WO2015178357A1 - Sealant for one-drop filling process, vertically conductive material, and liquid crystal display element - Google Patents
Sealant for one-drop filling process, vertically conductive material, and liquid crystal display element Download PDFInfo
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- WO2015178357A1 WO2015178357A1 PCT/JP2015/064252 JP2015064252W WO2015178357A1 WO 2015178357 A1 WO2015178357 A1 WO 2015178357A1 JP 2015064252 W JP2015064252 W JP 2015064252W WO 2015178357 A1 WO2015178357 A1 WO 2015178357A1
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- meth
- acrylate
- liquid crystal
- crystal dropping
- sealing agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/062—Copolymers with monomers not covered by C08L33/06
- C08L33/068—Copolymers with monomers not covered by C08L33/06 containing glycidyl groups
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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
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/106—Esters of polycondensation macromers
- C08F222/1067—Esters of polycondensation macromers of alcohol terminated epoxy functional polymers, e.g. epoxy(meth)acrylates
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1339—Gaskets; Spacers; Sealing of cells
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
Definitions
- the present invention relates to a sealing agent for a liquid crystal dropping method, which has a high curing rate, can suppress liquid crystal contamination, and is excellent in applicability and adhesiveness. Moreover, this invention relates to the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal dropping methods.
- a rectangular seal pattern is formed on one of two transparent substrates with electrodes by dispensing.
- a liquid crystal micro-droplet is dropped on the entire surface of the transparent substrate frame in a state where the sealant is uncured, and the other transparent substrate is immediately overlaid, and the seal portion is irradiated with light such as ultraviolet rays for temporary curing. .
- heating is performed to perform main curing, and a liquid crystal display element is manufactured.
- a liquid crystal display element can be manufactured with extremely high efficiency by bonding the substrates under a reduced pressure, and this dropping method is currently the mainstream method for manufacturing liquid crystal display elements.
- An object of this invention is to provide the sealing agent for liquid crystal dropping methods which has a quick hardening rate, can suppress liquid-crystal contamination, and is excellent in applicability
- the present invention is a sealing agent for a liquid crystal dropping method containing a curable resin and a thermal radical polymerization initiator, wherein the curable resin has three or more (meth) acryloyloxy groups in one molecule. It is the sealing agent for liquid crystal dropping methods containing the above epoxy (meth) acrylate.
- the present invention is described in detail below.
- the present inventor as a curable resin, blends a tri- or higher functional epoxy (meth) acrylate having 3 or more (meth) acryloyloxy groups in one molecule in combination with a thermal radical polymerization initiator, thereby increasing the curing rate. It has been found that a liquid crystal dripping method sealing agent can be obtained that is fast, can suppress liquid crystal contamination, and is excellent in coating properties and adhesiveness, and has completed the present invention.
- the sealing agent for liquid crystal dropping method of the present invention contains a curable resin.
- the curable resin contains a tri- or higher functional epoxy (meth) acrylate having three or more (meth) acryloyloxy groups in one molecule.
- the sealing agent for liquid crystal dropping method of the present invention has a high curing rate, can suppress liquid crystal contamination, and can be applied. And it becomes excellent in adhesiveness.
- (meth) acryloyloxy means acryloyloxy or methacryloyloxy
- (meth) acrylate means acrylate or methacrylate
- epoxy (meth) acrylate Means a compound obtained by reacting all epoxy groups in the epoxy resin with (meth) acrylic acid, and the above “(meth) acryl” means acryl or methacryl.
- a preferable lower limit of the dielectric constant of the tri- or higher functional epoxy (meth) acrylate is 3. When the dielectric constant is 3 or more, it is difficult to elute into the liquid crystal. A more preferable lower limit of the dielectric constant is 4. The dielectric constant is preferably as high as possible, but the practical upper limit is 20. In addition, when the sealing compound for liquid crystal dropping method of the present invention contains two or more compounds as the above-described trifunctional or higher functional epoxy (meth) acrylate, the dielectric constant of the above trifunctional or higher functional epoxy (meth) acrylate is as described above.
- dielectric constant can be measured by measuring the complex dielectric constant under the conditions of 25 ° C. and 1 MHz using an impedance analyzer (for example, “1260 type” manufactured by Solartron), and is defined by the real part. .
- the tri- or higher functional epoxy (meth) acrylate has at least one hydrogen-bonding functional group such as —OH group, —NH— group, and —NH 2 group in one molecule.
- the tri- or higher functional epoxy (meth) acrylate preferably has three or more hydrogen-bonding functional groups in one molecule.
- the tri- or higher functional epoxy (meth) acrylate has a structure in which three or more molecular chains each having one (meth) acryloyloxy group are branched from one carbon atom from the viewpoint of the thermosetting reaction rate. Is preferred. Moreover, it is preferable that the reactive functional group which the said epoxy (meth) acrylate more than trifunctional has is only a (meth) acryloyloxy group from a viewpoint of suppressing liquid-crystal contamination.
- the “reactive functional group” means a polymerizable functional group that contributes to the curing reaction.
- tri- or higher functional epoxy (meth) acrylate examples include, for example, trimethylolpropane triglycidyl ether (meth) acrylate, trimethylolethane triglycidyl ether (meth) acrylate, methanetriyl tris (glycidyl ether (meth) ) Acrylate), (propane-1,2,3-triyl) tris (glycidyl ether (meth) acrylate), pentaerythritol tetraglycidyl ether (meth) acrylate, phenol novolac type epoxy (meth) acrylate, naphthalene type epoxy acrylate, etc. Can be mentioned.
- the tri- or higher functional epoxy (meth) acrylate preferably does not have a novolac structure, and is more preferably an aliphatic epoxy (meth) acrylate having no aromatic ring. preferable.
- the sealing agent for liquid crystal dropping method of the present invention is a trifunctional epoxy (meth) acrylate and / or a tetrafunctional epoxy (meth) acrylate as the above trifunctional or higher functional epoxy (meth) acrylate. It is preferable to contain, and it is more preferable to contain the compound represented by following formula (1).
- R 1 is hydrogen, an alkyl group having 1 to 5 carbon atoms, or a group represented by the following formula (2), and each R 2 is independently hydrogen or a methyl group.
- L, m, and n are each independently an integer of 1 to 5.
- R 3 is hydrogen or a methyl group
- k is an integer of 1 to 5.
- Examples of the tri- or higher functional epoxy (meth) acrylate include, for example, a tri- or higher functional epoxy compound having three or more epoxy groups in one molecule and (meth) acrylic acid in the presence of a basic catalyst according to a conventional method. And the like obtained by reacting with.
- tri- or higher functional epoxy compound examples include trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether, methanetriyl tris (glycidyl ether), (propane-1,2,3-triyl) tris (glycidyl ether). ), Pentaerythritol tetraglycidyl ether, phenol novolac type epoxy, naphthalene type epoxy compound and the like.
- the preferable lower limit of the content of the tri- or higher functional epoxy (meth) acrylate in 100 parts by weight of the curable resin is 2 parts by weight, and the preferable upper limit is 30 parts by weight. If the content of the tri- or higher functional epoxy (meth) acrylate is less than 2 parts by weight, the effect of suppressing the liquid crystal contamination by increasing the curing rate may not be sufficiently exhibited. If the content of the above-mentioned trifunctional or higher functional epoxy (meth) acrylate exceeds 30 parts by weight, display unevenness may occur when the resulting liquid crystal display element is exposed to a high temperature and high humidity environment.
- the more preferable lower limit of the content of the trifunctional or higher functional epoxy (meth) acrylate is 4 parts by weight, and the more preferable upper limit is 15 parts by weight.
- the curable resin may contain other curable resins in addition to the tri- or higher functional epoxy (meth) acrylate as long as the object of the present invention is not impaired.
- the other curable resin include other (meth) acryl compounds other than trifunctional or higher functional epoxy (meth) acrylates, and epoxy compounds.
- the “(meth) acrylic compound” means a compound having a (meth) acryloyloxy group.
- Examples of the other (meth) acrylic compounds include bifunctional or lower epoxy (meth) acrylates, ester compounds obtained by reacting (meth) acrylic acid with a compound having a hydroxyl group, and isocyanate compounds having a hydroxyl group ( Examples thereof include urethane (meth) acrylate obtained by reacting a (meth) acrylic acid derivative.
- bifunctional or lower epoxy (meth) acrylates are preferable from the viewpoint of improving adhesiveness and suppressing liquid crystal contamination.
- bifunctional or lower epoxy (meth) acrylate examples include those obtained by reacting a bifunctional or lower epoxy compound with (meth) acrylic acid in the presence of a basic catalyst according to a conventional method. It is done.
- bifunctional or lower epoxy compound examples include, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, 2,2′-diallyl bisphenol A type epoxy resin, hydrogenated bisphenol type epoxy resin, propylene Oxide-added bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, sulfide type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol novolak type epoxy resin, orthocresol novolak type Epoxy resin, dicyclopentadiene novolac epoxy resin, biphenyl novolac epoxy resin, naphthalene phenol novolac epoxy resin, Rishijiruamin type epoxy resin, alkyl polyol type epoxy resin, rubber modified epoxy resin, glycidyl ester compounds, among such as bisphenol A type episulfide resins include those having more than two epoxy groups per molecule.
- the sealing agent for liquid crystal dropping method of the present invention contains the bifunctional or lower epoxy (meth) acrylate, the content ratio of the trifunctional or higher epoxy (meth) acrylate and the bifunctional or lower epoxy (meth) acrylate.
- the content ratio of the trifunctional or higher epoxy (meth) acrylate and the bifunctional or lower epoxy (meth) acrylate is preferably within this range, the obtained liquid crystal dropping method sealing agent is particularly excellent in applicability and adhesiveness. It is excellent and has an excellent effect of suppressing liquid crystal contamination.
- Examples of monofunctional compounds of the ester compounds include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl ( (Meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, isomyristyl (meth) acrylate , Stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate Rate,
- bifunctional ester compound examples include 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexanediol di (meth).
- ester compound having three or more functions examples include trimethylolpropane tri (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) acrylate, propylene oxide-added trimethylolpropane tri (meth) acrylate, and caprolactone.
- the urethane (meth) acrylate obtained by reacting the isocyanate compound with a hydroxyl group-containing (meth) acrylic acid derivative is, for example, a (meth) acrylic acid derivative having a hydroxyl group with respect to 1 equivalent of a compound having two isocyanate groups. Two equivalents can be obtained by reacting in the presence of a catalytic amount of a tin-based compound.
- isocyanate compound used as the raw material for the urethane (meth) acrylate examples include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and diphenylmethane-4,4.
- MDI '-Diisocyanate
- hydrogenated MDI polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanate) Phenyl) thiophosphate, tetramethylxylene diisocyanate, 1,6,11-undecanetriiso Aneto and the like.
- isocyanate compound 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 ethylene glycol, glycerin, sorbitol, trimethylolpropane, (poly) propylene Chain-extended isocyanate compounds obtained by reaction of polyols such as glycols, carbonate diols, polyether diols, polyester diols, polycaprolactone diols and excess isocyanate compounds can also be used.
- Examples of the (meth) acrylic acid derivative having a hydroxyl group as a raw material for the urethane (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.
- Hydroxyalkyl mono (meth) acrylates such as 2-hydroxybutyl (meth) acrylate, ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, polyethylene glycol, etc.
- Examples of commercially available urethane (meth) acrylates include M-1100, M-1200, M-1210, M-1600 (all manufactured by Toagosei Co., Ltd.), EBECRYL230, EBECRYL270, EBECRYL4858, EBECRYL8402, EBECRYL8804, EBECRYL8803, EBECRYL8807, EBECRYL9260, EBECRYL1290, EBECRYL5129, EBECRYL4842, EBECRYL210, EBECRYL4827, EBECRYL6700, EBECRYL6700, EBECRYL6700, EBECRYL6700, EBECRYL6700 , Art resin N-1255, Art Resin UN-330, Art Resin UN-3320HB, Art Resin UN-1200TPK, Art Resin SH-500B (all manufactured by Negami Industrial Co., Ltd.), U-122P, U-108A, U-340P,
- the other (meth) acrylic compounds preferably have a hydrogen bonding functional group such as —OH group, —NH— group, and —NH 2 group in order to suppress adverse effects on the liquid crystal.
- the sealing agent for liquid crystal dropping method of the present invention contains a thermal radical polymerization initiator.
- the sealing compound for liquid crystal dropping methods of this invention can be rapidly hardened
- thermal radical polymerization initiator examples include organic peroxides and azo compounds.
- a polymer azo initiator composed of a polymer azo compound is preferable.
- the polymer azo initiator means a compound having an azo group and generating a radical capable of curing a (meth) acryloyloxy group by heat and having a number average molecular weight of 300 or more. .
- the preferable lower limit of the number average molecular weight of the polymeric azo initiator is 1000, and the preferable upper limit is 300,000.
- the number average molecular weight of the polymer azo initiator is less than 1000, the polymer azo initiator may adversely affect the liquid crystal.
- the number average molecular weight of the polymeric azo initiator exceeds 300,000, mixing with the curable resin may be difficult.
- the more preferable lower limit of the number average molecular weight of the polymeric azo initiator is 5000, the more preferable upper limit is 100,000, the still more preferable lower limit is 10,000, and the still more preferable upper limit is 90,000.
- the said number average molecular weight is a value calculated
- GPC gel permeation chromatography
- Examples of the column for measuring the number average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko KK).
- Examples of the polymer azo initiator include those having a structure in which a plurality of units such as polyalkylene oxide and polydimethylsiloxane are bonded via an azo group.
- Examples of the polymer azo initiator having a structure in which a plurality of units such as polyalkylene oxide are bonded via the azo group those having a polyethylene oxide structure are preferable.
- Examples of such a polymer azo initiator include polycondensates of 4,4′-azobis (4-cyanopentanoic acid) and polyalkylene glycol, and 4,4′-azobis (4-cyanopentanoic acid) Examples include polycondensates of polydimethylsiloxane having a terminal amino group.
- organic peroxide examples include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, peroxyester, diacyl peroxide, and peroxydicarbonate.
- thermal radical polymerization initiators examples include perbutyl O, perhexyl O, perbutyl PV (all manufactured by NOF Corporation), V-30, V-501, V-601, VPE-0201. VPE-0401, VPE-0601 (both manufactured by Wako Pure Chemical Industries, Ltd.) and the like.
- the content of the thermal radical polymerization initiator is preferably 0.01 parts by weight and preferably 10 parts by weight with respect to 100 parts by weight of the curable resin.
- the content of the thermal radical polymerization initiator is less than 0.01 parts by weight, the obtained sealing agent for liquid crystal dropping method may not be sufficiently cured.
- content of the said thermal radical polymerization initiator exceeds 10 weight part, storage stability may fall.
- the sealing agent for a liquid crystal dropping method of the present invention preferably contains a photo radical polymerization initiator in addition to the thermal radical polymerization initiator from the viewpoint of suppressing liquid crystal contamination.
- a photo radical polymerization initiator include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, thioxanthone compounds, and the like.
- photo radical polymerization initiators examples include IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, all manufactured by Rusilin TPO ), NCI-930 (manufactured by ADEKA), SPEEDCURE EMK (manufactured by Nippon Sebel Hegner), benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether (all manufactured by Tokyo Chemical Industry Co., Ltd.) and the like.
- the sealing agent for the liquid crystal dropping method of the present invention has curability, effects of suppressing liquid crystal contamination, and adhesiveness. It can be made more excellent.
- the sealing agent for liquid crystal dropping method of the present invention may contain a thermosetting agent.
- thermosetting agent include organic acid hydrazides, imidazole derivatives, amine compounds, polyhydric phenol compounds, acid anhydrides, and the like. Among these, solid organic acid hydrazide is preferably used.
- solid organic acid hydrazide examples include 1,3-bis (hydrazinocarbonoethyl) -5-isopropylhydantoin, sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide, and the like.
- SDH SDH
- MDH all manufactured by Nippon Finechem Co., Ltd.
- ADH manufactured by Otsuka Chemical Co., Ltd.
- Amicure VDH Amicure VDH-J
- Amicure UDH all manufactured by Ajinomoto Fine Techno Co., Ltd.
- the content of the thermosetting agent is preferably 1 part by weight with respect to 100 parts by weight of the curable resin, and 50 parts by weight with respect to the preferable upper limit.
- the content of the thermosetting agent is less than 1 part by weight, the sealing agent for liquid crystal dropping method of the present invention may not be sufficiently cured.
- content of the said thermosetting agent exceeds 50 weight part, the viscosity of the sealing compound for liquid crystal dropping methods of this invention will become high, and coating property may deteriorate.
- the upper limit with more preferable content of the said thermosetting agent is 30 weight part.
- the sealing agent for liquid crystal dropping method of the present invention may further contain a filler for the purpose of improving the adhesiveness by the stress dispersion effect and improving the linear expansion coefficient.
- a filler for the purpose of improving the adhesiveness by the stress dispersion effect and improving the linear expansion coefficient.
- the filler include talc, asbestos, silica, diatomaceous earth, smectite, bentonite, calcium carbonate, magnesium carbonate, alumina, montmorillonite, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, magnesium hydroxide, water Inorganic fillers such as aluminum oxide, glass beads, silicon nitride, barium sulfate, gypsum, calcium silicate, sericite, activated clay, aluminum nitride, and organic materials such as polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, and acrylic polymer fine particles A filler is mentioned.
- the minimum with preferable content of the said filler in 100 weight part of sealing agents for liquid crystal dropping methods of this invention is 5 weight part, and a preferable upper limit is 70 weight part.
- a preferable upper limit is 70 weight part.
- content of the filler is less than 5 parts by weight, effects such as improvement of adhesiveness may not be sufficiently exhibited.
- content of the said filler exceeds 70 weight part, the viscosity of the sealing compound for liquid crystal dropping methods obtained will become high too much, and coating property may deteriorate.
- the minimum with more preferable content of the said filler is 10 weight part, and a more preferable upper limit is 60 weight part.
- the sealing agent for liquid crystal dropping method of the present invention may contain a silane coupling agent.
- a silane coupling agent for example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane and the like are preferably used. These may be used independently and 2 or more types may be used together.
- the minimum with preferable content of the said silane coupling agent in 100 weight part of sealing agents for liquid crystal dropping methods of this invention is 0.1 weight part, and a preferable upper limit is 20 weight part.
- a preferable upper limit is 20 weight part.
- the content of the silane coupling agent is less than 0.1 parts by weight, the effect of blending the silane coupling agent may not be sufficiently exhibited.
- content of the said silane coupling agent exceeds 20 weight part, the sealing compound for liquid crystal dropping methods obtained may cause liquid-crystal contamination.
- the minimum with more preferable content of the said silane coupling agent is 0.5 weight part, and a more preferable upper limit is 10 weight part.
- the sealing agent for liquid crystal dropping method of the present invention may contain a light shielding agent.
- the sealing compound for liquid crystal dropping methods of this invention can be used suitably as a light shielding sealing agent.
- Examples of the light-shielding agent include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. Of these, titanium black is preferable.
- Titanium black is a substance having a higher transmittance in the vicinity of the ultraviolet region, particularly for light having a wavelength of 370 to 450 nm, compared to the average transmittance for light having a wavelength of 300 to 800 nm. That is, the above-described titanium black sufficiently shields light having a wavelength in the visible light region, thereby providing light shielding properties to the sealing agent for liquid crystal dropping method of the present invention, while transmitting light having a wavelength in the vicinity of the ultraviolet region.
- a shading agent Therefore, by using the photo radical polymerization initiator or the photo cationic polymerization initiator that can start the reaction with light having a wavelength (370 to 450 nm) at which the transmittance of the titanium black is high, the liquid crystal of the present invention is used.
- the light shielding agent contained in the liquid crystal dropping method sealing agent of the present invention is preferably a highly insulating material, and titanium black is also suitable as the highly insulating light shielding agent.
- the titanium black preferably has an optical density (OD value) per ⁇ m of 3 or more, more preferably 4 or more. The higher the light-shielding property of the titanium black, the better.
- the OD value of the titanium black is not particularly limited, but is usually 5 or less.
- the above-mentioned titanium black exhibits a sufficient effect even if it is not surface-treated, but the surface is treated with an organic component such as a coupling agent, silicon oxide, titanium oxide, germanium oxide, aluminum oxide, oxidized Surface-treated titanium black such as those coated with an inorganic component such as zirconium or magnesium oxide can also be used. Especially, what is processed with the organic component is preferable at the point which can improve insulation more.
- the liquid crystal display device manufactured using the sealing agent for liquid crystal dropping method of the present invention containing the above-described titanium black as a light-shielding agent has a sufficient light-shielding property, and thus has a high contrast without light leakage. A liquid crystal display element having excellent image display quality can be realized.
- titanium black examples include 12S, 13M, 13M-C, 13R-N (all manufactured by Mitsubishi Materials Corporation), Tilak D (manufactured by Ako Kasei Co., Ltd.), and the like.
- the preferable lower limit of the specific surface area of the titanium black is 13 m 2 / g, the preferable upper limit is 30 m 2 / g, the more preferable lower limit is 15 m 2 / g, and the more preferable upper limit is 25 m 2 / g.
- the preferred lower limit of the volume resistance of the titanium black is 0.5 ⁇ ⁇ cm, the preferred upper limit is 3 ⁇ ⁇ cm, the more preferred lower limit is 1 ⁇ ⁇ cm, and the more preferred upper limit is 2.5 ⁇ ⁇ cm.
- the primary particle diameter of the light-shielding agent is not particularly limited as long as it is not more than the distance between the substrates of the liquid crystal display element, but the preferred lower limit is 1 nm and the preferred upper limit is 5 ⁇ m.
- the primary particle diameter of the light-shielding agent is less than 1 nm, the viscosity and thixotropy of the obtained liquid crystal dropping method sealing agent are greatly increased, and workability may be deteriorated.
- the primary particle diameter of the light-shielding agent exceeds 5 ⁇ m, the coating property of the obtained liquid crystal dropping method sealing agent on the substrate may be deteriorated.
- the more preferable lower limit of the primary particle diameter of the light shielding agent is 5 nm, the more preferable upper limit is 200 nm, the still more preferable lower limit is 10 nm, and the still more preferable upper limit is 100 nm.
- the preferable lower limit of the content of the light shielding agent in 100 parts by weight of the sealing agent for liquid crystal dropping method of the present invention is 5 parts by weight, and the preferable upper limit is 80 parts by weight. If the content of the light shielding agent is less than 5 parts by weight, sufficient light shielding properties may not be obtained. When the content of the light-shielding agent exceeds 80 parts by weight, the adhesion of the obtained sealing agent for liquid crystal dropping method to the substrate and the strength after curing may be lowered, or the drawing property may be lowered.
- the more preferable lower limit of the content of the light shielding agent is 10 parts by weight, the more preferable upper limit is 70 parts by weight, the still more preferable lower limit is 30 parts by weight, and the still more preferable upper limit is 60 parts by weight.
- the sealing agent for the liquid crystal dropping method of the present invention further includes a reactive diluent for adjusting the viscosity, a thixotropic agent for adjusting thixotropy, a spacer such as a polymer bead for adjusting the panel gap, an eraser, if necessary.
- a reactive diluent for adjusting the viscosity
- a thixotropic agent for adjusting thixotropy
- a spacer such as a polymer bead for adjusting the panel gap
- an eraser if necessary.
- You may contain other well-known additives, such as a foaming agent, a leveling agent, and a polymerization inhibitor.
- the sealing agent for liquid crystal dropping method of the present invention for example, a curable resin, a thermal radical polymerization initiator, a silane coupling agent added as necessary, a homodisper, a homomixer, Examples include a method of mixing using a mixer such as a universal mixer, a planetary mixer, a kneader, or a three roll.
- the sealing agent for liquid crystal dropping method of the present invention has a preferred lower limit of 100 Pa ⁇ s and a preferred upper limit of 800 Pa ⁇ s, measured using an E-type viscometer at 25 ° C. and 1 rpm. When the viscosity is within this range, the obtained sealing agent for liquid crystal dropping method has excellent coating properties.
- the more preferable lower limit of the viscosity is 150 Pa ⁇ s, and the more preferable upper limit is 500 Pa ⁇ s.
- a vertical conduction material can be produced by blending conductive fine particles with the sealant for the liquid crystal dropping method of the present invention. If such a vertical conduction material is used, the electrodes can be reliably conductively connected.
- the vertical conduction material containing the sealing agent for liquid crystal dropping method of the present invention and conductive fine particles is also one aspect of the present invention.
- electroconductive fine particles what formed the conductive metal layer on the surface of a metal ball
- the one in which the conductive metal layer is formed on the surface of the resin fine particles is preferable because the conductive connection is possible without damaging the transparent substrate due to the excellent elasticity of the resin fine particles.
- the liquid crystal display element using the sealing agent for liquid crystal dropping method of the present invention or the vertical conduction material of the present invention is also one aspect of the present invention.
- the liquid crystal dropping method sealing agent of the present invention is applied to one of two substrates having an ITO thin film by screen printing, dispenser application, etc.
- the step of forming the seal pattern, the step of applying and dropping the liquid crystal micro droplets on the entire surface of the frame of the seal pattern, the step of superposing the other substrate under vacuum, and heating to cure the liquid crystal dropping method sealing agent of the present invention examples thereof include a method having a step.
- the cure rate is quick, can suppress liquid-crystal contamination, and can provide the sealing compound for liquid crystal dropping methods excellent in applicability
- the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal dropping methods can be provided.
- trifunctional epoxy acrylate A As a trifunctional epoxy compound, 1000 parts by weight of trimethylolpropane triglycidyl ether (manufactured by Kyoeisha Chemical Co., “Epolite 100MF”), 2 parts by weight of p-methoxyphenol as a polymerization inhibitor, 2 parts by weight of triethylamine as a reaction catalyst, and 700 parts by weight of acrylic acid was reacted by stirring at 90 ° C. for 5 hours while feeding air.
- tetrafunctional epoxy acrylate A As a tetrafunctional epoxy compound, 1000 parts by weight of pentaerythritol polyoxyethylene ether (Nippon Emulsifier Co., Ltd., “PNT-40”), 2 parts by weight of p-methoxyphenol as a polymerization inhibitor, 2 parts by weight of triethylamine as a reaction catalyst, and Then, 500 parts by weight of acrylic acid was reacted by stirring at 90 ° C. for 5 hours while feeding air.
- pentaerythritol polyoxyethylene ether Nippon Emulsifier Co., Ltd., “PNT-40”
- p-methoxyphenol as a polymerization inhibitor
- triethylamine As a reaction catalyst, and Then, 500 parts by weight of acrylic acid was reacted by stirring at 90 ° C. for 5 hours while feeding air.
- R 1 is a group represented by the above formula (2) (R 3 is hydrogen, k is 1), R 2 is all hydrogen, and l, m, and n are All obtained tetrafunctional epoxy acrylate A which was 1.
- Example 1 As a curable resin, 2 parts by weight of trifunctional epoxy acrylate A, 73 parts by weight of bisphenol A type epoxy acrylate ("EBECRYL3700" manufactured by Daicel Ornex Co., Ltd.), which is a bifunctional epoxy acrylate, and partially methacryl-modified bisphenol A type epoxy resin 25 Parts by weight, 2 parts by weight of 2,2-dimethoxy-2-phenylacetophenone (manufactured by BASF, “IRGACURE 651”) as a photoradical polymerization initiator, and an azo compound (manufactured by Wako Pure Chemical Industries, Ltd.) as a thermal radical polymerization initiator , "V-30”), 3 parts by weight of malonic acid dihydrazide (manufactured by Nihon Finechem, "MDH”) as a thermosetting agent, and silica (manufactured by Admatechs, "Admafine SO-C2”) as a filler.
- Examples 2 to 12, Comparative Examples 1 and 2 The sealants for liquid crystal dropping method of Examples 2 to 12 and Comparative Examples 1 and 2 were prepared in the same manner as in Example 1 except that the materials having the blending ratios shown in Tables 1 and 2 were used.
- Viscosity For each liquid crystal dropping method sealing agent obtained in the Examples and Comparative Examples, the viscosity at 25 ° C. and 1 rpm was measured using an E-type viscometer (manufactured by Brookfield, “DV-III”). It was measured.
- the obtained cell was irradiated with 3000 mJ / cm 2 ultraviolet rays with a metal halide lamp, and then heated at 120 ° C. for 60 minutes to thermally cure the sealing agent to produce a liquid crystal display element.
- the liquid crystal leakage rate was measured. “ ⁇ ” when the liquid crystal leakage rate is 0%, “ ⁇ ” when the liquid crystal leakage rate exceeds 0% and 5% or less, and “ ⁇ ” when it exceeds 5% and 10% or less. The case of exceeding 10% was evaluated as “x”, and the curability of the sealant was evaluated.
- the sealing compound for liquid crystal dropping methods obtained in Example 11 and Example 12 only the heating for 60 minutes was performed at 120 degreeC, without performing ultraviolet irradiation with a metal halide lamp.
- Adhesiveness 1% by weight of a silica spacer (Sekisui Chemical Co., Ltd., “SI-H055”) was added to each of the liquid crystal dropping method sealants obtained in the Examples and Comparative Examples, and two ITO films After irradiating 3000 mJ / cm 2 of ultraviolet rays with a metal halide lamp onto a glass sample with a glass plate (30 ⁇ 40 mm), which was finely dropped onto one and the other glass sample was bonded in a cross shape.
- the adhesive test piece was obtained by heating at 120 ° C. for 60 minutes.
- a test (5 mm / sec) was performed by placing an iron bar above and below the adhesion test piece.
- the value obtained by dividing the obtained measured value (kgf) by the seal coating diameter (cm) is 3.0 kgf / cm 2 or more “ ⁇ ”, 2.5 kgf / cm 2 or more and less than 3.0 kgf / cm 2 the case had been a " ⁇ ", " ⁇ " the case was less than 2.0kgf / cm 2 or more 2.5kgf / cm 2, the case was less than 0kgf / cm 2 or more 2.0kgf / cm 2 "
- the adhesiveness was evaluated as “ ⁇ ”.
- about the sealing compound for liquid crystal dropping methods obtained in Example 11 and Example 12 only the heating for 60 minutes was performed at 120 degreeC, without performing ultraviolet irradiation with a metal halide lamp.
- the moisture permeability was measured by putting it in a high-temperature and high-humidity oven.
- the sealing compound for liquid crystal dropping methods obtained in Example 11 and Example 12 only the heating for 60 minutes was performed at 120 degreeC, without performing ultraviolet irradiation with a metal halide lamp.
- the obtained liquid crystal display element was stored for 36 hours in an environment of a temperature of 80 ° C. and a humidity of 90% RH, and then driven with a voltage of AC 3.5 V, and the periphery of the halftone sealant was visually observed.
- " ⁇ ” when there is no color unevenness around the sealant part " ⁇ ” when there is slight color unevenness, " ⁇ ” when there is little color unevenness, and when there is considerable color unevenness.
- Liquid crystal contamination was evaluated as “ ⁇ ”.
- the liquid crystal display elements with the evaluations “ ⁇ ” and “O” are at a level where there is no problem in practical use, and “ ⁇ ” is a level that may cause a problem depending on the display design of the liquid crystal display element.
- "X” is a level that cannot be practically used.
- the cure rate is quick, can suppress liquid-crystal contamination, and can provide the sealing compound for liquid crystal dropping methods excellent in applicability
- the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal dropping methods can be provided.
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Abstract
Description
しかしながら、滴下工法で狭額縁設計の液晶表示素子を製造すると、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光硬化性樹脂の部分が生じ、仮硬化工程後に未硬化の光硬化性樹脂が溶出してしまい、液晶が汚染されるという問題があった。
そこで、シール剤を熱のみによって硬化させるために、熱硬化性樹脂と熱硬化剤とを含有するシール剤を用いることが検討されてきたが、このようなシール剤は硬化に時間がかかるため、硬化途中のシール剤が液晶に溶出して液晶が汚染されたり、液晶がシール剤へ差し込んだりすることがあるという問題があった。 By the way, in the present age when mobile devices with various liquid crystal panels such as mobile phones and portable game machines are widespread, downsizing of devices is the most demanded issue. As a technique for miniaturization, there is a narrow frame of the liquid crystal display unit, and for example, the position of the seal portion is arranged under the black matrix (hereinafter also referred to as a narrow frame design).
However, when a liquid crystal display element with a narrow frame design is manufactured by the dropping method, there is a portion where the light does not shine on the seal part due to the black matrix. There is a problem that the uncured photocurable resin is eluted after the temporary curing step and the liquid crystal is contaminated.
Therefore, in order to cure the sealing agent only by heat, it has been studied to use a sealing agent containing a thermosetting resin and a thermosetting agent, but since such a sealing agent takes time to cure, There is a problem that the sealing agent in the middle of curing is eluted into the liquid crystal and the liquid crystal is contaminated, or the liquid crystal may be inserted into the sealing agent.
以下に本発明を詳述する。 The present invention is a sealing agent for a liquid crystal dropping method containing a curable resin and a thermal radical polymerization initiator, wherein the curable resin has three or more (meth) acryloyloxy groups in one molecule. It is the sealing agent for liquid crystal dropping methods containing the above epoxy (meth) acrylate.
The present invention is described in detail below.
上記硬化性樹脂は、(メタ)アクリロイルオキシ基を1分子中に3個以上有する3官能以上のエポキシ(メタ)アクリレートを含有する。
上記3官能以上のエポキシ(メタ)アクリレートを熱ラジカル重合開始剤と組み合わせて用いることにより、本発明の液晶滴下工法用シール剤は、硬化速度が速く、液晶汚染を抑制することができ、塗布性及び接着性に優れるものとなる。
なお、本明細書において、上記「(メタ)アクリロイルオキシ」は、アクリロイルオキシ又はメタクリロイルオキシを意味し、上記「(メタ)アクリレート」は、アクリレート又はメタクリレートを意味し、上記「エポキシ(メタ)アクリレート」は、エポキシ樹脂中の全てのエポキシ基を(メタ)アクリル酸と反応させた化合物のことを意味し、上記「(メタ)アクリル」は、アクリル又はメタクリルを意味する。 The sealing agent for liquid crystal dropping method of the present invention contains a curable resin.
The curable resin contains a tri- or higher functional epoxy (meth) acrylate having three or more (meth) acryloyloxy groups in one molecule.
By using the above-mentioned tri- or higher functional epoxy (meth) acrylate in combination with a thermal radical polymerization initiator, the sealing agent for liquid crystal dropping method of the present invention has a high curing rate, can suppress liquid crystal contamination, and can be applied. And it becomes excellent in adhesiveness.
In the present specification, “(meth) acryloyloxy” means acryloyloxy or methacryloyloxy, “(meth) acrylate” means acrylate or methacrylate, and “epoxy (meth) acrylate”. Means a compound obtained by reacting all epoxy groups in the epoxy resin with (meth) acrylic acid, and the above “(meth) acryl” means acryl or methacryl.
なお、本発明の液晶滴下工法用シール剤が、上記3官能以上のエポキシ(メタ)アクリレートとして2種以上の化合物を含有する場合、上記3官能以上のエポキシ(メタ)アクリレートの誘電率は、上記3官能以上のエポキシ(メタ)アクリレートとして含有されるそれぞれの化合物の誘電率と上記3官能以上のエポキシ(メタ)アクリレート中における重量分率とから算出できる。
上記「誘電率」は、インピーダンスアナライザー(例えば、ソーラトロン社製、「1260型」等)を用いて25℃、1MHzの条件で複素比誘電率を測定することにより測定でき、実数部で定義される。 A preferable lower limit of the dielectric constant of the tri- or higher functional epoxy (meth) acrylate is 3. When the dielectric constant is 3 or more, it is difficult to elute into the liquid crystal. A more preferable lower limit of the dielectric constant is 4. The dielectric constant is preferably as high as possible, but the practical upper limit is 20.
In addition, when the sealing compound for liquid crystal dropping method of the present invention contains two or more compounds as the above-described trifunctional or higher functional epoxy (meth) acrylate, the dielectric constant of the above trifunctional or higher functional epoxy (meth) acrylate is as described above. It can be calculated from the dielectric constant of each compound contained as a tri- or higher functional epoxy (meth) acrylate and the weight fraction in the tri- or higher functional epoxy (meth) acrylate.
The above-mentioned “dielectric constant” can be measured by measuring the complex dielectric constant under the conditions of 25 ° C. and 1 MHz using an impedance analyzer (for example, “1260 type” manufactured by Solartron), and is defined by the real part. .
また、上記3官能以上のエポキシ(メタ)アクリレートの有する反応性官能基は、液晶汚染を抑制する観点から、(メタ)アクリロイルオキシ基のみであることが好ましい。
なお、上記「反応性官能基」とは、硬化反応に寄与する重合性の官能基を意味する。 The tri- or higher functional epoxy (meth) acrylate has a structure in which three or more molecular chains each having one (meth) acryloyloxy group are branched from one carbon atom from the viewpoint of the thermosetting reaction rate. Is preferred.
Moreover, it is preferable that the reactive functional group which the said epoxy (meth) acrylate more than trifunctional has is only a (meth) acryloyloxy group from a viewpoint of suppressing liquid-crystal contamination.
The “reactive functional group” means a polymerizable functional group that contributes to the curing reaction.
上記その他の硬化性樹脂としては、例えば、3官能以上のエポキシ(メタ)アクリレート以外のその他の(メタ)アクリル化合物や、エポキシ化合物等が挙げられる。
なお、本明細書において、上記「(メタ)アクリル化合物」は、(メタ)アクリロイルオキシ基を有する化合物を意味する。 The curable resin may contain other curable resins in addition to the tri- or higher functional epoxy (meth) acrylate as long as the object of the present invention is not impaired.
Examples of the other curable resin include other (meth) acryl compounds other than trifunctional or higher functional epoxy (meth) acrylates, and epoxy compounds.
In the present specification, the “(meth) acrylic compound” means a compound having a (meth) acryloyloxy group.
上記熱ラジカル重合開始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は、加熱により速やかに硬化できるものとなる。 The sealing agent for liquid crystal dropping method of the present invention contains a thermal radical polymerization initiator.
By containing the said thermal radical polymerization initiator, the sealing compound for liquid crystal dropping methods of this invention can be rapidly hardened | cured by heating.
なお、本明細書において高分子アゾ開始剤とは、アゾ基を有し、熱によって(メタ)アクリロイルオキシ基を硬化させることができるラジカルを生成する、数平均分子量が300以上の化合物を意味する。 Examples of the thermal radical polymerization initiator include organic peroxides and azo compounds. Among these, a polymer azo initiator composed of a polymer azo compound is preferable.
In the present specification, the polymer azo initiator means a compound having an azo group and generating a radical capable of curing a (meth) acryloyloxy group by heat and having a number average molecular weight of 300 or more. .
なお、本明細書において、上記数平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)で測定を行い、ポリスチレン換算により求められる値である。GPCによってポリスチレン換算による数平均分子量を測定する際のカラムとしては、例えば、Shodex LF-804(昭和電工社製)等が挙げられる。 The preferable lower limit of the number average molecular weight of the polymeric azo initiator is 1000, and the preferable upper limit is 300,000. When the number average molecular weight of the polymer azo initiator is less than 1000, the polymer azo initiator may adversely affect the liquid crystal. When the number average molecular weight of the polymeric azo initiator exceeds 300,000, mixing with the curable resin may be difficult. The more preferable lower limit of the number average molecular weight of the polymeric azo initiator is 5000, the more preferable upper limit is 100,000, the still more preferable lower limit is 10,000, and the still more preferable upper limit is 90,000.
In addition, in this specification, the said number average molecular weight is a value calculated | required by polystyrene conversion by measuring with gel permeation chromatography (GPC). Examples of the column for measuring the number average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko KK).
上記アゾ基を介してポリアルキレンオキサイド等のユニットが複数結合した構造を有する高分子アゾ開始剤としては、ポリエチレンオキサイド構造を有するものが好ましい。このような高分子アゾ開始剤としては、例えば、4,4’-アゾビス(4-シアノペンタン酸)とポリアルキレングリコールの重縮合物や、4,4’-アゾビス(4-シアノペンタン酸)と末端アミノ基を有するポリジメチルシロキサンの重縮合物等が挙げられる。 Examples of the polymer azo initiator include those having a structure in which a plurality of units such as polyalkylene oxide and polydimethylsiloxane are bonded via an azo group.
As the polymer azo initiator having a structure in which a plurality of units such as polyalkylene oxide are bonded via the azo group, those having a polyethylene oxide structure are preferable. Examples of such a polymer azo initiator include polycondensates of 4,4′-azobis (4-cyanopentanoic acid) and polyalkylene glycol, and 4,4′-azobis (4-cyanopentanoic acid) Examples include polycondensates of polydimethylsiloxane having a terminal amino group.
上記光ラジカル重合開始剤としては、例えば、ベンゾフェノン系化合物、アセトフェノン系化合物、アシルフォスフィンオキサイド系化合物、チタノセン系化合物、オキシムエステル系化合物、ベンゾインエーテル系化合物、チオキサントン系化合物等が挙げられる。 The sealing agent for a liquid crystal dropping method of the present invention preferably contains a photo radical polymerization initiator in addition to the thermal radical polymerization initiator from the viewpoint of suppressing liquid crystal contamination.
Examples of the photo radical polymerization initiator include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, thioxanthone compounds, and the like.
上記熱硬化剤としては、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。 The sealing agent for liquid crystal dropping method of the present invention may contain a thermosetting agent.
Examples of the thermosetting agent include organic acid hydrazides, imidazole derivatives, amine compounds, polyhydric phenol compounds, acid anhydrides, and the like. Among these, solid organic acid hydrazide is preferably used.
上記充填剤としては、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、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、セリサイト、活性白土、窒化アルミニウム等の無機充填剤や、ポリエステル微粒子、ポリウレタン微粒子、ビニル重合体微粒子、アクリル重合体微粒子等の有機充填剤が挙げられる。 The sealing agent for liquid crystal dropping method of the present invention may further contain a filler for the purpose of improving the adhesiveness by the stress dispersion effect and improving the linear expansion coefficient.
Examples of the filler include talc, asbestos, silica, diatomaceous earth, smectite, bentonite, calcium carbonate, magnesium carbonate, alumina, montmorillonite, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, magnesium hydroxide, water Inorganic fillers such as aluminum oxide, glass beads, silicon nitride, barium sulfate, gypsum, calcium silicate, sericite, activated clay, aluminum nitride, and organic materials such as polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, and acrylic polymer fine particles A filler is mentioned.
上記シランカップリング剤としては、例えば、3-アミノプロピルトリメトキシシラン、3-メルカプトプロピルトリメトキシシラン、3-グリシドキシプロピルトリメトキシシラン、3-イソシアネートプロピルトリメトキシシラン等が好適に用いられる。これら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 sealing agent for liquid crystal dropping method of the present invention may contain a silane coupling agent.
As the silane coupling agent, for example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane and the like are preferably used. These may be used independently and 2 or more types may be used together.
上記チタンブラックは、1μmあたりの光学濃度(OD値)が、3以上であることが好ましく、4以上であることがより好ましい。上記チタンブラックの遮光性は高ければ高いほどよく、上記チタンブラックのOD値に好ましい上限は特にないが、通常は5以下となる。 Titanium black is a substance having a higher transmittance in the vicinity of the ultraviolet region, particularly for light having a wavelength of 370 to 450 nm, compared to the average transmittance for light having a wavelength of 300 to 800 nm. That is, the above-described titanium black sufficiently shields light having a wavelength in the visible light region, thereby providing light shielding properties to the sealing agent for liquid crystal dropping method of the present invention, while transmitting light having a wavelength in the vicinity of the ultraviolet region. A shading agent. Therefore, by using the photo radical polymerization initiator or the photo cationic polymerization initiator that can start the reaction with light having a wavelength (370 to 450 nm) at which the transmittance of the titanium black is high, the liquid crystal of the present invention is used. The photocurability of the sealing agent for the dripping method can be further increased. On the other hand, the light shielding agent contained in the liquid crystal dropping method sealing agent of the present invention is preferably a highly insulating material, and titanium black is also suitable as the highly insulating light shielding agent.
The titanium black preferably has an optical density (OD value) per μm of 3 or more, more preferably 4 or more. The higher the light-shielding property of the titanium black, the better. The OD value of the titanium black is not particularly limited, but is usually 5 or less.
また、遮光剤として上記チタンブラックを含有する本発明の液晶滴下工法用シール剤を用いて製造した液晶表示素子は、充分な遮光性を有するため、光の漏れ出しがなく高いコントラストを有し、優れた画像表示品質を有する液晶表示素子を実現することができる。 The above-mentioned titanium black exhibits a sufficient effect even if it is not surface-treated, but the surface is treated with an organic component such as a coupling agent, silicon oxide, titanium oxide, germanium oxide, aluminum oxide, oxidized Surface-treated titanium black such as those coated with an inorganic component such as zirconium or magnesium oxide can also be used. Especially, what is processed with the organic component is preferable at the point which can improve insulation more.
In addition, the liquid crystal display device manufactured using the sealing agent for liquid crystal dropping method of the present invention containing the above-described titanium black as a light-shielding agent has a sufficient light-shielding property, and thus has a high contrast without light leakage. A liquid crystal display element having excellent image display quality can be realized.
また、上記チタンブラックの体積抵抗の好ましい下限は0.5Ω・cm、好ましい上限は3Ω・cmであり、より好ましい下限は1Ω・cm、より好ましい上限は2.5Ω・cmである。 The preferable lower limit of the specific surface area of the titanium black is 13 m 2 / g, the preferable upper limit is 30 m 2 / g, the more preferable lower limit is 15 m 2 / g, and the more preferable upper limit is 25 m 2 / g.
Further, the preferred lower limit of the volume resistance of the titanium black is 0.5 Ω · cm, the preferred upper limit is 3 Ω · cm, the more preferred lower limit is 1 Ω · cm, and the more preferred upper limit is 2.5 Ω · cm.
本発明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上下導通材料もまた、本発明の1つである。 A vertical conduction material can be produced by blending conductive fine particles with the sealant for the liquid crystal dropping method of the present invention. If such a vertical conduction material is used, the electrodes can be reliably conductively connected.
The vertical conduction material containing the sealing agent for liquid crystal dropping method of the present invention and conductive fine particles is also one aspect of the present invention.
本発明の液晶表示素子を製造する方法としては、例えば、ITO薄膜等を有する2枚の基板の一方に、本発明の液晶滴下工法用シール剤をスクリーン印刷、ディスペンサー塗布等により塗布し、長方形状のシールパターンを形成する工程、液晶の微小滴をシールパターンの枠内全面に滴下塗布し、真空下で他方の基板を重ね合わせる工程、加熱して本発明の液晶滴下工法用シール剤を硬化させる工程を有する方法等が挙げられる。また、加熱して本発明の液晶滴下工法用シール剤を硬化させる工程の前に、紫外線等の光を照射して本発明の液晶滴下工法用シール剤を仮硬化させる工程を行ってもよい。 The liquid crystal display element using the sealing agent for liquid crystal dropping method of the present invention or the vertical conduction material of the present invention is also one aspect of the present invention.
As a method for producing the liquid crystal display element of the present invention, for example, the liquid crystal dropping method sealing agent of the present invention is applied to one of two substrates having an ITO thin film by screen printing, dispenser application, etc. The step of forming the seal pattern, the step of applying and dropping the liquid crystal micro droplets on the entire surface of the frame of the seal pattern, the step of superposing the other substrate under vacuum, and heating to cure the liquid crystal dropping method sealing agent of the present invention Examples thereof include a method having a step. Moreover, you may perform the process of irradiating light, such as an ultraviolet-ray, and temporarily hardening the sealing agent for liquid crystal dropping methods of this invention before the process of heating and hardening the sealing agent for liquid crystal dropping methods of this invention.
3官能のエポキシ化合物として、トリメチロールプロパントリグリシジルエーテル(共栄社化学社製、「エポライト100MF」)1000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、及び、アクリル酸700重量部を、空気を送り込みながら90℃で5時間還流撹拌して反応させた。得られた反応物100重量部を、反応物中のイオン性不純物を吸着させる為にクオルツとカオリンの天然結合物(ホフマンミネラル社製、「シリチンV85」)10重量部が充填されたカラムで濾過し、上記式(1)におけるR1がエチル基であり、R2が全て水素であり、l、m、及び、nがいずれも1である3官能エポキシアクリレートAを得た。 (Production of trifunctional epoxy acrylate A)
As a trifunctional epoxy compound, 1000 parts by weight of trimethylolpropane triglycidyl ether (manufactured by Kyoeisha Chemical Co., “Epolite 100MF”), 2 parts by weight of p-methoxyphenol as a polymerization inhibitor, 2 parts by weight of triethylamine as a reaction catalyst, and 700 parts by weight of acrylic acid was reacted by stirring at 90 ° C. for 5 hours while feeding air. 100 parts by weight of the obtained reaction product was filtered through a column packed with 10 parts by weight of a natural combination of quartz and kaolin (manufactured by Hoffman Mineral, “Siritin V85”) to adsorb ionic impurities in the reaction product. Then, trifunctional epoxy acrylate A in which R 1 in the above formula (1) was an ethyl group, R 2 was all hydrogen, and l, m, and n were all 1 was obtained.
4官能のエポキシ化合物として、ペンタエリスリトールポリオキシエチレンエーテル(日本乳化剤社製、「PNT-40」)1000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、及び、アクリル酸500重量部を、空気を送り込みながら90℃で5時間還流撹拌して反応させた。得られた反応物100重量部を、反応物中のイオン性不純物を吸着させる為にクオルツとカオリンの天然結合物(ホフマンミネラル社製、「シリチンV85」)10重量部が充填されたカラムで濾過し、上記式(1)におけるR1が上記式(2)で表される基(R3が水素、kが1)であり、R2が全て水素であり、l、m、及び、nがいずれも1である4官能エポキシアクリレートAを得た。 (Production of tetrafunctional epoxy acrylate A)
As a tetrafunctional epoxy compound, 1000 parts by weight of pentaerythritol polyoxyethylene ether (Nippon Emulsifier Co., Ltd., “PNT-40”), 2 parts by weight of p-methoxyphenol as a polymerization inhibitor, 2 parts by weight of triethylamine as a reaction catalyst, and Then, 500 parts by weight of acrylic acid was reacted by stirring at 90 ° C. for 5 hours while feeding air. 100 parts by weight of the obtained reaction product was filtered through a column packed with 10 parts by weight of a natural combination of quartz and kaolin (manufactured by Hoffman Mineral, “Siritin V85”) to adsorb ionic impurities in the reaction product. In the above formula (1), R 1 is a group represented by the above formula (2) (R 3 is hydrogen, k is 1), R 2 is all hydrogen, and l, m, and n are All obtained tetrafunctional epoxy acrylate A which was 1.
ビスフェノールA型エポキシ樹脂(三菱化学社製、「jER828EL」)1000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、及び、メタクリル酸253重量部を、空気を送り込みながら90℃で5時間還流攪拌して反応させた。得られた樹脂100重量部を、反応物中のイオン性不純物を吸着させる為にクオルツとカオリンの天然結合物(ホフマンミネラル社製、「シリチンV85」)10重量部が充填されたカラムで濾過し、50%部分メタクリル変性ビスフェノールA型エポキシ樹脂を得た。 (Synthesis of partially methacryl-modified bisphenol A type epoxy resin)
1000 parts by weight of a bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, “jER828EL”), 2 parts by weight of p-methoxyphenol as a polymerization inhibitor, 2 parts by weight of triethylamine as a reaction catalyst, and 253 parts by weight of methacrylic acid, While feeding, the mixture was reacted with stirring at 90 ° C. for 5 hours. In order to adsorb ionic impurities in the reaction product, 100 parts by weight of the obtained resin was filtered through a column packed with 10 parts by weight of a natural combination of quartz and kaolin (manufactured by Hoffman Mineral Co., Ltd., “Siritin V85”). A 50% partially methacryl-modified bisphenol A type epoxy resin was obtained.
硬化性樹脂として、3官能エポキシアクリレートA2重量部、2官能エポキシアクリレートであるビスフェノールA型エポキシアクリレート(ダイセル・オルネクス社製、「EBECRYL3700」)73重量部、及び、部分メタクリル変性ビスフェノールA型エポキシ樹脂25重量部と、光ラジカル重合開始剤として2,2-ジメトキシ-2-フェニルアセトフェノン(BASF社製、「IRGACURE 651」)2重量部と、熱ラジカル重合開始剤としてアゾ化合物(和光純薬工業社製、「V-30」)3重量部と、熱硬化剤としてマロン酸ジヒドラジド(日本ファインケム社製、「MDH」)4重量部と、充填剤としてシリカ(アドマテックス社製、「アドマファインSO-C2」)30重量部と、シランカップリング剤として3-グリシドキシプロピルトリメトキシシラン(チッソ社製、「S510」)2重量部とを、遊星式撹拌機(シンキー社製、「あわとり練太郎」)を用いて混合した後、更に3本ロールを用いて混合することにより実施例1の液晶滴下工法用シール剤を調製した。 Example 1
As a curable resin, 2 parts by weight of trifunctional epoxy acrylate A, 73 parts by weight of bisphenol A type epoxy acrylate ("EBECRYL3700" manufactured by Daicel Ornex Co., Ltd.), which is a bifunctional epoxy acrylate, and partially methacryl-modified bisphenol A type epoxy resin 25 Parts by weight, 2 parts by weight of 2,2-dimethoxy-2-phenylacetophenone (manufactured by BASF, “IRGACURE 651”) as a photoradical polymerization initiator, and an azo compound (manufactured by Wako Pure Chemical Industries, Ltd.) as a thermal radical polymerization initiator , "V-30"), 3 parts by weight of malonic acid dihydrazide (manufactured by Nihon Finechem, "MDH") as a thermosetting agent, and silica (manufactured by Admatechs, "Admafine SO-C2") as a filler. ]) 30 parts by weight and 3 as silane coupling agent -After mixing 2 parts by weight of glycidoxypropyltrimethoxysilane (manufactured by Chisso, "S510") using a planetary stirrer (manufactured by Shinky, "Netaro Awatori"), three more rolls The liquid crystal dropping method sealant of Example 1 was prepared by mixing using
表1、2に記載された配合比の各材料を用いたこと以外は実施例1と同様にして、実施例2~12、比較例1、2の液晶滴下工法用シール剤を調製した。 (Examples 2 to 12, Comparative Examples 1 and 2)
The sealants for liquid crystal dropping method of Examples 2 to 12 and Comparative Examples 1 and 2 were prepared in the same manner as in Example 1 except that the materials having the blending ratios shown in Tables 1 and 2 were used.
実施例及び比較例で得られた各液晶滴下工法用シール剤について以下の評価を行った。結果を表1、2に示した。 <Evaluation>
The following evaluation was performed about each sealing compound for liquid crystal dropping methods obtained by the Example and the comparative example. The results are shown in Tables 1 and 2.
実施例及び比較例で得られた各液晶滴下工法用シール剤について、E型粘度計(ブルックフィールド社製、「DV-III」)を用いて25℃、1rpmの条件における粘度を測定した。 (1) Viscosity For each liquid crystal dropping method sealing agent obtained in the Examples and Comparative Examples, the viscosity at 25 ° C. and 1 rpm was measured using an E-type viscometer (manufactured by Brookfield, “DV-III”). It was measured.
実施例及び比較例で得られた各液晶滴下工法用シール剤をディスペンス用のシリンジ(武蔵エンジニアリング社製、「PSY-10E」)に充填し、脱泡処理を行った。次いで、ディスペンサー(武蔵エンジニアリング社製、「SHOTMASTER300」)を用いて、2枚のITO薄膜付きの透明電極基板のうちの一方に長方形の枠を描く様にシール剤を塗布した。続いて、TN液晶(チッソ社製、「JC-5001LA」)の微小滴を液晶滴下装置にて滴下塗布し、他方の透明基板を、真空貼り合わせ装置にて5Paの減圧下にて貼り合わせ、セルを得た。得られたセルにメタルハライドランプにて3000mJ/cm2の紫外線を照射した後、120℃で60分加熱することによってシール剤を熱硬化させて液晶表示素子を作製し、得られた液晶表示素子の液晶漏れ率を測定した。
液晶漏れ率が0%であった場合を「◎」、液晶漏れ率が0%を超え5%以下であった場合を「○」、5%を超え10%以下であった場合を「△」、10%を超えた場合を「×」としてシール剤の硬化性を評価した。
なお、実施例11及び実施例12で得られた液晶滴下工法用シール剤については、メタルハライドランプによる紫外線の照射を行わずに120℃で60分加熱のみを行った。 (2) Curability Each of the liquid crystal dropping method sealing agents obtained in Examples and Comparative Examples was filled in a dispensing syringe (“PSY-10E” manufactured by Musashi Engineering Co., Ltd.), and defoamed. Next, using a dispenser (“SHOTMASTER 300” manufactured by Musashi Engineering Co., Ltd.), a sealing agent was applied so as to draw a rectangular frame on one of the two transparent electrode substrates with an ITO thin film. Subsequently, fine droplets of TN liquid crystal (manufactured by Chisso Corporation, “JC-5001LA”) were applied dropwise with a liquid crystal dropping device, and the other transparent substrate was bonded under a reduced pressure of 5 Pa with a vacuum bonding device. I got a cell. The obtained cell was irradiated with 3000 mJ / cm 2 ultraviolet rays with a metal halide lamp, and then heated at 120 ° C. for 60 minutes to thermally cure the sealing agent to produce a liquid crystal display element. The liquid crystal leakage rate was measured.
“◎” when the liquid crystal leakage rate is 0%, “◯” when the liquid crystal leakage rate exceeds 0% and 5% or less, and “△” when it exceeds 5% and 10% or less. The case of exceeding 10% was evaluated as “x”, and the curability of the sealant was evaluated.
In addition, about the sealing compound for liquid crystal dropping methods obtained in Example 11 and Example 12, only the heating for 60 minutes was performed at 120 degreeC, without performing ultraviolet irradiation with a metal halide lamp.
実施例及び比較例で得られた各液晶滴下工法用シール剤に、シリカスペーサー(積水化学工業社製、「SI-H055」)を1重量%配合し、2枚のITO膜付きアルカリガラス試験片(30×40mm)のうち一方に微小滴下し、これにもう一方のガラス試験片を十字状に貼り合わせたものに、メタルハライドランプにて3000mJ/cm2の紫外線を照射した後、120℃で60分加熱することによって接着試験片を得た。接着試験片の上下に鉄棒を配して押す試験(5mm/sec)を行った。得られた測定値(kgf)をシール塗布直径(cm)で除した値が3.0kgf/cm2以上であった場合を「◎」、2.5kgf/cm2以上3.0kgf/cm2未満であった場合を「○」、2.0kgf/cm2以上2.5kgf/cm2未満であった場合を「△」、0kgf/cm2以上2.0kgf/cm2未満であった場合を「×」として接着性を評価した。
なお、実施例11及び実施例12で得られた液晶滴下工法用シール剤については、メタルハライドランプによる紫外線の照射を行わずに120℃で60分加熱のみを行った。 (3) Adhesiveness 1% by weight of a silica spacer (Sekisui Chemical Co., Ltd., “SI-H055”) was added to each of the liquid crystal dropping method sealants obtained in the Examples and Comparative Examples, and two ITO films After irradiating 3000 mJ / cm 2 of ultraviolet rays with a metal halide lamp onto a glass sample with a glass plate (30 × 40 mm), which was finely dropped onto one and the other glass sample was bonded in a cross shape. The adhesive test piece was obtained by heating at 120 ° C. for 60 minutes. A test (5 mm / sec) was performed by placing an iron bar above and below the adhesion test piece. The value obtained by dividing the obtained measured value (kgf) by the seal coating diameter (cm) is 3.0 kgf / cm 2 or more “「 ”, 2.5 kgf / cm 2 or more and less than 3.0 kgf / cm 2 the case had been a "○", "△" the case was less than 2.0kgf / cm 2 or more 2.5kgf / cm 2, the case was less than 0kgf / cm 2 or more 2.0kgf / cm 2 " The adhesiveness was evaluated as “×”.
In addition, about the sealing compound for liquid crystal dropping methods obtained in Example 11 and Example 12, only the heating for 60 minutes was performed at 120 degreeC, without performing ultraviolet irradiation with a metal halide lamp.
実施例及び比較例で得られた各液晶滴下工法用シール剤を、平滑な離型フィルム状にコーターで厚さ200~300μmに塗行した。次いで、メタルハライドランプにて3000mJ/cm2の紫外線を照射した後、120℃で60分加熱することによって透湿度測定用硬化フィルムを得た。JIS Z 0208の防湿包装材料の透湿度試験方法(カップ法)に準じた方法で透湿度試験用カップを作製し、得られた透湿度測定用硬化フィルムを取り付け、温度80℃湿度90%RHの高温高湿オーブンに投入して透湿度を測定した。得られた透湿度の値が70g/m2・24hr以下であった場合を「◎」、60g/m2・24hrを超え、90g/m2・24hr以下であった場合を「○」、90g/m2・24hrを超え、110g/m2・24hr未満であった場合を「△」、110g/m2・24hr以上であった場合を「×」として透湿防止性を評価した。
なお、実施例11及び実施例12で得られた液晶滴下工法用シール剤については、メタルハライドランプによる紫外線の照射を行わずに120℃で60分加熱のみを行った。 (4) Moisture permeation prevention properties Each of the liquid crystal dropping method sealing agents obtained in the Examples and Comparative Examples was applied to a smooth release film in a thickness of 200 to 300 μm with a coater. Subsequently, after irradiating 3000 mJ / cm < 2 > of ultraviolet-rays with the metal halide lamp, the cured film for moisture permeability measurement was obtained by heating at 120 degreeC for 60 minutes. A moisture permeability test cup was prepared by a method according to JIS Z 0208 for moisture proof packaging materials (cup method), and the obtained cured film for moisture permeability measurement was attached, and the temperature was 80 ° C. and the humidity was 90% RH. The moisture permeability was measured by putting it in a high-temperature and high-humidity oven. The case where the value of moisture permeability obtained is 70 g / m 2 · 24 hr or less is “◎”, the case where it exceeds 60 g / m 2 · 24 hr and 90 g / m 2 · 24 hr or less is “◯”, 90 g / m exceeded 2 · 24 hr or, "△" the case was less than 110g / m 2 · 24 hr or, to evaluate the anti-moisture permeability as "×" the case was 110g / m 2 · 24 hr or more.
In addition, about the sealing compound for liquid crystal dropping methods obtained in Example 11 and Example 12, only the heating for 60 minutes was performed at 120 degreeC, without performing ultraviolet irradiation with a metal halide lamp.
実施例及び比較例で得られた各液晶滴下工法用シール剤をディスペンス用のシリンジ(武蔵エンジニアリング社製、「PSY-10E」)に充填し、脱泡処理を行った。次いで、ディスペンサー(武蔵エンジニアリング社製、「SHOTMASTER300」)を用いて、2枚のITO薄膜付きの透明電極基板のうちの一方に長方形の枠を描く様にシール剤を塗布した。続いて、TN液晶(チッソ社製、「JC-5001LA」)の微小滴を液晶滴下装置にて滴下塗布し、他方の透明基板を、真空貼り合わせ装置にて5Paの減圧下にて貼り合わせ、セルを得た。得られたセルにメタルハライドランプにて3000mJ/cm2の紫外線を照射した後、120℃で60分加熱することによってシール剤を熱硬化させ、液晶表示素子を各シール剤につき5枚ずつ作製した。
なお、実施例11及び実施例12で得られた液晶滴下工法用シール剤については、メタルハライドランプによる紫外線の照射を行わずに120℃で60分加熱のみを行った。
得られた液晶表示素子を温度80℃、湿度90%RHの環境下にて36時間保管した後、AC3.5Vの電圧駆動をさせ、中間調のシール剤周辺を目視で観察した。シール剤部周辺に色むらが全くなかった場合を「◎」、色むらが微かにあった場合を「○」、色むらが少しあった場合を「△」、色むらがかなりあった場合を「×」として液晶汚染性を評価した。
なお、評価が「◎」、「○」の液晶表示素子は、実用に全く問題のないレベルであり、「△」は液晶表示素子の表示設計によって問題になる可能性があるレベルであり、「×」は実用に耐えないレベルである。 (5) Display performance of liquid crystal display elements (evaluation of color unevenness of liquid crystal display elements driven after storage under high temperature and high humidity)
Each of the liquid crystal dropping method sealing agents obtained in Examples and Comparative Examples was filled in a dispensing syringe (“PSY-10E” manufactured by Musashi Engineering Co., Ltd.) and subjected to defoaming treatment. Next, using a dispenser (“SHOTMASTER 300” manufactured by Musashi Engineering Co., Ltd.), a sealing agent was applied so as to draw a rectangular frame on one of the two transparent electrode substrates with an ITO thin film. Subsequently, fine droplets of TN liquid crystal (manufactured by Chisso Corporation, “JC-5001LA”) were applied dropwise with a liquid crystal dropping device, and the other transparent substrate was bonded under a reduced pressure of 5 Pa with a vacuum bonding device. I got a cell. The obtained cell was irradiated with 3000 mJ / cm 2 of ultraviolet rays with a metal halide lamp and then heated at 120 ° C. for 60 minutes to thermally cure the sealing agent, thereby producing five liquid crystal display elements for each sealing agent.
In addition, about the sealing compound for liquid crystal dropping methods obtained in Example 11 and Example 12, only the heating for 60 minutes was performed at 120 degreeC, without performing ultraviolet irradiation with a metal halide lamp.
The obtained liquid crystal display element was stored for 36 hours in an environment of a temperature of 80 ° C. and a humidity of 90% RH, and then driven with a voltage of AC 3.5 V, and the periphery of the halftone sealant was visually observed. "◎" when there is no color unevenness around the sealant part, "○" when there is slight color unevenness, "△" when there is little color unevenness, and when there is considerable color unevenness. Liquid crystal contamination was evaluated as “×”.
In addition, the liquid crystal display elements with the evaluations “◎” and “O” are at a level where there is no problem in practical use, and “Δ” is a level that may cause a problem depending on the display design of the liquid crystal display element. "X" is a level that cannot be practically used.
Claims (8)
- 硬化性樹脂と熱ラジカル重合開始剤とを含有する液晶滴下工法用シール剤であって、
前記硬化性樹脂は、(メタ)アクリロイルオキシ基を1分子中に3個以上有する3官能以上のエポキシ(メタ)アクリレートを含有する
ことを特徴とする液晶滴下工法用シール剤。 A liquid crystal dropping method sealing agent containing a curable resin and a thermal radical polymerization initiator,
The said curable resin contains the trifunctional or more than trifunctional epoxy (meth) acrylate which has 3 or more (meth) acryloyloxy groups in 1 molecule, The sealing compound for liquid crystal dropping methods characterized by the above-mentioned. - 3官能以上のエポキシ(メタ)アクリレートは、芳香族環を有さない脂肪族エポキシ(メタ)アクリレートであ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。 2. The sealing agent for liquid crystal dropping method according to claim 1, wherein the trifunctional or higher functional epoxy (meth) acrylate is an aliphatic epoxy (meth) acrylate having no aromatic ring.
- 3官能以上のエポキシ(メタ)アクリレートは、それぞれ1つの(メタ)アクリロイルオキシ基を有する3以上の分子鎖が1つの炭素原子から分岐してなる構造を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。 The trifunctional or higher functional epoxy (meth) acrylate has a structure in which three or more molecular chains each having one (meth) acryloyloxy group are branched from one carbon atom. The sealing agent for liquid crystal dropping methods as described.
- 3官能以上のエポキシ(メタ)アクリレートの有する反応性官能基は、(メタ)アクリロイルオキシ基のみであ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 reactive functional group possessed by a tri- or higher functional epoxy (meth) acrylate is only a (meth) acryloyloxy group, The sealing agent for liquid crystal dropping method according to claim 1, 2 or 3.
- 3官能以上のエポキシ(メタ)アクリレートとして、3官能エポキシ(メタ)アクリレート及び/又は4官能エポキシ(メタ)アクリレート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。 5. The liquid crystal dropping method according to claim 1, comprising a trifunctional epoxy (meth) acrylate and / or a tetrafunctional epoxy (meth) acrylate as a trifunctional or higher functional epoxy (meth) acrylate. Sealing agent.
- 3官能以上のエポキシ(メタ)アクリレートとして、下記式(1)で表される化合物を含有することを特徴とする請求項1、2、3、4又は5記載の液晶滴下工法用シール剤。
- 請求項1、2、3、4、5又は6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。 A vertical conduction material comprising the sealing agent for liquid crystal dropping method according to claim 1, 2, 3, 4, 5 or 6, and conductive fine particles.
- 請求項1、2、3、4、5若しくは6記載の液晶滴下工法用シール剤又は請求項7記載の上下導通材料を用いて製造されることを特徴とする液晶表示素子。 A liquid crystal display element manufactured using the sealing agent for liquid crystal dropping method according to claim 1, 2, 3, 4, 5, or 6, or the vertical conduction material according to claim 7.
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CN201580004354.6A CN105900003B (en) | 2014-05-23 | 2015-05-19 | Sealant for liquid crystal dripping process, upper and lower conductive material and liquid crystal display element |
KR1020167011048A KR102285528B1 (en) | 2014-05-23 | 2015-05-19 | Sealant for one-drop filling process, vertically conductive material, and liquid crystal display element |
JP2015527604A JP6523167B2 (en) | 2014-05-23 | 2015-05-19 | Sealant for liquid crystal dropping method, vertical conduction material, and liquid crystal display element |
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WO2017183583A1 (en) * | 2016-04-20 | 2017-10-26 | 積水化学工業株式会社 | Sealant for liquid crystal display element, method for manufacturing sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element |
CN107636524A (en) * | 2016-01-07 | 2018-01-26 | 积水化学工业株式会社 | Sealing material for liquid crystal display device, upper and lower conductive material and liquid crystal display cells |
CN107683435A (en) * | 2016-01-07 | 2018-02-09 | 积水化学工业株式会社 | Sealing material for liquid crystal display device, upper and lower conductive material and liquid crystal display cells |
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WO2018116928A1 (en) * | 2016-12-20 | 2018-06-28 | 積水化学工業株式会社 | Sealing agent for liquid crystal display elements, vertically conducting material and liquid crystal display element |
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CN107636524A (en) * | 2016-01-07 | 2018-01-26 | 积水化学工业株式会社 | Sealing material for liquid crystal display device, upper and lower conductive material and liquid crystal display cells |
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CN107636524B (en) * | 2016-01-07 | 2021-07-06 | 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 |
CN107683435B (en) * | 2016-01-07 | 2022-01-04 | 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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KR20170012184A (en) | 2017-02-02 |
TW201600588A (en) | 2016-01-01 |
CN105900003B (en) | 2019-07-19 |
JPWO2015178357A1 (en) | 2017-04-20 |
CN105900003A (en) | 2016-08-24 |
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JP6523167B2 (en) | 2019-05-29 |
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