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
  • C08G59/14—Polycondensates modified by chemical after-treatment
  • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
  • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
  • C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
  • C08G59/1461—Unsaturated monoacids
  • C08G59/1466—Acrylic or methacrylic acids
• • 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
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
• • 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 sealing agent for a liquid crystal display element which is excellent in coatability, curability, and low liquid crystal contamination. Further, the present invention relates to a vertical conduction material and a liquid crystal display element formed by using the sealing agent for the liquid crystal display element.
• a liquid crystal dropping method called a dropping method using a sealing agent is used.
• a rectangular seal pattern is formed by dispensing on one of the two electrode-attached substrates.
• minute droplets of liquid crystal are dropped into the seal frame of the substrate, the other substrate is superposed under vacuum, and light such as ultraviolet light is irradiated to the seal portion to perform temporary curing.
• heating is carried out to carry out main curing to produce a liquid crystal display element.
• this drop method is the mainstream of the method of manufacturing a liquid crystal display element.
• the present invention is a sealing agent for a liquid crystal display element containing a curable resin and a polymerization initiator, wherein the curable resin is a partial (meth) acrylic-modified novolac epoxy resin (A) and a partial (meth) An acrylic modified non-novolak epoxy resin (B) and a non novolac epoxy (meth) acrylate (C) are contained, and the content of the partial (meth) acrylic modified novolac epoxy resin (A) is the above-mentioned curing The content is 3 parts by weight or more and 9 parts by weight or less in 100 parts by weight of resin, and the content of the partial (meth) acrylic-modified non-novolak epoxy resin (B) is 25 parts by weight or less in 100 parts by weight of the curable resin And the partial (meth) acrylic-modified non-novolak epoxy resin to the partial (meth) acrylic-modified novolac epoxy resin (A) The ratio of B) is 1 or more, and the content of the non-novol
• the present inventor examined using a (meth) acrylic-modified epoxy resin having a relatively high molecular weight as the curable resin in order to improve the low liquid crystal contamination of the sealing agent for a liquid crystal display element.
• the obtained sealing agent for a liquid crystal display element may be inferior in coatability and curability. Therefore, the present inventors have made it so that the partial (meth) acrylic modified novolac epoxy resin, the partial (meth) acrylic modified non novolac epoxy resin, and the non novolac epoxy (meth) acrylate have specific content ratios, respectively.
• We considered using in combination As a result, it has been found that a sealing agent for a liquid crystal display element which is excellent in coating property, curing property, and low liquid crystal staining property can be obtained, and the present invention has been completed.
• the sealing agent for a liquid crystal display element of the present invention contains a curable resin.
• the curable resin is a partial (meth) acrylic-modified novolac epoxy resin (A) (hereinafter also referred to as “component (A)”) and a partial (meth) acrylic-modified non-novolak epoxy resin (B) (hereinafter, And a non-novolak type epoxy (meth) acrylate (C) (hereinafter also referred to as a "(C) component”).
• partial (meth) acrylic-modified novolac epoxy resin a part of epoxy groups of the novolac epoxy resin react with (meth) acrylic acid to introduce a (meth) acryloyl group.
• partial (meth) acrylic modified non novolac epoxy resin a part of epoxy groups of epoxy resin which is not novolak type (hereinafter also referred to as “non novolac epoxy resin") reacts with (meth) acrylic acid, It means that a (meth) acryloyl group is introduced.
• non-novolak epoxy (meth) acrylate means that all epoxy groups of the non-novolak epoxy resin react with (meth) acrylic acid to introduce a (meth) acryloyl group.
• (meth) acrylic means acrylic or methacrylic
• (meth) acrylate means acrylate or methacrylate
• (meth) acryloyl means acryloyl or methacryloyl.
• the component (A) is a novolak type, the viscosity increase is moderate even if the molecular weight is relatively high from the viewpoint of low liquid crystal contamination, and the coatability is hardly deteriorated.
• the lower limit of the weight average molecular weight of the component (A) is 700 and the upper limit thereof is 2000.
• the weight average molecular weight of the said (A) component being 700 or more, the obtained sealing compound for liquid crystal display elements will be excellent in low liquid-crystal contamination property.
• the weight average molecular weight of the said (A) component being 2000 or less, the obtained sealing compound for liquid crystal display elements will be excellent in applicability.
• the lower limit of the weight average molecular weight of the component (A) is preferably 750, the upper limit is preferably 1,500, the lower limit is more preferably 800, and the upper limit is more preferably 1,200.
• the above-mentioned weight average molecular weight is a value obtained by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent and measuring in terms of polystyrene.
• GPC gel permeation chromatography
• Shodex LF-804 made by Showa Denko
• the component (A) includes, for example, partial (meth) acrylic modified phenol novolac epoxy resin, partial (meth) acrylic modified orthocresol novolac epoxy resin, partial (meth) acrylic modified dicyclopentadiene novolac epoxy resin, partial Examples thereof include (meth) acrylic-modified biphenyl novolac epoxy resins and partial (meth) acrylic-modified naphthalenephenol novolac epoxy resins. Among these, partial (meth) acrylic modified phenol novolac epoxy resins are preferable.
• the component (A) reacts with the component (A) and the novolac epoxy resin by reacting a part of the epoxy group of the novolac epoxy resin with (meth) acrylic acid in the presence of a basic catalyst according to a conventional method.
• a novolac type epoxy (meth) acrylate e.g., novolac epoxy (meth) acrylate.
• novolac epoxy resin to be the raw material of the component (A) for example, phenol novolac epoxy resin, ortho cresol novolac epoxy resin, dicyclopentadiene novolac epoxy resin, biphenyl novolac epoxy resin, naphthalene phenol novolac epoxy Resin etc. are mentioned.
• the lower limit of the content of the component (A) is 3 parts by weight and the upper limit is 9 parts by weight in 100 parts by weight of the curable resin.
• the content of the component (A) is 3 parts by weight or more, the obtained sealing agent for a liquid crystal display element is excellent in low liquid crystal contamination.
• the content of the component (A) is 9 parts by weight or less, the obtained sealing agent for a liquid crystal display element is excellent in coatability.
• the preferable lower limit of the content of the component (A) is 4 parts by weight, the preferable upper limit is 8 parts by weight, and the more preferable upper limit is 7 parts by weight.
• a partial (meth) acryl modified bisphenol A-type epoxy resin a partial (meth) acrylic modified bisphenol F-type epoxy resin, a partial (meth) acrylic modified bisphenol E-type epoxy resin, a partial (meth) Acrylic modified bisphenol S type epoxy resin, Partial (meth) acrylic modified 2,2'-diallyl bisphenol A type epoxy resin, Partial (meth) acrylic modified hydrogenated bisphenol type epoxy resin, Partial (meth) acrylic modified propylene oxide added bisphenol A Type epoxy resin, partially (meth) acrylic modified resorcinol type epoxy resin, partially (meth) acrylic modified biphenyl type epoxy resin, partially (meth) acrylic modified sulfide type epoxy resin, partially (meth) acrylic modified diphenyl ether type Xyresin, partially (meth) acrylic modified dicyclopentadiene type epoxy resin, partially (meth) acrylic modified naphthalene type epoxy resin, partially (meth) acrylic modified glycidyl amine type epoxy resin
• the component (B) reacts with the component (B) with the non-novolak type by reacting a part of the epoxy group of the non-novolak type epoxy resin with (meth) acrylic acid in the presence of a basic catalyst according to a conventional method. It can be obtained in a mixture of epoxy resin and non novolac type epoxy (meth) acrylate.
• non-novolak epoxy resin to be a raw material of the component (B), for example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol E epoxy resin, bisphenol S epoxy resin, 2,2'-diallyl bisphenol A type epoxy resin, hydrogenated bisphenol type epoxy resin, propylene oxide added bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, sulfide type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type Epoxy resin, glycidyl amine type epoxy resin, alkyl polyol type epoxy resin, rubber modified epoxy resin, etc. may be mentioned.
• the upper limit of the content of the component (B) in 100 parts by weight of the curable resin is 25 parts by weight.
• the content of the component (B) in 100 parts by weight of the curable resin is 25 parts by weight or less, the obtained sealing agent for a liquid crystal display element is excellent in low liquid crystal contamination.
• the upper limit of the content of the component (B) in 100 parts by weight of the curable resin is preferably 22 parts by weight, and more preferably 20 parts by weight.
• the ratio of the component (B) to the component (A) is 1 or more. By making the ratio of the said (B) component with respect to the said (A) component 1 or more, the sealing compound for liquid crystal display elements obtained becomes what is excellent in applicability.
• the preferable lower limit of the ratio of the (B) component to the (A) component is 1.2, and the more preferable lower limit is 1.5.
• the ratio of the said (B) component with respect to the said (A) component means content of the content / the said (A) component of the said (B) component.
• component (C) examples include bisphenol A epoxy (meth) acrylate, bisphenol F epoxy (meth) acrylate, bisphenol E epoxy (meth) acrylate, bisphenol S epoxy (meth) acrylate, and 2,2 ′.
• Component (C) can be obtained by reacting all epoxy groups of the non-novolak epoxy resin with (meth) acrylic acid in the presence of a basic catalyst according to a conventional method.
• a non novolak-type epoxy resin used as the raw material of the said (C) component the thing similar to the non novolak-type epoxy resin used as the raw material of the said (B) component is mentioned.
• the lower limit of the content of the component (C) is 10 parts by weight and the upper limit is 45 parts by weight in 100 parts by weight of the curable resin.
• the content of the component (C) in 100 parts by weight of the curable resin is 10 parts by weight or more, the obtained sealing agent for a liquid crystal display element is excellent in photocurability.
• content of the said (C) component is 45 weight part or less, the obtained sealing compound for liquid crystal display elements will be excellent in adhesiveness.
• the lower limit of the content of the component (C) in 100 parts by weight of the curable resin is preferably 14 parts by weight, and more preferably 18 parts by weight.
• the sealing agent for a liquid crystal display element of the present invention may further contain another polymerizable compound as the curable resin as long as the object of the present invention is not impaired.
• the other polymerizable compounds include the above-mentioned novolak epoxy resins, the above-mentioned non-novolak epoxy resins, the above-mentioned novolak epoxy (meth) acrylates and other (meth) acrylic compounds. .
• Examples of the other (meth) acrylic compounds include (meth) acrylic acid ester compounds obtained by reacting a compound having a hydroxyl group with (meth) acrylic acid, and (meth) acrylic acid derivatives having a hydroxyl group in an isocyanate compound The urethane (meth) acrylate etc. which are obtained by making it react are mentioned. From the viewpoint of reactivity, the other (meth) acrylic compounds preferably have two or more (meth) acryloyl groups in one molecule.
• methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate is mentioned, for example , 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-hydroxy 2)
• the urethane (meth) acrylate can be obtained, for example, by reacting a (meth) acrylic acid derivative having a hydroxyl group to an isocyanate compound in the presence of a catalytic amount of a tin-based compound.
• isocyanate compound examples include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), and hydrogenation.
• MDI polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate, tetramethyl xylylene And isocyanate, 1,6,11-undecanetriisocyanate, etc.
• a chain-extended isocyanate compound obtained by the reaction of a polyol and an excess 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.
• the (meth) acrylic acid derivative having a hydroxyl group for example, hydroxyalkyl mono (meth) acrylate, mono (meth) acrylate of dihydric alcohol, mono (meth) acrylate or di (meth) acrylate of trihydric alcohol Etc.
• hydroxyalkyl mono (meth) acrylate examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like. It can be mentioned.
• dihydric alcohol examples include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, polyethylene glycol and the like.
• trihydric alcohol examples include trimethylol ethane, trimethylol propane and glycerin.
• the other (meth) acrylic compounds preferably have a hydrogen bonding unit such as -OH group, -NH- group, -NH 2 group and the like.
• the sealing agent for a liquid crystal display element of the present invention contains a polymerization initiator.
• a radical polymerization initiator, a cationic polymerization initiator, etc. are mentioned, for example.
• produces a radical by light irradiation
• produces a radical by heating
• photo radical polymerization initiator examples include benzophenone compounds, acetophenone compounds, acyl phosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, thioxanthone compounds and the like.
• photoradical polymerization initiator examples include 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, and 1,2- (dimethylamino).
• thermal radical polymerization initiator what consists of an azo compound, an organic peroxide, etc. is mentioned, for example.
• an initiator composed of a polymeric azo compound (hereinafter, also referred to as "polymer azo initiator") is preferable.
• the said thermal radical polymerization initiator may be used independently, and 2 or more types may be used in combination.
• a polymeric azo compound means a compound having an azo group and having a number average molecular weight of 300 or more, which generates a radical capable of curing a (meth) acryloyl group by heat.
• the preferable lower limit of the number average molecular weight of the above-mentioned high molecular weight azo compound is 1000, and the preferable upper limit is 300,000.
• the number average molecular weight of the high molecular weight azo compound is in this range, it can be easily mixed with the curable resin while suppressing liquid crystal contamination.
• a more preferable lower limit of the number average molecular weight of the above-mentioned high molecular weight azo compound is 5,000, a more preferable upper limit is 100,000, a further preferable lower limit is 10,000, and a still more preferable upper limit is 90,000.
• the above-mentioned number average molecular weight is a value obtained by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent and measuring in terms of polystyrene.
• GPC gel permeation chromatography
• Shodex LF-804 made by Showa Denko
• said high molecular weight azo compound what has the structure which multiple units, such as a polyalkylene oxide and polydimethylsiloxane, couple
• a polymeric azo compound having a structure in which a plurality of units such as a polyalkylene oxide is bonded via the above azo group one having a polyethylene oxide structure is preferable.
• Specific examples of the high molecular weight azo compound include polycondensates of 4,4'-azobis (4-cyanopentanoic acid) and polyalkylene glycol, and 4,4'-azobis (4-cyanopentanoic acid) And polydimethylsiloxanes having a terminal amino group, and the like.
• VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 all are Fujifilm Wako Pure Chemical Industries, Ltd. make
• V-65 and V-501 both manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
• organic peroxide examples include ketone peroxide, peroxy ketal, hydroperoxide, dialkyl peroxide, peroxy ester, diacyl peroxide, peroxy dicarbonate and the like.
• a cationic photopolymerization initiator As said cationic polymerization initiator, a cationic photopolymerization initiator is used suitably.
• the photocationic polymerization initiator is not particularly limited as long as it generates a protonic acid or a Lewis acid upon irradiation with light, and may be of an ionic photoacid generation type, or a nonionic photoacid generation type. It may be
• photocationic polymerization initiator examples include onium salts such as aromatic diazonium salts, aromatic halonium salts and aromatic sulfonium salts, organic metal complexes such as iron-allene complex, titanocene complex, arylsilanol-aluminum complex, etc. Can be mentioned.
• photo cationic polymerization initiators commercially available ones include Adeka Optomer SP-150, Adeka Optomer SP-170 (all manufactured by ADEKA), and the like.
• the content of the polymerization initiator is preferably 0.01 parts by weight with a preferable lower limit and 10 parts by weight with a preferable upper limit based on 100 parts by weight of the curable resin.
• the content of the polymerization initiator is in this range, the obtained sealing agent for a liquid crystal display element is excellent in storage stability and curability while suppressing liquid crystal contamination.
• a more preferable lower limit of the content of the polymerization initiator is 0.1 parts by weight, and a more preferable upper limit is 5 parts by weight.
• the sealing compound for liquid crystal display elements of this invention contains a thermosetting agent.
• a thermosetting agent an organic acid hydrazide, an imidazole derivative, an amine compound, a polyhydric phenol type compound, an acid anhydride etc. are mentioned, for example. Among them, solid organic acid hydrazide is suitably used.
• the said thermosetting agent may be used independently, and 2 or more types may be used in combination.
• Examples of the solid organic acid hydrazide include 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin, sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide and the like.
• Examples of commercially available solid organic acid hydrazides include organic acid hydrazides manufactured by Otsuka Chemical Co., Ltd., organic acid hydrazides manufactured by Nippon Fine Chem, Inc., and organic acid hydrazides manufactured by Ajinomoto Fine Techno Co., Ltd. Examples of the organic acid hydrazide manufactured by Otsuka Chemical Co., Ltd.
• Examples of the organic acid hydrazide manufactured by Japan Fine Chem Co., Ltd. include MDH. Examples of the organic acid hydrazide manufactured by Ajinomoto Fine Techno Co., Ltd. include Amicure VDH, Amicure VDH-J, Amicure UDH and the like.
• the preferable lower limit of the content of the thermosetting agent is 1 part by weight, and the preferable upper limit is 50 parts by weight with respect to 100 parts by weight of the entire curable resin.
• the content of the thermosetting agent is in this range, the obtained sealing agent for a liquid crystal display element is excellent in curability while maintaining excellent coating properties and storage stability.
• a more preferable upper limit of the content of the thermosetting agent is 30 parts by weight.
• the sealing agent for a liquid crystal display element of the present invention may contain a filler for the purpose of improving viscosity, further improving adhesion due to stress dispersion effect, improving linear expansion coefficient, improving moisture resistance of cured product, etc. preferable.
• an inorganic filler or an organic filler can be used as the filler.
• the inorganic filler include silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, smectite, bentonite, montmorillonite, sericite, activated clay, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide And 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, and acrylic polymer fine particles. The above fillers may be used alone or in combination of two or more.
• the preferable lower limit of the content of the filler in 100 parts by weight of the sealant for a liquid crystal display element of the present invention is 10 parts by weight, and the preferable upper limit is 70 parts by weight.
• the content of the filler is in this range, effects such as improvement in adhesion can be further exhibited while suppressing deterioration in coating property and the like.
• the more preferable lower limit of the content of the filler is 20 parts by weight, and the more preferable upper limit is 60 parts by weight.
• the sealing agent for a liquid crystal display element of the present invention improves the flexibility and adhesiveness of the cured product, and prevents the insertion of the liquid crystal into the sealing agent and the suppression of the elution of the sealing agent into the liquid crystal. It is preferred to contain soft particles.
• the flexible particles include silicone particles, vinyl particles, urethane particles, fluorine particles, and nitrile particles. Among them, silicone particles and vinyl particles are preferable.
• the flexible particles may be used alone or in combination of two or more.
• silicone rubber particles are preferable as the silicone particles.
• (meth) acrylic particles are suitably used as the vinyl-based particles.
• the (meth) acrylic particles can be obtained by polymerizing monomers as raw materials by a known method. Specifically, for example, a method of suspension polymerization of a monomer in the presence of a radical polymerization initiator, swelling of the seed particles by causing the non-crosslinked seed particles to absorb the monomer in the presence of the radical polymerization initiator And a method of seed polymerization.
• alkyl (meth) acrylates As a monomer used as the raw material for forming said (meth) acryl particle
• grains for example, alkyl (meth) acrylates, oxygen atom containing (meth) acrylates, nitrile containing monomer, fluorine containing (meth) acrylate And monofunctional monomers such as Examples of the alkyl (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2- Ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and
• oxygen atom-containing (meth) acrylates examples include 2-hydroxyethyl (meth) acrylate, glycerol (meth) acrylate, polyoxyethylene (meth) acrylate, glycidyl (meth) acrylate and the like.
• nitrile containing monomer examples include (meth) acrylonitrile etc.
• fluorine-containing (meth) acrylates include trifluoromethyl (meth) acrylate and pentafluoroethyl (meth) acrylate.
• alkyl (meth) acrylates are preferable because the Tg of the homopolymer is low and the amount of deformation when a 1 g load is applied can be increased.
• a polyfunctional monomer as a monomer used as the raw material for forming the said (meth) acrylic particle.
• the polyfunctional monomer include tetramethylolmethane tetra (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane di (meth) acrylate, trimethylolpropane tri (meth) acrylate and dipentaerythritol.
• Poly) tetramethylene di (meth) acrylate, 1,4-butanediol di (meth) acrylate and 1,6-hexanediol di (meth) acrylate are preferred.
• the use amount of the crosslinkable monomer is preferably 1% by weight, and 90% by weight, based on the whole monomer serving as a raw material for forming the (meth) acrylic particles.
• the amount of the crosslinkable monomer used is 1% by weight or more, the solvent resistance is improved, and problems such as swelling do not occur when kneading with other sealing agent components, and the resin is easily dispersed uniformly.
• the amount of the crosslinkable monomer used is 90% by weight or less, the recovery rate can be lowered.
• the more preferable lower limit of the amount of the crosslinkable monomer used is 3% by weight, and the more preferable upper limit is 80% by weight.
• styrenic monomers vinyl ethers, carboxylic acid vinyl esters, unsaturated hydrocarbons, halogen-containing monomers, triallyl cyanurate, triallyl isocyanurate, Monomers such as triallyl trimellitate, divinyl benzene, diallyl phthalate, diallyl acrylamide, diallyl ether, ⁇ - (meth) acryloxypropyl trimethoxysilane, vinyltrimethoxysilane may be used.
• the styrene-based monomer include styrene, ⁇ -methylstyrene, trimethoxysilylstyrene and the like.
• Examples of the vinyl ethers include methyl vinyl ether, ethyl vinyl ether and propyl vinyl ether.
• Examples of the carboxylic acid vinyl esters include vinyl acetate, vinyl butyrate, vinyl laurate and vinyl stearate.
• Examples of the unsaturated hydrocarbon include ethylene, propylene, isoprene, butadiene and the like.
• Examples of the halogen-containing monomer include vinyl chloride, vinyl fluoride, chlorostyrene and the like.
• core-shell (meth) acrylate copolymer fine particles are also suitably used.
• fine-particles F351 (made by Aika Kogyo Co., Ltd.) etc. are mentioned, for example.
• vinyl-based particles for example, polydivinylbenzene particles, polychloroprene particles, butadiene rubber particles and the like may be used.
• the preferable lower limit of the average particle diameter of the flexible particles is 0.01 ⁇ m, and the preferable upper limit is 10 ⁇ m.
• the more preferable lower limit of the average particle diameter of the soft particles is 0.1 ⁇ m, and the more preferable upper limit is 8 ⁇ m.
• the average particle diameter of the said flexible particle means the value obtained by measuring using a laser diffraction type particle size distribution measuring apparatus.
• Mastersizer 2000 manufactured by Malvern Co., Ltd.
• the preferable lower limit of the hardness of the flexible particle is 10, and the preferable upper limit is 50.
• the more preferable lower limit of the hardness of the flexible particle is 20, and the more preferable upper limit is 40.
• the hardness of the said flexible particle in this specification means durometer A hardness measured by the method based on JISK6253.
• the preferable lower limit of the content of the soft particles in 100 parts by weight of the sealing agent for a liquid crystal display element of the present invention is 5 parts by weight, and the preferable upper limit is 50 parts by weight.
• the content of the soft particles is in this range, the effect of improving the flexibility and adhesiveness of the cured product of the obtained sealing agent for a liquid crystal display element can be improved.
• a more preferable lower limit of the content of the flexible particles is 10 parts by weight, and a more preferable upper limit is 30 parts by weight.
• the sealing agent for a liquid crystal display element of the present invention preferably contains a silane coupling agent for the purpose of further improving the adhesiveness.
• the above-mentioned silane coupling agent mainly serves as an adhesion aiding agent for favorably bonding the sealing agent and the substrate and the like.
• As the above-mentioned silane coupling agent for example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane and the like are suitably used.
• the above-mentioned silane coupling agents may be used alone or in combination of two or more.
• the preferable lower limit of the content of the silane coupling agent in 100 parts by weight of the liquid crystal display element sealing agent of the present invention is 0.1 parts by weight, and the preferable upper limit is 10 parts by weight.
• the content of the silane coupling agent is in this range, the effect of improving the adhesiveness can be further exhibited while suppressing the occurrence of liquid crystal contamination.
• a more preferable lower limit of 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 sealing agent for a liquid crystal display element of the present invention may contain a light shielding agent.
• the sealing compound for liquid crystal display elements of this invention can be used suitably as a light-shielding sealing compound.
• the light shielding agent examples include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, resin-coated carbon black and the like. Among them, titanium black is preferred.
• the light shielding agents may be used alone or in combination of two or more.
• the titanium black is a substance having a high transmittance to light in the vicinity of the ultraviolet region, particularly to light of 370 nm to 450 nm, as compared to the average transmittance of light of 300 nm to 800 nm. That is, while the titanium black imparts a light shielding property to the sealing agent for a liquid crystal display element of the present invention by sufficiently shielding light having a wavelength in the visible light range, it has a property of transmitting light having a wavelength near the ultraviolet range. It is a light shielding agent.
• the light shielding agent contained in the sealing agent for a liquid crystal display element of the present invention is preferably a substance having a high insulating property, and titanium black is also preferable as a light shielding agent having a high insulating property.
• the above-mentioned titanium black exhibits sufficient effects even if it is not surface-treated, but the surface is treated with an organic component such as a coupling agent, silicon oxide, titanium oxide, germanium oxide, aluminum oxide, oxide It is also possible to use surface-treated titanium black, such as those coated with inorganic components such as zirconium and magnesium oxide. Especially, what is processed by the organic component is preferable at the point which can improve insulation more.
• a liquid crystal display device manufactured using the sealing agent for a liquid crystal display device of the present invention containing the above titanium black as a light shielding agent has a sufficient light shielding property and therefore has no light leakage and has high contrast. A liquid crystal display element having excellent image display quality can be realized.
• titanium black As what is marketed among the said titanium black, the titanium black by Mitsubishi Materials Co., Ltd., the titanium black by Akaho Kasei Co., Ltd., etc. are mentioned, for example.
• Examples of titanium black manufactured by Mitsubishi Materials Corporation include 12S, 13M, 13M-C, 13R-N, 14M-C and the like.
• Examples of titanium black manufactured by Akaho Kasei Co., Ltd. include Tilac D and the like.
• the lower limit of the specific surface area of the titanium black is preferably 13 m 2 / g, preferably 30 m 2 / g, more preferably 15 m 2 / g, and still more preferably 25 m 2 / g.
• the lower limit of the volume resistance of titanium black is preferably 0.5 ⁇ ⁇ cm, and the upper limit is preferably 3 ⁇ ⁇ cm.
• the lower limit is more preferably 1 ⁇ ⁇ cm, and the upper limit is preferably 2.5 ⁇ ⁇ cm.
• the primary particle diameter of the light shielding agent is not particularly limited as long as it is equal to or less than the distance between the substrates of the liquid crystal display element, but a preferable lower limit is 1 nm and a preferable upper limit is 5 ⁇ m. When the primary particle diameter of the light shielding agent is in this range, the viscosity and the thixotropy of the obtained sealing agent for a liquid crystal display element do not increase significantly, and the coating property becomes excellent.
• the lower limit of the primary particle diameter of the light shielding agent is more preferably 5 nm, more preferably 200 nm, still more preferably 10 nm, and still more preferably 100 nm.
• the primary particle diameter of the light shielding agent is measured by dispersing the light shielding agent in a solvent (water, organic solvent, etc.) using a particle size distribution analyzer (for example, "NICOMP 380 ZLS" manufactured by PARTICLE SIZING SYSTEMS). be able to.
• a particle size distribution analyzer for example, "NICOMP 380 ZLS” manufactured by PARTICLE SIZING SYSTEMS.
• the preferable lower limit of the content of the light shielding agent in 100 parts by weight of the sealant for a liquid crystal display element of the present invention is 5 parts by weight, and the preferable upper limit is 80 parts by weight.
• the lower limit of the light shielding agent content is preferably 10 parts by weight, more preferably 70 parts by weight, still more preferably 30 parts by weight, and still more preferably 60 parts by weight.
• the sealant for a liquid crystal display element of the present invention further comprises, if necessary, a stress relaxation agent, a reactive diluent, a thixotropic agent, a spacer, a curing accelerator, an antifoamer, a leveling agent, a polymerization inhibitor and the like. It may contain an agent.
• a curable resin, a polymerization agent, and a polymerization machine using a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and three rolls.
• a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and three rolls.
• examples thereof include a method of mixing an initiator and an additive such as a heat curing agent and a silane coupling agent which is added as necessary.
• the preferable lower limit of the viscosity measured under the conditions of 25 ° C. and 1 rpm using an E-type viscometer is 100 Pa ⁇ s, and the preferable upper limit is 800 Pa ⁇ s.
• the obtained sealing compound for liquid crystal display elements will be excellent in applicability
• the more preferable lower limit of the viscosity is 200 Pa ⁇ s, and the more preferable upper limit is 700 Pa ⁇ s.
• a vertical conduction material can be manufactured by mix
• the vertical conduction material containing the sealing agent for a liquid crystal display element of the present invention and the conductive fine particles is also one of the present invention.
• electroconductive fine particle what formed the conductive metal layer in the surface of a metal ball and resin fine particles etc. can be used.
• those in which a conductive metal layer is formed on the surface of resin fine particles are preferable because the excellent elasticity of the resin fine particles allows conductive connection without damaging the transparent substrate and the like.
• a liquid crystal display device using the sealing agent for a liquid crystal display device of the present invention or the vertical conduction material of the present invention is also one of the present invention.
• a liquid crystal dropping method is suitably used, and specifically, for example, a method having the following respective steps can be mentioned.
• the sealing agent for a liquid crystal display element of the present invention is applied by screen printing, dispenser coating, or the like to one of two substrates such as a glass substrate with an electrode such as ITO thin film and a polyethylene terephthalate substrate.
• the process of forming a pattern is performed.
• a step of applying minute droplets of liquid crystal to the inside of the frame of the seal pattern of the substrate by a drop in a state where the sealing agent for a liquid crystal display element of the present invention is uncured is dropped, and another substrate is superposed under vacuum.
• the sealing pattern portion of the sealing agent for a liquid crystal display element of the present invention is irradiated with light such as ultraviolet light to temporarily cure the sealing agent, and the temporarily cured sealing agent is heated to perform main curing
• a liquid crystal display element can be obtained by the method.
• the sealing compound for liquid crystal display elements which is excellent in applicability
• Novolak-type curable resin mixture (A1) Preparation of Novolak-type curable resin mixture (A1)) After 557 parts by weight of a phenol novolac epoxy resin (manufactured by DIC, “EPICLON N-740”) was dissolved in 900 mL of toluene, 0.3 g of triphenylphosphine was added to prepare a uniform solution. After adding 122 parts by weight of acrylic acid dropwise to the obtained solution under reflux and stirring for 2 hours, the solution was further stirred under reflux for 6 hours. Subsequently, toluene was removed under reduced pressure to obtain a novolak-type curable resin mixture (A1).
• a phenol novolac epoxy resin manufactured by DIC, “EPICLON N-740”
• the novolak-type curable resin mixture (A1) is 11.8% by weight of a partial acrylic modified phenol novolac epoxy resin and 68 for a phenol novolac epoxy resin It was confirmed to be a mixture containing 6 wt% and 19.6 wt% of phenol novolac epoxy acrylate. In addition, the weight average molecular weight of the obtained partial acrylic resin-modified phenol novolac epoxy resin was 1,200.
• Novolak-type curable resin mixture (A2) After dissolving 395 parts by weight of a phenol novolac epoxy resin (manufactured by DIC, "EPICLON N-730S") in 900 mL of toluene, 0.3 g of triphenylphosphine was added to obtain a uniform solution. After 94 parts by weight of acrylic acid was added dropwise to the obtained solution under reflux stirring for 2 hours, the mixture was further stirred under reflux for 6 hours. Subsequently, toluene was removed under reduced pressure to obtain a novolak-type curable resin mixture (A2).
• a phenol novolac epoxy resin manufactured by DIC, "EPICLON N-730S”
• the novolak-type curable resin mixture (A2) is 11.8% by weight of a partial acrylic resin-modified phenol novolac epoxy resin and 68 for a phenol novolac epoxy resin It was confirmed to be a mixture containing 6 wt% and 19.6 wt% of phenol novolac epoxy acrylate. Moreover, the weight average molecular weight of the obtained partial acrylic resin-modified phenol novolac epoxy resin was 800.
• Novolak-type curable resin mixture (A3) After dissolving 965 parts by weight of a phenol novolac epoxy resin (manufactured by DIC, "EPICLON N-770") in 1,800 mL of toluene, 0.3 g of triphenylphosphine was added to obtain a uniform solution. After adding 216 parts by weight of acrylic acid dropwise to the obtained solution under reflux and stirring for 2 hours, the mixture was further stirred under reflux for 6 hours. Subsequently, toluene was removed under reduced pressure to obtain a novolak-type curable resin mixture (A3).
• a phenol novolac epoxy resin manufactured by DIC, "EPICLON N-770”
• the novolak type curable resin mixture (A3) is 11.8% by weight of a partially acrylic modified phenol novolac type epoxy resin and 68 as a phenol novolac type epoxy resin It was confirmed to be a mixture containing 6 wt% and 19.6 wt% of phenol novolac epoxy acrylate. Moreover, the weight average molecular weight of the obtained partial acrylic resin-modified phenol novolac epoxy resin was 2,500.
• non-novolak type curable resin mixture (B1) After dissolving 326 parts by weight of bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, “jER 828EL”) in 900 mL of toluene, 0.3 g of triphenylphosphine was added to make a uniform solution. After 72 parts by weight of acrylic acid was added dropwise to the obtained solution under reflux and stirring for 2 hours, the mixture was further stirred under reflux for 6 hours. Subsequently, toluene was removed under reduced pressure to obtain a non-novolak type curable resin mixture (B1).
• bisphenol A type epoxy resin manufactured by Mitsubishi Chemical Corporation, “jER 828EL”
• the non-novolak type curable resin mixture (B1) is 50% by weight of partially acrylic modified bisphenol A type epoxy resin and 25 weight of bisphenol A type epoxy resin % And a mixture containing 25% by weight of bisphenol A epoxy acrylate.
• Examples 1 to 10 Comparative Examples 1 to 8
• a planetary stirrer (“Awatori Neritaro” manufactured by Shinky Co., Ltd.) according to the compounding ratio described in Tables 1 and 2, and then uniformly mixed by a ceramic three-roll Sealing agents for liquid crystal display devices of Examples 1 to 10 and Comparative Examples 1 to 8 were obtained.
• viscosity The viscosity of each of the sealing agents for liquid crystal display devices obtained in Examples and Comparative Examples was measured at 25 ° C. and 1 rpm using an E-type viscometer (“DV-III” manufactured by Brookfield, Inc.).
• the sealing compound for liquid crystal display elements which is excellent in applicability

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