WO2013061837A1 - Agent de scellement de cristaux liquides et cellule d'affichage à cristaux liquides l'utilisant - Google Patents

Agent de scellement de cristaux liquides et cellule d'affichage à cristaux liquides l'utilisant Download PDF

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Publication number
WO2013061837A1
WO2013061837A1 PCT/JP2012/076801 JP2012076801W WO2013061837A1 WO 2013061837 A1 WO2013061837 A1 WO 2013061837A1 JP 2012076801 W JP2012076801 W JP 2012076801W WO 2013061837 A1 WO2013061837 A1 WO 2013061837A1
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Prior art keywords
liquid crystal
component
ether
sealing agent
crystal sealant
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PCT/JP2012/076801
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English (en)
Japanese (ja)
Inventor
常俊 坂野
林原　昌一
広明 三輪
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日本化薬株式会社
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Priority to CN201280051938.5A priority Critical patent/CN103890649B/zh
Priority to JP2013540738A priority patent/JP5969492B2/ja
Publication of WO2013061837A1 publication Critical patent/WO2013061837A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/182—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents
    • C08G59/184—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents with amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5046—Amines heterocyclic
    • C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
    • C08G59/508—Amines heterocyclic containing only nitrogen as a heteroatom having three nitrogen atoms in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0645—Macromolecular organic compounds, e.g. prepolymers obtained otherwise than by reactions involving carbon-to-carbon unsaturated bonds
    • C09K2200/0647—Polyepoxides
    • 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 liquid crystal sealant and a liquid crystal display cell using the same.
  • the liquid crystal dropping method is a method of manufacturing a liquid crystal display cell by applying a liquid crystal sealant on a transparent glass substrate or plastic substrate appropriately provided with a transparent electrode and an alignment film, dropping liquid crystal inside the weir, Demand is growing from the viewpoint of shortening production tact time (time required for one process) and easy enlargement.
  • the liquid crystal injection method is a method in which an upper cell and a lower glass substrate are previously bonded with a liquid crystal sealant to create an empty cell, liquid crystal is injected from the injection port, and finally the injection port is sealed.
  • this method it is possible to produce a high-quality liquid crystal display cell, and it is also possible to cure the liquid crystal sealant only by heat, so that it is effective particularly in the production of a small-sized liquid crystal display cell. It is a manufacturing method.
  • a liquid crystal sealant is applied to the substrate by dispensing or screen printing, followed by preliminary overheating (precure), and then the opposite substrate is overlaid, and the liquid crystal sealant is applied. It is cured.
  • the liquid crystal sealant is a curable resin composition that has a role of adhering a glass substrate or a plastic substrate and containing liquid crystal inside thereof.
  • the liquid crystal sealant used in the liquid crystal dropping method is mainly a photocurable resin composition
  • the liquid crystal sealant used in the liquid crystal injection method is mainly a thermosetting resin composition. That is, the characteristics required for the liquid crystal sealant differ greatly depending on the method of use.
  • the liquid crystal sealant used in the liquid crystal injection method it is excellent in coating workability, the thickening behavior by preheating (stable cure) is stable, and is transported in an uncured state after bonding, It is a specific problem that it is excellent in contact with the counter substrate (substrate on which the liquid crystal sealant is not applied) and has shape retention during thermosetting.
  • the contact property to the counter substrate is good when the liquid crystal sealant is sufficiently crushed and bonded to the counter substrate when the substrate is bonded to the counter substrate after preheating, and ideally the liquid crystal This is a case where contact is made in the same area as the substrate to which the sealing agent is applied.
  • the case where the contact property is poor is a case where the viscosity increase due to the preheating is too large, the liquid crystal sealant is not sufficiently crushed, and the contact area with the counter substrate is reduced.
  • liquid crystal display cells have adopted a multi-processing process in which a large number of electrodes are formed on a large glass substrate and then assembled by laminating upper and lower substrates, and then divided into individual liquid crystal display cells. Since the number of processed sheets is increased and the mother glass (substrate before dividing) is also enlarged, the stress applied to the liquid crystal sealant after curing is increasing. In connection with this, the further improvement of the adhesive strength and flexibility of a liquid-crystal sealing compound is calculated
  • Patent Document 1 discloses a thermosetting liquid crystal sealing agent that is excellent in adhesiveness, moisture resistance reliability, and flexibility.
  • Patent Document 2 discloses a thermosetting liquid crystal sealing agent excellent in adhesiveness, moisture resistance reliability, flexibility, and thermosetting.
  • Patent Document 3 discloses a thermosetting liquid crystal sealing agent having excellent screen printability and moisture resistance reliability.
  • Patent Document 4 discloses a thermosetting liquid crystal sealing agent having strong adhesive strength at high temperatures.
  • the present invention does not cause peeling of the substrate at the time of production, particularly at the time of thermal curing of the liquid crystal sealant, and is extremely excellent in adhesive strength and flexibility after curing.
  • An object of the present invention is to provide a thermosetting liquid crystal sealant that is excellent in viscosity stability after overheating.
  • the present inventors have been able to reinforce the effect by suppressing the peeling of the upper and lower substrates by ensuring the presence of the phenol novolac resin and ensuring a constant reaction rate.
  • the inventors have found that these synergistic effects can solve the above-mentioned problems, and have completed the present invention.
  • the present invention relates to the following 1) to 11).
  • the liquid crystal sealing agent of the present invention does not cause peeling of the substrate at the time of production of the liquid crystal display cell, particularly at the time of thermal curing of the liquid crystal sealing agent, and is extremely excellent in adhesive strength and flexibility after curing. Excellent contact with the counter substrate and viscosity stability after preheating. Therefore, it is possible to easily manufacture a liquid crystal display cell having high reliability.
  • the component (a) used in the present invention is a phenol novolac resin such as bisphenol A, tetrabromobisphenol A, bisphenol F, bisphenol S, 4,4-biphenylphenol, 2,2,6,6-tetramethyl- 4,4-biphenylphenol, 2,2-methylene-bis (4-methyl-6-tert-butylphenol), trishydroxyphenylmethane, pyrogallol, phenols having a diisopropylidene skeleton, 1,1-di-4- Phenols having a fluorene skeleton such as hydroxyphenylfluorene, polyphenol compounds such as phenolized polybutadiene, phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, allylphenols Novolak resins made from various phenols such as brominated bisphenol A, bisphenol F, bisphenol S, naphthols, etc .;
  • Phenol novolac resins phenols, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, brominated bisphenol A, bisphenol F, bisphenol S, naphthols and other phenols represented by the following formulas (2) to (4) And phenol novolak resins bonded with any one of the crosslinking groups (aralkylene group).
  • R 1 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an allyl group, or a halogen atom, and m represents an integer of 1 to 4.
  • m represents 2 or more, each R 1 is They may be the same or different.
  • R 2 and R 3 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an allyl group, or a halogen atom, and n and p each independently represents an integer of 1 to 4).
  • n or p is 2 or more, each R 2 and R 3 may be the same or different.
  • R 4 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an allyl group, a halogen atom or a hydroxyl group, and q represents an integer of 1 to 5. When q is 2 or more, each R 4 may be the same or different.
  • Preferable phenol novolak resins include phenols, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, allylphenols, bisphenol F, bisphenol S, naphthols and other novolac resins made from raw materials; xylylene Phenol novolac resin having a skeleton; Phenol novolak resin having a dicyclopentadiene skeleton; Phenol novolac resin having a fluorene skeleton; Phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, brominated bisphenol A, bisphenol F Various phenols such as bisphenol S, naphthols and the like with any of the crosslinking groups represented by the above formulas (2) to (4) Phenol novolak resin which was coupled with alkylene group); and the like.
  • More preferred phenol novolak resins include novolak resins made from various phenols such as phenols, cresols, octylphenol, bisphenol A, bisphenol F, bisphenol S, naphthols; phenols, cresols, octylphenols, bisphenol A, And phenol novolak resins in which various phenols such as bisphenol F, bisphenol S, naphthols and the like are bonded by a crosslinking group (aralkylene group) represented by the above formulas (2) to (4).
  • a crosslinking group aralkylene group
  • phenol novolac resins include phenol novolac resins made from phenol, novolak resins made from monophenols typified by cresol novolak resins made from cresols, etc .; phenols, cresols, bisphenol A, etc. And phenol novolac resins obtained by bonding various phenols of the formula (5) to (9) with a crosslinking group of any one of the following formulas (5) to (9).
  • a particularly preferred phenol novolak resin used in the present invention is a phenol novolak resin using monophenols as a raw material, and is represented by the following formula (1).
  • R 5 represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a halogen atom, and r represents an integer of 1 to 3. When r is 2 or 3, each R 5 is the same. And may be different, s represents 0 or a positive integer.
  • examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl and the like.
  • examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, n-propyl, isopropyl, pentyl, hexyl, octyl and the like.
  • Examples of the lower alkyl group include alkyl groups having 1 to 8 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, preferably methyl, ethyl, n-propyl, isopropyl, Examples thereof include alkyl groups having 1 to 4 carbon atoms such as n-butyl, isobutyl, t-butyl and the like.
  • Examples of the lower alkoxy group include alkoxy groups having 1 to 8 carbon atoms such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, t-butoxy, preferably methoxy, ethoxy, n-propoxy, Examples thereof include alkoxy groups having 1 to 4 carbon atoms such as isopropoxy and n-butoxy.
  • Examples of the halogen atom include a bromine atom, a chlorine atom, and a fluorine atom. In the above formula (1), 0 or a positive integer in s is preferably 0 to 15, more preferably 0 to 10.
  • Component (a) is preferably a phenol novolac resin having a softening point of 75 ° C. or lower, more preferably a softening point of 65 ° C. or lower, and still more preferably a phenol novolac resin having a softening point of 50 ° C. or lower.
  • the lower limit of a softening point is not specifically limited, Preferably it is 40 degreeC or more.
  • the softening point is measured by the ring and ball method defined in JIS K7234. Specifically, PN-152 (manufactured by Nippon Kayaku Co., Ltd.) or the like is easily available from the market as a commercial product.
  • phenol novolac resins are used alone or in admixture of two or more.
  • the amount of the phenol novolac resin used in the present invention is 0.2 to 1.4 chemical equivalents, preferably 0 as the equivalent of the hydroxyl groups in the novolac resin to 1 equivalent of the epoxy groups in the epoxy resin in the liquid crystal sealant. .3 to 1.0 chemical equivalent, more preferably 0.5 to 1.0 chemical equivalent.
  • the amount of the phenol novolac resin used affects the contact property of the liquid crystal sealant to the counter substrate.
  • the phenol novolac resin suitably used in the present invention is a compound represented by the above formula (1).
  • the phenol novolac resin suitably used in the present invention has a low resin viscosity, it is excellent in screen printability, and it becomes easy to bond the upper and lower glass substrates and form a gap when manufacturing a liquid crystal display device.
  • the content of the component (a) is preferably 5 to 40 parts by mass, more preferably 7 to 30 parts by mass, still more preferably 10 to 25 parts by mass.
  • Component (b) used in the present invention is at least selected from 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct and an epoxy resin amine adduct.
  • One type. These compounds are used as curing accelerators. It is very advantageous from the viewpoint of reactivity to contain these curing accelerators.
  • the curing accelerator functions as a catalyst, it may remain in a free state in the cured liquid crystal sealant without forming a bond, but 2,4-diamino-6- [2′-methyl
  • the imidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct and the epoxy resin amine adduct are less likely to dissolve in the liquid crystal and contaminate the liquid crystal.
  • These compounds can be obtained from the market as 2MAOK-PW (manufactured by Shikoku Kasei Kogyo Co., Ltd.) and MY-H (manufactured by Ajinomoto Fine Techno Co., Ltd.).
  • the content of the component (b) is preferably 38% by mass or more and 70% by mass or less with respect to the content of the component (a). Even if it is not this amount, it is possible to achieve the effect of the present invention, but the effect is particularly remarkable when the amount is 38% by mass or more and 70% by mass or less, which is much larger than the addition amount of the conventional curing accelerator. It will be something.
  • the curing accelerator is selected from 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct and an epoxy resin amine adduct.
  • the content of 38% by mass or more which is much higher than usual, is possible. That is, even if the amount of the curing accelerator that may remain in the free state increases as described above, the influence on the liquid crystal is extremely small. However, when the amount is too large, the reaction is too fast, and the storage stability of the liquid crystal sealing agent is deteriorated.
  • the component (c) used in the present invention is not particularly limited as long as it is a compound having a glycidyl group.
  • Specific examples include, for example, bisphenol A type epoxy resin; bisphenol F type epoxy resin; bisphenol S type epoxy resin; 4,4′-biphenylphenol diglycidyl ether; 2,2 ′, 6,6′-tetramethyl-4 , 4'-biphenylphenol diglycidyl ether; 2,2'-methylene-bis (4-methyl-6-tert-butylphenol) glycidyl ether; trishydroxyphenylmethane triglycidyl ether; pyrogallol triglycidyl ether; diisopropylidene skeleton Glycidyl ether of phenol having fluorene; glycidyl ether of phenol having a fluorene skeleton such as 1,1-di-4-hydroxyphenylfluorene; phenol, cresols, e
  • N, N-diglycidyl-o-toluidine, N, N-diglycidylaniline, (3,4-4 ′, 4′epoxycyclo) hexylmethylhexanecarboxylate, hexahydro anhydride phthalate It is diglycidyl oxalate, more preferably bisphenol A type epoxy resin. These epoxy resins may be used as a mixture of two or more. Moreover, although the said epoxy resin has a liquid thing and a solid thing, it can also be mixed and used suitably according to desired viscosity.
  • the epoxy equivalent of the epoxy resin used in the present invention is preferably 230 or less, more preferably 210 or less, and still more preferably 190 or less. If it is 230 or more, the reactivity with the curing agent is inferior, and the workability is also problematic.
  • the total amount of chlorine in the liquid epoxy resin used in the present invention is preferably 1500 ppm or less, more preferably 1200 or less, and still more preferably 1000 or less. When the total chlorine amount is 1500 or more, corrosion of the ITO electrode of the liquid crystal cell becomes significant.
  • the epoxy equivalent is measured by JIS K7236, and the total chlorine content is measured by a hydrolysis method.
  • the content of the component (c) is preferably 20 to 70 parts by mass, more preferably 25 to 60 parts by mass, and further preferably 30 to 50 parts by mass.
  • the liquid crystal sealant of the present invention has a gel time at 120 ° C. of 100 seconds to 270 seconds.
  • the gel time is longer than 270 seconds, the liquid crystal sealant is not sufficiently cured after the heat press, and if the temperature is increased to 150 ° C. or the like during the main curing, it is applied to the substrate due to the influence of residual air in the panel.
  • the problem is that the liquid crystal seal is peeled off due to the stress, or micro bubbles are encased in the seal edge portion.
  • the time is shorter than 100 seconds, the storage stability of the liquid crystal sealant itself is affected.
  • a more preferable gel time is 120 seconds or more and 270 seconds or less.
  • the gel time is an automatic gelling tester (manufactured by Iyo Denshi), with a measurement temperature of 120 ° C. and a 0.4 mL liquid crystal sealant placed in the measurement part and attached. It is defined as the time until the torque sensor detects a torque of 70 gcm after the needle made of the trademark) is rotated at a rotation speed of 300 rpm to stir the liquid crystal sealant.
  • the liquid crystal sealing agent of the present invention may contain a coupling agent as the component (d) for the purpose of further improving the adhesive strength.
  • the coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri Methoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyltrimethoxysilane, 3- Aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl)
  • a silane coupling agent is preferred, and an aminosilane coupling agent is more preferred.
  • a liquid crystal sealant having excellent moisture resistance reliability and little decrease in adhesive strength after moisture absorption can be obtained.
  • KBM-573 manufactured by Shin-Etsu Chemical Co., Ltd.
  • the content of the coupling agent (d) in the liquid crystal sealant is preferably 0.05 to 3 parts by mass when the total amount of the liquid crystal sealant of the present invention is 100 parts by mass.
  • the liquid crystal sealant of the present invention may contain a component (e) organic solvent for the purpose of reducing the viscosity in order to improve workability.
  • organic solvent examples include alcohol solvents, ether solvents, acetate solvents, and dibasic acid dimethyl esters. These may be used alone, or two or more may be used in any ratio. You may mix and use.
  • the alcohol solvent examples include alkyl alcohols such as ethanol and isopropyl alcohol; 3-methyl-3-methoxybutanol, 3-methyl-3-ethoxybutanol, 3-methyl-3-n-propoxybutanol, 3-methyl -3-Isopropoxybutanol, 3-methyl-3-n-butoxysibutanol, 3-methyl-3-isobutoxysibutanol, 3-methyl-3-sec-butoxybutanol, 3-methyl-3-tert-butoxy Alkoxy alcohols such as sibutanol; and the like.
  • alkyl alcohols such as ethanol and isopropyl alcohol
  • 3-methyl-3-methoxybutanol 3-methyl-3-ethoxybutanol, 3-methyl-3-n-propoxybutanol, 3-methyl -3-Isopropoxybutanol, 3-methyl-3-n-butoxysibutanol, 3-methyl-3-isobutoxysibutanol, 3-methyl-3-sec-butoxybutan
  • ether solvents include monohydric alcohol ether solvents, alkylene glycol monoalkyl ether solvents, alkylene glycol dialkyl ether solvents, dialkylene glycol alkyl ether solvents, trialkylene glycol alkyl ether solvents, and the like.
  • Examples of monohydric alcohol ether solvents include 3-methyl-3-methoxybutanol methyl ether, 3-methyl-3-ethoxybutanol ethyl ether, 3-methyl-3-n-butoxysibutanol ethyl ether, 3-methyl -3-Isobutoxybutanol propyl ether, 3-methyl-3-sec-butoxybutanol-isopropyl ether, 3-methyl-3-tert-butoxybutanol-n-butyl ether, and the like.
  • alkylene glycol monoalkyl ether solvent examples include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monoisopropyl ether, propylene glycol mono-n-butyl ether, propylene glycol monoisobutyl ether, propylene Glycol mono-sec-butyl ether, propylene glycol mono-tert-butyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monoisobutyl A Le, ethylene glycol monobutyl -sec- butyl ether, and ethylene glycol monobutyl -tert- butyl ether.
  • alkylene glycol dialkyl ether solvent examples include propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol diisopropyl ether, propylene glycol di-n-butyl ether, propylene glycol diisobutyl ether, propylene glycol di-sec- Butyl ether, propylene glycol di-tert-butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol diisopropyl ether, ethylene glycol di-n-butyl ether, ethylene glycol diisobutyl ether, ethylene glycol di-s c- butyl ether, ethylene glycol di -tert- butyl ether, and ethylene glycol dibutyl ether.
  • Dialkylene glycol alkyl ether solvents include, for example, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol dipropyl ether, dipropylene glycol diisopropyl ether, dipropylene glycol di-n-butyl ether, dipropylene glycol diisobutyl.
  • Trialkylene glycol alkyl ether solvents include, for example, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tridipropylene glycol dipropyl ether, tripropylene glycol diisopropyl ether, tripropylene glycol di-n-butyl ether, tripropylene glycol diisobutyl ether.
  • acetate solvents include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monoisopropyl ether acetate, ethylene glycol mono-n-butyl ether acetate, ethylene glycol mono-sec- Butyl ether acetate, ethylene glycol monoisobutyl ether acetate, ethylene glycol mono-tert-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monoisopropyl ether acetate, propylene glycol monopropyl ether acetate Propylene glycol mono-n-butyl ether acetate, propylene glycol mono-sec-butyl ether acetate, propylene glycol monoisobutyl ether acetate, propylene glycol mono-tert
  • propylene glycol diacetate propylene glycol monoethyl ether acetate, dibasic acid dimethyl ester (such as Rhodia Solve RPDE), ethylene glycol dibutyl ether, and ethylene glycol monobutyl ether are preferable, and propylene glycol is more preferable.
  • the amount of the organic solvent used can be any amount necessary to adjust the viscosity (for example, 15 to 60 Pa ⁇ s (25 ° C.)) that the liquid crystal sealant can be applied by a method such as dispensing or screen printing.
  • the non-volatile component in the liquid crystal sealant is used in an amount of 70% by mass or more, preferably 85 to 95% by mass.
  • the component (f) inorganic filler can be used to improve the adhesive strength and improve the moisture resistance reliability.
  • this (f) inorganic filler fused silica, crystalline silica, silicon carbide, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, magnesium oxide, zirconium oxide , Aluminum hydroxide, magnesium hydroxide, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber, molybdenum disulfide, asbestos, etc., preferably fused silica, crystalline silica, Silicon nitride, boron nitride, calcium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, aluminum hydroxide, calcium silicate, aluminum silicate, more
  • the particle size can be measured with a laser diffraction / scattering particle size distribution analyzer (dry type) (manufactured by Seishin Enterprise Co., Ltd .; LMS-30).
  • the content of the inorganic filler (f) that can be used in the liquid crystal sealant of the present invention in the liquid crystal sealant is usually 10 to 60 parts by mass, preferably 100 parts by mass when the total amount of the liquid crystal sealant of the present invention is 100 parts by mass. Is 20 to 50 parts by mass.
  • the content of the inorganic filler is less than 10 parts by mass, the adhesion strength to the glass substrate is lowered, and the moisture resistance reliability is inferior.
  • the content of the inorganic filler is more than 60 parts by mass, the liquid crystal cell may not be able to form a gap due to being hardly crushed.
  • additives such as an organic filler, a pigment, a leveling agent, and an antifoaming agent can be further blended as necessary.
  • An example of a method for obtaining the liquid crystal sealant of the present invention is the following method. First, component (a), component (c), and component (e) as necessary are dissolved and mixed, and component (d) is added thereto as necessary. Component (f) and organic filler, antifoaming agent, leveling agent, etc. are added to this mixed solution as necessary, and mixed uniformly by a known mixing device such as a three-roll, sand mill, ball mill, etc.
  • the liquid crystal sealant of the present invention can be produced by adding the component (b), stirring and mixing, and filtering with a metal mesh.
  • the liquid crystal display cell of the present invention is a cell in which a pair of substrates having predetermined electrodes formed on a substrate are arranged opposite to each other at a predetermined interval, the periphery is sealed with the liquid crystal sealant of the present invention, and the liquid crystal is sealed in the gap. is there.
  • the kind of liquid crystal to be sealed is not particularly limited.
  • the substrate is composed of a combination of substrates made of at least one of glass, quartz, plastic, silicon, etc. and having light transmission properties.
  • a spacer spacer (gap control material) such as glass fiber
  • the liquid crystal sealant was applied to one of the pair of substrates using a dispenser, a screen printing apparatus or the like.
  • the liquid crystal display cell of the present invention can be obtained by injecting liquid crystal in a vacuum from a break (injection port) of the liquid crystal sealant provided in advance in this empty cell.
  • the liquid crystal display cell of the present invention thus obtained is excellent in adhesiveness and flexibility, and is extremely resistant to impacts such as dropping. It is also excellent in moisture resistance reliability.
  • the spacer examples include glass fiber, silica beads, and polymer beads.
  • the diameter varies depending on the purpose, but is usually 2 to 8 ⁇ m, preferably 4 to 7 ⁇ m.
  • the amount used is usually about 0.1 to 4 parts by weight, preferably 0.5 to 2 parts by weight, more preferably about 0.9 to 1.5 parts by weight with respect to 100 parts by weight of the liquid crystal sealant of the present invention. is there.
  • the liquid crystal sealant of the present invention is very excellent in workability. That is, the coating workability by dispensing, screen printing, etc. is good, and it is easily used because it quickly rises to a certain viscosity during preliminary overheating and then stabilizes. Further, as described above, no substrate peeling occurs in the thermosetting process. Furthermore, since the contact with the counter substrate is excellent, the substrates do not peel off during transportation, and the thermosetting property is very good, and the substrate is cured quickly in the heating step. Therefore, the uncured component does not remain, and the elution of the constituent components into the liquid crystal is extremely small, so that display defects of the liquid crystal display cell can be reduced.
  • the cured product is excellent in various cured product characteristics such as adhesive strength, heat resistance, and moisture resistance, it is possible to produce a liquid crystal display cell with excellent reliability by using the liquid crystal sealant of the present invention. is there.
  • the liquid crystal display cell prepared using the liquid crystal sealant of the present invention satisfies the characteristics required for a liquid crystal display cell having a high voltage holding ratio and a low ion density.
  • a liquid crystal sealant obtained by adding 1% by mass of a 5 ⁇ m glass fiber (PF-50S: manufactured by Nippon Electric Glass Co., Ltd.) to a cleaned 1.5 cm ⁇ 3 cm glass substrate with respect to the liquid crystal sealant has a thickness of 5 ⁇ m. It was applied so that the diameter when crushed was 0.8 to 1.2 mm. Preheating was performed for 10 minutes on a hot plate set at 90 ° C., and a cleaned glass substrate of 1.5 cm ⁇ 3 cm was bonded in a cross shape as a counter substrate. At 155 (manufactured by Lion Office Equipment), two places were fixed and the substrate was fixed. The test piece was put into an electric dryer set at 150 ° C.
  • PF-50S manufactured by Nippon Electric Glass Co., Ltd.
  • a UV curable liquid crystal sealant (KAYATRON HM-1400: manufactured by Nippon Kayaku Co., Ltd.) in which 1% by mass of glass fiber (PF-50S: manufactured by Nippon Electric Glass Co., Ltd.) was added to the glass substrate returned to room temperature, It was applied with a dispenser in a square pattern of 7 cm on a side with a cross-sectional area of 10,000 ⁇ m 2 .
  • This glass substrate was bonded at a pressure of 7 Pa with a vacuum bonding apparatus using an 8 cm ⁇ 8 cm, 0.7 mm thick glass substrate coated with NATCO SPACER KSEB-525F manufactured by NATCO Corporation as a counter substrate. went.
  • UV irradiation was performed to cure the outer UV curable liquid crystal sealant, and this was left in an electric dryer set at 150 ° C. for 7 minutes to form a sealant gap.
  • a glass cutter was used to cut a corner portion of the glass substrate together with a part of the UV curable liquid crystal sealant, and the inside of the UV curable liquid crystal sealant was brought to atmospheric pressure.
  • the cut portion was sealed with a sealing agent UV-RESIN LCB-610 manufactured by EHC Co., Ltd. and irradiated with UV to cure the sealing agent. It was put into an electric dryer set at 150 ° C. for 60 minutes to expand the remaining air in the substrate, and stress was applied to the prepared liquid crystal sealant.
  • the liquid crystal sealant portion of the substrate was observed with an optical microscope. The observation results were evaluated according to the following criteria. The evaluation results are shown in Table 1. ⁇ ⁇ ⁇ ⁇ There are no peeling or micro bubbles in the seal part. ⁇ : Micro bubbles are observed in the corner portion of the liquid crystal sealant in a range of less than 20% with respect to the seal width. ⁇ : Micro bubbles are observed in a corner portion or a straight portion of the liquid crystal sealant in a range of less than 30% with respect to the seal width. X: The corner portion or the straight portion of the liquid crystal sealant is peeled off, or microbubbles are observed in a range of 30% or more with respect to the seal width.
  • the liquid crystal sealant of the present invention was excellent in printability and dispenseability, excellent in workability during production of the liquid crystal panel, and not peelable during thermosetting. Moreover, the result which was excellent also in adhesiveness, hygroscopicity, and liquid-crystal stain
  • the liquid crystal sealant of the present invention does not cause a phenomenon in which the upper and lower substrates are peeled off in the thermosetting process, is excellent in coating workability, etc., and is extremely excellent in adhesive strength after curing, low liquid crystal contamination, and the like. Therefore, a highly reliable liquid crystal display cell can be easily manufactured.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Liquid Crystal (AREA)
  • Sealing Material Composition (AREA)

Abstract

La présente invention concerne un agent de scellement de cristaux liquides thermodurcissable qui n'entraîne pas la séparation d'un substrat pendant la production d'une cellule d'affichage à cristaux liquides, en particulier pendant le thermodurcissement dudit agent, tout en montrant une excellente puissance de liaison et une excellente flexibilité après le durcissement et possédant une excellente exploitabilité en application, d'excellentes propriétés de contact par rapport à un contre-substrat, et une excellente stabilité de la viscosité après un chauffage préalable. Un agent de scellement de cristaux liquides de la présente invention contient (a) une résine phénolique novolaque, (b) au moins une substance qui est sélectionnée parmi des adduits d'acide 2,4-diamino-6-[2'-méthylimidazolyl-(1')]-éthyl-s-triazine isocyanurique et des adduits aminés de résine époxy, et (c) une résine époxy. L'agent de scellement à cristaux liquides possède un temps de gélification à 120 °C allant de 100 à 270 secondes (inclus).
PCT/JP2012/076801 2011-10-24 2012-10-17 Agent de scellement de cristaux liquides et cellule d'affichage à cristaux liquides l'utilisant WO2013061837A1 (fr)

Priority Applications (2)

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CN201280051938.5A CN103890649B (zh) 2011-10-24 2012-10-17 液晶密封剂及使用其的液晶显示单元
JP2013540738A JP5969492B2 (ja) 2011-10-24 2012-10-17 液晶シール剤及びそれを用いた液晶表示セル

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11193049B2 (en) 2016-11-25 2021-12-07 Lg Chem, Ltd. Curable composition

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1115005A (ja) * 1997-06-27 1999-01-22 Hitachi Ltd 液晶表示素子とその製造方法
WO2006016507A1 (fr) * 2004-08-11 2006-02-16 Nippon Kayaku Kabushiki Kaisha Matériau d’étanchéité pour cristaux liquides et cellule d’affichage à cristaux liquides utilisant ledit matériau
JP2009013282A (ja) * 2007-07-04 2009-01-22 Nippon Kayaku Co Ltd 液晶シール剤およびそれを用いた液晶表示セル

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008138065A (ja) * 2006-12-01 2008-06-19 Sekisui Chem Co Ltd 熱硬化性樹脂組成物、成形体、及びプリント基板用の層間絶縁膜

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1115005A (ja) * 1997-06-27 1999-01-22 Hitachi Ltd 液晶表示素子とその製造方法
WO2006016507A1 (fr) * 2004-08-11 2006-02-16 Nippon Kayaku Kabushiki Kaisha Matériau d’étanchéité pour cristaux liquides et cellule d’affichage à cristaux liquides utilisant ledit matériau
JP2009013282A (ja) * 2007-07-04 2009-01-22 Nippon Kayaku Co Ltd 液晶シール剤およびそれを用いた液晶表示セル

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11193049B2 (en) 2016-11-25 2021-12-07 Lg Chem, Ltd. Curable composition

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TW201333097A (zh) 2013-08-16
JP5969492B2 (ja) 2016-08-17
CN103890649B (zh) 2016-04-13
JPWO2013061837A1 (ja) 2015-04-02
CN103890649A (zh) 2014-06-25

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