Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C243/00—Compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
  • C07C243/24—Hydrazines having nitrogen atoms of hydrazine groups acylated by carboxylic acids
  • C07C243/38—Hydrazines having nitrogen atoms of hydrazine groups acylated by carboxylic acids with acylating carboxyl groups bound to carbon atoms of six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
  • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
  • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
  • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
  • C07D251/30—Only oxygen atoms
  • C07D251/34—Cyanuric or isocyanuric esters
• • 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
• • 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
  • C08G59/40—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
• • 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
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/08—Polyhydrazides; Polytriazoles; Polyaminotriazoles; Polyoxadiazoles
• • 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 novel hydrazide compounds.
• the present invention also provides a curable resin composition containing the hydrazide compound and having excellent storage stability and adhesiveness, and a liquid crystal display element comprising the curable resin composition and having excellent low liquid crystal contamination resistance.
• the present invention relates to a sealant and 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. In some cases, the curing was insufficient with the sealant of . Insufficient curing of the sealant causes a problem that uncured sealant components are eluted and precipitated in the liquid crystal, which tends to cause display defects in the liquid crystal display element. In particular, in recent years, as the polarity of liquid crystals has become higher, there has been a problem that display defects are more likely to occur even when a sealant, which has not been problematic in the past, is used.
• An object of the present invention is to provide a novel hydrazide compound.
• the present invention also provides a curable resin composition containing the hydrazide compound and having excellent storage stability and adhesiveness, and a liquid crystal display element comprising the curable resin composition and having excellent low liquid crystal contamination resistance.
• An object of the present invention is to provide a sealant and a liquid crystal display element.
• the present disclosure 1 is a hydrazide compound characterized by having one or more structures represented by the following formula (1) and two or more hydrazide groups in one molecule.
• the present disclosure 2 is the hydrazide compound of the present disclosure 1 having two or more structures represented by the above formula (1) in one molecule.
• Present Disclosure 3 is a hydrazide compound according to Present Disclosure 1 or 2, which has a structure represented by the following formula (2) as the structure containing the hydrazide group.
• the present disclosure 4 is a hydrazide compound of the present disclosure 1, 2 or 3 represented by the following formula (3).
• the present disclosure 5 is a hydrazide compound of the present disclosure 1, 2, 3 or 4 represented by the following formula (4).
• the present disclosure 6 is a curable resin composition containing a curable resin and a thermosetting agent, wherein the thermosetting agent is a curable resin containing the hydrazide compound of the present disclosure 1, 2, 3, 4 or 5 composition.
• the present disclosure 7 is the curable resin composition of the present disclosure 6, further containing a radical photopolymerization initiator.
• 8 of the present disclosure is a sealant for liquid crystal display elements using the curable resin composition of 6 or 7 of the present disclosure.
• a ninth aspect of the present disclosure is a liquid crystal display device having a cured product of the sealant for a liquid crystal display device of the eighth aspect of the present disclosure.
• * is a binding position
• Ar is an optionally substituted aromatic ring
• m is 1 or 2
• * is a bonding position
• Y is an organic group
• Ar is an optionally substituted aromatic ring
• m is 1 or 2
• n is 2 or 3.
• X is a polyfunctional glycidyloxy compound residue
• Ar is an optionally substituted aromatic ring
• m is 1 or 2
• n is 2 or 3.
• the present invention will be described in detail below.
• the present inventors have found that by using a hydrazide compound having a specific structure as a thermosetting agent, it is possible to obtain a curable resin composition having excellent storage stability and adhesiveness, and furthermore, the curable resin composition
• the present inventors have found that a sealant for liquid crystal display elements using a material is excellent in low liquid crystal contamination, and have completed the present invention.
• the hydrazide compound of the present invention has one or more structures represented by the above formula (1) in one molecule.
• a curable resin composition having excellent storage stability and adhesiveness can be obtained.
• a liquid crystal display device sealant using the curable resin composition can provide a liquid crystal display device with excellent display performance.
• the curable resin composition containing the hydrazide compound of the present invention as a thermosetting agent has excellent curability.
• the hydrazide compound of the present invention preferably has two or more structures represented by the above formula (1) in one molecule.
• the hydrazide compound of the present invention has two or more hydrazide groups in one molecule.
• the hydrazide compound of the present invention more preferably has three or more hydrazide groups in one molecule, and still more preferably four or more.
• the hydrazide compound of the present invention preferably has the structure represented by the above formula (2) as the structure containing the hydrazide group.
• Examples of the optionally substituted aromatic ring represented by Ar in the above formula (2), the above formula (3), the above formula (4), and the below-described formula (11) include a benzene ring, pyridine ring, naphthalene ring, and the like. Among them, a benzene ring is preferred. Further, as the substituent when the aromatic ring represented by Ar in the above formula (2), the above formula (3), the above formula (4), and the below-described formula (11) is substituted, for example , methylene group, aryl group, alkynyl group, amino group, nitro group, hydroxyl group, carboxy group and the like.
• the hydrazide compound of the present invention is preferably represented by the above formula (3), more preferably represented by the above formula (4).
• Examples of the polyfunctional glycidyloxy compound from which the polyfunctional glycidyloxy compound residue in the formula (4) is derived include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol E diglycidyl ether, and bisphenol S diglycidyl.
• bis(4-glycidyloxyphenyl) ether is preferred.
• the "polyfunctional glycidyloxy compound” means a compound having two or more diglycidyloxy groups in one molecule
• the "polyfunctional glycidyloxy compound residue” refers to the polyfunctional glycidyl It means the structure of the portion other than the glycidyloxy group in the oxy compound.
• hydrazide compound of the present invention include compounds represented by the following formulas (5) to (10).
• R 1 to R 8 are each independently a hydrogen atom, a methylene group, an aryl group, an alkynyl group, an amino group, a nitro group, a hydroxyl group, or a carboxy group.
• R 9 to R 16 are each independently a methylene group, an aryl group, an alkynyl group, an amino group, a nitro group, a hydroxyl group, or a carboxy group.
• R 17 to R 28 are each independently a methylene group, an aryl group, an alkynyl group, an amino group, a nitro group, a hydroxyl group, or a carboxy group.
• R 29 to R 36 are each independently a methylene group, an aryl group, an alkynyl group, an amino group, a nitro group, a hydroxyl group, or a carboxy group.
• R 37 to R 42 are each independently a methylene group, an aryl group, an alkynyl group, an amino group, a nitro group, a hydroxyl group, or a carboxy group.
• R 43 to R 50 are each independently a methylene group, an aryl group, an alkynyl group, an amino group, a nitro group, a hydroxyl group, or a carboxy group.
• Examples of the method for producing the hydrazide compound of the present invention include the following methods. That is, first, the polyfunctional glycidyloxy compound and the compound represented by the following formula (11) are reacted by heating in toluene in the presence of a catalyst. Then, the hydrazide compound of the present invention can be obtained by adding hydrazine to the obtained reactant in methanol for reaction.
• R is an alkyl group having 1 to 4 carbon atoms
• Ar is an optionally substituted aromatic ring.
• Examples of compounds represented by the above formula (11) include methyl p-hydroxybenzoate, methyl 3-hydroxybenzoate, methyl 4-(hydroxymethyl)benzoate, methyl 4-hydroxyphenylacetate, (R)- (+)-Methyl 2-(4-hydroxyphenoxy)propionate, Methyl 6-hydroxy-2-naphthoate, Methyl 2-hydroxy-1-naphthoate, Methyl 3-hydroxy-2-naphthoate, 5-Hydroxynicotine methyl acid, methyl salicylate, dimethyl 5-hydroxyisophthalate, dimethyl 4-hydroxyisophthalate and the like. Among them, methyl p-hydroxybenzoate and dimethyl 5-hydroxyisophthalate are preferred.
• the hydrazide compound of the present invention is suitably used as a thermosetting agent blended in a curable resin composition.
• a curable resin composition containing a curable resin and a thermosetting agent, wherein the thermosetting agent comprises the hydrazide compound of the present invention is also one aspect of the present invention.
• a preferable lower limit of the content of the hydrazide compound of the present invention is 3 parts by weight, and a preferable upper limit thereof is 20 parts by weight based on 100 parts by weight of the curable resin.
• the resulting curable resin composition is more excellent in curability and adhesiveness.
• the content of the hydrazide compound of the present invention is 20 parts by weight or less, the resulting curable resin composition has excellent storage stability, and when used as a sealant for liquid crystal display elements, the liquid crystal contamination is reduced. It will be superior in terms of properties.
• a more preferred lower limit to the content of the hydrazide compound of the present invention is 5 parts by weight, and a more preferred upper limit is 15 parts by weight.
• the curable resin composition of the present invention may contain other thermosetting agents in addition to the hydrazide compound of the present invention within a range that does not hinder the object of the present invention.
• other thermosetting agents include hydrazide compounds other than the hydrazide compound of the present invention, imidazole derivatives, amine compounds, polyhydric phenolic compounds, acid anhydrides, and the like.
• the curable resin composition of the present invention contains a curable resin.
• the curable resin preferably contains an epoxy compound.
• the epoxy compound include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, 2,2'-diallylbisphenol A type epoxy resin, and hydrogenated bisphenol type epoxy resin.
• propylene oxide-added bisphenol A type epoxy resin propylene oxide-added bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, sulfide type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, ortho cresol Novolak type epoxy resin, dicyclopentadiene novolak type epoxy resin, biphenyl novolak type epoxy resin, naphthalenephenol novolac type epoxy resin, glycidylamine type epoxy resin, alkyl polyol type epoxy resin, rubber modified type epoxy resin, glycidyl ester compound, etc. be done.
• bisphenol A type epoxy resins include, for example, jER828EL, jER1004 (all manufactured by Mitsubishi Chemical Corporation), EPICLON850 (manufactured by DIC Corporation), and the like.
• bisphenol F type epoxy resins include, for example, jER806, jER4004 (both manufactured by Mitsubishi Chemical Corporation) and EPICLON EXA-830CRP (manufactured by DIC Corporation).
• Examples of commercially available bisphenol E type epoxy resins include Epomic R710 (manufactured by Mitsui Chemicals, Inc.).
• Examples of commercially available bisphenol S-type epoxy resins include EPICLON EXA-1514 (manufactured by DIC Corporation).
• 2,2'-diallylbisphenol A type epoxy resins include, for example, RE-810NM (manufactured by Nippon Kayaku Co., Ltd.).
• Commercially available hydrogenated bisphenol type epoxy resins include, for example, EPICLON EXA-7015 (manufactured by DIC Corporation).
• Commercially available propylene oxide-added bisphenol A type epoxy resins include, for example, EP-4000S (manufactured by ADEKA).
• commercially available resorcinol-type epoxy resins include, for example, EX-201 (manufactured by Nagase ChemteX Corporation).
• biphenyl-type epoxy resins include, for example, jER YX-4000H (manufactured by Mitsubishi Chemical Corporation).
• commercially available sulfide-type epoxy resins include, for example, YSLV-50TE (manufactured by Nippon Steel Chemical & Materials Co., Ltd.).
• Examples of commercially available diphenyl ether type epoxy resins include YSLV-80DE (manufactured by Nippon Steel Chemical & Materials Co., Ltd.).
• dicyclopentadiene type epoxy resins include, for example, EP-4088S (manufactured by ADEKA).
• Examples of commercially available naphthalene-type epoxy resins include EPICLON HP-4032 and EPICLON EXA-4700 (both manufactured by DIC Corporation).
• Commercially available phenolic novolac epoxy resins include, for example, EPICLON N-770 (manufactured by DIC Corporation).
• Examples of commercially available ortho-cresol novolak type epoxy resins include EPICLON N-670-EXP-S (manufactured by DIC Corporation).
• Commercially available dicyclopentadiene novolac type epoxy resins include, for example, EPICLON HP-7200 (manufactured by DIC Corporation).
• biphenyl novolak type epoxy resins include, for example, NC-3000P (manufactured by Nippon Kayaku Co., Ltd.).
• commercially available naphthalene phenol novolac type epoxy resins include, for example, ESN-165S (manufactured by Nippon Steel Chemical & Materials Co., Ltd.).
• Examples of commercially available glycidylamine epoxy resins include jER630 (manufactured by Mitsubishi Chemical Corporation), EPICLON430 (manufactured by DIC Corporation), and TETRAD-X (manufactured by Mitsubishi Gas Chemical Company, Inc.).
• alkyl polyol type epoxy resins examples 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.
• commercially available rubber-modified epoxy resins include, for example, 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)acrylic-modified epoxy resins are also suitably used as the epoxy compound.
• the partially (meth)acrylic-modified epoxy resin 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 resins include UVACURE 1561 and KRM8287 (both 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 curable resin composition 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 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 curable resin composition has excellent adhesiveness, and when used as a sealant for liquid crystal display elements, it exhibits excellent low liquid crystal contamination resistance. become a thing.
• the curable resin preferably has a hydrogen-bonding unit such as —OH group, —NH— group, or —NH 2 group.
• the curable resin composition of the present invention preferably further contains a radical photopolymerization initiator.
• a radical photopolymerization initiator examples 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
• a preferable lower limit is 0.5 parts by weight and a preferable upper limit is 10 parts by weight with respect to 100 parts by weight of the curable resin.
• the content of the photoradical polymerization initiator is within this range, the resulting curable resin composition is excellent in storage stability and photocurability, and when used as a sealant for liquid crystal display elements. It becomes excellent due to low liquid crystal contamination.
• a more preferable lower limit to the content of the radical photopolymerization initiator is 1 part by weight, and a more preferable upper limit is 7 parts by weight.
• the curable resin composition 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 when the resulting curable resin composition is used as a sealing agent for liquid crystal display elements, an initiator composed of an azo compound (hereinafter also referred to as an "azo initiator”) is used. An initiator composed of a polymeric azo compound (hereinafter also referred to as “polymeric azo 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, generating a radical capable of curing a (meth)acryloyl group by heat, and having a number average molecular weight of 300 or more. 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 number average molecular weight of the high-molecular-weight azo compound is within this range, the resulting curable resin composition can be easily converted into a curable resin while preventing adverse effects on the liquid crystal when used as a sealing agent for a liquid crystal display element.
• 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 weight and a preferable upper limit of 10 parts by weight with respect to 100 parts by weight of the curable resin.
• the resulting curable resin composition has excellent storage stability and thermosetting properties, and when used as a sealant for liquid crystal display elements, It becomes excellent due to low liquid crystal contamination.
• a more preferable lower limit to the content of the thermal radical polymerization initiator is 0.3 parts by weight, and a more preferable upper limit is 5 parts by weight.
• the curable resin composition of the present invention may contain a filler for the purpose of improving viscosity, improving adhesiveness 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 weight of the curable resin composition of the present invention is 10 parts by weight, and a preferable upper limit thereof is 70 parts by weight.
• a more preferable lower limit of the filler content is 20 parts by weight, and a more preferable upper limit thereof is 60 parts by weight.
• the curable resin composition of the invention may contain a silane coupling agent.
• the silane coupling agent mainly serves as an adhesion aid for good adhesion between the curable resin composition 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 substrates and the like, and when the obtained curable resin composition is used as a sealing agent for liquid crystal display elements, it is possible to suppress the outflow of the curable resin into the liquid crystal. can.
• 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 weight of the curable resin composition of the present invention is 0.1 parts by weight, and a preferable upper limit thereof is 10 parts by weight.
• the content of the silane coupling agent is within this range, the effect of improving the adhesiveness is excellent, and when the obtained curable resin composition is used as a sealing agent for a liquid crystal display element, the liquid crystal content is low. It becomes more excellent in stain resistance.
• a more preferable lower limit to the content of the silane coupling agent is 0.3 parts by weight, and a more preferable upper limit is 5 parts by weight.
• the curable resin composition of the present invention may contain a light shielding agent.
• the curable resin composition 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 preferable.
• 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 imparts a light-shielding property to the curable resin composition of the present invention by sufficiently shielding light with a wavelength in the visible light region, while transmitting light with a wavelength in the vicinity of the ultraviolet region. It is a light shielding agent.
• the photoradical polymerization initiator one capable of initiating the reaction by light having a wavelength at which the transmittance of the titanium black increases, the photocurability of the curable resin composition of the present invention is further increased. be able to.
• the light shielding agent contained in the curable resin composition of the present invention is preferably a highly insulating substance, and titanium black is also suitable as the highly insulating light shielding agent.
• 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 display element manufactured using the curable resin composition of the present invention containing the above titanium black as a light shielding agent has sufficient light shielding properties, so that light does not leak out and has high contrast. A display element having 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.
• a preferable lower limit of the primary particle size of the light shielding agent is 1 nm, and a preferable upper limit thereof is 5000 nm.
• 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 weight of the curable resin composition of the present invention is 5 parts by weight, and a preferable upper limit thereof is 80 parts by weight.
• the content of the light-shielding agent is within this range, the resulting curable resin composition exhibits excellent light-shielding properties without significantly deteriorating the adhesiveness, strength after curing, and drawability. can be done.
• a more preferable lower limit of the content of the light shielding agent is 10 parts by weight, a more preferable upper limit is 70 parts by weight, a still more preferable lower limit is 30 parts by weight, and a further preferable upper limit is 60 parts by weight.
• the curable resin composition of the present invention may further contain additives such as stress relaxation agents, reactive diluents, thixotropic agents, spacers, curing accelerators, antifoaming agents, leveling agents, polymerization inhibitors, etc. may contain.
• additives such as stress relaxation agents, reactive diluents, thixotropic agents, spacers, curing accelerators, antifoaming agents, leveling agents, polymerization inhibitors, etc. may contain.
• a mixer is used to mix a curable resin, a thermosetting agent, and a photoradical polymerization initiator to be added as necessary.
• the mixer include a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and three rolls.
• the curable resin composition of the present invention is suitably used as a sealant for display elements, and particularly suitably used as a sealant for liquid crystal display elements.
• a sealant for liquid crystal display elements using the curable resin composition of the present invention is also one aspect of the present invention.
• 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. Since the hydrazide compound of the present invention is difficult to elute in the liquid crystal having a polar group, the liquid crystal display element of the present invention uses a liquid crystal containing liquid crystal molecules having a polar group. , the effect of suppressing display defects is more pronounced than with conventional sealants. That is, the liquid crystal display element of the present invention preferably uses liquid crystal containing liquid crystal molecules having polar groups. Polar groups of the liquid crystal molecules include, for example, a fluoro group, a chloro group, and a cyano group.
• 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.
• novel hydrazide compounds can be provided.
• the present invention also provides a curable resin composition containing the hydrazide compound and having excellent storage stability and adhesiveness, and a liquid crystal display element comprising the curable resin composition and having excellent low liquid crystal contamination resistance.
• a sealant and a liquid crystal display element can be provided.
• the obtained reaction solution was cooled, and the precipitate was collected by filtration using a Kiriyama funnel, washed with methanol, and then vacuum-dried to obtain a compound represented by the following formula (12).
• the structure of the obtained compound represented by formula (12) was confirmed by 1 H-NMR and FT-IR.
• Each curable resin composition obtained in Examples and Comparative Examples was filled in a syringe for dispensing (manufactured by Musashi Engineering Co., Ltd., "PSY-10E") and defoamed.
• the curable resin composition after the defoaming treatment was dispensed with a dispenser (manufactured by Musashi Engineering Co., Ltd., "SHOTMASTER 300") 30 mm inward from the edge of the glass substrate (150 mm ⁇ 150 mm), and another glass substrate (110 mm ⁇ 110 mm). were laminated together under vacuum.
• Spacer particles having an average particle diameter of 5 ⁇ m are dispersed in 100 parts by weight of each curable resin composition obtained in Examples and Comparative Examples, and are added to a syringe. It was filled and deaerated with a centrifugal deaerator (AWATRON AW-1).
• the curable resin composition after defoaming treatment is applied to two alignment films and ITO under the conditions of a nozzle diameter of 0.4 mm ⁇ , a nozzle gap of 42 ⁇ m, a syringe discharge pressure of 100 to 400 kPa, and a coating speed of 60 mm / sec. It was coated in a frame shape on one side of the attached substrate. At this time, the discharge pressure was adjusted so that the line width of the curable resin composition was about 1.5 mm.
• microdroplets of liquid crystal (“4-pentyl-4-biphenylcarbonitrile” manufactured by Tokyo Chemical Industry Co., Ltd.) were applied dropwise to the entire frame of the curable resin composition of the substrate coated with the curable resin composition. , and bonded the other substrate together under vacuum.
• the curable resin composition portion was irradiated with ultraviolet rays of 100 mW/cm 2 for 30 seconds using a metal halide lamp to temporarily cure the curable resin composition.
• the composition was heated at 120° C. for 1 hour for final curing, thereby producing a liquid crystal display device.
• the liquid crystal alignment disorder (display unevenness) in the vicinity of the sealant immediately after the liquid crystal display element was produced was visually confirmed. Orientation disorder was judged from the color unevenness of the display part, and the case where no display unevenness was observed on the liquid crystal display element was " ⁇ ", and the case where there was display unevenness in the peripheral area (within 500 ⁇ m from the curable resin composition). Low liquid crystal contamination was evaluated as " ⁇ ” and "x” when the display unevenness extended not only to the peripheral portion but also to the central portion by 500 ⁇ m or more.
• novel hydrazide compounds can be provided.
• the present invention also provides a curable resin composition containing the hydrazide compound and having excellent storage stability and adhesiveness, and a liquid crystal display element comprising the curable resin composition and having excellent low liquid crystal contamination resistance.
• a sealant and a liquid crystal display element can be provided.

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• 2022
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