CN109564371B - Polymerizable compound, sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element - Google Patents
Polymerizable compound, sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element Download PDFInfo
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- CN109564371B CN109564371B CN201780050484.2A CN201780050484A CN109564371B CN 109564371 B CN109564371 B CN 109564371B CN 201780050484 A CN201780050484 A CN 201780050484A CN 109564371 B CN109564371 B CN 109564371B
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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
- C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
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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
Abstract
The present invention is a sealant for a liquid crystal display element, which contains a polymerizable compound represented by the formula (1). In the formula (1), A represents a methylene group, a methylmethylene group, a dimethylmethylene group, an oxygen atom, a sulfur atom or a sulfonyl group, X represents an ethyleneoxyethyl group, a di (ethyleneoxy) ethyl group, a tri (ethyleneoxy) ethyl group, a tetra (ethyleneoxy) ethyl group, a propyleneoxypropyl group, a di (propyleneoxy) propyl group, a tri (propyleneoxy) propyl group, a tetra (propyleneoxy) propyl group, a butyleneoxybutyl group, a di (butyleneoxy) butyl group, a tri (butyleneoxy) butyl group, a tetra (butyleneoxy) butyl group, or an alkylene group having 2 or more and 15 or less carbon atoms, Y1 and Y2 each independently represent a group represented by the following formula (2-1) or (2-2), at least one of Y1 and Y2 is a group represented by the following formula (2-1), and n is 1 or more and 5 or less (average value). In the formulae (2-1) and (2-2), the symbols represent bonding positions; in the formula (2-1), R represents a hydrogen atom or a methyl group.
Description
Technical Field
The present invention relates to a polymerizable compound which can be used in a sealant for a liquid crystal display element having excellent adhesiveness, moisture permeation resistance and low liquid crystal contamination. The present invention also relates to a sealant for a liquid crystal display element containing the polymerizable compound, and a vertical conduction material and a liquid crystal display element produced using the sealant for a liquid crystal display element.
Background
In recent years, as a method for manufacturing a liquid crystal display element such as a liquid crystal display unit, a method called a liquid crystal dropping method using a photo-thermal curing type sealing agent containing a curable resin, a photo-polymerization initiator, and a thermal curing agent as disclosed in patent documents 1 and 2 has been used from the viewpoint of shortening the tact time and optimizing the amount of liquid crystal used.
In the liquid crystal dropping process, first, a rectangular seal pattern is formed on one of two substrates with electrodes by dispensing. Next, in a state where the sealant is not cured, droplets of liquid crystal are dropped into a sealing frame of the substrate, another substrate is stacked under vacuum, and the sealing portion is irradiated with light such as ultraviolet rays to perform precuring. Thereafter, the liquid crystal display element is manufactured by heating and main curing. This one drop fill process is currently the mainstream of a method for manufacturing a liquid crystal display element.
However, in the modern day in which various mobile devices with liquid crystal panels such as mobile phones and portable game machines are increasingly widespread, miniaturization of the devices is the most problematic issue to be solved. As a method for downsizing, narrowing of the frame of the liquid crystal display portion, for example, an operation of disposing the position of the sealing portion under the black matrix (hereinafter, also referred to as "narrow frame design") is performed.
In such a narrow-edge design, the sealant itself is also drawn to be thin, and therefore, the conventional sealant has the following problems: the adhesiveness and moisture permeation prevention are insufficient, and display failure of the liquid crystal display element is likely to occur due to liquid crystal contamination or the like.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2001-133794
Patent document 2: international publication No. 02/092718
Disclosure of Invention
Problems to be solved by the invention
The purpose of the present invention is to provide a polymerizable compound that can be used in a sealant for a liquid crystal display element, which has excellent adhesion, moisture permeation prevention, and low liquid crystal contamination. Further, another object of the present invention is to provide a sealant for a liquid crystal display element containing the polymerizable compound, and a vertical conduction material and a liquid crystal display element produced using the sealant for a liquid crystal display element.
Means for solving the problems
The present invention 1 is a polymerizable compound represented by the following formula (1).
[ solution 1]
In the formula (1), A represents a methylene group, a methylmethylene group, a dimethylmethylene group, an oxygen atom, a sulfur atom or a sulfonyl group, X represents an ethyleneoxyethyl group, a di (ethyleneoxy) ethyl group, a tri (ethyleneoxy) ethyl group, a tetra (ethyleneoxy) ethyl group, a propyleneoxypropyl group, a di (propyleneoxy) propyl group, a tri (propyleneoxy) propyl group, a tetra (propyleneoxy) propyl group, a butyleneoxybutyl group, a di (butyleneoxy) butyl group, a tri (butyleneoxy) butyl group, a tetra (butyleneoxy) butyl group or an alkylene group having 2 to 15 carbon atoms, and Y represents1And Y2Each independently represents a group represented by the following formula (2-1) or (2-2), and Y1And Y2At least one of them is a group represented by the following formula (2-1), and n is 1 or more and 5 or less (average value).
[ solution 2]
In the formulae (2-1) and (2-2), the symbols represent bonding positions; in the formula (2-1), R represents a hydrogen atom or a methyl group.
The present invention 2 is a sealant for a liquid crystal display element, which contains a curable resin containing a polymerizable compound represented by the following formula (1).
[ solution 3]
In the formula (1), A represents a methylene group, a methylmethylene group, a dimethylmethylene group, an oxygen atom, a sulfur atom or a sulfonyl group, X represents an ethyleneoxyethyl group, a di (ethyleneoxy) ethyl group, a tri (ethyleneoxy) ethyl group, a tetra (ethyleneoxy) ethyl group, a propyleneoxypropyl group, a di (propyleneoxy) propyl group, a tri (propyleneoxy) propyl group, a tetra (propyleneoxy) propyl group, a butyleneoxybutyl group, a di (butyleneoxy) butyl group, a tri (butyleneoxy) propyl groupA group) butyl group, a tetra (butylideneoxy) butyl group, or an alkylene group having 2 to 15 carbon atoms, Y1And Y2Each independently represents a group represented by the following formula (2-1) or (2-2), and Y1And Y2At least one of them is a group represented by the following formula (2-1), and n is 1 or more and 5 or less (average value).
[ solution 4]
In the formulae (2-1) and (2-2), the symbols represent bonding positions; in the formula (2-1), R represents a hydrogen atom or a methyl group.
The present invention is described in detail below.
The inventors have surprisingly found that: the polymerizable compound having a specific structure has low staining properties to liquid crystals and is excellent in adhesion and moisture permeation prevention. Thus, the present inventors found that: the present inventors have completed the present invention by formulating the polymerizable compound as a curable resin to obtain a sealant for a liquid crystal display element which is excellent in adhesiveness, moisture permeation resistance and low liquid crystal contamination.
The polymerizable compound of the present invention 1 (hereinafter also simply referred to as "polymerizable compound of the present invention") is represented by the above formula (1).
The polymerizable compound of the present invention has low staining properties to liquid crystals and excellent adhesiveness and moisture permeation prevention properties, and therefore can be suitably used as a curable resin for a sealant for a liquid crystal display element.
The sealant for a liquid crystal display element of the present invention 2 (hereinafter also simply referred to as "the sealant for a liquid crystal display element of the present invention") contains a curable resin.
The curable resin contains a polymerizable compound represented by the formula (1) (i.e., the polymerizable compound of the present invention). By containing the polymerizable compound of the present invention as the curable resin, the sealant for a liquid crystal display element of the present invention is excellent in adhesiveness, moisture permeation resistance, and low liquid crystal contamination.
In the formula (1), A represents a methylene group, a methylmethylene group, a dimethylmethylene group, an oxygen atom, a sulfur atom or a sulfonyl group. Among them, methylene, methylmethylene, and dimethylmethylene are preferable from the viewpoint of easy availability of raw materials.
In the formula (1), X represents an ethyleneoxyethyl group, a di (ethyleneoxy) ethyl group, a tri (ethyleneoxy) ethyl group, a tetra (ethyleneoxy) ethyl group, a propyleneoxypropyl group, a di (propyleneoxy) propyl group, a tri (propyleneoxy) propyl group, a tetra (propyleneoxy) propyl group, a butyleneoxybutyl group, a di (butyleneoxy) butyl group, a tri (butyleneoxy) butyl group, a tetra (butyleneoxy) butyl group, or an alkylene group having 2 to 15 carbon atoms. Among them, from the viewpoint of handling properties, preferred are an ethyleneoxyethyl group, a di (ethyleneoxy) ethyl group, a tri (ethyleneoxy) ethyl group, and an alkylene group having 2 to 8 carbon atoms.
In the above formula (1), Y1And Y2Each independently represents a group represented by the above formula (2-1) or (2-2), and Y1And Y2At least one of them is a group represented by the above formula (2-1). That is, the polymerizable compound of the present invention may have (meth) acryloyl groups at both ends, or may have a (meth) acryloyl group at one end and an epoxy group at the other end.
In the present specification, the "(meth) acryloyl group" refers to an acryloyl group or a methacryloyl group.
In the formula (1), n is 1 or more and 5 or less (average value).
The preferable upper limit of n is 3. When n is 3 or less, the viscosity of the obtained sealant for a liquid crystal display element is not excessively high, and the coating property and handling property are more excellent.
Examples of the method for producing the polymerizable compound of the present invention include a method of reacting a compound corresponding to Y in the above formula (1)1And Y2A method of reacting a part or all of epoxy groups of a diepoxy compound in which all of the groups are represented by the above formula (2-2) with (meth) acrylic acid, and the like.
Examples of the method for producing the diepoxy compound include a method in which a bisphenol such as bisphenol a is reacted with a divinyl ether compound having a structure corresponding to X in the formula (1) such as triethylene glycol divinyl ether, and the compound having phenolic hydroxyl groups at both ends obtained by the reaction is further reacted with epichlorohydrin.
Further, examples of the commercially available products among the above-mentioned diepoxy compounds include EPICLON EXA4850 series (available from DIC).
The lower limit of the content of the polymerizable compound of the present invention in 100 parts by weight of the curable resin is preferably 5 parts by weight, and the upper limit is preferably 80 parts by weight. When the content of the polymerizable compound of the present invention is 5 parts by weight or more, the sealant for a liquid crystal display element of the present invention has more excellent adhesiveness. By setting the content of the polymerizable compound of the present invention to 80 parts by weight or less, the viscosity of the sealant for a liquid crystal display element of the present invention does not become too high, and the coating property and handling property become more excellent. The lower limit of the content of the polymerizable compound of the present invention is more preferably 10 parts by weight, and the upper limit is more preferably 50 parts by weight.
The curable resin preferably contains a polymerizable compound other than the polymerizable compound of the present invention.
Examples of the other polymerizable compound include other (meth) acrylic compounds and other epoxy compounds in addition to the compounds contained in the polymerizable compound of the present invention.
In the present specification, the "(meth) acrylic" refers to an acrylic or methacrylic, and the "(meth) acrylic compound" refers to a compound having a (meth) acryloyl group.
Examples of the other (meth) acrylic compounds include epoxy (meth) acrylates, (meth) acrylate compounds, urethane (meth) acrylates, and the like. Among them, epoxy (meth) acrylates are preferable. In addition, from the viewpoint of high reactivity, the other (meth) acrylic compound preferably has 2 or more (meth) acryloyl groups in the molecule.
In the present specification, the "(meth) acrylate" refers to an acrylate or a methacrylate, and the "epoxy (meth) acrylate" refers to a compound obtained by reacting all epoxy groups in an epoxy compound with (meth) acrylic acid.
Examples of the epoxy (meth) acrylate include epoxy (meth) acrylates obtained by reacting an epoxy compound with (meth) acrylic acid in the presence of a basic catalyst according to a conventional method.
Examples of the epoxy compound to be used as a raw material for synthesizing the epoxy (meth) acrylate include bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, 2' -diallylbisphenol a type epoxy resin, hydrogenated bisphenol type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, thioether type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, o-cresol novolac type epoxy resin, dicyclopentadiene novolac type epoxy resin, biphenol novolac type epoxy resin, naphthol novolac type epoxy resin, glycidyl amine type epoxy resin, rubber-modified epoxy resin, and glycidyl ester compound.
Examples of commercially available products among the bisphenol A epoxy resins include jER828EL, jER1004 (both manufactured by Mitsubishi chemical corporation), EPICLON EXA-850CRP (manufactured by DIC corporation), and the like.
Examples of commercially available products among the above bisphenol F-type epoxy resins include jER806 and jER4004 (both manufactured by Mitsubishi chemical corporation).
Examples of commercially available products among the bisphenol E type epoxy resins include R710 (manufactured by PRINTEC).
As a commercial product among the above bisphenol S type epoxy resins, EPICLON EXA-1514 (available from DIC) and the like are exemplified.
Examples of commercially available products among the above-mentioned 2, 2' -diallylbisphenol A-type epoxy resins include RE-810NM (manufactured by Nippon chemical Co., Ltd.).
Examples of commercially available products among the above-mentioned hydrogenated bisphenol epoxy resins include EPICLON EXA-7015 (available from DIC).
Examples of commercially available products among the above-mentioned resorcinol type epoxy resins include EX-201 (manufactured by Nagase ChemteX).
Examples of the commercially available biphenyl-type epoxy resin include jER YX-4000H (manufactured by Mitsubishi chemical corporation).
Examples of commercially available products among the thioether-type epoxy resins include YSLV-50TE (manufactured by Nippon Tekken chemical Co., Ltd.).
Examples of commercially available products among the above-mentioned diphenyl ether type epoxy resins include YSLV-80DE (manufactured by Nippon Tekken chemical Co., Ltd.).
Examples of commercially available products among the above-mentioned dicyclopentadiene type epoxy resins include EP-4088S (manufactured by ADEKA).
Examples of the naphthalene epoxy resin include EPICLON HP4032 and EPICLON EXA-4700 (both DIC).
Examples of the commercially available phenol novolac epoxy resin include EPICLON-770 (available from DIC).
Examples of the commercially available products of the o-cresol novolac type epoxy resin include EPICLON-670-EXP-S (available from DIC).
Examples of commercially available products among the dicyclopentadiene phenol type epoxy resins include EPICLON HP7200 (available from DIC).
Examples of the commercially available products among the above-mentioned diphenol-aldehyde type epoxy resins include NC-3000P (manufactured by Nippon chemical Co., Ltd.).
As a commercial product among the above naphthol novolac type epoxy resins, for example, ESN-165S (manufactured by Nissian chemical Co., Ltd.) is mentioned.
Examples of commercially available products among the glycidyl amine type epoxy resins include jER630 (manufactured by Mitsubishi chemical corporation), EPICLON430 (manufactured by DIC corporation), and TETRAD-X (manufactured by Mitsubishi gas chemical corporation).
Examples of commercially available products among the rubber-modified epoxy resins include YR-450, YR-207 (both manufactured by Nippon Tekken chemical Co., Ltd.), Epolead PB (manufactured by Daiiol Co., Ltd.).
Examples of commercially available products among the glycidyl ester compounds include Denacol EX-147 (manufactured by Nagase ChemteX).
Examples of the monofunctional compound among the above-mentioned (meth) acrylate 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, cyclohexyl (meth) acrylate, and mixtures thereof, Isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, methoxyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ethylcarbitol (meth) acrylate, 2, 2, 2-trifluoroethyl (meth) acrylate, 2, 2, 3, 3-tetrafluoropropyl (meth) acrylate, 1H, 5H-octafluoropentyl (meth) acrylate, and mixtures thereof, Imide (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, 2- (meth) acryloyloxyethyl phosphate, glycidyl (meth) acrylate, and the like.
Examples of the bifunctional compound among the (meth) acrylate compounds include 1, 3-butanediol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 2-n-butyl-2-ethyl-1, 3-propanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and mixtures thereof, Neopentyl glycol di (meth) acrylate, ethylene oxide-added bisphenol a di (meth) acrylate, propylene oxide-added bisphenol a di (meth) acrylate, ethylene oxide-added bisphenol F di (meth) acrylate, dimethylol dicyclopentadienyl di (meth) acrylate, ethylene oxide-modified isocyanuric acid di (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, carbonate diol di (meth) acrylate, polyether diol di (meth) acrylate, polyester diol di (meth) acrylate, polycaprolactone diol di (meth) acrylate, polybutadiene diol di (meth) acrylate, and the like.
Further, as the trifunctional or higher compound among the above (meth) acrylate compounds, examples thereof include trimethylolpropane tri (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) acrylate, propylene oxide-added trimethylolpropane tri (meth) acrylate, caprolactone-modified trimethylolpropane tri (meth) acrylate, ethylene oxide-added isocyanuric acid tri (meth) acrylate, glycerol tri (meth) acrylate, propylene oxide-added glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri (meth) acryloyloxyethyl phosphate, bis (trimethylolpropane) tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.
The urethane (meth) acrylate can be obtained, for example, by reacting 2 equivalents of a (meth) acrylic acid derivative having a hydroxyl group with 1 equivalent of an isocyanate compound having 2 isocyanate groups in the presence of a catalytic amount of a tin-based compound.
Examples of the isocyanate compound include isophorone diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4, 4' -diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1, 5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, Xylylene Diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate, tetramethylxylylene diisocyanate, 1, 6, 11-undecane triisocyanate, and the like.
Further, as the isocyanate compound, an isocyanate compound having a chain extended by a reaction of a polyol and an excess amount of the isocyanate compound may be used.
Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, and polycaprolactone diol.
Examples of the (meth) acrylic acid derivative having a hydroxyl group include hydroxyalkyl mono (meth) acrylates, mono (meth) acrylates of diols, mono (meth) acrylates or di (meth) acrylates of triols, epoxy (meth) acrylates, and the like.
Examples of the hydroxyalkyl mono (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.
Examples of the dihydric alcohol include ethylene glycol, propylene glycol, 1, 3-propanediol, 1, 3-butanediol, 1, 4-butanediol, and polyethylene glycol.
Examples of the trihydric alcohol include trimethylolethane, trimethylolpropane, glycerol, and the like.
Examples of the epoxy (meth) acrylate include bisphenol a type epoxy acrylates.
Examples of commercially available products among the above urethane (meth) acrylates include urethane (meth) acrylates manufactured by east asia synthesis, urethane (meth) acrylates manufactured by DAICEL-ALLNEX, urethane (meth) acrylates manufactured by seiko industries, urethane (meth) acrylates manufactured by seiko chemical industries, urethane (meth) acrylates manufactured by coyoto chemical companies, and the like.
Examples of the urethane (meth) acrylates produced by Toyo Synthesis Co.Ltd include M-1100, M-1200, M-1210 and M-1600.
Examples of the urethane (meth) acrylate produced by DAICEL-ALLNEX include EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, EBECRYL1290, EBECRYL2220, EBECRYL4827, EBECRYL4842, EBECRYL4858, EBECRYL5129, EBECRYL6700, EBECRYL8402, EBECRYL8803, EBECRYL8804, EBECRYL8807 and EBECRYL 9260.
Examples of the urethane (meth) acrylates produced by the above-mentioned Industrial Co company include Art Resin UN-330, Art Resin SH-500B, Art Resin UN-1200TPK, Art Resin UN-1255, Art Resin UN-3320HB, Art Resin UN-7100, Art Resin UN-9000A and Art Resin UN-9000H.
Examples of the urethane (meth) acrylates produced by Nikamura chemical industries include U-2HA, U-2PHA, U-3HA, U-4HA, U-6H, U-6HA, U-6LPA, U-10H, U-15HA, U-108A, U-122A, U-122P, U-324A, U-340A, U-340P, U-1084A, U-2061BA, UA-340P, UA-4000, UA-4100, UA-4200, UA-4400, UA-5201P, UA-7100, UA-7200 and UA-W2A.
Examples of the urethane (meth) acrylate manufactured by Kyoeisha chemical company include AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA-306T, and the like.
As the other epoxy compound, the same epoxy compound as the epoxy compound to be a raw material for synthesizing the epoxy (meth) acrylate can be used.
The other polymerizable compound may contain a compound having an epoxy group and a (meth) acryloyl group in 1 molecule. Examples of such a compound include a partially (meth) acrylic-modified epoxy resin obtained by reacting a part of epoxy groups of an epoxy compound having 2 or more epoxy groups in 1 molecule with (meth) acrylic acid.
Examples of commercially available products among the above partially (meth) acrylic-modified epoxy resins include UVACURE1561 (manufactured by DAICEL-ALLNEX).
The other polymerizable compound preferably has-OH group, -NH-group, or-NH group from the viewpoint of suppressing liquid crystal contamination2Hydrogen bonding units such as radicals.
In the sealant for a liquid crystal display element of the present invention, the ratio of (meth) acryloyl groups in the total of (meth) acryloyl groups and epoxy groups in the curable resin is preferably 30% or more and 95% or less. When the ratio of the (meth) acryloyl group is 30% or more, the uncured epoxy resin component hardly remains after polymerization, and the liquid crystal contamination resistance becomes more excellent. When the ratio of the (meth) acryloyl group is 95% or less, the obtained sealant for a liquid crystal display element has more excellent adhesiveness.
The sealant for a liquid crystal display element of the present invention may contain a polymerization initiator.
As the polymerization initiator, a radical polymerization initiator can be suitably used.
Examples of the radical polymerization initiator include a photo radical polymerization initiator which generates radicals by light irradiation, a thermal radical polymerization initiator which generates radicals by heating, and the like.
Examples of the photo radical polymerization initiator include oxime ester compounds, benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, benzoin ether compounds, and thioxanthone compounds.
Examples of commercially available products among the photo radical polymerization initiators include a photo radical polymerization initiator manufactured by BASF corporation and a photo radical polymerization initiator manufactured by tokyo chemical industry corporation.
Examples of the photo radical polymerization initiator manufactured by BASF include IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, and Lucirin TPO.
Examples of the photo radical polymerization initiator manufactured by tokyo chemical industry include benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.
The content of the photo radical polymerization initiator is preferably 0.1 part by weight in the lower limit and 10 parts by weight in the upper limit, based on 100 parts by weight of the curable resin. By setting the content of the photo radical polymerization initiator to 0.1 parts by weight or more, the sealing agent for a liquid crystal dropping process of the present invention is more excellent in photocurability. By setting the content of the photo radical polymerization initiator to 10 parts by weight or less, the sealant for liquid crystal dropping process of the present invention is more excellent in low liquid crystal contamination and storage stability.
Examples of the thermal radical polymerization initiator include thermal radical polymerization initiators formed from azo compounds, organic peroxides, and the like. Among them, an initiator composed of a macromolecular azo compound (hereinafter, also referred to as "macromolecular azo initiator") is preferable.
In the present specification, the macromolecular azo compound means: a compound having an azo group, which generates a radical capable of curing a (meth) acryloyl group by heat, and which has a number average molecular weight of 300 or more.
The number average molecular weight of the macromolecular azo compound preferably has a lower limit of 1000 and an upper limit of 30 ten thousand. When the number average molecular weight of the macromolecular azo compound is in this range, the compound can be easily mixed with a curable resin while suppressing liquid crystal contamination. The number average molecular weight of the macromolecular azo compound is preferably 5000 as a lower limit, more preferably 10 ten thousand as an upper limit, still more preferably 1 ten thousand as a lower limit, and yet more preferably 9 ten thousand as an upper limit.
In the present specification, the number average molecular weight is a value measured by Gel Permeation Chromatography (GPC) and determined in terms of polystyrene. 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 K.K.).
Examples of the macromolecular azo compound include compounds having a structure in which a plurality of units such as polyalkylene oxide and polydimethylsiloxane are bonded via an azo group.
The macromolecular azo compound having a structure in which a plurality of units such as polyalkylene oxide are bonded via an azo group preferably has a polyethylene oxide structure.
Specific examples of the macromolecular azo compound include a polycondensate of 4, 4 '-azobis (4-cyanovaleric acid) and a polyalkylene glycol, and a polycondensate of 4, 4' -azobis (4-cyanovaleric acid) and a polydimethylsiloxane having a terminal amino group.
Examples of commercially available products among the above-mentioned macromolecular azo compounds include VPE-0201, VPE-0401, VPE-0601, VPS-0501 and VPS-1001 (all manufactured by Wako pure chemical industries, Ltd.).
Further, examples of commercially available azo compounds of non-polymer include V-65 and V-501 (both manufactured by Wako pure chemical industries, Ltd.).
Examples of the organic peroxide include ketone peroxide, peroxyketal, hydrogen peroxide, dialkyl peroxide, peroxyester, diacyl peroxide, and peroxydicarbonate.
The lower limit of the content of the thermal radical polymerization initiator is preferably 0.05 parts by weight, and the upper limit is preferably 10 parts by weight, based on 100 parts by weight of the curable resin. By setting the content of the thermal radical polymerization initiator to 0.05 parts by weight or more, the sealant for a liquid crystal display element of the present invention is more excellent in thermosetting property. By setting the content of the thermal radical polymerization initiator to 10 parts by weight or less, the sealant for a liquid crystal display element of the present invention is more excellent in low liquid crystal contamination and storage stability. The lower limit of the content of the thermal radical polymerization initiator is more preferably 0.1 part by weight, and the upper limit is more preferably 5 parts by weight.
The sealant for a liquid crystal display element of the present invention may contain a thermosetting agent.
Examples of the heat-curing agent include organic acid hydrazides, amine compounds, polyphenol compounds, and acid anhydrides. Among them, organic acid hydrazide can be suitably used.
Examples of the organic acid hydrazide include sebacic dihydrazide, isophthalic dihydrazide, adipic dihydrazide, malonic dihydrazide, and 1, 3-bis (hydrazinocarbonylethyl) -5-isopropylhydantoin.
Examples of commercially available products among the above-mentioned organic acid hydrazides include organic acid hydrazides available from Otsuka chemical company, and organic acid hydrazides available from Aomoto optical science company.
Examples of the organic acid hydrazide available from Otsuka chemical company include SDH and ADH.
Examples of the organic acid hydrazide manufactured by Aomoto-Guest Fine science and technology company include AMICURE VDH, AMICURE VDH-J, AMICURE UDH, and AMICURE UDH-J.
The lower limit of the content of the heat-curing agent is preferably 1 part by weight, and the upper limit is preferably 50 parts by weight, based on 100 parts by weight of the curable resin. By setting the content of the thermosetting agent to 1 part by weight or more, the sealant for a liquid crystal display element of the present invention is more excellent in thermosetting property. By setting the content of the thermosetting agent to 50 parts by weight or less, the viscosity of the sealant for a liquid crystal display element of the present invention does not become too high, and the coating property and the handling property become more excellent. The more preferable upper limit of the content of the thermal curing agent is 30 parts by weight.
The sealant for a liquid crystal display element of the present invention preferably contains a filler for the purpose of adjusting viscosity, further improving adhesiveness by a stress dispersion effect, improving a linear expansion coefficient, further improving moisture permeation resistance of a cured product, and the like.
As the filler, an inorganic filler or an organic filler can be used.
Examples of the inorganic filler include silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, smectite, bentonite, montmorillonite, sericite, activated clay, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, calcium carbonate, magnesium hydroxide, aluminum nitride, silicon nitride, barium sulfate, and calcium silicate.
Examples of the organic filler include polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, and acrylic polymer fine particles.
The lower limit of the content of the filler in 100 parts by weight of the sealant for a liquid crystal display element of the present invention is preferably 5 parts by weight, and the upper limit is preferably 70 parts by weight. By setting the content of the filler to 5 parts by weight or more, the effect of further improving the adhesiveness and the like becomes more excellent. By setting the content of the filler to 70 parts by weight or less, the viscosity of the sealant for a liquid crystal display element of the present invention does not become too high, and the coating property and the handling property become more excellent. The lower limit of the content of the filler is more preferably 10 parts by weight, and the upper limit is more preferably 60 parts by weight.
The sealant for a liquid crystal display element of the present invention preferably contains a silane coupling agent. The silane coupling agent mainly functions as an adhesion aid for better adhesion of the sealant to a substrate or the like.
As the silane coupling agent, for example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane and the like can be suitably used. These silane coupling agents have an excellent effect of improving adhesion to a substrate or the like, and can inhibit outflow of a curable resin into a liquid crystal by chemically bonding with the curable resin.
The content of the silane coupling agent in 100 parts by weight of the sealant for a liquid crystal display element of the present invention preferably has a lower limit of 0.1 part by weight and an upper limit of 10 parts by weight. By setting the content of the silane coupling agent to 0.1 parts by weight or more, the effect of further improving the adhesion and the like becomes more excellent. By setting the content of the silane coupling agent to 10 parts by weight or less, the sealant for a liquid crystal display element of the present invention is more excellent in low liquid crystal contamination. The lower limit of the content of the silane coupling agent is more preferably 0.3 part by weight, and the upper limit is more preferably 5 parts by weight.
The sealant for a liquid crystal display element of the present invention may contain a light-shading agent. By containing the light-shading agent, the sealant for a liquid crystal display element of the present invention can be suitably used as a light-shielding sealant.
Examples of the light-shading agent include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. Among them, titanium black is preferable.
The titanium black has a higher transmittance for light in the vicinity of the ultraviolet region, particularly at a wavelength of 370nm to 450nm, than the average transmittance for light at a wavelength of 300nm to 800 nm. That is, the titanium black is a light-shading agent having the following properties: the sealant for a liquid crystal display element of the present invention provides light-shielding properties by sufficiently shielding light having a wavelength in the visible light region, while transmitting light having a wavelength in the vicinity of the ultraviolet region. The light-shading agent contained in the sealant for a liquid crystal display element of the present invention is preferably a high-insulating material, and titanium black is also suitable as a high-insulating light-shading agent.
The above titanium black exerts a sufficient effect even without being surface-treated, but a titanium black surface-treated with an organic component such as a coupling agent may be used; surface-treated titanium black such as titanium black coated with an inorganic component such as silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide, or magnesium oxide. Among them, titanium black treated with an organic component is preferable from the viewpoint of further improving the insulation properties.
Further, since the liquid crystal display element produced using the sealant for a liquid crystal display element of the present invention containing the titanium black as a light-shielding agent has sufficient light-shielding properties, a liquid crystal display element having high contrast without light leakage and excellent image display quality can be realized.
Examples of commercially available products among the above titanium blacks include titanium black manufactured by mitsubishi integrated materials corporation, and titanium black manufactured by gibberella chemical corporation.
Examples of the titanium black manufactured by Mitsubishi Integrated materials include 12S, 13M-C, 13R-N and 14M-C.
Examples of the titanium black manufactured by red spike formation company include Tilack D.
The lower limit of the specific surface area of the titanium black is preferably 13m2A preferred upper limit of 30m2A more preferred lower limit is 15m2A more preferable upper limit of 25m2/g。
The volume resistance of the titanium black is preferably 0.5 Ω · cm at the lower limit and 3 Ω · cm at the upper limit, more preferably 1 Ω · cm at the lower limit and 2.5 Ω · cm at the upper limit.
The primary particle size of the light-shading agent is not particularly limited as long as it is not more than the distance between the substrates of the liquid crystal display element, and the lower limit is preferably 1nm, and the upper limit is preferably 5000 nm. By setting the primary particle size of the light-shielding agent in this range, the light-shielding property can be further improved without deteriorating the image-forming property and the like of the obtained sealant for a liquid crystal display element. The lower limit of the primary particle diameter of the light-shading agent is more preferably 5nm, the upper limit is more preferably 200nm, the lower limit is more preferably 10nm, and the upper limit is more preferably 100 nm.
The primary PARTICLE size of the light-shading agent can be measured by dispersing the light-shading agent in a solvent (water, organic solvent, etc.) using NICOMP 380ZLS (manufactured by PARTICLE SIZING SYSTEMS).
The content of the light-shading agent in 100 parts by weight of the sealant for a liquid crystal display element of the present invention preferably has a lower limit of 5 parts by weight and an upper limit of 80 parts by weight. By setting the content of the light-shielding agent to 5 parts by weight or more, the sealant for a liquid crystal display element of the present invention can exhibit more excellent light-shielding properties. By setting the content of the light-shading agent to 80 parts by weight or less, the sealant for a liquid crystal display element of the present invention is more excellent in adhesiveness, strength after curing, and coatability. The lower limit of the content of the light-shading agent is more preferably 10 parts by weight, and the upper limit is more preferably 70 parts by weight.
The sealant for a liquid crystal display element of the present invention may further contain additives such as a reactive diluent, a spacer, a curing accelerator, an antifoaming agent, a leveling agent, and a polymerization inhibitor, as necessary.
Examples of the method for producing the sealant for a liquid crystal display element of the present invention include a method of mixing a curable resin, and a polymerization initiator, a thermosetting agent, a filler, a silane coupling agent, and the like added as necessary, using a mixer such as a homomixer, a universal mixer, a planetary mixer, a kneader, or a triple roll mill.
By adding conductive fine particles to the sealant for a liquid crystal display element of the present invention, a vertical conduction material can be produced. Such a vertical conduction material containing the sealant for a liquid crystal display element of the present invention and conductive fine particles is also one aspect of the present invention.
As the conductive fine particles, metal balls, conductive fine particles in which a conductive metal layer is formed on the surface of resin fine particles, or the like can be used. Among these, the conductive fine particles having the conductive metal layer formed on the surface of the resin fine particles are preferable because the conductive connection can be performed without damaging the transparent substrate or the like due to the excellent elasticity of the resin fine particles.
A liquid crystal display element produced using the sealant for a liquid crystal display element 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 manufacturing the liquid crystal display element of the present invention, a liquid crystal dropping method can be suitably used, and specifically, the following method and the like can be exemplified.
A liquid crystal display element can be obtained by a method including the steps of, first: a step of forming a frame-shaped seal pattern by applying the sealant for a liquid crystal display element of the present invention to one of two substrates such as a glass substrate with an electrode such as an ITO film and a polyethylene terephthalate substrate by screen printing, dispenser coating, or the like; next, the following steps are performed: a step of applying a liquid crystal droplet in a state where the sealant for a liquid crystal display element of the present invention is not cured to a frame of a seal pattern of a substrate, and stacking another substrate under vacuum; thereafter, the following steps are performed: a step of irradiating a seal pattern portion of the sealant for a liquid crystal display element of the present invention with light such as ultraviolet rays to precure the sealant; and a step of heating the precured sealant to perform main curing.
ADVANTAGEOUS EFFECTS OF INVENTION
The present invention can provide a polymerizable compound that can be used in a sealant for a liquid crystal display element, which has excellent adhesiveness, moisture permeation prevention, and low liquid crystal contamination. Further, the present invention can provide a sealant for a liquid crystal display element containing the polymerizable compound, and a vertical conduction material and a liquid crystal display element produced using the sealant for a liquid crystal display element.
Detailed Description
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
(Synthesis of intermediate epoxy Compound (A-1))
456 parts by weight of bisphenol A and 202 parts by weight of triethylene glycol divinyl ether were charged into a flask, and the mixture was stirred at 120 ℃ for 6 hours to react, thereby obtaining an intermediate phenol compound.
After the liquid temperature was returned to normal temperature, 925 parts by weight of epichlorohydrin and 150 parts by weight of n-butanol were added to prepare a uniform solution, and the temperature was raised to 60 ℃. Then, 220 parts by weight of a 40% aqueous sodium hydroxide solution was added dropwise over 5 hours, followed by reaction at 60 ℃ for 1 hour. After completion of the reaction, the residual epichlorohydrin was distilled off by distillation under reduced pressure to obtain a crude epoxy compound. To the crude epoxy compound thus obtained, 600 parts by weight of methyl isobutyl ketone and 100 parts by weight of n-butanol were added to prepare a solution, 30 parts by weight of a 10% aqueous sodium hydroxide solution was added to the solution, the reaction was carried out at 80 ℃ for 2 hours, and then washing with 200 parts by weight of water was repeated 3 times, and the pH of the washing solution was measured to confirm that the solution was neutral. Then, azeotropic dehydration was carried out, and the solvent was distilled off to obtain an intermediate epoxy compound (A-1).
(Synthesis of the polymerizable Compound (B-1) of the present invention)
A flask was charged with 404 parts by weight of the intermediate epoxy compound (A-1), 36 parts by weight of acrylic acid, 0.5 part by weight of triphenylphosphine and 0.05 part by weight of dibutylhydroxytoluene, and the mixture was stirred at 100 ℃ for 6 hours to react. The resultant reaction product was washed 3 times with 1000 parts by weight of pure water, and then water was removed by distillation under reduced pressure to obtain the polymerizable compound (B-1) of the present invention.
By the way of illustration1H-NMR、13C-NMR and FT-IR analyses confirmed that: in the obtained polymerizable compound (B-1) of the present invention, A in the formula (1) is dimethylmethylene, X is bis (ethyleneoxy) ethyl, Y is1And Y2One of them is a group represented by the formula (2-1) (R is a hydrogen atom), and the other is a group represented by the formula (2-2). It was furthermore ascertained that: the polymerizable compound (B-1) of the present invention is a compound of the formula (1) wherein n (average value) is 1.3.
(Synthesis of the polymerizable Compound (C-1) of the present invention)
A flask was charged with 404 parts by weight of the intermediate epoxy compound (A-1), 72 parts by weight of acrylic acid, 0.5 part by weight of triphenylphosphine and 0.05 part by weight of dibutylhydroxytoluene, and the mixture was stirred at 100 ℃ for 6 hours to react. The resultant reaction product was washed 3 times with 1000 parts by weight of pure water, and then water was removed by distillation under reduced pressure to obtain the polymerizable compound (C-1) of the present invention.
By the way of illustration1H-NMR、13C-NMR and FT-IR analyses confirmed that: in the obtained polymerizable compound (C-1) of the present invention, A in the formula (1) is dimethylmethylene, X is bis (ethyleneoxy) ethyl, Y is1And Y2Are each a group represented by the formula (2-1) (R is a hydrogen atom). It was furthermore ascertained that: the polymerizable compound (C-1) of the present invention is a compound represented by the formula (1) wherein n (average value) is 1.3。
(Synthesis of the polymerizable Compound (C-1M) of the present invention)
The same procedure as in the above "(Synthesis of the polymerizable Compound (C-1) of the present invention)" was carried out except that 86 parts by weight of methacrylic acid was used instead of 72 parts by weight of acrylic acid, to obtain the polymerizable Compound (C-1M) of the present invention.
By the way of illustration1H-NMR、13C-NMR and FT-IR analyses confirmed that: in the obtained polymerizable compound (C-1M) of the present invention, A in the formula (1) is dimethylmethylene, X is bis (ethyleneoxy) ethyl, Y is1And Y2All are groups represented by the formula (2-1) (R is methyl). It was furthermore ascertained that: the polymerizable compound (C-1M) of the present invention is a compound of the formula (1) wherein n (average value) is 1.3.
(Synthesis of intermediate epoxy Compound (A-2))
The same operation as in the above "(synthesis of intermediate epoxy compound (A-1)") was carried out except that 170 parts by weight of 1, 6-bis (vinyloxy) hexane was used instead of 202 parts by weight of triethylene glycol divinyl ether to obtain an intermediate epoxy compound (A-2).
(Synthesis of the polymerizable Compound (C-2) of the present invention)
The same procedure as in the aforementioned "(Synthesis of the polymerizable Compound (C-1) of the present invention)" was carried out except that 388 parts by weight of the intermediate epoxy compound (A-2) was used instead of 404 parts by weight of the intermediate epoxy compound (A-1), to obtain the polymerizable Compound (C-2) of the present invention.
By the way of illustration1H-NMR、13C-NMR and FT-IR analyses confirmed that: in the obtained polymerizable compound (C-2) of the present invention, A in the formula (1) is dimethylmethylene, X is hexamethylene, and Y is1And Y2Are each a group represented by the formula (2-1) (R is a hydrogen atom). It was furthermore ascertained that: the polymerizable compound (C-2) of the present invention is a compound of formula (1) wherein n (average value) is 1.2.
(Synthesis of propylene oxide-modified bisphenol A type epoxy acrylate)
The same procedure as in the "synthesis of the polymerizable compound (C-1) of the present invention" was carried out except that 260 parts by weight of the propylene oxide-modified bisphenol A epoxy resin was used instead of 404 parts by weight of the intermediate epoxy compound (A-1), to obtain a propylene oxide-modified bisphenol A epoxy acrylate. As the propylene oxide-modified bisphenol A epoxy resin, ADEKA RESIN EP-4000S (manufactured by ADEKA) was used.
Examples 1 to 11 and comparative examples 1 to 3
The respective materials were mixed with a planetary mixer (manufactured by THINKY, "あわとり tylan") at the mixing ratios shown in tables 1 and 2, and then mixed with a three-roll mill to prepare sealants for liquid crystal display elements of examples 1 to 11 and comparative examples 1 to 3.
< evaluation >
The following evaluations were made with respect to the sealants for liquid crystal display elements obtained in examples and comparative examples. The results are shown in tables 1 and 2.
(adhesiveness)
1 part by weight of spacer particles (Micropearl SI-H050, manufactured by hydroprocess chemical industries, Ltd.) was uniformly dispersed in 100 parts by weight of each of the sealants for liquid crystal display elements obtained in examples and comparative examples by using a planetary stirring apparatus, and a very small amount was applied to the center of a Corning glass 1737 (length 50 mm. times. width 20 mm. times. thickness 0.7 mm). The same type of glass was laminated thereon, and the liquid crystal display element was spread with a sealant, and irradiated with a metal halide lamp for 30 seconds at 100mW/cm2And then heated at 120 ℃ for 1 hour to cure the sealant, to obtain an adhesion test piece.
The adhesion strength of the obtained adhesion test piece was measured by using a tensiometer.
(Low liquid Crystal contamination and moisture permeation prevention)
1 part by weight of spacer particles (manufactured by waterlogging chemical industry, "Micropearl SI-H050") was dispersed in 100 parts by weight of each of the sealants for liquid crystal display elements obtained in examples and comparative examples, and one of the two substrates with the rubbed alignment film and the transparent electrode was coated with a dispenser so that the line width of the sealant became 1 mm. Is connected withThen, a minute droplet of liquid crystal (JC-5004 LA, manufactured by CHISSO Co., Ltd.) was applied dropwise onto the entire surface of the sealant of the substrate with a transparent electrode, another substrate with a transparent electrode was immediately bonded, and the sealant portion was irradiated with a metal halide lamp for 30 seconds at 100mW/cm2And then heated at 120 ℃ for 1 hour to cure the sealant, thereby obtaining a liquid crystal display element. Liquid crystal display elements for evaluation of low liquid crystal contamination and moisture permeation prevention were produced for each of the liquid crystal display element sealants obtained in examples and comparative examples.
The evaluation of low liquid crystal contamination was performed as follows: the liquid crystal display element thus obtained was brought into a state in which a voltage was applied at 60 ℃ for 1000 hours, and then the degree of disorder of the liquid crystal alignment in the vicinity of the sealant was visually confirmed. Further, evaluation of moisture permeability resistance was performed as follows: the liquid crystal display element thus obtained was brought into a state in which a voltage was applied at 60 ℃ and 95% RH for 1000 hours, and then the degree of disturbance in the alignment of the liquid crystal in the vicinity of the sealant was visually confirmed.
The disorder of the liquid crystal alignment was judged by color unevenness, and the degree of color unevenness was evaluated as "excellent" when there was no color unevenness at all, as "o" when there was slight color unevenness, as "Δ" when there was slight color unevenness, and as "x" when there was a large amount of color unevenness.
The liquid crystal display elements evaluated as ". circleincircle" and ". smallcircle" were of a level that had no practical problem at all.
[ Table 1]
[ Table 2]
Industrial applicability
The present invention can provide a polymerizable compound that can be used in a sealant for a liquid crystal display element, which has excellent adhesiveness, moisture permeation prevention, and low liquid crystal contamination. Further, the present invention can provide a sealant for a liquid crystal display element containing the polymerizable compound, and a vertical conduction material and a liquid crystal display element produced using the sealant for a liquid crystal display element.
Claims (5)
1. A sealant for a liquid crystal display element, characterized by comprising a curable resin,
the curable resin contains a polymerizable compound represented by the following formula (1),
in the formula (1), A represents a methylene group, a methylmethylene group, a dimethylmethylene group, an oxygen atom, a sulfur atom or a sulfonyl group, X represents an ethyleneoxyethyl group, a di (ethyleneoxy) ethyl group, a tri (ethyleneoxy) ethyl group, a tetra (ethyleneoxy) ethyl group, a propyleneoxypropyl group, a di (propyleneoxy) propyl group, a tri (propyleneoxy) propyl group, a tetra (propyleneoxy) propyl group, a butyleneoxybutyl group, a di (butyleneoxy) butyl group, a tri (butyleneoxy) butyl group, a tetra (butyleneoxy) butyl group or an alkylene group having 2 to 15 carbon atoms, and Y represents1And Y2Each independently represents a group represented by the following formula (2-1) or (2-2), and Y1And Y2At least one of which is a group represented by the following formula (2-1), n is 1 or more and 5 or less on the average,
in the formulae (2-1) and (2-2), R represents a hydrogen atom or a methyl group, and the bonding position is represented by the formula (2-1).
2. The sealant for a liquid crystal display element according to claim 1, wherein a content of the polymerizable compound represented by the formula (1) in 100 parts by weight of the curable resin is 5 parts by weight or more and 80 parts by weight or less.
3. A vertically conducting material comprising the sealant for liquid crystal display element according to claim 1 or 2 and conductive fine particles.
4. A liquid crystal display element produced by using the sealant for a liquid crystal display element according to claim 1 or 2 or the vertically conducting material according to claim 3.
5. A polymerizable compound represented by the following formula (1),
in the formula (1), A represents a methylene group, a methylmethylene group, a dimethylmethylene group, an oxygen atom, a sulfur atom or a sulfonyl group, X represents an ethyleneoxyethyl group, a di (ethyleneoxy) ethyl group, a tri (ethyleneoxy) ethyl group, a tetra (ethyleneoxy) ethyl group, a propyleneoxypropyl group, a di (propyleneoxy) propyl group, a tri (propyleneoxy) propyl group, a tetra (propyleneoxy) propyl group, a butyleneoxybutyl group, a di (butyleneoxy) butyl group, a tri (butyleneoxy) butyl group, a tetra (butyleneoxy) butyl group or an alkylene group having 2 to 15 carbon atoms, and Y represents1And Y2Each independently represents a group represented by the following formula (2-1) or (2-2), and Y1And Y2At least one of which is a group represented by the following formula (2-1), n is 1 or more and 5 or less on the average,
in the formulae (2-1) and (2-2), R represents a hydrogen atom or a methyl group, and the bonding position is represented by the formula (2-1).
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| JP3583326B2 (en) | 1999-11-01 | 2004-11-04 | 協立化学産業株式会社 | Sealant for dripping method of LCD panel |
| EP1405888A1 (en) | 2001-05-16 | 2004-04-07 | Sekisui Chemical Co., Ltd. | Curing resin composition and sealants and end-sealing materials for displays |
| JP2004189942A (en) * | 2002-12-12 | 2004-07-08 | Shin Etsu Chem Co Ltd | Silicone-modified acrylate resin and photocurable resin composition |
| KR100935774B1 (en) * | 2003-06-04 | 2010-01-06 | 세키스이가가쿠 고교가부시키가이샤 | Curing resin composition, sealing material for liquid crystal display device and liquid crystal display device |
| KR100943421B1 (en) * | 2007-12-24 | 2010-02-19 | 연세대학교 산학협력단 | Photopolymerizable monomers having epoxide and undaturated double bonds and their composition |
| KR101569333B1 (en) * | 2013-03-06 | 2015-11-13 | 세키스이가가쿠 고교가부시키가이샤 | Sealing agent for liquid crystal dropping methods, vertically conducting material, and liquid crystal display element |
| KR102215671B1 (en) * | 2013-06-11 | 2021-02-15 | 세키스이가가쿠 고교가부시키가이샤 | Sealing agent for liquid crystal dropping methods, vertically conducting material, and liquid crystal display element |
| KR102240965B1 (en) * | 2013-11-13 | 2021-04-15 | 세키스이가가쿠 고교가부시키가이샤 | Liquid-crystal-display-element sealant, vertical conductive material, and liquid-crystal display element |
| WO2015083663A1 (en) * | 2013-12-05 | 2015-06-11 | 積水化学工業株式会社 | Polymerizable monomer, polymer compound, photocurable resin composition, sealing element for liquid crystal display element, vertical conduction material, and liquid crystal display element |
| JP6754933B2 (en) * | 2014-04-09 | 2020-09-16 | 協立化学産業株式会社 | Liquid crystal sealant applicable to flexible liquid crystal panels |
| JP2016060744A (en) * | 2014-09-12 | 2016-04-25 | 積水化学工業株式会社 | Sealing agent for organic electroluminescence display element |
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| CN109564371A (en) | 2019-04-02 |
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