Classifications

• • 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
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/182—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents
  • C08G59/184—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents with amines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/50—Amines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • 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
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1339—Gaskets; Spacers; Sealing of cells

Definitions

• the present invention relates to a sealant for liquid crystal display elements which is excellent in storage stability, adhesiveness, and low liquid crystal contamination.
• the present invention also relates to a liquid crystal display element using the sealant for a liquid crystal display element.
• a method for manufacturing a liquid crystal display element such as a liquid crystal display cell
• dropping using a sealing agent as disclosed in Patent Documents 1 and 2 A liquid crystal dropping method called construction method is used.
• the dropping method first, a frame-shaped seal pattern is formed on one of the two electrode-attached substrates by dispensing.
• liquid crystal microdroplets are dropped into the frame of the seal pattern while the sealant is not yet cured, and the other substrate is superimposed under vacuum, and the sealant is cured to fabricate a liquid crystal display element.
• this dripping method is the mainstream method for manufacturing liquid crystal display elements.
• narrowing the frame of the liquid crystal display part is mentioned, and for example, the position of the seal part is arranged under the black matrix (hereinafter also referred to as narrow frame design).
• the sealant In the narrow frame design, the sealant is placed directly under the black matrix. The curing of the sealant is insufficient. Insufficient curing of the sealant causes the problem that the uncured sealant components are easily eluted into the liquid crystal to cause liquid crystal contamination. In particular, in recent years, as the polarity of liquid crystals has become higher, contamination of liquid crystals may occur even when using sealing agents that had no problems in the past.
• thermosetting agent is added to the sealant.
• the sealant is also placed on the alignment film, so there is a demand for a sealant for liquid crystal display elements that is excellent in adhesion not only to the substrate but also to the alignment film.
• the resulting sealant may have poor storage stability or cause liquid crystal contamination. was there.
• the present disclosure 1 is a sealant for liquid crystal display elements containing a curable resin and a thermosetting agent, wherein the thermosetting agent is an adduct of an amine compound having an amino group equivalent of 30 or less and an epoxy compound. It is a sealant for liquid crystal display elements containing.
• Present Disclosure 2 is the sealant for a liquid crystal display element according to Present Disclosure 1, wherein the amine-based compound having an amino group equivalent of 30 or less is at least one of hydrazine and carbohydrazide.
• Present Disclosure 3 is the sealant for a liquid crystal display element according to Present Disclosure 1 or 2, wherein the adduct of the amine-based compound having an amino group equivalent of 30 or less and the epoxy compound is solid at 25°C.
• Present Disclosure 4 is the sealant for a liquid crystal display element according to Present Disclosure 1, 2 or 3, wherein the epoxy compound is an epoxy compound having a structure derived from a compound having a phenolic hydroxyl group.
• 5 of the present disclosure is a liquid crystal display device having a cured product of the sealant for a liquid crystal display device of 1, 2, 3 or 4 of the present disclosure. The present invention will be described in detail below.
• the present inventors have studied the use of an amine adduct of an epoxy compound as a thermosetting agent to improve the storage stability and low liquid crystal contamination resistance of a sealant for liquid crystal display elements.
• the obtained sealant for liquid crystal display elements sometimes has poor adhesiveness (in particular, adhesiveness to the alignment film). Therefore, as a result of intensive studies, the present inventors have found that by using an adduct of an amine compound having an amino group equivalent of 30 or less and an epoxy compound as a heat curing agent, storage stability, adhesion, and low liquid crystal staining resistance can be achieved.
• the inventors have found that it is possible to obtain a sealing compound for liquid crystal display elements which is excellent in all of the above, and have completed the present invention.
• the sealant for liquid crystal display elements of the present invention contains a thermosetting agent.
• the thermosetting agent includes an adduct of an amine compound having an amino group equivalent of 30 or less and an epoxy compound (hereinafter also referred to as "adduct according to the present invention").
• adduct according to the present invention an epoxy compound
• the sealant for liquid crystal display elements of the present invention is excellent in all of storage stability, adhesiveness, and low liquid crystal contamination.
• the above-mentioned "amine-based compound” means a compound having an amino group such as an amine compound, a hydrazino compound, a hydrazide compound, and the like.
• amino group equivalent means a value calculated by (molecular weight of amine-based compound) / (number of amino groups in one molecule of amine-based compound), and the above-mentioned "number of amino groups” constitutes an amino group. It means the number of nitrogen atoms. For example, one hydrazino group ( -NHNH2 group) is calculated assuming that the number of amino groups is two.
• the adduct according to the present invention has a structure derived from an amine compound having an amino group equivalent of 30 or less and a structure derived from an epoxy compound.
• the preferred lower limit of the amino group equivalent weight of the amine compound having an amino group equivalent weight of 30 or less, from which the adduct of the present invention is derived, is 15, and the preferred upper limit thereof is 25.
• the amino group equivalent of the amine-based compound having an amino group equivalent of 30 or less is within this range, the resulting sealing agent for liquid crystal display elements is excellent in all of storage stability, adhesion, and low liquid crystal contamination. It becomes excellent by the effect to be made.
• a more preferable lower limit of the amino group equivalent weight of the amine-based compound having an amino group equivalent weight of 30 or less is 16, and a more preferable upper limit thereof is 23.
• amine compound having an amino group equivalent weight of 30 or less examples include hydrazine, carbodihydrazide, oxalyldihydrazide, and the like.
• hydrazine and carbohydrazide is used because it is excellent in the effect of making the resulting sealing agent for liquid crystal display elements excellent in all of storage stability, adhesiveness, and low liquid crystal contamination.
• hydrazine and carbohydrazide is used because it is excellent in the effect of making the resulting sealing agent for liquid crystal display elements excellent in all of storage stability, adhesiveness, and low liquid crystal contamination.
• Epoxy compounds derived from adducts according to the present invention include, for example, bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol E type epoxy compounds, bisphenol S type epoxy compounds, and 2,2'-diallylbisphenol A type. Epoxy compounds, hydrogenated bisphenol type epoxy compounds, propylene oxide added bisphenol A type epoxy compounds, resorcinol type epoxy compounds, biphenyl type epoxy compounds, sulfide type epoxy compounds, diphenyl ether type epoxy compounds, dicyclopentadiene type epoxy compounds, naphthalene type epoxy compounds , phenol novolak type epoxy compound, ortho-cresol novolak type epoxy compound, dicyclopentadiene novolak type epoxy compound, biphenyl novolak type epoxy compound, naphthalenephenol novolak type epoxy compound, glycidylamine type epoxy compound, alkyl polyol type epoxy compound, rubber modified type Examples include epoxy compounds and glycidyl ester compounds.
• an epoxy compound having a structure derived from a compound having a phenolic hydroxyl group is preferred.
• the epoxy compound having a structure derived from a compound having a phenolic hydroxyl group a bisphenol A-type epoxy compound, a bisphenol F-type epoxy compound, and a diphenyl ether-type epoxy compound are more preferable, and a diphenyl ether-type epoxy compound is even more preferable.
• the bisphenol A type epoxy compound include bisphenol A diglycidyl ether.
• the bisphenol F type epoxy compound include bisphenol F diglycidyl ether and bisphenol F type epoxy polymer.
• the diphenyl ether type epoxy compound include bis(4-glycidyloxyphenyl) ether and the like.
• the adduct according to the present invention preferably has a weight average molecular weight of 200 as a lower limit and 3,000 as an upper limit.
• the mass-average molecular weight of the adduct according to the present invention is 200 or more, the resulting sealing compound for liquid crystal display elements is excellent in low liquid crystal contamination.
• the mass-average molecular weight of the adduct according to the present invention is 3000 or less, the obtained sealing agent for liquid crystal display elements is superior in handleability.
• a more preferable lower limit of the mass-average molecular weight of the adduct according to the present invention is 300, and a more preferable upper limit thereof is 1,500.
• the said mass average molecular weight is a value which performs measurement using a tetrahydrofuran as a solvent by a gel permeation chromatography (GPC), and is calculated
• GPC gel permeation chromatography
• Examples of a column for measuring the weight average molecular weight by GPC in terms of polystyrene include Shodex LF-804 (manufactured by Showa Denko KK).
• the adduct according to the present invention is preferably solid at 25°C.
• a preferred lower limit of the melting point of the adduct according to the present invention is 60°C, and a more preferred lower limit is 90°C.
• the upper limit of the melting point of the adduct according to the present invention is preferably 180°C, more preferably 150°C.
• the melting point can be determined by differential scanning calorimetry or a commercially available melting point measuring instrument.
• a preferable lower limit of the content of the adduct according to the present invention to 100 parts by mass of the curable resin described later is 3 parts by mass, and a preferable upper limit is 70 parts by mass.
• the obtained sealing agent for liquid crystal display elements has excellent adhesiveness.
• the obtained sealing compound for liquid crystal display elements is excellent in low liquid crystal contamination and storage stability.
• a more preferable lower limit of the content of the adduct according to the present invention to 100 parts by mass of the curable resin is 6 parts by mass, and a more preferable upper limit is 35 parts by mass.
• the preferable lower limit of the content of the adduct according to the present invention with respect to 1 equivalent of the epoxy compound is 0.5 equivalents, and the preferable upper limit thereof is 2.0 equivalents.
• the content of the adduct according to the present invention relative to 1 equivalent of the epoxy compound is 0.5 equivalent or more, the obtained sealing agent for liquid crystal display elements is excellent in curability and adhesiveness.
• the obtained sealing agent for liquid crystal display elements is excellent in storage stability and low liquid crystal contamination resistance.
• a more preferable lower limit of the content of the adduct according to the present invention with respect to 1 equivalent of the epoxy compound is 0.8 equivalents, and a more preferable upper limit thereof is 1.2 equivalents.
• the sealant for liquid crystal display elements of the present invention contains a curable resin.
• the curable resin preferably contains an epoxy compound.
• the epoxy compounds include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol E type epoxy compounds, bisphenol S type epoxy compounds, 2,2′-diallylbisphenol A type epoxy compounds, and hydrogenated bisphenol type epoxy compounds.
• propylene oxide-added bisphenol A type epoxy compound propylene oxide-added bisphenol A type epoxy compound, resorcinol type epoxy compound, biphenyl type epoxy compound, sulfide type epoxy compound, diphenyl ether type epoxy compound, dicyclopentadiene type epoxy compound, naphthalene type epoxy compound, phenol novolac type epoxy compound, ortho-cresol Novolak-type epoxy compounds, dicyclopentadiene novolak-type epoxy compounds, biphenyl novolac-type epoxy compounds, naphthalenephenol novolak-type epoxy compounds, glycidylamine-type epoxy compounds, alkylpolyol-type epoxy compounds, rubber-modified epoxy compounds, glycidyl ester compounds, and the like. be done.
• bisphenol A type epoxy compounds include, for example, jER828EL, jER1004 (all manufactured by Mitsubishi Chemical Corporation), EPICLON850 (manufactured by DIC Corporation), and the like.
• bisphenol F-type epoxy compounds include, for example, jER806 and jER4004 (both manufactured by Mitsubishi Chemical Corporation) and EPICLON EXA-830CRP (manufactured by DIC Corporation).
• Examples of commercially available bisphenol E type epoxy compounds include Epomic R710 (manufactured by Mitsui Chemicals, Inc.).
• Examples of commercially available bisphenol S-type epoxy compounds include EPICLON EXA-1514 (manufactured by DIC Corporation).
• Examples of commercially available 2,2'-diallylbisphenol A type epoxy compounds include RE-810NM (manufactured by Nippon Kayaku Co., Ltd.).
• Commercially available hydrogenated bisphenol epoxy compounds include, for example, EPICLON EXA-7015 (manufactured by DIC).
• Examples of commercially available propylene oxide-added bisphenol A type epoxy compounds include EP-4000S (manufactured by ADEKA).
• Commercially available resorcinol-type epoxy compounds include, for example, EX-201 (manufactured by Nagase ChemteX Corporation).
• Commercially available biphenyl-type epoxy compounds include, for example, jER YX-4000H (manufactured by Mitsubishi Chemical Corporation).
• Examples of commercially available sulfide-type epoxy compounds include YSLV-50TE (manufactured by Nippon Steel Chemical & Materials Co., Ltd.). Examples of commercially available diphenyl ether type epoxy compounds include YSLV-80DE (manufactured by Nippon Steel Chemical & Materials Co., Ltd.). Examples of commercially available dicyclopentadiene type epoxy compounds include EP-4088S (manufactured by ADEKA). Examples of commercially available naphthalene-type epoxy compounds include EPICLON HP-4032 and EPICLON EXA-4700 (both manufactured by DIC Corporation). Examples of commercially available phenolic novolac type epoxy compounds include EPICLON N-770 (manufactured by DIC Corporation).
• Examples of commercially available ortho-cresol novolac type epoxy compounds include EPICLON N-670-EXP-S (manufactured by DIC Corporation).
• Examples of commercially available dicyclopentadiene novolac type epoxy compounds include EPICLON HP-7200 (manufactured by DIC Corporation).
• Commercially available biphenyl novolac type epoxy compounds include, for example, NC-3000P (manufactured by Nippon Kayaku Co., Ltd.).
• Examples of commercially available naphthalenephenol novolac type epoxy compounds include ESN-165S (manufactured by Nippon Steel Chemical & Materials Co., Ltd.).
• Examples of commercially available glycidylamine type epoxy compounds include jER630 (manufactured by Mitsubishi Chemical Corporation), EPICLON430 (manufactured by DIC Corporation), TETRAD-X (manufactured by Mitsubishi Gas Chemical Co., Ltd.), and the like.
• Examples of commercially available alkyl polyol type epoxy compounds include ZX-1542 (manufactured by Nippon Steel Chemical & Materials), EPICLON726 (manufactured by DIC), Epolite 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), Denacol EX- 611 (manufactured by Nagase ChemteX Corporation) and the like.
• Examples of commercially available rubber-modified epoxy compounds include YR-450 and YR-207 (both manufactured by Nippon Steel Chemical & Materials) and Epolead PB (manufactured by Daicel).
• Examples of commercially available glycidyl ester compounds include Denacol EX-147 (manufactured by Nagase ChemteX Corporation).
• Other commercially available epoxy compounds include YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel Chemical & Materials), XAC4151 (manufactured by Asahi Kasei), jER1031, and jER1032. (all manufactured by Mitsubishi Chemical), EXA-7120 (manufactured by DIC), TEPIC (manufactured by Nissan Chemical) and the like.
• Partially (meth)acryl-modified epoxy compounds are also suitably used as the epoxy compound.
• the partially (meth)acrylic-modified epoxy compound is obtained by reacting a partial epoxy group of an epoxy compound having two or more epoxy groups with (meth)acrylic acid. It means a compound having one or more epoxy groups and one or more (meth)acryloyl groups in the molecule.
• the above-mentioned "(meth)acryl” means acryl or methacryl
• the above-mentioned "(meth)acryloyl” means acryloyl or methacryloyl.
• Examples of commercially available partially (meth)acrylic-modified epoxy compounds include UVACURE 1561, KRM8030, and KRM8287 (all manufactured by Daicel Allnex).
• the curable resin may contain a (meth)acrylic compound.
• the (meth)acrylic compound include (meth)acrylic acid ester compounds, epoxy (meth)acrylates, and urethane (meth)acrylates. Among them, epoxy (meth)acrylate is preferred.
• the (meth)acrylic compound preferably has two or more (meth)acryloyl groups in one molecule from the viewpoint of reactivity.
• the said "(meth)acrylic compound” means the compound which has a (meth)acryloyl group.
• the above “(meth)acrylate” means acrylate or methacrylate
• the above "epoxy(meth)acrylate” is a compound obtained by reacting all epoxy groups in an epoxy compound with (meth)acrylic acid. represents
• monofunctional ones include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, and isobutyl (meth)acrylate.
• t-butyl (meth)acrylate 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, iso myristyl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexyl ( meth)acrylate, isobornyl (meth)acrylate, bicyclopentenyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate,
• bifunctional ones include, for example, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexane Diol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate (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, neopen
• trifunctional or higher ones include, for example, trimethylolpropane tri(meth)acrylate, ethylene oxide-added trimethylolpropane tri(meth)acrylate, propylene oxide-added trimethylolpropane tri( meth)acrylate, caprolactone-modified trimethylolpropane tri(meth)acrylate, ethylene oxide-added isocyanuric acid tri(meth)acrylate, glycerin tri(meth)acrylate, propylene oxide-added glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tris(meth)acryloyloxyethyl phosphate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol penta(meth)acryl
• Examples of the epoxy (meth)acrylate include those obtained by reacting an epoxy compound and (meth)acrylic acid in the presence of a basic catalyst according to a conventional method.
• the same epoxy compound as the curable resin contained in the sealing agent for liquid crystal display elements of the present invention can be used.
• epoxy (meth)acrylates include, for example, epoxy (meth)acrylate manufactured by Daicel Allnex, epoxy (meth)acrylate manufactured by Shin-Nakamura Chemical Industry, epoxy (meth)acrylate manufactured by Kyoeisha Chemical Co., Ltd. ( meth) acrylate, epoxy (meth) acrylate manufactured by Nagase ChemteX Corporation, and the like.
• Epoxy Ester M-600A Epoxy Ester 40EM, Epoxy Ester 70PA, Epoxy Ester 200PA, Epoxy Ester 80MFA, Epoxy Ester 3002M, Epoxy Ester 3002A, Epoxy Ester 1600A, Epoxy Ester 3000M, Epoxy Ester 3000A, Epoxy Ester 200EA, Epoxy Ester 400EA and the like.
• Examples of epoxy (meth)acrylates manufactured by Nagase ChemteX Co., Ltd. include Denacol acrylate DA-141, Denacol acrylate DA-314, Denacol acrylate DA-911, and the like.
• the urethane (meth)acrylate can be obtained, for example, by reacting an isocyanate compound with a (meth)acrylic acid derivative having a hydroxyl group in the presence of a catalytic amount of a tin compound.
• MDI diphenylmethane-4,4
• the isocyanate compound that is a raw material for the urethane (meth)acrylate a chain-extended isocyanate compound obtained by reacting a polyol with an excessive amount of an isocyanate compound can also be used.
• the polyol include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, polycaprolactone diol and the like.
• Examples of the (meth)acrylic acid derivative having a hydroxyl group include hydroxyalkyl mono(meth)acrylates, dihydric alcohol mono(meth)acrylates, trihydric alcohol mono(meth)acrylates and di(meth)acrylates. , epoxy (meth)acrylate, and the like.
• Examples of the hydroxyalkyl mono(meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and the like. mentioned.
• 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, glycerin and the like.
• Examples of the epoxy (meth)acrylate include bisphenol A type epoxy (meth)acrylate.
• urethane (meth) acrylates examples include urethane (meth) acrylate manufactured by Toagosei Co., Ltd., urethane (meth) acrylate manufactured by Daicel Allnex, and urethane (meth) acrylate manufactured by Negami Kogyo Co., Ltd. acrylate, urethane (meth)acrylate manufactured by Shin-Nakamura Chemical Co., Ltd., urethane (meth)acrylate manufactured by Kyoeisha Chemical Co., Ltd., and the like.
• Examples of the urethane (meth)acrylates manufactured by Toagosei Co., Ltd. examples include M-1100, M-1200, M-1210 and M-1600.
• urethane (meth)acrylate manufactured by Kyoeisha Chemical Co., Ltd. include AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, and UA-306T. be done.
• the epoxy group in the curable resin and the (meth) is 30 mol % or more and 95 mol % or less.
• the resulting sealant for liquid crystal display elements has excellent adhesion while suppressing the occurrence of liquid crystal contamination.
• the curable resin preferably has a hydrogen-bonding unit such as —OH group, —NH— group, or —NH 2 group.
• the sealant for liquid crystal display elements of the present invention preferably contains a radical photopolymerization initiator.
• the radical photopolymerization initiator include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, and thioxanthone compounds.
• photoradical polymerization initiator examples include 1-hydroxycyclohexylphenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-(dimethylamino )-2-((4-methylphenyl)methyl)-1-(4-(4-morpholinyl)phenyl)-1-butanone, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis( 2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 1-(4-(2-hydroxyethoxy)-phenyl) -2-hydroxy-2-methyl-1-propan-1-one, 1-(4-(phenylthio)phenyl)-1,2-octanedione 2-(O-benzoyloxime), 2,4,6-trimethyl and benzoyldiphenylphosphine
• the content of the radical photopolymerization initiator has a preferable lower limit of 0.5 parts by mass and a preferable upper limit of 10 parts by mass with respect to 100 parts by mass of the curable resin.
• the content of the radical photopolymerization initiator is within this range, the resulting sealing compound for liquid crystal display elements is excellent in storage stability and photocurability while suppressing liquid crystal contamination.
• a more preferable lower limit to the content of the radical photopolymerization initiator is 1 part by mass, and a more preferable upper limit is 7 parts by mass.
• the sealing compound for liquid crystal display elements of the present invention may contain a thermal radical polymerization initiator.
• the thermal radical polymerization initiator include those composed of azo compounds, organic peroxides, and the like. Among them, from the viewpoint of suppressing liquid crystal contamination, an initiator composed of an azo compound (hereinafter also referred to as an "azo initiator”) is preferable, and an initiator composed of a polymer azo compound (hereinafter referred to as a "polymer azo initiator”) is preferable. Also referred to as "initiator”) is more preferred.
• the thermal radical polymerization initiators may be used alone, or two or more of them may be used in combination.
• polymeric azo compound means a compound having an azo group, a number average molecular weight of 300 or more, which generates a radical capable of reacting with a (meth)acryloyl group by heat. do.
• a preferable lower limit of the number average molecular weight of the above high-molecular azo compound is 1,000, and a preferable upper limit thereof is 300,000.
• the lower limit of the number average molecular weight of the high-molecular azo compound is more preferably 5,000, the upper limit is 100,000, the lower limit is still more preferably 10,000, and the upper limit is still more preferably 90,000.
• the said number average molecular weight is a value which measures by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent, and is calculated
• GPC gel permeation chromatography
• Examples of a column for measuring the number average molecular weight by GPC in terms of polystyrene include Shodex LF-804 (manufactured by Showa Denko KK).
• Examples of the polymer azo compound include those having a structure in which a plurality of units such as polyalkylene oxide and polydimethylsiloxane are bonded via an azo group.
• the polymer azo compound having a structure in which a plurality of units such as polyalkylene oxide are bonded via the azo group one having a polyethylene oxide structure is preferable.
• Specific examples of the high-molecular azo compound include polycondensates of 4,4′-azobis(4-cyanopentanoic acid) and polyalkylene glycol, and 4,4′-azobis(4-cyanopentanoic acid). and a polycondensate of polydimethylsiloxane having a terminal amino group.
• polymeric azo initiators include, for example, VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 (all manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) and the like. mentioned.
• non-polymeric azo initiators include V-65 and V-501 (both manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.).
• organic peroxides examples include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, peroxyesters, diacyl peroxides and peroxydicarbonates.
• the content of the thermal radical polymerization initiator has a preferable lower limit of 0.1 parts by mass and a preferable upper limit of 10 parts by mass with respect to 100 parts by mass of the curable resin.
• the content of the thermal radical polymerization initiator is within this range, the obtained sealing compound for liquid crystal display elements is excellent in storage stability and thermosetting property while suppressing liquid crystal contamination.
• a more preferable lower limit to the content of the thermal radical polymerization initiator is 0.3 parts by mass, and a more preferable upper limit is 5 parts by mass.
• the sealant for liquid crystal display elements of the present invention may contain a filler for the purpose of improving viscosity, improving adhesion due to stress dispersion effect, improving coefficient of linear expansion, improving moisture resistance of the cured product, and the like.
• An inorganic filler or an organic filler can be used as the filler.
• inorganic fillers include silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, smectite, bentonite, montmorillonite, sericite, activated clay, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, and titanium oxide. , calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate, calcium silicate and the like.
• the organic filler include polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, acrylic polymer fine particles, and the like. The above fillers may be used alone, or two or more of them may be used in combination.
• a preferable lower limit of the content of the filler in 100 parts by mass of the sealing compound for liquid crystal display elements of the present invention is 10 parts by mass, and a preferable upper limit thereof is 70 parts by mass.
• the content of the filler is within this range, the effect of improving adhesiveness and the like is excellent without deteriorating coatability and the like.
• a more preferable lower limit of the filler content is 20 parts by mass, and a more preferable upper limit is 60 parts by mass.
• the sealing compound for liquid crystal display elements of the present invention may contain a silane coupling agent.
• the silane coupling agent mainly functions as an adhesion assistant for good adhesion between the liquid crystal display element sealing compound and the substrate.
• silane coupling agent for example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane and the like are preferably used. These are excellent in the effect of improving the adhesiveness to a substrate or the like, and can suppress the outflow of the curable resin into the liquid crystal by chemically bonding with the curable resin. Among them, 3-glycidoxypropyltrimethoxysilane is preferred.
• the silane coupling agents may be used alone, or two or more of them may be used in combination.
• a preferable lower limit of the content of the silane coupling agent in 100 parts by mass of the liquid crystal display element sealing compound of the present invention is 0.1 parts by mass, and a preferable upper limit thereof is 10 parts by mass.
• the content of the silane coupling agent is within this range, the effect of improving adhesion while suppressing the occurrence of liquid crystal contamination is more excellent.
• a more preferable lower limit to the content of the silane coupling agent is 0.3 parts by mass, and a more preferable upper limit is 5 parts by mass.
• the sealant for liquid crystal display elements of the present invention may contain a light shielding agent.
• the sealant for liquid crystal display elements of the present invention can be suitably used as a light shielding sealant.
• Examples of the light shielding agent include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. Among them, titanium black is preferred.
• Titanium black is a substance that exhibits a higher transmittance for light in the vicinity of the ultraviolet region, particularly light with a wavelength of 370 nm or more and 450 nm or less, than average transmittance for light with a wavelength of 300 nm or more and 800 nm or less. That is, the titanium black has a property of imparting a light-shielding property to the sealing agent for a liquid crystal display element of the present invention by sufficiently shielding light of wavelengths in the visible light region, while transmitting light of wavelengths in the vicinity of the ultraviolet region.
• the photoradical polymerization initiator one capable of initiating the reaction by light of a wavelength that increases the transmittance of the titanium black, the photocurability of the sealant for a liquid crystal display element of the present invention is further increased.
• the light shielding agent contained in the sealing compound for liquid crystal display elements of the present invention a substance with high insulating properties is preferable, and titanium black is also suitable as the light shielding agent with high insulating properties.
• the above titanium black preferably has an optical density (OD value) per 1 ⁇ m of 3 or more, more preferably 4 or more. The higher the light shielding property of the titanium black, the better. Although there is no particular upper limit for the OD value of the titanium black, it is usually 5 or less.
• the above titanium black exerts a sufficient effect even if it is not surface-treated, but it can also be used when the surface is treated with an organic component such as a coupling agent, silicon oxide, titanium oxide, germanium oxide, aluminum oxide, oxide.
• an organic component such as a coupling agent, silicon oxide, titanium oxide, germanium oxide, aluminum oxide, oxide.
• Surface-treated titanium blacks such as those coated with inorganic components such as zirconium and magnesium oxide, can also be used. Among them, those treated with an organic component are preferable because they can further improve the insulating properties.
• the liquid crystal display device manufactured using the sealing agent for a liquid crystal display device of the present invention in which the above-described titanium black is blended as a light shielding agent has sufficient light shielding properties, so that light does not leak out and has high contrast. A liquid crystal display element having excellent image display quality can be realized.
• titanium blacks include, for example, titanium black manufactured by Mitsubishi Materials Corporation, titanium black manufactured by Ako Kasei Co., Ltd., and the like. Examples of titanium black manufactured by Mitsubishi Materials Corporation include 12S, 13M, 13M-C, 13R-N, and 14M-C. Examples of the titanium black manufactured by Ako Kasei Co., Ltd. include Tilak D and the like.
• the specific surface area of the titanium black has a preferred lower limit of 13 m 2 /g, a preferred upper limit of 30 m 2 /g, a more preferred lower limit of 15 m 2 /g, and a more preferred upper limit of 25 m 2 /g.
• the preferred lower limit of the volume resistivity of 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 size of the light shielding agent is not particularly limited as long as it is equal to or smaller 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 5000 nm. When the primary particle size of the light shielding agent is within this range, the obtained sealing agent for liquid crystal display elements can be made more excellent in light shielding properties without deteriorating the applicability or the like.
• the primary particle size of the light shielding agent has a more preferable lower limit of 5 nm, a more preferable upper limit of 200 nm, a still more preferable lower limit of 10 nm, and a still more preferable upper limit of 100 nm.
• the primary particle size of the light shielding agent can be measured by dispersing the light shielding agent in a solvent (water, organic solvent, etc.) using NICOMP 380ZLS (manufactured by PARTICLE SIZING SYSTEMS).
• a preferable lower limit of the content of the light shielding agent in 100 parts by mass of the liquid crystal display element sealing compound of the present invention is 5 parts by mass, and a preferable upper limit thereof is 80 parts by mass.
• the content of the light-shielding agent is within this range, the obtained sealant for liquid crystal display elements exhibits excellent light-shielding properties without significantly deteriorating the adhesiveness, strength after curing, and drawability. be able to.
• a more preferable lower limit of the content of the light shielding agent is 10 parts by mass, a more preferable upper limit is 70 parts by mass, a still more preferable lower limit is 30 parts by mass, and a further preferable upper limit is 60 parts by mass.
• the sealant for liquid crystal display elements of the present invention may further contain, if necessary, stress relaxation agents, reactive diluents, thixotropic agents, spacers, curing accelerators, antifoaming agents, leveling agents, polymerization inhibitors, and the like. It may contain an agent.
• a mixer is used to mix a curable resin, a thermosetting agent, and a photoradical polymerization initiator to be added as necessary. and the like.
• the mixer include a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and three rolls.
• the conductive fine particles for example, metal balls, resin fine particles having a conductive metal layer formed on the surface thereof, and the like can be used.
• the one in which a conductive metal layer is formed on the surface of the resin fine particles is preferable because the excellent elasticity of the resin fine particles enables conductive connection without damaging the transparent substrate or the like.
• a liquid crystal display element having a cured product of the sealant for a liquid crystal display element of the present invention is also one aspect of the present invention.
• a liquid crystal display element having a narrow frame design is preferable. Specifically, it is preferable that the width of the frame portion around the liquid crystal display section is 2 mm or less. Moreover, it is preferable that the coating width of the sealant for a liquid crystal display element of the present invention when manufacturing the liquid crystal display element of the present invention is 1 mm or less.
• the sealing compound for liquid crystal display elements of the present invention can be suitably used for manufacturing liquid crystal display elements by the liquid crystal dropping method.
• Examples of the method for manufacturing the liquid crystal display element of the present invention by the liquid crystal dropping method include the following methods. First, a step of forming a frame-shaped seal pattern on a substrate by screen printing, applying with a dispenser, or the like, is performed with the sealant for a liquid crystal display element of the present invention. Next, a step of applying liquid crystal microdroplets to the entire surface of the frame of the seal pattern while the sealant for a liquid crystal display element of the present invention is in an uncured state, and immediately superimposing another substrate is performed. After that, a liquid crystal display element can be obtained by a method of performing a step of heating and curing the sealant. Moreover, before the step of heating and curing the sealant, a step of temporarily curing the sealant by irradiating the seal pattern portion with light such as ultraviolet rays may be performed.
• the sealing compound for liquid crystal display elements which is excellent in storage stability, adhesiveness, and low-liquid-crystal contamination property can be provided. Further, according to the present invention, it is possible to provide a liquid crystal display element using the sealant for a liquid crystal display element.
• adduct A that was solid at 25°C.
• the mass average molecular weight of adduct A was 1,200.
• 1 H-NMR, 13 C-NMR, and FT-IR confirmed that the adduct A had a hydrazine-derived structure and a bisphenol F diglycidyl ether-derived structure.
• the mass average molecular weight of adduct F was 1,350.
• 1 H-NMR, 13 C-NMR, and FT-IR confirmed that the adduct F had a structure derived from carbodihydrazide and a structure derived from bisphenol F diglycidyl ether.
• Examples 1 to 10 Comparative Examples 1 to 4
• a planetary stirrer manufactured by Thinky Co., Ltd., "Awatori Mixer”
• Sealants for liquid crystal display elements of Examples 1 to 10 and Comparative Examples 1 to 4 were prepared.
• spacer fine particles 1 part by mass of spacer fine particles was dispersed in 100 parts by mass of each sealant for liquid crystal display elements obtained in Examples and Comparative Examples.
• Micropearl SI-H050 manufactured by Sekisui Chemical Co., Ltd.
• a liquid crystal display element sealing compound in which spacer particles were dispersed was minutely dropped onto one of two glass substrates (length 4.5 mm, width 2.5 mm) with an ITO thin film.
• Another ITO thin film-coated glass substrate was attached to this in a cross shape, irradiated with ultraviolet rays of 3000 mJ/cm 2 with a metal halide lamp, and then heated at 120° C.
• the bonded substrates were allowed to stand still for 15 minutes after bonding, and then the portion of the liquid crystal display element sealing agent was irradiated with ultraviolet rays of 100 mW/cm 2 for 30 seconds using a metal halide lamp to temporarily remove the liquid crystal display element sealing agent. Hardened.
• the composition was heated at 120° C. for 1 hour for final curing, thereby producing a liquid crystal display device.
• the resulting liquid crystal display device was checked for alignment disorder (display unevenness) using a polarizing microscope ("VHX-5000" manufactured by Keyence Corporation). Orientation disorder was judged from color unevenness in the display portion, and the low liquid crystal contamination resistance was evaluated as "O" when no display unevenness was observed in the liquid crystal display element, and as "X" when display unevenness was observed.
• the sealing compound for liquid crystal display elements which is excellent in storage stability, adhesiveness, and low-liquid-crystal contamination property can be provided. Further, according to the present invention, it is possible to provide a liquid crystal display element using the sealant for a liquid crystal display element.

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