－Ｏ－ＣＯ－、－ＮＨ－ＣＯ－、－ＣＯ－ＮＨ－、－Ｏ－又は－Ｓ－である。 In formula (I), 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-.
上記一般式（Ｉ）中、Ｒ１２、Ｒ１３、Ｒ２２及びＲ２３で表わされる炭素原子数１～１０のアルキル基は、メチル、エチル、プロピル、イソプロピル、ブチル、ｓ－ブチル、ｔ－ブチル、イソブチル、アミル、イソアミル、ｔ－アミル、ヘキシル、シクロヘキシル、シクロヘキシルメチル、シクロヘキシルエチル、ヘプチル、イソヘプチル、ｔ－ヘプチル、ｎ－オクチル、イソオクチル、ｔ－オクチル、２－エチルヘキシル、ｎ－ノニル、ｎ－デシル等が挙げられる。 In the general formula (I), 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.
上記一般式（Ｉ）中、Ａ１１及びＡ１２で表わされる高分子鎖は特に限定されず、例えば、ポリオキシレン鎖、ポリメチレン鎖、ポリエーテル鎖、ポリエステル鎖、ポリシロキサン鎖、ポリ（メタ）アクリレート鎖、ポリスチレン－酢酸ビニル鎖、ポリアミド鎖、ポリイミド鎖、ポリウレタン鎖、ポリウレア鎖、ポリペプチド鎖等が挙げられる。なかでも、Ｙ１１が－Ｏ－ＣＯ－であり、Ｙ１２が－ＣＯ－Ｏ－である化合物が好ましく、Ａ１１及びＡ１２で表される高分子鎖が、ポリエーテル鎖及びポリエステル鎖であるものが、特に安価で製造が容易であるのでより好ましい。 In the above general formula (I), the polymer chains represented by A 11 and A 12 are not particularly limited. For example, polyoxylene chain, polymethylene chain, polyether chain, polyester chain, polysiloxane chain, poly (meth) acrylate Chains, polystyrene-vinyl acetate chains, polyamide chains, polyimide chains, polyurethane chains, polyurea chains, polypeptide chains and the like. Among them, 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.
上記一般式（Ｉ）のうち、Ａ１１及びＡ１２がポリエーテル鎖である高分子アゾ化合物の中では、下記一般式（ＩＩ）で示される化合物が、溶解性がよく、重合開始剤の分子量制御が容易で分散性の高いグラフト化顔料を与えるので、より好ましい。 Of the above-mentioned general formula (I), among the polymeric azo compounds in which A 11 and A 12 are polyether chains, 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.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
式（ＩＩ）中、Ｒ１２、Ｒ１３、Ｒ２２、Ｒ２３、ａ及びｂは、上記一般式（Ｉ）と同じであり、Ｒ１１及びＲ２１は、それぞれ独立に、炭素原子数１～２４のアルキル基を表し、Ｚ１１、Ｚ１２、Ｚ２１及びＺ２２は、それぞれ独立に、炭素原子数１～４のアルキレン基を表し、ｍ、ｎ、ｓ及びｔは、それぞれ独立に、０～１０００の数であり、ｍ＋ｎの和、ｓ＋ｔの和は、それぞれ独立に、２以上である。） In formula (II), 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. )
上記一般式（ＩＩ）中、Ｚ１１、Ｚ１２、Ｚ２１及びＺ２２で表わされる炭素原子数１～４のアルキレン基は、メチレン、エチレン、トリメチレン、プロピレン、プロピリデン、イソプロピリデン、テトラメチレン、ブチレン、イソブチレン、エチルエチレン、ジメチルエチレン等が挙げられ、Ｒ１１及びＲ２１で表わされる炭素原子数１～２４のアルキル基は、メチル、エチル、プロピル、イソプロピル、ブチル、ｓ－ブチル、ｔ－ブチル、イソブチル、アミル、イソアミル、ｔ－アミル、ヘキシル、シクロヘキシル、シクロヘキシルメチル、シクロヘキシルエチル、ヘプチル、イソヘプチル、ｔ－ヘプチル、ｎ－オクチル、イソオクチル、ｔ－オクチル、２－エチルヘキシル、ｎ－ノニル、ｎ－デシル、ラウリル、ステアリル、ベヘニル等が挙げられる。Ｒ１１及びＲ２１で表わされる炭素原子数１～２４のアルキル基は、炭素原子数が１～４であるのが、分散性の高いグラフト化顔料を与え、また鎖状重合体の一方の末端にヒドロキシル基を有する化合物とアゾジカルボン酸化合物のエステル化反応の反応性が高いので好ましい。 In the above general formula (II), 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, and 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-octyl, 2-ethylhexyl, n-nonyl, n-decyl, Lauryl, stearyl, bee Alkylsulfonyl and the like. 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.
上記一般式（Ｉ）で示される高分子アゾ化合物のＡ１１及びＡ１２がポリエステル鎖であるものの中では、下記一般式（ＩＩＩ）で示される化合物が、溶解性が良く、耐水性に優れているので好ましい。 Among the high molecular weight azo compounds represented by the above general formula (I) in which A 11 and A 12 are polyester chains, compounds represented by the following general formula (III) have good solubility and excellent water resistance. Because it is preferable.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
式（ＩＩＩ）中、Ｒ１２、Ｒ１３、Ｒ２２、Ｒ２３、ａ及びｂは、上記一般式（Ｉ）と同じであり、Ｚ１３及びＺ２３は、それぞれ独立に、炭素原子数１～１８のアルキレン基を表し、Ｒ３１及びＲ４１は、それぞれ独立に、水素原子又は炭素原子数１～２４のアルキル基を表し、ｐ及びｕは、それぞれ独立に、１～１０００の数である。） In formula (III), 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. )
上記一般式（ＩＩＩ）中、Ｚ１３、Ｚ２３で表わされる炭素原子数１～１８のアルキレン基は、メチレン、エチレン、トリメチレン、プロピレン、プロピリデン、イソプロピリデン、テトラメチレン、ブチレン、イソブチレン、エチルエチレン、ジメチルエチレン、ペンタメチレン、ヘキサメチレン、ヘプタメチレン、オクタメチレン、１，４－ペンタンジイル、デカメチレン、ウンデカメチレン、１，４－ウンデカンジイル、ドデカメチレン、１，１１－ヘプタデカンジイル、オクタデカメチレン等が挙げられ、Ｒ３１及びＲ４１で表わされる炭素原子数１～２４のアルキル基は、上記一般式（ＩＩ）におけるＲ１１及びＲ２１として例示したものが挙げられる。Ｒ３１及びＲ４１で表わされる炭素原子数１～２４のアルキル基は、炭素原子数が１～４であるのが、分散性の高いグラフト化顔料を与え、また鎖状重合体の一方の末端にヒドロキシル基を有する化合物とアゾジカルボン酸化合物のエステル化反応の反応性が高いので好ましい。 In the above general formula (III), 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.
上記一般式（ＩＩＩ）中、ｐ及びｕが２０～１００であるのが、分散性の高いグラフト化顔料を与え、また鎖状重合体の一方の末端にヒドロキシル基を有する化合物とアゾジカルボン酸化合物のエステル化反応の反応性が高いので好ましい。 In the above general formula (III), when p and u are from 20 to 100, a grafted pigment having high dispersibility is obtained, and a compound having a hydroxyl group at one end of a chain polymer and an azodicarboxylic acid compound Is preferable because of high reactivity of the esterification reaction.
本発明の液晶滴下工法用シール剤における上記高分子アゾ開始剤の含有量は特に限定されないが、上記（メタ）アクリル基を有する樹脂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３０重量部である。上記高分子アゾ開始剤の含有量が０．１重量部未満であると、上記（メタ）アクリル基を有する樹脂の重合が充分に進まないことがある。上記高分子アゾ開始剤の含有量が３０重量部を超えると、得られる液晶滴下工法用シール剤の粘度が高くなり、塗布作業性等に悪影響を与えることがある。上記高分子アゾ開始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 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.
本発明の液晶滴下工法用シール剤は、（メタ）アクリル基を有する樹脂を含有する。
上記（メタ）アクリル基を有する樹脂は特に限定されず、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。 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.
上記（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エステル化合物は特に限定されず、単官能のエステル化合物は、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、４－ヒドロキシブチル（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、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、イソオクチル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソボルニル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、２－メトキシエチル（メタ）アクリレート、メトキシエチレングリコール（メタ）アクリレート、２－エトキシエチル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、ベンジル（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、フェノキシエチル（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、メトキシポリエチレングリコール（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、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－ブチル（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、シクロヘキシル（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、イソノニル（メタ）アクリレート、イソミリスチル（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、ビシクロペンテニル（メタ）アクリレート、イソデシル（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、ジメチルアミノエチル（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、グリシジル（メタ）アクリレート、２－（メタ）アクリロイロキシエチルホスフェート等が挙げられる。 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, benzyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) Acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H, -octafluoropentyl (meth) acrylate, imide (Meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate , Cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isononyl (meth) acrylate, isomyristyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-phenoxyethyl (2-phenoxyethyl (meth) acrylate Meta) acrylate, bicyclopentenyl (meth) acrylate, isodecyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acrylic acid Leuoxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl 2-hydroxypropyl phthalate, glycidyl (meth) acrylate, 2- (meth) acryloyloxyethyl phosphate, etc. Can be mentioned.
また、２官能のエステル化合物は、例えば、１，４－ブタンジオールジ（メタ）アクリレート、１，３－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（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、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、１，３－ブチレングリコールジ（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。 Moreover, 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 (meth) acrylate, ethylene oxide-added bisphenol A di (meth) acrylate, ethylene oxide-added bisphenol F di (meth) acrylate, dimethylol dicyclopentadienyl di (meth) acrylate, 1,3-butylene glycol Di (meth) acrylate, neopentyl glycol 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 Oruji (meth) acrylate.
また、３官能以上のエステル化合物は、例えば、ペンタエリスリトールトリ（メタ）アクリレート、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、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、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、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、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、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、トリス（メタ）アクリロイルオキシエチルフォスフェート等が挙げられる。 Moreover, 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 (meth) acryloyloxyethyl phosphate, and the like.
上記（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）アクリレートは特に限定されず、例えば、エポキシ樹脂と（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することにより得られるもの等が挙げられる。 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.
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は特に限定されず、市販されているものは、例えば、エピコート８２８ＥＬ、エピコート１００４（いずれもジャパンエポキシレジン社製）等のビスフェノールＡ型エポキシ樹脂や、エピコート８０６、エピコート４００４（いずれもジャパンエポキシレジン社製）等のビスフェノールＦ型エポキシ樹脂や、エピクロンＥＸＡ１５１４（大日本インキ社製）等のビスフェノールＳ型エポキシ樹脂や、ＲＥ－８１０ＮＭ（日本化薬社製）等の２，２’－ジアリルビスフェノールＡ型エポキシ樹脂や、エピクロンＥＸＡ７０１５（大日本インキ社製）等の水添ビスフェノール型エポキシ樹脂や、ＥＰ－４０００Ｓ（旭電化社製）等のプロピレンオキシド付加ビスフェノールＡ型エポキシ樹脂や、ＥＸ－２０１（ナガセケムテックス社製）等のレゾルシノール型エポキシ樹脂や、エピコートＹＸ－４０００Ｈ（ジャパンエポキシレジン社製）等のビフェニル型エポキシ樹脂や、ＹＳＬＶ－５０ＴＥ（東都化成社製）等のスルフィド型エポキシ樹脂や、ＹＳＬＶ－８０ＤＥ（東都化成社製）等のエーテル型エポキシ樹脂や、ＥＰ－４０８８Ｓ（旭電化社製）等のジシクロペンタジエン型エポキシ樹脂や、エピクロンＨＰ４０３２、エピクロンＥＸＡ－４７００（いずれも大日本インキ社製）等のナフタレン型エポキシ樹脂や、エピクロンＮ－７７０（大日本インキ社製）等のフェノールノボラック型エポキシ樹脂や、エピクロンＮ－６７０－ＥＸＰ－Ｓ（大日本インキ社製）等のオルトクレゾールノボラック型エポキシ樹脂や、エピクロンＨＰ７２００（大日本インキ社製）等のジシクロペンタジエンノボラック型エポキシ樹脂や、ＮＣ－３０００Ｐ（日本化薬社製）等のビフェニルノボラック型エポキシ樹脂や、ＥＳＮ－１６５Ｓ（東都化成社製）等のナフタレンフェノールノボラック型エポキシ樹脂や、エピコート６３０（ジャパンエポキシレジン社製）、エピクロン４３０（大日本インキ社製）、ＴＥＴＲＡＤ－Ｘ（三菱ガス化学社製）等のグリシジルアミン型エポキシ樹脂や、ＺＸ－１５４２（東都化成社製）、エピクロン７２６（大日本インキ社製）、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）等のアルキルポリオール型エポキシ樹脂や、ＹＲ－４５０、ＹＲ－２０７（いずれも東都化成社製）、エポリードＰＢ（ダイセル化学社製）等のゴム変性型エポキシ樹脂や、デナコールＥＸ－１４７（ナガセケムテックス社製）等のグリシジルエステル化合物や、エピコートＹＬ－７０００（ジャパンエポキシレジン社製）等のビスフェノールＡ型エピスルフィド樹脂や、その他ＹＤＣ－１３１２、ＹＳＬＶ－８０ＸＹ、ＹＳＬＶ－９０ＣＲ（いずれも東都化成社製）、ＸＡＣ４１５１（旭化成社製）、エピコート１０３１、エピコート１０３２（いずれもジャパンエポキシレジン社製）、ＥＸＡ－７１２０（大日本インキ社製）、ＴＥＰＩＣ（日産化学社製）等が挙げられる。 The epoxy compound used as a raw material for synthesize | 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 Epicoat 806, Epicoat 4004 (all manufactured by Japan Epoxy Resins Co., Ltd.), bisphenol S epoxy resin such as Epiclon EXA 1514 (manufactured by Dainippon Ink Co., Ltd.), RE-810NM (Japan Products such as Kayaku Co., Ltd., etc., hydrogenated bisphenol epoxy resins such as Epiclon EXA 7015 (Dainippon Ink Co., Ltd.), EP-4000S (Asahi Denka Co., Ltd.), etc. 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.), Epiclon N-670-EXP-S Ortho cresol novolac type such as (made by Dainippon Ink and Chemicals) Epoxy resin, a dicyclopentadiene novolac epoxy resin such as Epiclon HP 7200 (made by Dainippon Ink Co., Ltd.), a biphenyl novolac epoxy resin such as NC-3000P (made by Nippon Kayaku Co., Ltd.), ESN-165S (Toto Kasei Co., Ltd.) Etc., Epicoat 630 (made by Japan Epoxy Resins Co., Ltd.), glycidylamine epoxy resins such as Epiclon 430 (made by Dainippon Ink Co., Ltd.), TETRAD-X (made by Mitsubishi Gas Chemical Co.), etc. 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.), XAC4151 (Asahi Kasei Co., Ltd.), Epicoat 1031, Epicoat 1032 (all are Japan Epoxy Resins Co., Ltd.) And EXA-7120 (manufactured by Dainippon Ink and Chemicals, Inc.), TEPIC (manufactured by Nissan Chemical Industries, Ltd.), and the like.
上記（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）アクリレートは、具体的には、例えば、レゾルシノール型エポキシ樹脂（ＥＸ－２０１、ナガセケムテックス社製）３６０重量部、重合禁止剤としてｐ－メトキシフェノール２重量部、反応触媒としてトリエチルアミン２重量部、アクリル酸２１０重量部を空気を送り込みながら、９０℃で還流攪拌しながら５時間反応させることによって得ることができる。 Specifically, 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.
また、上記エポキシ（メタ）アクリレートの市販品は、例えば、エベクリル３７００、エベクリル３６００、エベクリル３７０１、エベクリル３７０３、エベクリル３２００、エベクリル３２０１、エベクリル３６００、エベクリル３７０２、エベクリル３４１２、エベクリル８６０、エベクリルＲＤＸ６３１８２、エベクリル６０４０、エベクリル３８００（いずれもダイセルサイテック社製）、ＥＡ－１０２０、ＥＡ－１０１０、ＥＡ－５５２０、ＥＡ－５３２３、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。 In addition, commercially available products of the above epoxy (meth) acrylates are, for example, Ebecryl 3700, Ebecryl 3600, Ebecryl 3701, Ebecryl 3703, Ebecryl 3200, Ebecryl 3201, Ebecryl 3600, Ebecryl 3702, Ebecryl 3412, Ebecryl 860, Ebecryl RDX 64062 , Ebecryl 3800 (all by Daicel-Cytec), EA-1020, EA-1010, EA-5520, EA-5323, EA-CHD, EMA-1020 (all by Shin-Nakamura Chemical Co., Ltd.), epoxy ester M- 600A, epoxy ester 40 EM, epoxy ester 70 PA, epoxy ester 200 PA, epoxy ester 80 MFA, epoxy ester 3002 M, epoxy ester 002A, epoxy ester 1600 A, epoxy ester 3000 M, epoxy ester 3000 A, epoxy ester 200 EA, epoxy ester 400 EA (all from Kyoeisha Chemical Co., Ltd.), Denacol acrylate DA-141, Denacol acrylate DA-314, Denacol acrylate DA-911 (All are Nagase ChemteX company make) etc. are mentioned.
上記イソシアネートに水酸基を有する（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）アクリレートは、例えば、２つのイソシアネート基を有する化合物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。 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.
上記イソシアネートに水酸基を有する（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）アクリレートの原料となるイソシアネートは特に限定されず、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ネート、トリジンジイソシアネート、キシリレンジイオシアネート（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、テトラメチルキシレンジイソシアネート、１，６，１０－ウンデカントリイソシアネート等が挙げられる。 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. For example, isophorone diisocyanate, 2,4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xyli Rendisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanatophenyl) thiof Sufeto, tetramethyl xylene diisocyanate, 1,6,10- undecene country isocyanate.
また、上記イソシアネートに水酸基を有する（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）アクリレートの原料となるイソシアネートは特に限定されず、例えば、エチレングリコール、グリセリン、ソルビトール、トリメチロールプロパン、（ポリ）プロピレングリコール、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。 Further, 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. For example, 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.
上記イソシアネートに水酸基を有する（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）アクリレートの原料となる、水酸基を有する（メタ）アクリル酸誘導体は特に限定されず、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、４－ヒドロキシブチル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート等の市販品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、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、ビスフェノールＡ変性エポキシアクリレート等のエポキシアクリレート等が挙げられる。 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, and mono (meth) acrylates of trihydric alcohols such as trimethylolethane, trimethylolpropane and glycerin or (Meth) acrylates, epoxy acrylates such as bisphenol A-modified epoxy acrylate.
上記イソシアネートに水酸基を有する（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）アクリレートは、具体的には、例えば、トリメチロールプロパン１３４重量部、重合禁止剤としてＢＨＴ０．２重量部、反応触媒としてジブチル錫ジラウリレート０．０１重量部、イソホロンジイソシアネート６６６重量部を加え、６０℃で還流攪拌しながら２時間反応させ、次に、２－ヒドロキシエチルアクリレート５１重量部を加え、空気を送り込みながら９０℃で還流攪拌しながら２時間反応させることにより得ることができる。 Specifically, 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.
上記ウレタン（メタ）アクリレートで市販されているものは、例えば、Ｍ－１１００、Ｍ－１２００、Ｍ－１２１０、Ｍ－１６００（いずれも東亞合成社製）、エベクリル２３０、エベクリル２７０、エベクリル４８５８、エベクリル８４０２、エベクリル８８０４、エベクリル８８０３、エベクリル８８０７、エベクリル９２６０、エベクリル１２９０、エベクリル５１２９、エベクリル４８４２、エベクリル２１０、エベクリル４８２７、エベクリル６７００、エベクリル２２０、エベクリル２２２０（いずれもダイセルサイテック社製）、アートレジンＵＮ－９０００Ｈ、アートレジンＵＮ－９０００Ａ、アートレジンＵＮ－７１００、アートレジンＵＮ－１２５５、アートレジンＵＮ－３３０、アートレジンＵＮ－３３２０ＨＢ、アートレジンＵＮ－１２００ＴＰＫ、アートレジンＳＨ－５００Ｂ（いずれも根上工業社製）、Ｕ－１２２Ｐ、Ｕ－１０８Ａ、Ｕ－３４０Ｐ、Ｕ－４ＨＡ、Ｕ－６ＨＡ、Ｕ－３２４Ａ、Ｕ－１５ＨＡ、ＵＡ－５２０１Ｐ、ＵＡ－Ｗ２Ａ、Ｕ－１０８４Ａ、Ｕ－６ＬＰＡ、Ｕ－２ＨＡ、Ｕ－２ＰＨＡ、ＵＡ－４１００、ＵＡ－７１００、ＵＡ－４２００、ＵＡ－４４００、ＵＡ－３４０Ｐ、Ｕ－３ＨＡ、ＵＡ－７２００、Ｕ－２０６１ＢＡ、Ｕ－１０Ｈ、Ｕ－１２２Ａ、Ｕ－３４０Ａ、Ｕ－１０８、Ｕ－６Ｈ、ＵＡ－４０００（いずれも新中村化学工業社製）、ＡＨ－６００、ＡＴ－６００、ＵＡ－３０６Ｈ、ＡＩ－６００、ＵＡ－１０１Ｔ、ＵＡ－１０１Ｉ、ＵＡ－３０６Ｔ、ＵＡ－３０６Ｉ等が挙げられる。 Commercially available urethane (meth) acrylates mentioned above 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-4HA, U-6HA, U-324A, U-15HA, UA-5201P , UA-W2A, U-1084A, U-6LPA, U-2HA, U-2PHA, UA-4100, UA-7100, UA-4200, UA-4400, UA-340P, U-3HA, UA-7200, U -2061BA, U-10H, U-122A, U-340A, U-108, U-6H, UA-4000 (all from Shin-Nakamura Chemical Co., Ltd.), AH-600, AT-600, UA-306H, AI -600, UA-101T, UA-101I, UA-306T, UA-306I and the like.
上記（メタ）アクリル基を有する樹脂は、液晶への悪影響を抑える点で、－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く、合成の容易さ等からエポキシ（メタ）アクリレートが特に好ましい。
また、上記（メタ）アクリル基を有する樹脂は、反応性の高さから分子中に（メタ）アクリル基を２～３個有するものが好ましい。 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.
本発明の液晶滴下工法用シール剤は、接着性を向上させるために、更にエポキシ基を有する樹脂を含有することが好ましい。 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.
上記エポキシ基を有する樹脂は特に限定されず、市販されているものは、例えば、エピコート８２８ＥＬ、エピコート１００４（いずれもジャパンエポキシレジン社製）等のビスフェノールＡ型エポキシ樹脂や、エピコート８０６、エピコート４００４（いずれもジャパンエポキシレジン社製）等のビスフェノールＦ型エポキシ樹脂や、エピクロンＥＸＡ１５１４（大日本インキ社製）等のビスフェノールＳ型エポキシ樹脂や、ＲＥ－８１０ＮＭ（日本化薬社製）等の２，２’－ジアリルビスフェノールＡ型エポキシ樹脂や、エピクロンＥＸＡ７０１５（大日本インキ社製）等の水添ビスフェノール型エポキシ樹脂や、ＥＰ－４０００Ｓ（旭電化社製）等のプロピレンオキシド付加ビスフェノールＡ型エポキシ樹脂や、ＥＸ－２０１（ナガセケムテックス社製）等のレゾルシノール型エポキシ樹脂ふ、エピコートＹＸ－４０００Ｈ（ジャパンエポキシレジン社製）等のビフェニル型エポキシ樹脂や、ＹＳＬＶ－５０ＴＥ（東都化成社製）等のスルフィド型エポキシ樹脂や、ＹＳＬＶ－８０ＤＥ（東都化成社製）等のエーテル型エポキシ樹脂や、ＥＰ－４０８８Ｓ（旭電化社製）等のジシクロペンタジエン型エポキシ樹脂や、エピクロンＨＰ４０３２、エピクロンＥＸＡ－４７００（いずれも大日本インキ社製）等のナフタレン型エポキシ樹脂や、エピクロンＮ－７７０（大日本インキ社製）等のフェノールノボラック型エポキシ樹脂や、エピクロンＮ－６７０－ＥＸＰ－Ｓ（大日本インキ社製）等のオルトクレゾールノボラック型エポキシ樹脂や、エピクロンＨＰ７２００（大日本インキ社製）等のジシクロペンタジエンノボラック型エポキシ樹脂や、ＮＣ－３０００Ｐ（日本化薬社製）等のビフェニルノボラック型エポキシ樹脂や、ＥＳＮ－１６５Ｓ（東都化成社製）等のナフタレンフェノールノボラック型エポキシ樹脂や、エピコート６３０（ジャパンエポキシレジン社製）、エピクロン４３０（大日本インキ社製）、ＴＥＴＲＡＤ－Ｘ（三菱ガス化学社製）等のグリシジルアミン型エポキシ樹脂や、ＺＸ－１５４２（東都化成社製）、エピクロン７２６（大日本インキ社製）、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）等のアルキルポリオール型エポキシ樹脂や、ＹＲ－４５０、ＹＲ－２０７（いずれも東都化成社製）、エポリードＰＢ（ダイセル化学社製）等のゴム変性型エポキシ樹脂や、デナコールＥＸ－１４７（ナガセケムテックス社製）等のグリシジルエステル化合物や、エピコートＹＬ－７０００（ジャパンエポキシレジン社製）等のビスフェノールＡ型エピスルフィド樹脂や、その他ＹＤＣ－１３１２、ＹＳＬＶ－８０ＸＹ、ＹＳＬＶ－９０ＣＲ（いずれも東都化成社製）、ＸＡＣ４１５１（旭化成社製）、エピコート１０３１、エピコート１０３２（いずれもジャパンエポキシレジン社製）、ＥＸＡ－７１２０（大日本インキ社製）、ＴＥＰＩＣ（日産化学社製）等が挙げられる。 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 as Epicoat YX-4000H (made by Japan Epoxy Resins Co., Ltd.), sulfide type epoxy resin such as YSLV-50TE (made by Tohto Kasei Co., Ltd.), YSLV- Ether type epoxy resin such as 80DE (made by Tohto Kasei Co., Ltd.), dicyclopentadiene type epoxy resin such as EP-4088S (made by Asahi Denka Co., Ltd.), Epiclon HP4032, Epiclon EXA-4700 (all manufactured by Dainippon Ink Co., Ltd.) And naphthalene type epoxy resins, phenol novolac type epoxy resins such as Epiclon N-770 (made by Dainippon Ink Co., Ltd.), and orthocresol novolac type epoxys such as Epiclon N-670-EXP-S (made by Dainippon Ink Co., Ltd.) Resin and Epiclon HP 7200 (Dainippon Dicyclopentadiene novolac type epoxy resin such as Nikki), biphenyl novolac type epoxy resin such as NC-3000P (made by Nippon Kayaku Co., Ltd.), and naphthalene phenol novolac type epoxy such as ESN-165S (made by Tohto Kasei Co., Ltd.) Resin, glycidyl amine type epoxy resin such as Epicoat 630 (made by Japan Epoxy Resin), Epiclon 430 (made by Dainippon Ink), TETRAD-X (made by Mitsubishi Gas Chemical), ZX-1542 (made by Tohto Kasei Co., Ltd.) ), Alkyl polyol epoxy resins such as Epiclon 726 (manufactured by Dainippon Ink Co., Ltd.), Epolight 80 MFA (manufactured by Kyoeisha Chemical Co., Ltd.), Denacol EX-611, (manufactured by Nagase ChemteX Corporation), YR-450, YR-207 (manufactured by All of them are manufactured by Toto Kasei Co., Ltd., and Epolide PB (manufactured by Daicel Chemical Industries, Ltd.) Etc., glycidyl ester compounds such as Denacol EX-147 (manufactured by Nagase ChemteX Corp.), bisphenol A type episulfide resin such as Epicoat YL-7000 (manufactured by Japan Epoxy Resins Co., Ltd.), and others YDC- 1312, YSLV-80XY, YSLV-90CR (all manufactured by Tohto Kasei Co., Ltd.), XAC4151 (Asahi Kasei Co., Ltd.), Epicoat 1031, Epicoat 1032 (all manufactured by Japan Epoxy Resins Co., Ltd.), EXA-7120 (manufactured by Dainippon Ink Co., Ltd.) And TEPIC (manufactured by Nissan Chemical Industries, Ltd.).
また、上記エポキシ基を有する樹脂は、例えば、１分子中に（メタ）アクリル基とエポキシ基とを有する化合物であってもよい。このような化合物は、例えば、２以上のエポキシ基を有する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られる化合物等が挙げられる。 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.
上記２以上のエポキシ基を有する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られる化合物は、例えば、エポキシ樹脂と（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することにより得られる。具体的には、例えば、フェノールノボラック型エポキシ樹脂Ｎ－７７０（大日本インキ社製）１９０ｇをトルエン５００ｍＬに溶解させ、この溶液にトリフェニルホスフィン０．１ｇを加え、均一な溶液とし、この溶液にアクリル酸３５ｇを還流撹拌下２時間かけて滴下後、更に還流撹拌を６時間行い、次に、トルエンを除去することによって５０ｍｏｌ％のエポキシ基が（メタ）アクリル酸と反応したノボラック型固形変性エポキシ樹脂を得ることができる（この場合５０％部分アクリル化されている）。 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. After 35 g of acrylic acid was added dropwise over 2 hours while stirring under reflux, stirring under reflux was further carried out for 6 hours, and then novolac-type solid-modified epoxy in which 50 mol% of epoxy groups were reacted with (meth) acrylic acid by removing toluene. A resin can be obtained (in this case 50% partially acrylated).
上記２以上のエポキシ基を有する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られる化合物のうち、市販品は、例えば、エベクリル１５６１（ダイセルサイテック社製）が挙げられる。 Among the compounds obtained by reacting the epoxy group of a part of the compound having two or more epoxy groups with (meth) acrylic acid, commercially available products include, for example, Ebecryl 1561 (manufactured by Daicel Corporation).
本発明の液晶滴下工法用シール剤が上記エポキシ基を有する樹脂を含有する場合、（メタ）アクリル基とエポキシ基との比が５０：５０～９５：５になるように（メタ）アクリル基を有する樹脂とエポキシ基を有する樹脂とを配合することが好ましい。（メタ）アクリル基の比率が５０％以下であると、アゾ開始剤による熱重合完了時にも未硬化のエポキシ樹脂成分が多く存在するため液晶を汚染してしまうことがある。（メタ）アクリル基の比率が９５％以上であると、充分な接着力が出ない場合がある。 When the sealing agent for a liquid crystal dropping method of the present invention contains the above-mentioned epoxy group-containing resin, 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. When 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.
本発明の液晶滴下工法用シール剤が上記エポキシ基を有する樹脂を含有する場合には、更にエポキシ熱硬化剤を含有することが好ましい。上記エポキシ熱硬化剤は特に限定されず、例えば、有機酸ヒドラジド、イミダゾール誘導体、アミン化合物、多価フェノール系化合物、酸無水物等が挙げられる。なかでも、固形の有機酸ヒドラジドが好適に用いられる。
上記固形の有機酸ヒドラジドは特に限定されず、例えば、セバチン酸ジヒドラジド、イソフタル酸ジヒドラジド、アジピン酸ジヒドラジド、マロン酸ヒドラジドその他アミキュアＶＤＨ、アミキュアＵＤＨ（いずれも、味の素ファインテクノ社製）等が挙げられる。 When 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.
上記エポキシ熱硬化剤の含有量は特に限定されないが、上記エポキシ基を有する樹脂１００重量部に対して好ましい下限が１重量部、好ましい上限が５０重量部である。上記エポキシ熱硬化剤の含有量が１重量部未満であると、熱硬化剤を含有させる効果がほとんど得られない。上記エポキシ熱硬化剤の含有量が５０重量部を超えると、本発明の液晶滴下工法用シール剤の粘度が高くなり、塗布性等を損ねる場合がある。上記エポキシ熱硬化剤の含有量のより好ましい上限は３０重量部である。 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.
上述したように、本発明の液晶滴下工法用シール剤は、上記高分子アゾ開始剤を用いることにより、上記（メタ）アクリル基を有する樹脂を熱硬化させるのみならず、光硬化させることができるが、必要に応じて更に光重合開始剤を含有してもよい。上記光重合開始剤は特に限定されず、市販されているものは、例えば、イルガキュア１８４、イルガキュア２９５９、イルガキュア９０７、イルガキュア８１９、イルガキュア６５１、イルガキュア３６９、イルガキュア３７９、イルガキュアＯＸＥ０１（いずれもチバ・スペシャリティーケミカルズ社製）、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、ルシリンＴＰＯ（ＢＡＳＦ　Ｊａｐａｎ社製）等が挙げられる。 As described above, 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.
上記光重合開始剤の含有量は特に限定されないが、上記（メタ）アクリル基を有する樹脂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。上記光重合開始剤の含有量が０．１重量部未満であると、本発明の液晶滴下工法用シール剤を充分に光硬化させることができないことがある。上記光重合開始剤の含有量が１０重量部を超えると、貯蔵安定性が低下することがある。 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. When the content of the photopolymerization initiator is less than 0.1 parts by weight, the sealant for a liquid crystal dropping method of the present invention may not be sufficiently photocured. When the content of the photopolymerization initiator exceeds 10 parts by weight, the storage stability may be reduced.
本発明の液晶滴下工法用シール剤は、更に、遮光性着色剤を含有してもよい。
上記遮光性着色剤を含有することにより本発明の液晶滴下工法用シール剤が着色する。これにより、ブラックマスクの幅が狭くシール剤がブラックマスクの直下から外側にはみ出した場合でも、シール剤かちバックライトの光が漏れだしコントラストを下げてしまう野を防止することができる。
従来の液晶滴下工法用シール剤に上記遮光性着色剤を添加すると、光照射を阻害して硬化性が損なわれることがあった。しかしながら、本発明の液晶滴下工法用シール剤は、上記（メタ）アクリル基を有する樹脂と高分子アゾ開始剤とを含有することにより、熱により確実に硬化させることができる。
なお、本明細書において、「遮光性」とは、波長３７０～８００ｎｍの光を８０％以上遮光することを意味する。 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.
When 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. However, 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.
In the present specification, “light shielding property” means that light having a wavelength of 370 to 800 nm is shielded by 80% or more.
上記遮光性着色剤は、硬化後の本発明の液晶滴下工法用シール剤に遮光性を付与し、液晶への不純物が少ないものであれば特に限定されない。上記遮光性着色剤は、例えば、黒色顔料や、混合すると黒色になる補色関係にある複数の顔料及び／又は染料が好適である。 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.
上記黒色顔料は特に限定されず、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。上記黒色顔料は単独で用いられてもよく、２種以上が併用されてもよい。なかでも、絶縁性、作業性の面より、チタンブラック及び／又はカーボンブラックが好適である。 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.
上記カーボンブラックは、液晶中への不純物の溶出が少ないものであれば特に限定されないが、例えば、チャンネルブラック、ランプブラック、ファーネスブラック、サーマルブラック等の公知のカーボンブラックを用いることができる。なかでも、絶縁性の観点から、表面がグラフト化されたグラフト化カーボンブラック、表面が絶縁無機物若しくは絶縁性有機物で被覆された被覆カーボンブラック及び／又は表面に酸化処理が施された酸性カーボンブラックが好ましい。このようなカーボンブラックは、未処理のカーボンブラックと比較して導電性が低いことから本発明の液晶滴下工法用シール剤に用いると、電流のリークが少なく信頼性の高い液晶表示素子を得ることができる。 The carbon black is not particularly limited as long as the elution of impurities into the liquid crystal is small. For example, known carbon blacks such as channel black, lamp black, furnace black and thermal black can be used. Among them, from the viewpoint of insulating properties, 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.
上記チタンブラックは特に限定されず、具体的な市販品は、例えば、１２Ｓ、１３Ｍ、１３ＭＣ、１３Ｒ－Ｎ（以上、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。また、上記チタンブラックの表面がカップリング剤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も用いることができる。 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 In addition, it is also possible to use one in which the surface of the above-mentioned titanium black is treated with 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.
上記混合すると黒色になる補色関係にある複数の有機顔料は特に限定されないが、例えば、不溶アゾ顔料、溶性アゾ顔料等のアゾ系顔料や、銅フタロシアニンブルー顔料、ハロゲン化銅フタロシアニン顔料、スルホン化銅フタロシアニン顔料、無金属フタロシアニン顔料、異種金属フタロシアニン顔料等のフタロシアニン系顔料や、アミノアントラキノン顔料、インダンスロン顔料、イソインドリノン顔料、キナクリドン顔料、ジオキサジン顔料、ペリノン顔料、ペリレン顔料等の縮合多環顔料等が挙げられる。なかでも、ハロゲン化銅フタロシアニン顔料や縮合多感顔料が好適に用いられる。これらの有機顔料は、上記黒色顔料の補助着色成分としても使用可能である。 There are no particular limitations on the plurality of 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. Among these, 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.
上記混合すると黒色になる補色関係にある複数の染料は特に限定されないが、例えば、シアニン系染料、メタシアニン系染料、ローダシアニン系染料、オキソノール系染料、スチリル系染料、ベーススチリル系染料、ベンゾピラン系染料、キノリジン系染料、クマリン系染料、チアゾール系染料、インダントロン系染料、ピラントロン系染料、アントラキノンカルバゾール系染料、アントラキノンオキサゾール系染料、インジゴ、チオインジゴ、ピラゾロンアゾ系染料、γ－酸アゾ系染料、Ｈ－酸アゾ系染料、トリアリルメタン系染料、オキサジン系染料等が挙げられる。これらの染料は、上記黒色顔料の補助着色成分としても使用可能である。 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, γ-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-mentioned black pigment.
上記遮光性着色剤の粒径は特に限定されないが、一次粒子の好ましい下限は１０ｎｍ、好ましい上限は５００ｎｍである。上記遮光性着色剤の粒径がこの範囲外であると、本発明の滴下工法用シール剤中における分散性が悪くなる。 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.
上記遮光性着色剤の含有量は特に限定されないが、本発明の滴下工法用シール剤の総重量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５０重量部である。上記遮光性着色剤の含有量が５重量部未満であると、充分な遮光性が得られないことがあり、５０重量部を超えると、本発明の液晶滴下工法用シール剤の基板に対する密着性や硬化後の強度が低下したり、描画性が低下したりすることがある。上記遮光性着色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４０重量部である。 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. When the content of the light-shielding coloring agent is less than 5 parts by weight, sufficient light shielding properties may not be obtained, and when it exceeds 50 parts by weight, the adhesion of the sealing agent for liquid crystal dropping method of the present invention to a substrate Also, the strength after curing may decrease or the drawability may decrease. 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.
本発明の滴下工法用シール剤は、上記遮光性着色剤に加えて、補助着色成分として顔料（有機顔料、無機顔料）　や染料等を含有してもよい。例えば、上記黒色顔料が赤みがかった黒色である場合、赤色の補色である青色を呈する補助着色成分を添加することにより、上記遮光性着色剤をより好ましい黒色を呈するようにすることができる。 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. For example, when 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.
本発明の液晶滴下工法用シール剤は、更に、シランカップリング剤を含有することが好ましい。上記シランカップリング剤は、主に液晶滴下工法用シール剤と液晶表示素子基板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 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.
上記シランカップリング剤は特に限定されないが、ガラス基板等との接着性向上効果に優れ、硬化性樹脂と化学結合することにより液晶中への流出を防止することができることから、例えば、γ－アミノプロピルトリメトキシシラン、γ－メルカプトプロピルトリメトキシシラン、γ－グリシドキシプロピルトリメトキシシラン、γ－イソシアネートプロピルトリメトキシシラン等が好適に用いられる。これらのシランカップリング剤は単独で用いられてもよいし、２種以上が併用されてもよい。 The above-mentioned 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, γ-amino Propyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-isocyanatopropyltrimethoxysilane and the like are preferably used. These silane coupling agents may be used alone or in combination of two or more.
本発明の液晶滴下工法用シール剤は、応力分散効果による接着性の改善、線膨張率の改善等を目的としてフィラーを含有してもよい。
上記フィラーは特に限定されず、例えば、タルク、石綿、シリカ、珪藻土、スメクタイト、ベントナイト、炭酸カルシウム、炭酸マグネシウム、アルミナ、モンモリロナイト、珪藻土、酸化亜鉛、酸化鉄、酸化マグネシウム、酸化錫、酸化チタン、水酸化マグネシウム、水酸化アルミニウム、ガラスビーズ、窒化珪素、硫酸バリウム、石膏、珪酸カルシウム、タルク、ガラスビーズ、セリサイト活性白土、ベントナイト、窒化アルミニウム等の無機フィラーや、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フィラーが挙げられる。 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. For example, talc, asbestos, silica, diatomaceous earth, smectite, bentonite, calcium carbonate, magnesium carbonate, alumina, montmorillonite, diatomaceous earth, zinc oxide, iron oxide, magnesium oxide, magnesium oxide, tin oxide, titanium oxide, water Magnesium oxide, aluminum hydroxide, glass beads, silicon nitride, barium sulfate, gypsum, calcium silicate, talc, glass beads, sericite activated clay, inorganic fillers such as bentonite and aluminum nitride, polyester fine particles, polyurethane fine particles, vinyl polymer Organic fillers, such as microparticles | fine-particles and acrylic polymer microparticles | fine-particles, are mentioned.
本発明の液晶滴下工法用シール剤は、更に、必要に応じて、粘度調整の為の反応性希釈剤、チクソ性を調整する揺変剤、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、その他添加剤等を含有してもよい。 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.
本発明の液晶表示素子用シール剤を製造する方法は特に限定されず、例えば、上記（メタ）アクリル基を有する樹脂、高分子アゾ開始剤、及び、必要に応じて配合される添加剤等を、従来公知の方法により混合する方法等が挙げられる。 The method for producing the sealing agent for a liquid crystal display element of the present invention is not particularly limited. For example, the above-described (meth) acrylic group-containing resin, a polymeric azo initiator, and additives optionally compounded, etc. And the method etc. of mixing by a conventionally well-known method.
本発明の液晶滴下工法用シール剤に、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。 An up-and-down conduction material can be manufactured by mix | blending electroconductive fine particles with the sealing compound for liquid crystal dropping methods of this invention.
上記導電性微粒子は特に限定されず、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、電極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。 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.
本発明の液晶滴下工法用シール剤及び／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。 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.
本発明の液晶表示素子を製造する方法は、例えば、ＩＴＯ薄膜等の２枚の電極付き基板の一方に、本発明の液晶滴下工法用シール剤等をスクリーン印刷、ディスペンサー塗布等により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に滴下塗布し、真空下で他方の基板を重ねあわせる工程、及び、本発明の液晶滴下工法用シール剤等に紫外線等の光を照射して仮硬化させる工程、及び、加熱して本発明の液晶滴下工法用シール剤等からなるシールパターンを本硬化させる工程を有する方法等が挙げられる。
このような本発明の液晶滴下工法用シール剤及び／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。 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 step of applying minute droplets of liquid crystal into the frame of the seal pattern and applying the other substrate under vacuum, and irradiating the sealing agent for liquid crystal dropping method of the present invention with light such as ultraviolet light. 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.
上記（メタ）アクリル基を有する樹脂と上記高分子アゾ開始剤とを含有する液晶パネル用封口剤もまた、本発明の１つである。
従来工法である真空注入方式により液晶表示装置の製造する場合にも、上記液晶滴下方式により液晶表示装置の製造する場合と同様に、液晶パネル用封口剤が液晶封止時に未硬化の状態で液晶と接触する。このとき液晶パネル用封口剤に充分な光が照射されない場合には、やはり封口部の周りに色ムラが発生し、高品位な画像の液晶表示素子を得ることができない。本発明の液晶パネル用封口剤を真空注入方式により液晶表示装置の製造する際の封止剤として用いれば、色ムラが少ない高品位な画像の液晶表示素子を製造することができる。特に紫外線が充分に照射されないパネル設計の場合には極めて有効である。 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. If 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 | pouring system, the liquid crystal display element of a high quality image with few color nonuniformity can be manufactured. In particular, in the case of the panel design which is not fully irradiated with an ultraviolet-ray, it is very effective.
本発明の液晶パネル用封口剤は、本発明の液晶滴下工法用シール剤と同様に、エポキシ基を有する樹脂、エポキシ熱硬化剤、光重合開始剤、遮光性着色剤、シランカップリング剤、フィラー、各種添加剤等を含有してもよい。 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.
本発明によれば、滴下工法により液晶表示素子を製造した場合であっても、色ムラが少ない高品位な画像の液晶表示素子を製造することができる液晶滴下工法用シール剤を提供することができる。また、真空注入方式により液晶表示装置の製造する場合に、色ムラが少ない高品位な画像の液晶表示素子を製造することができる液晶パネル用封口剤を提供することができる。 According to the present invention, it is possible to provide 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. it can. Moreover, when manufacturing a liquid crystal display device by a vacuum injection system, 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.
実施例、比較例において、液晶滴下方式により液晶表示素子を作製する手順を模式的に示した図である。In the Example and the comparative example, it is the figure which showed typically the procedure which produces a liquid crystal display element by a liquid crystal dropping system. 実施例、比較例において、真空注入方式により液晶表示素子を作製する手順を模式的に示した図である。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.
以下に実施例を挙げて本発明の態様を更に詳しく説明するが、本発明はこれら実施例にのみ限定されるものではない。 EXAMPLES The embodiments of the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.
（エポキシアクリレート（ＥＸ－２０１変性品）の合成）
ＥＸ－２０１（レゾルシノール型エポキシ樹脂）１２０ｇをトルエン５００ｍＬに溶解させ、この溶液にトリフェニルホスフィン０．１ｇを加え、均一な溶液とした。この溶液にアクリル酸７０ｇを還流撹拌下２時間かけて滴下後、更に還流撹拌を８時間行った。次に、トルエンを除去することによって、全てのエポキシ基をアクリル基に変性したエポキシアクリレート（ＥＸ－２０１変性品）を得た。 (Synthesis of epoxy acrylate (EX-201 modified product))
120 g of EX-201 (resorcinol type epoxy resin) was dissolved in 500 mL of toluene, and 0.1 g of triphenylphosphine was added to this solution to obtain a uniform solution. After 70 g of acrylic acid was added dropwise to this solution under reflux and stirring for 2 hours, the mixture was further stirred under reflux for 8 hours. Next, the toluene was removed to obtain an epoxy acrylate (EX-201 modified product) in which all epoxy groups were modified to acrylic groups.
（部分アクリル化エポキシアクリレート（Ｎ－７７０部分変性品）の合成）
Ｎ－７７０（フェノールノボラック型エポキシ樹脂）１９０ｇをトルエン５００ｍＬに溶解させ、この溶液にトリフェニルホスフィン０．１ｇを加え、均一な溶液とし、この溶液にアクリル酸３５ｇを還流撹拌下２時間かけて滴下後、更に還流撹拌を６時間行い。次に、トルエンを除去することによって５０ｍｏｌ％のエポキシ基をアクリル基に変性した部分アクリル化エポキシアクリレート（Ｎ－７７０部分変性品）を得た。 (Synthesis of partially acrylated epoxy acrylate (N-770 partially modified product))
190 g of N-770 (phenol novolac type epoxy resin) is dissolved in 500 mL of toluene, 0.1 g of triphenylphosphine is added to this solution to make a homogeneous solution, and 35 g of acrylic acid is dropped into this solution under reflux stirring for 2 hours After that, the mixture is further stirred under reflux for 6 hours. Next, by removing toluene, a partially acrylated epoxy acrylate (N-770 partially modified product) in which 50 mol% of the epoxy group was modified to an acrylic group was obtained.
（実施例１～１０、及び、比較例１～３）
表１に記載された配合比に従い、各材料を遊星式撹拌機（シンキー社製「あわとり練太郎」）を用いて混合後、更に３本ロールを用いて混合させることにより実施例１～１０、比較例１～３の液晶滴下工法用シール剤を調製した。 (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.
図１に示すように、透明電極と配向膜とが形成された基板に、得られた液晶滴下工法用シール剤を正方形の枠を描くようにディスペンサーで塗布し、また、正方形の枠の内部に得られた液晶滴下工法用シール剤を点打ちした。続いて液晶（チッソ社製「ＪＣ－５００４ＬＡ」）の微小滴を透明基盤の枠内全面に滴下塗布し、真空中にて別の透明電極と配向膜とが形成された基板を重ね合わせ、真空解除後、外枠シール部に高圧水銀ランプを用い紫外線を１００ｍＷ／ｃｍ２で３０秒照射した。この時、点打ちした液晶滴下工法用シール剤にはＵＶが照射されないようにマスクをした。その後液晶アニールを１２０℃１ｈ行い同時に液晶滴下工法用シール剤を熱硬化させて液晶表示素子を得た。 As shown in FIG. 1, 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. Subsequently, 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. After release, the outer frame seal portion was irradiated with ultraviolet light for 30 seconds at 100 mW / cm 2 using a high pressure mercury lamp. At this time, a mask was used so that UV was not irradiated to the sealing agent for liquid crystal dropping method which has been spotted. Thereafter, liquid crystal annealing was performed at 120 ° C. for 1 h, and at the same time, the sealing agent for liquid crystal dropping method was thermally cured to obtain a liquid crystal display element.
＜評価＞
実施例１～１０、及び、比較例１～３で得られた液晶滴下工法用シール剤、及び、液晶表示素子について以下の評価を行った。結果を表１に示した。 <Evaluation>
The following evaluations were performed on the sealing agent for liquid crystal dropping method obtained in Examples 1 to 10 and Comparative Examples 1 to 3 and the liquid crystal display element. The results are shown in Table 1.
（パネル表示ムラ評価）
得られた液晶表示素子について、点打ちした液晶滴下工法用シール剤周辺の液晶に生じる色ムラを通電状態及び非通電状態で目視にて観察した。その結果、色ムラが全くなかった場合を「◎」、色ムラがほとんどなかった場合を「○」、少し色ムラがあった場合を「△」、色ムラがかなりあった場合を「×」と評価した。 (Panel display unevenness evaluation)
About the obtained liquid crystal display element, the color nonuniformity which arises in the liquid crystal around the sealing agent for liquid crystal dropping methods which had been dotted | punched was visually observed by the conduction state and the non-conduction state. As a result, "」 "when there is no color unevenness at all," ○ "when there is almost no color unevenness," △ "when there is a little color unevenness," △ ", and when there is considerable color unevenness" × " It was evaluated.
（接着強度評価）
得られた液晶滴下工法用シール剤１００重量部に対して平均粒径５μｍのポリマービーズ（積水化学工業社製「ミクロパールＳＰ」）３重量部を遊星式撹拌装置によって分散させ均一な液とし、極微量をコーニングガラス１７３７（２０ｍｍ×５０ｍｍ×１．１ｍｍｔ）の中央部に取り、同型のガラスをその上に重ね合わせて液晶滴下工法用シール剤を押し広げ、紫外線を１００ｍＷ／ｃｍ２で２０秒照射した。その後１２０℃１ｈの加熱を行い、接着試験片を得た。この試験片についてテンションゲージを用いて接着強度を測定した（比較単位はＮ／ｃｍ２）。 (Adhesive strength evaluation)
Three parts by weight of polymer beads having an average particle diameter of 5 μm (“Micropearl SP” manufactured by Sekisui Chemical Co., Ltd.) are dispersed by a planetary stirrer to 100 parts by weight of the obtained sealing agent for liquid crystal dropping method, A very small amount is taken at the center of Corning glass 1737 (20mm x 50mm x 1.1mmt), the same type of glass is superimposed on it, the sealant for liquid crystal dropping method is spread and UV light is applied for 20 seconds at 100mW / cm 2 Irradiated. Thereafter, heating was performed at 120 ° C. for 1 h to obtain an adhesion test piece. The adhesive strength of this test piece was measured using a tension gauge (comparison unit: N / cm 2 ).
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
（実施例１１～１５、及び、比較例４～５）
表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」）を用いて混合させることにより実施例１１～１５、比較例４～５の液晶パネル用封口剤を調製した。 (Examples 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.
図２に示すように、透明電極と配向膜とが形成された基板に、実施例１の液晶滴下工法用シール剤を正方形の枠の一部が途切れる用にディスペンサーで塗布し、続いて別の透明電極と配向膜とが形成された基板を重ね合わせシール剤が所定のギャップになるまで加圧し、１２０℃１ｈの加熱処理を行うことにより液晶注入前の空セルを得た。ついで空セルを真空状態にしたのち、液晶（チッソ社製「ＪＣ－５００４ＬＡ」）を正方形の枠の一部が途切れた箇所に接触させた後、常圧に戻し、２ｈ放置することにより、内部が液晶で満たされたセルを得た。 As shown in FIG. 2, on the substrate on which the transparent electrode and the alignment film were formed, 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. Next, 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.
次に実施例１１～１５、及び、比較例４～５の封口剤を用いて正方形の枠の一部が途切れた箇所を、得られた液晶パネル用封口剤を用いた封止した後、該封口剤に高圧水銀ランプを用い紫外線を１００ｍＷ／ｃｍ２で３０秒照射した。その後液晶アニールを１２０℃、１時間行い同時に封口剤を熱硬化させて液晶表示素子を得た。またこのとき、封口剤に紫外線を照射せず、１２０℃１ｈの液晶アニールを行った条件での液晶表示素子も得た。 Next, 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.
＜評価＞
実施例１１～１５、及び、比較例４～５で得られた液晶表示素子について、以下の方法によりパネル表示ムラの評価を行った。
結果を表２に示した。 <Evaluation>
For the liquid crystal display elements obtained in Examples 11 to 15 and Comparative Examples 4 to 5, the panel display unevenness was evaluated by the following method.
The results are shown in Table 2.
（パネル表示ムラ評価）
得られた液晶表示素子について、封口部周辺の液晶に生じる色ムラを通電状態及び非通電状態で目視にて観察した。その結果、色ムラが全くなかった場合を「◎」、色ムラがほとんどなかった場合を「○」、少し色ムラがあった場合を「△」、色ムラがかなりあった場合を「×」と評価した。 (Panel display unevenness evaluation)
About the obtained liquid crystal display element, the color nonuniformity which arises in the liquid crystal around a sealing part was observed visually in an electricity_supplying state and a non-energized state. As a result, "」 "when there is no color unevenness at all," ○ "when there is almost no color unevenness," △ "when there is a little color unevenness," △ ", and when there is considerable color unevenness" × " It was evaluated.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
（参考例１～５）
表３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」）を用いて混合後、更に３本ロールを用いて混合させることにより参考例１～５の液晶滴下工法用シール剤を調製した。 (Reference Examples 1 to 5)
According to the compounding ratio described in Table 3, after mixing each material using a planetary stirrer ("Awatori Neritaro" manufactured by Shinky Co., Ltd.), it is further mixed using a three-roll system for reference examples 1 to 5 A sealing agent for liquid crystal dropping method was prepared.
＜評価＞
参考例１～５で得られた液晶滴下工法用シール剤について、以下の方法によりＯＤ値と硬化性との評価を行った。更に、実施例と同様の方法によりパネル表示ムラ評価を行った。
結果を表３に示した。 <Evaluation>
With respect to the sealing agent for liquid crystal dropping method obtained in Reference Examples 1 to 5, the OD value and the curing property were evaluated by the following method. Furthermore, the panel display unevenness evaluation was performed by the method similar to the Example.
The results are shown in Table 3.
（光学濃度（ＯＤ値）の測定）
得られた液晶滴下工法用シール剤１００ｇにスペーサとして直径５μｍのシリカスペーサ（積水化学工業社製、ミクロパールＳＩ）１ｇを添加して混合撹拌を行った。
得られたスペーサ入り液晶滴下工法用シール剤を５０ｍｍ×５０ｍｍのガラス基板上に塗布し、その基板に同サイズのガラス基板を重ね合わせ、荷重をかけ、スペーサの直径まで押しつぶして厚さを均一にした。次に、メタルハライドランプを用いて１００ｍＷ／ｃｍ２で３０秒照射した。その後１２０℃オーブンにて１時間硬化を行い、遮光シール剤の測定サンプルを得た。得られたサンプルについてコニカ社製、ＰＤＡ－１００を用いて光学濃度（ＯＤ値）を測定した。 (Measurement of optical density (OD value))
1 g of a silica spacer (Micropearl SI, manufactured by Sekisui Chemical Co., Ltd.) having a diameter of 5 μm 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. Next, 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.
（硬化性の評価）
液晶滴下工法用シール剤を、シール剤の厚さが約５μｍとなるようにして２枚のポリエチレンテレフタレートフィルム間に挟みサンプルを作成した。このサンプルに、高圧水銀ランプを用い紫外線を１００ｍＷ／ｃｍ２で３０秒照射した後、１２０℃、１時間熱処理を行った。熱処理後にポリエチレンテレフタレートフィルムを剥がしたときに、両面にタックが残らない場合を「○」、どちらか一方でもタックが残った場合を「×」と評価した。 (Evaluation of curability)
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 μm, 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. When 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".
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
本発明によれば、滴下工法により液晶表示素子を製造した場合であっても、色ムラが少ない高品位な画像の液晶表示素子を製造することができる液晶滴下工法用シール剤を提供することができる。また、真空注入方式により液晶表示装置の製造する場合に、色ムラが少ない高品位な画像の液晶表示素子を製造することができる液晶パネル用封口剤を提供することができる。 According to the present invention, it is possible to provide 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. it can. Moreover, when manufacturing a liquid crystal display device by a vacuum injection system, 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.

Claims (9)

  1. （メタ）アクリル基を有する樹脂と高分子アゾ開始剤とを含有することを特徴とする液晶滴下工法用シール剤。 A sealing agent for liquid crystal dropping method comprising a resin having a (meth) acrylic group and a high molecular weight azo initiator.
  2. 高分子アゾ開始剤は、ポリジメチルシロキサンユニット又はポリアルキレンオキサイドユニットを有することを特徴とする請求項１記載の液晶滴下工法用シール剤。 The sealing agent for liquid crystal dropping method according to claim 1, wherein the high molecular weight azo initiator has a polydimethylsiloxane unit or a polyalkylene oxide unit.
  3. 更に、エポキシ基を有する樹脂、及び、エポキシ熱硬化剤を含有することを特徴とする請求項１又は２記載の液晶滴下工法用シール剤。 Furthermore, the resin which has an epoxy group, and an epoxy thermosetting agent are contained, The sealing compound for liquid crystal dropping methods of Claim 1 or 2 characterized by the above-mentioned.
  4. 更に、光重合開始剤を含有することを特徴とする請求項１、２又は３記載の液晶滴下工法用シール剤。 The sealing agent for liquid crystal dropping method according to claim 1, 2 or 3, further comprising a photopolymerization initiator.
  5. 更に、遮光性着色剤を含有することを特徴とする請求項１、２、３又は４記載の液晶滴下工法用シール剤。 The sealing agent for liquid crystal dropping method according to claim 1, 2, 3 or 4, further comprising a light shielding coloring agent.
  6. 請求項１、２、３、４又は５記載の液晶滴下工法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。 An up-and-down conducting material comprising the sealing agent for liquid crystal dropping method according to any one of claims 1, 2, 3, 4 or 5 and conductive fine particles.
  7. （メタ）アクリル基を有する樹脂と高分子アゾ開始剤とを含有することを特徴とする液晶パネル用封口剤。 A sealing agent for a liquid crystal panel comprising a resin having a (meth) acrylic group and a high molecular weight azo initiator.
  8. 請求項１、２、３、４又は５記載の液晶滴下工法用シール剤及び／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 device comprising the sealing agent for a liquid crystal dropping method according to claim 1, 2, 3, 4 or 5 and / or the upper and lower conducting material according to claim 6.
  9. 請求項７記載の液晶パネル用封口剤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 sealing agent for a liquid crystal panel according to claim 7.
PCT/JP2009/057568 2008-04-18 2009-04-15 Sealing agent for use in liquid crystal dropping process, sealing agent for liquid crystal panel, vertical-conduction material, and liquid crystal display element WO2009128470A1 (en)

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JP2009516789A JP4616404B2 (en) 2008-04-18 2009-04-15 Liquid crystal dropping method sealing agent, liquid crystal panel sealing agent, vertical conduction material, and liquid crystal display element
CN200980112979.9A CN102007447B (en) 2008-04-18 2009-04-15 Sealing agent for use in liquid crystal dropping process, sealing agent for liquid crystal panel, vertical-conduction material, and liquid crystal display element
KR1020107018271A KR101194202B1 (en) 2008-04-18 2009-04-15 Sealing agent for use in liquid crystal dropping process, sealing agent for liquid crystal panel, vertical-conduction material, and liquid crystal display element

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012088412A (en) * 2010-10-18 2012-05-10 Sekisui Chem Co Ltd Light-shielding sealing agent for liquid crystal display element, vertical conducting material and liquid crystal display element
WO2012077572A1 (en) * 2010-12-09 2012-06-14 積水化学工業株式会社 Sealing material for liquid-crystal dropping process, material for vertical conduction, and liquid-crystal display element
WO2012137749A1 (en) * 2011-04-05 2012-10-11 積水化学工業株式会社 Light-shielding sealing agent for liquid crystal display element, top-to-bottom conductive material, and liquid crystal display element
JP2013011879A (en) * 2011-06-01 2013-01-17 Sekisui Chem Co Ltd Light-shielding sealing agent for liquid crystal display element, vertical conduction material, and liquid crystal display element
WO2013024844A1 (en) * 2011-08-18 2013-02-21 積水化学工業株式会社 Epoxy compound, epoxy compound mixture, curable composition, and connecting structure
JP2013514449A (en) * 2009-12-15 2013-04-25 チュンホン・リ Hybrid polymer materials for liquid crystal alignment layers
JP2014006325A (en) * 2012-06-22 2014-01-16 Nippon Kayaku Co Ltd Liquid crystal sealing agent and liquid crystal display cell using the same
KR20160028404A (en) 2013-07-03 2016-03-11 세키스이가가쿠 고교가부시키가이샤 Sealant for liquid crystal dropping method, vertical-conduction material, liquid crystal display element, and light-shielding flexible silicone particles
JP6114893B1 (en) * 2015-10-26 2017-04-12 積水化学工業株式会社 Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element

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JP5281204B1 (en) * 2011-08-17 2013-09-04 積水化学工業株式会社 Sealant for liquid crystal display element and liquid crystal display element
WO2015178357A1 (en) * 2014-05-23 2015-11-26 積水化学工業株式会社 Sealant for one-drop filling process, vertically conductive material, and liquid crystal display element
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CN109196413B (en) * 2016-12-27 2021-03-16 积水化学工业株式会社 Sealing agent for liquid crystal display element, vertical conduction material, and liquid crystal display element
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KR102337864B1 (en) * 2019-05-03 2021-12-10 얍엑스 주식회사 Sealing composition for preventing light leakage and display panel comprising sealing part for preventing light leakage

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000298352A (en) * 1999-04-14 2000-10-24 Jsr Corp Material for electronic parts and method for using same
WO2007114184A1 (en) * 2006-03-29 2007-10-11 Sekisui Chemical Co., Ltd. Sealing material for liquid-crystal dropping process, vertical-conduction material, and liquid-crystal display element
WO2008029893A1 (en) * 2006-09-07 2008-03-13 Mitsui Chemicals, Inc. Liquid crystal sealing agent, method for manufacturing liquid crystal display panel using the liquid crystal sealing agent, and liquid crystal display panel
WO2008102550A1 (en) * 2007-02-20 2008-08-28 Mitsui Chemicals, Inc. Curable resin composition for sealing liquid crystal, and method for production of liquid crystal display panel using the same

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6074628A (en) * 1997-04-25 2000-06-13 Procter & Gamble Hairspray compositions containing silicon block copolymers
JP4157896B2 (en) * 2005-07-06 2008-10-01 積水化学工業株式会社 Sealant for liquid crystal dropping method, vertical conduction material, and liquid crystal display element

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000298352A (en) * 1999-04-14 2000-10-24 Jsr Corp Material for electronic parts and method for using same
WO2007114184A1 (en) * 2006-03-29 2007-10-11 Sekisui Chemical Co., Ltd. Sealing material for liquid-crystal dropping process, vertical-conduction material, and liquid-crystal display element
WO2008029893A1 (en) * 2006-09-07 2008-03-13 Mitsui Chemicals, Inc. Liquid crystal sealing agent, method for manufacturing liquid crystal display panel using the liquid crystal sealing agent, and liquid crystal display panel
WO2008102550A1 (en) * 2007-02-20 2008-08-28 Mitsui Chemicals, Inc. Curable resin composition for sealing liquid crystal, and method for production of liquid crystal display panel using the same

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013514449A (en) * 2009-12-15 2013-04-25 チュンホン・リ Hybrid polymer materials for liquid crystal alignment layers
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WO2012077572A1 (en) * 2010-12-09 2012-06-14 積水化学工業株式会社 Sealing material for liquid-crystal dropping process, material for vertical conduction, and liquid-crystal display element
JP5049409B2 (en) * 2010-12-09 2012-10-17 積水化学工業株式会社 Liquid crystal dropping method sealing agent, vertical conduction material, and liquid crystal display element
CN103261957B (en) * 2010-12-09 2015-04-29 积水化学工业株式会社 Sealing material for liquid-crystal dropping process, material for vertical conduction, and liquid-crystal display element
KR101298418B1 (en) 2010-12-09 2013-08-20 세키스이가가쿠 고교가부시키가이샤 Sealing material for liquid-crystal dropping process, material for vertical conduction, and liquid-crystal display element
CN103261957A (en) * 2010-12-09 2013-08-21 积水化学工业株式会社 Sealing material for liquid-crystal dropping process, material for vertical conduction, and liquid-crystal display element
KR101321694B1 (en) 2011-04-05 2013-10-23 세키스이가가쿠 고교가부시키가이샤 Light-shielding sealing agent for liquid crystal display element, top-to-bottom conductive material, and liquid crystal display element
WO2012137749A1 (en) * 2011-04-05 2012-10-11 積水化学工業株式会社 Light-shielding sealing agent for liquid crystal display element, top-to-bottom conductive material, and liquid crystal display element
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JP2013011879A (en) * 2011-06-01 2013-01-17 Sekisui Chem Co Ltd Light-shielding sealing agent for liquid crystal display element, vertical conduction material, and liquid crystal display element
JPWO2013024844A1 (en) * 2011-08-18 2015-03-05 積水化学工業株式会社 Epoxy compound, mixture of epoxy compound, curable composition, and connection structure
WO2013024844A1 (en) * 2011-08-18 2013-02-21 積水化学工業株式会社 Epoxy compound, epoxy compound mixture, curable composition, and connecting structure
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