WO2013047579A1 - 液晶シール剤及びそれを用いた液晶表示セル - Google Patents
液晶シール剤及びそれを用いた液晶表示セル Download PDFInfo
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- WO2013047579A1 WO2013047579A1 PCT/JP2012/074681 JP2012074681W WO2013047579A1 WO 2013047579 A1 WO2013047579 A1 WO 2013047579A1 JP 2012074681 W JP2012074681 W JP 2012074681W WO 2013047579 A1 WO2013047579 A1 WO 2013047579A1
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- liquid crystal
- component
- ether
- crystal sealant
- sealing agent
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1339—Gaskets; Spacers; Sealing of cells
-
- 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
- G02F2202/00—Materials and properties
- G02F2202/28—Adhesive materials or arrangements
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 employ a multi-processing process in which a large number of electrodes are formed on a large glass substrate, and then the upper and lower substrates are bonded together 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 property 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.
- thermosetting liquid crystal sealant that is excellent in coating workability, contact property to a counter substrate, viscosity stability after preheating, and extremely excellent in adhesive strength and flexibility after curing. Objective.
- the present inventors have intensively studied and contain a phenol novolac resin having specific properties and an acrylic polymer having a core-shell structure, and further have a gel time at 150 ° C. of 50 seconds to 200 seconds.
- the present inventors have found that the following liquid crystal sealant solves the above-mentioned problems and completed the present invention.
- the present invention relates to the following 1) to 12).
- 1) A solid phenol novolak resin having a softening point of 75 ° C. or less, (b) an acrylic polymer having a core-shell structure, (c) an epoxy resin, and (d) an organic solvent, and having a gel time at 150 ° C. of 50 seconds Liquid crystal sealant that is 200 seconds or longer.
- 2) The liquid crystal sealant according to 1) above, wherein the core layer of the component (b) is a polymer of n-butyl acrylate, and the shell layer is a polymer of methyl methacrylate.
- the component (d) is one or more organic solvents selected from the group consisting of propylene glycol diacetate, dibasic acid dimethyl ester, propylene glycol monoethyl ether acetate, and ethylene glycol dibutyl ether.
- Liquid crystal sealing agent as described in. 4) The liquid crystal sealing agent according to any one of 1) to 3), wherein the component (a) is a compound represented by the following formula (1).
- R 5 represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a halogen atom
- r represents an integer of 1 to 3. When r is 2 or 3, each R 5 is the same.
- the component (e) is at least one selected from 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct and an epoxy resin amine adduct.
- Liquid crystal sealing agent as described in said 7).
- (f) Liquid crystal sealing agent as described in any one of said 1) thru
- the liquid crystal sealant of the present invention is excellent in contact with the counter substrate after pre-curing, has excellent adhesion strength after curing, and is excellent in moisture resistance. Therefore, a liquid crystal display cell having high reliability can be manufactured.
- the liquid crystal sealant of the present invention essentially comprises component (a) a phenol novolac resin having a softening point of 75 ° C. or less, component (b) an acrylic polymer having a core-shell structure, component (c) an epoxy resin, and component (d) an organic solvent. Contains as a component.
- the component (a) used in the present invention is a phenol novolac resin having a softening point of 75 ° C. or lower, preferably 65 ° C. or lower, more preferably 50 ° C. or lower, and is not particularly limited as long as it has this property.
- 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.
- phenol novolac resin examples include 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, phenols having a fluorene skeleton such as 1,1-di-4-hydroxyphenylfluorene , Polyphenol compounds such as phenolized polybutadiene, phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, allylphenols, brominated bisphenol A, Novolak resins made from various phenols such as Sphenol F, bisphenol S, naphthols, etc .; phenol novolac resins having a x
- phenols such as phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, brominated bisphenol A, bisphenol F, bisphenol S, naphthols represented by any of the following formulas (2) to (4) And phenol novolak resin bonded with a crosslinking group (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
- More preferable phenol novolac resins include phenol novolac resins using phenol as a raw material, novolak resins using monophenols represented by cresol novolac resins using cresols as raw materials; phenols, cresols, bisphenol A, and the like. 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
- r represents an integer of 1 to 3.
- r is 2 or 3
- each R 5 is the same.
- s is 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, iso Examples thereof include alkoxy groups having 1 to 4 carbon atoms such as propoxy and n-butoxy.
- Examples of the halogen atom include a bromine atom, a chlorine atom, and a fluorine atom.
- 0 or a positive integer in s is preferably 0 to 15, more preferably 0 to 10.
- PN-152 manufactured by Nippon Kayaku Co., Ltd.
- PN-152 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 preferably 0.2 to 1.4 chemical equivalents as the equivalent of the hydroxyl group in the novolac resin, with respect to 1 equivalent of the epoxy group in the epoxy resin in the liquid crystal sealant.
- the amount of the novolak resin used affects the contact property of the liquid crystal sealant to the counter substrate.
- the curing agent comprising a phenol novolac resin that is preferably 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 component (b) used in the present invention is fine particles composed of two layers of a core layer made of an acrylic polymer and a shell layer also made of an acrylic polymer.
- the components of the acrylic polymer used for the core layer and the acrylic polymer used for the shell layer may be the same or different.
- the raw materials include (meth) acrylate monomers such as n-propyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-decyl (meth) acrylate; styrene, vinyltoluene, Aromatic vinyl compounds such as ⁇ -methylstyrene; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; vinylidene cyanide, 2-hydroxyethyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 2-hydroxyethyl fuma Rate, hydroxybutyl vinyl ether, monobutyl maleate, butoxyethyl methacrylate; and the like.
- acrylate monomers such as n-propyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate
- Crosslinkable monomers having two or more reactive groups such as acrylates, oligoethylene di (meth) acrylate oligoethylene tri (meth) acrylates; aromatic divinyl monomers such as divinylbenzene; triallylic acid triallyl, triallyl isocyanate; Etc., and those in which one or more of these are selected can be used.
- Paraloid EXL-2655 (Rohm and Haas) can be obtained from the market as a commercial product.
- the core layer is a polymer of n-butyl acrylate and the shell layer is a polymer of methyl methacrylate are particularly preferable. This is available from the market as F-351 (Ganz Chemical Co., Ltd.).
- meta (acrylate) means one or both of acrylate and methacrylate.
- 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
- 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 component (d) used in the present invention is added for the purpose of reducing the viscosity in order to improve workability.
- the organic solvent that can be used include alcohol solvents, ether solvents, acetate solvents, and dibasic acid dimethyl esters. These may be used alone or in combination of two or more in any ratio. May be used.
- 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, and ethylene glycol dibutyl ether are preferable, and propylene glycol diacetate, propylene glycol monoethyl ether acetate, and rhodia are more preferable.
- Component (b) has the property of absorbing organic solvents and resins and swelling them little by little. For this reason, depending on the selection of the organic solvent, it becomes a liquid crystal sealant with poor storage stability.
- Organic solvents such as propylene glycol diacetate, propylene glycol monoethyl ether acetate, rhodiasolve RPDE, and ethylene glycol dibutyl ether have sufficient ability to dissolve component (a), component (c), etc., but component (b) It is inferior in compatibility with. Therefore, insufficient dissolution of the resin component does not cause insoluble components to precipitate or cause layer separation, and the component (b) is swollen during storage, and properties such as the viscosity of the liquid crystal sealant are improved. There is no change.
- the boiling point of the organic solvent is desirably in the range of 150 to 230 ° C.
- the boiling point When the boiling point is lower than 150 ° C., the increase in viscosity during screen printing of the liquid crystal sealant is large and the use time is shortened. When the boiling point is higher than 230 ° C., the solvent does not volatilize when the solvent is dried, and air bubbles are caught in the liquid crystal sealant after the main curing, or the cured physical properties are deteriorated.
- 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 liquid crystal sealant of the present invention has a property that the gel time at 150 ° C. is from 50 seconds to 200 seconds.
- the gel time at 150 ° C. is longer than 200 seconds, the liquid crystal sealant cures slowly, so that the liquid crystal sealant leaks due to the difference between the internal pressure and the external pressure of the liquid crystal sealant during heat press, or the seal width due to capillary action. Inconveniences such as being disturbed are likely to occur. Conversely, if it is shorter than 50 seconds, the storage stability of the liquid crystal sealant itself is affected.
- a more preferable gel time is 70 seconds or more and 200 seconds or less, still more preferably 100 seconds or more and 200 seconds or less, and particularly preferably 100 seconds or more and 150 seconds or less.
- gel time means an automatic gelling tester (manufactured by Iyo Denshi), a measurement temperature of 150 ° C., a 0.4 mL liquid crystal sealant placed in a measurement part, and an attached Teflon (registered) It is defined as the time until the torque sensor detects a torque of 70 gcm by rotating the needle made by the trademark) at 100 rpm and stirring the liquid crystal sealant.
- the liquid crystal sealant of the present invention may further contain a curing accelerator as a component (e) for the purpose of improving thermal reactivity.
- a curing accelerator as a component (e) for the purpose of improving thermal reactivity.
- the curing accelerator (e) used in the present invention include imidazoles; imidazoles, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid, oxalic acid, and the like.
- Salts with polyvalent carboxylic acids amides such as dicyandiamide; salts of the amides with phenols, polyvalent carboxylic acids or phosphinic acids; 1,8-diaza-bicyclo (5.4.0) undecene Diaza compounds such as -7; salts of the diaza compounds with phenols, the above polyvalent carboxylic acids, or phosphinic acids; phosphines such as triphenylphosphine and tetraphenylphosphonium tetraphenylborate; 2,4,6-tris Phenols such as aminomethylphenol; amine adducts and the like.
- amides such as dicyandiamide
- salts of the amides with phenols, polyvalent carboxylic acids or phosphinic acids 1,8-diaza-bicyclo (5.4.0) undecene Diaza compounds such as -7; salts of the diaza compounds with phenols, the above polyvalent carboxylic acids,
- curing accelerators preferred are salts of imidazoles and polyvalent carboxylic acids, and amine adducts. Particularly preferred is 2,4-diamino-6- [2′-methylimidazolyl- (1 ′). ] -Ethyl-s-triazine isocyanuric acid adduct, epoxy resin amine adduct. Since these curing accelerators are difficult to dissolve in solvents and have high potential, the pot life of the liquid crystal sealing agent is long, and further, when heated at 100 ° C. or higher, it cures quickly. This is because the liquid crystal sealant is prevented from leaking due to the stress due to the difference between the external pressure and the external pressure.
- the addition amount of the curing accelerator is preferably 0.5 to 20 parts by mass, more preferably 1 to 18 parts by mass with respect to 100 parts by mass of the epoxy resin.
- Latent curing accelerators are solid at room temperature and have the property of dissolving when heated and reacting as curing accelerators for the first time.
- microcapsule-type curing accelerators in which these curing accelerators are made into microcapsules
- a solid dispersion type curing accelerator for example, imidazoles which is difficult to dissolve in a solvent or an epoxy resin, and an amine adduct.
- the average particle size of the solid dispersion type latent curing accelerator is preferably 6 ⁇ m or less, more preferably 4 ⁇ m or less, and even more preferably about 3 ⁇ m or less as measured by a laser method.
- a latent curing accelerator having an average particle size of more than 6 ⁇ m is used, it is difficult to apply the dispenser, and the shape after application is not uniform, and therefore the seal shape after sealing is not uniform.
- the rough coarseness of a filler is confirmed in the seal
- the liquid crystal sealant of the present invention may contain a coupling agent as the component (f) 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)
- silane coupling agents are preferred, and epoxy silane coupling agents are more preferred.
- a liquid crystal sealant having excellent moisture resistance reliability and little decrease in adhesive strength after moisture absorption can be obtained.
- Silaace S-510 manufactured by Chisso Corporation is available from the market.
- the component (g) inorganic filler can be used to improve adhesive strength and moisture resistance reliability.
- this (g) 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 preferably fuse
- 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 component (g) inorganic filler 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 when the total amount of the liquid crystal sealant of the present invention is 100 parts by mass, The amount is preferably 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 (d) are dissolved and mixed, and if necessary, component (f), component (g), organic filler, antifoaming agent, leveling agent, etc. are added thereto. , Uniformly mixed with a known mixing device, for example, a three roll, sand mill, ball mill, etc., and then component (b) and component (e) are added and mixed uniformly with a three roll or planetary mixer.
- the liquid crystal sealing agent of the present invention can be produced by filtering with a 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 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. 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.
- PF-50S manufactured by Nippon Electric Glass Co., Ltd.
- Adhesive strength is 16 MPa or more ⁇ ... Adhesive strength is 10 MPa or more and less than 16 MPa x ... Adhesive strength is less than 10 MPa
- a liquid crystal sealant is applied on a 5 cm ⁇ 5 cm glass substrate in a pattern with an injection port so that the cross-sectional area is 5000 ⁇ m 2 with a dispenser, and solvent drying (precure) is performed for 10 minutes with an electric dryer set at 90 ° C. It was. After cooling the substrate to a room temperature atmosphere, a 5 cm ⁇ 5 cm counter glass substrate was overlaid, a 10 kg weight was placed for 30 seconds, the crushability of the liquid crystal sealant was observed with an optical microscope, and the width of the liquid crystal sealant was measured.
- the measurement is performed from two directions of the glass substrate side coated with the liquid crystal sealant and the counter substrate, and by comparing the width of the liquid crystal sealant on the side coated with the liquid crystal sealant and the width of the liquid crystal sealant on the counter substrate side, The degree of collapse was evaluated.
- the criteria for evaluation are as follows. The results are shown in Table 1.
- B The width of the counter glass substrate is 40% or more and less than 70% of the width of the substrate coated with the liquid crystal sealant.
- the width of the counter glass substrate is 10% or more and less than 40% of the width of the substrate coated with the liquid crystal sealant x .
- the width of the counter glass substrate is less than 10% of the width of the substrate coated with the liquid crystal sealant Not touching
- a liquid crystal sealant is applied on a 5 cm ⁇ 5 cm glass substrate in a pattern with an injection port so that the cross-sectional area is 5000 ⁇ m 2 with a dispenser, and solvent drying (precure) is performed for 10 minutes with an electric dryer set at 90 ° C. It was. After cooling the substrate to the room temperature atmosphere, a 5 cm ⁇ 5 cm counter glass substrate was overlaid, and the four sides were bonded with a binder clip no. 155 (manufactured by Lion Office Equipment) and put in an electric dryer set at 150 ° C. for 60 minutes. After cooling the substrate to room temperature, the state of the liquid crystal sealant on the substrate was observed with an optical microscope.
- the liquid crystal sealant of the present invention was excellent in printability, dispensing property, and contact property to the counter substrate, and was excellent in workability when manufacturing a liquid crystal panel.
- the seal shape was not disturbed after bonding and pressing, and showed excellent values for adhesion, moisture-proof adhesion, and liquid crystal contamination.
- the comparative example even if it is excellent in printability and dispensing property, the contact property to the counter substrate is poor, the workability is good but the adhesiveness is poor, or the bleeding occurs after pressing. was there. Therefore, it can be said that the liquid crystal sealant of the present invention is a highly reliable sealant with no problem in workability throughout the process.
- the liquid crystal sealant of the present invention is excellent in coating workability, contact property to the counter substrate, viscosity stability after preliminary overheating, and extremely excellent in adhesive strength and flexibility after curing. Therefore, a highly reliable liquid crystal display cell can be easily manufactured.
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Abstract
Description
例えば、特許文献1には接着性、耐湿信頼性、可撓性に優れる熱硬化型液晶シール剤が開示されている。
特許文献2には接着性、耐湿信頼性、可撓性、熱硬化性に優れる熱硬化型液晶シール剤が開示されている。
特許文献3にはスクリーン印刷性、耐湿信頼性に優れる熱硬化型液晶シール剤が開示されている。
1)
(a)軟化点が75℃以下の固形フェノールノボラック樹脂、(b)コアシェル構造を有するアクリル重合体、(c)エポキシ樹脂、及び(d)有機溶剤を含有し、150℃でのゲルタイムが50秒以上200秒以下である液晶シール剤。
2)
上記成分(b)のコア層がn-ブチルアクリレートの重合体であり、シェル層がメチルメタクリレートの重合体である上記1)に記載の液晶シール剤。
3)
上記成分(d)が、プロピレングリコールジアセテート、二塩基酸ジメチルエステル、プロピレングリコールモノエチルエーテルアセテート、及びエチレングリコールジブチルエーテルからなる群から選択される1種以上の有機溶剤である上記1)又は2)に記載の液晶シール剤。
4)
上記成分(a)が、下記式(1)で表される化合物である上記1)乃至3)のいずれか一項に記載の液晶シール剤。
5)
上記成分(c)のエポキシ基1当量に対する上記成分(a)の水酸基の当量が0.2~1.4化学当量である上記1)乃至4)のいずれか一項に記載の液晶シール剤。
6)
上記成分(c)が、ビスフェノールA型エポキシ樹脂である上記1)乃至5)のいずれか一項に記載の液晶シール剤。
7)
更に、(e)硬化促進剤を含有する上記1)乃至6)のいずれか一項に記載の液晶シール剤。
8)
上記成分(e)が、2,4-ジアミノ-6-[2’-メチルイミダゾリル-(1’)]-エチル-s-トリアジンイソシアヌル酸付加物及びエポキシ樹脂アミンアダクトから選ばれる少なくとも1種である上記7)に記載の液晶シール剤。
9)
更に、(f)カップリング剤を含有する上記1)乃至8)のいずれか一項に記載の液晶シール剤。
10)
上記成分(f)が、エポキシシランカップリング剤である上記9)に記載の液晶シール剤。
11)
更に、(g)無機充填剤を含有する上記1)乃至10)のいずれか一項に記載の液晶シール剤。
12)
上記1)乃至11)のいずれか一項に記載の液晶シール剤を硬化して得られる硬化物でシールされた液晶表示セル。
なお、本明細書において、メタ(アクリレート)とは、アクリレート及びメタクリレートの一方又は両方を意味する。
有機溶剤の沸点は150~230℃の範囲が望ましい。沸点が150℃より低いと液晶シール剤スクリーン印刷時の粘度増加が大きく、使用時間が短くなってしまう。沸点が230℃よりも高いと溶剤乾燥時に溶剤が揮発せず、本硬化後の液晶シール剤に気泡が噛みこんだり、硬化物性が低下したりする。
下記表1に示す割合で各樹脂成分(成分(a)、成分(c))及び有機溶剤(成分(d))を混合し、加熱溶解した。室温まで冷却後、必要に応じてカップリング剤(成分(f)、無機充填剤(成分(g))等を適宜添加し、コアシェル構造を有するアクリル重合体(成分(b))、必要に応じて硬化促進剤(成分(e))を添加し、3本ロールにて均一に混合し金属メッシュで濾過し、実施例1~8、比較例1~4の液晶シール剤を調製した。
自動ゲル化テスタ(伊予電子製)を使用し、測定温度150℃雰囲気下にて、調製した液晶シール剤を測定部に0.4mL入れ、取り付けたテフロン(登録商標)製ニードルを自転部100rpmにて回転させてシール剤を撹拌し、トルクセンサーが70gcmのトルクを検出するまでの時間をゲルタイムとした。結果を表1に示す。
E型粘度計(VISCONIC EHD型、コーン3°×R14:東京精機株式会社製)にて25℃、10rpmの粘度を測定した。結果を表1に示す。
E型粘度計(VISCONIC EHD型、コーン3°×R14:東京精機株式会社製)にて25℃での、10rpm及び1rpmの粘度を測定し、1rpmの粘度/10rpmの粘度の値をチクソ比とした。結果を表1に示す。
調製した液晶シール剤を25℃雰囲気に48時間保管したものをE型粘度計(VISCONIC EHD型、コーン3°×R14:東京精機株式会社製)にて25℃、10rpmの粘度を測定し、初期粘度からの増粘度を算出し、48時間後の増粘率とした。計算式は、{(48時間後の粘度-初期粘度)/(初期粘度)}×100とした。結果を表1に示す。
洗浄した1.5cm×3cmのITO膜付きガラス基板に、5μmのガラスファイバー(PF-50S:日本電気硝子株式会社製)を液晶シール剤に対して1質量%添加した液晶シール剤を、5μmの厚さに潰したときの直径が0.8~1.2mmになるように塗布した。90℃設定のホットプレートにて10分間予備加熱を行い、対向基板として、洗浄した1.5cm×3cmのITO膜付きガラス基板をITO面側が液晶シール剤側になるように、十字の形にて貼り合わせ、バインダークリップNo.155(ライオン事務機器製)にて2箇所をとめ、基板を固定させた。150℃設定の電気乾燥機にこの試験片を投入し、室温まで冷却した。ボンドテスター(SS-30WD:西進商事製)の引っ張りモードにて3.3mm/秒の速度にて引っ張り方向の強度を測定した。強度をシールの単位面積当たりに換算し、接着強度とした。評価の基準は以下による。結果を表1に示す。
○・・・接着強度が16MPa以上
△・・・接着強度が10MPa以上16MPa未満
×・・・接着強度が10MPa未満
上記[接着性テスト]と同様の手順にて、試験片の作成を行った。その後60℃90%に設定した恒温恒湿槽(HPAV-80-20:いすゞ製作所製)に12時間投入後、室温にて冷却したものを測定用試験片とした。ボンドテスター(西進商事製SS-30WD)の引っ張りモードにて3.3mm/秒の速度にて引っ張り方向の強度を測定した。強度をシールの単位面積当たりに換算し、耐湿接着強度とした。評価の基準は以下による。結果を表1に示す。
○・・・耐湿接着強度が16MPa以上
△・・・耐湿接着強度が10MPa以上16MPa未満
×・・・耐湿接着強度が10MPa未満
5cm×5cmのガラス基板上に注入口付きのパターンで液晶シール剤をディスペンサーにて断面積5000μm2になるように塗布し、90℃設定の電気乾燥機にて10分間溶剤乾燥(プリキュア)を行った。基板を室温雰囲気まで冷却後、5cm×5cmの対向ガラス基板を重ね合わせ、10kgの錘を30秒間のせ、液晶シール剤の潰れ性を光学顕微鏡にて観察し、液晶シール剤の幅を測定した。測定は液晶シール剤を塗布したガラス基板側と、対向基板の2方向から行い、液晶シール剤を塗布した側の液晶シール剤の幅と、対向基板側の液晶シール剤の幅との比較によって、どの程度潰れているかを評価した。評価の基準は以下による。結果を表1に示す。
◎・・・対向ガラス基板の幅が液晶シール剤を塗布した基板の幅の70%以上
○・・・対向ガラス基板の幅が液晶シール剤を塗布した基板の幅の40%以上70%未満
△・・・対向ガラス基板の幅が液晶シール剤を塗布した基板の幅の10%以上40%未満
×・・・対向ガラス基板の幅が液晶シール剤を塗布した基板の幅の10%未満あるいは全く接していない
5cm×5cmのガラス基板上に注入口付きのパターンで液晶シール剤をディスペンサーにて断面積5000μm2になるように塗布し、90℃設定の電気乾燥機にて10分間溶剤乾燥(プリキュア)を行った。基板を室温雰囲気まで冷却後、5cm×5cmの対向ガラス基板を重ね合わせ、4辺をバインダークリップNo.155(ライオン事務機器製)にて挟み、150℃設定の電気乾燥器にて60分間投入した。基板を室温まで冷却後基板の液晶シール剤の様子を光学顕微鏡にて観察した。本試験においては、硬化性等の影響から、樹脂成分の染み出しの有無(樹脂成分とフィラー成分の相分離の有無)を確認する。評価の基準は以下による。結果を表1に示す。
○・・・樹脂成分の染み出しが無い
×・・・樹脂成分の染み出しが有る
調製した液晶シール剤を、スクリーン印刷機(LS-150:ニューロング精密工業株式回社製)にてガラス基板に印刷塗布した。これを目視にて確認した。かすれ、液晶シール剤の切れ等の有無を観察した。評価の基準は以下による。結果を表1に示す。
○・・・かすれ、切れが無い
×・・・かすれ、切れが有る
調製した液晶シール剤をシリンジに充填・脱泡した後、ディスペンサー(ショットマスター300:武蔵エンジニアリング社製)にてガラス基板上に30mm/secで塗布し、形状を目視にて確認した。かすれ、液晶シール剤の切れ等の有無を観察した。評価の基準は以下による。結果を表1に示す。
○・・・かすれ、切れが無い
×・・・かすれ、切れが有る
10mLサンプル瓶の底に調製した液晶シール剤を100mg程度均一に塗布した後、90℃に設定した電気乾燥機にて10分間溶剤乾燥(プリキュア)を行った。その後150℃に設定した電気乾燥機にて60分硬化した。室温に冷却後、液晶(MLC-6866-100:メルク株式会社製)を液晶シール剤の10倍量加えた。90℃設定の電気乾燥機にて24時間加熱した後、30分間冷却した。それぞれの上澄みをデカンテーションにて分け取り、デジタル超高抵抗計(R8340:株式会社アドバンテスト製)にて比抵抗値を測定した。評価の基準は以下による。結果を表1に示す。
○・・・比抵抗値が1.0×10E+12以上
×・・・比抵抗値が1.0×10E+12未満
なお、比抵抗値の「1.0E+12」は「1.0×1012」を表し、他の記載も同様である。
5cm×7cmのガラス基板上に調製した液晶シール剤を25μmのクリアランスのアプリケーターを使用して塗布した。90℃に設定した電気乾燥機にて10分間溶剤乾燥を行い、150℃に設定した電気乾燥機にて60分間硬化させた。60℃90%に設定した恒温恒湿槽(HPAV-80-20:いすゞ製作所)に24時間投入後室温にて冷却した液晶シール剤と硬化直後の液晶シール剤との重量変化から吸水率を算出した。算出式は{(吸水後のシール剤重量-吸水前のシール剤重量)/(吸水前のシール剤重量)}×100とした。結果を表1に示す。
したがって、本発明の液晶シール剤は、工程を通じて作業性に問題がなく、信頼性に非常に優れたシール剤であるといえる。
Claims (12)
- (a)軟化点が75℃以下の固形フェノールノボラック樹脂、(b)コアシェル構造を有するアクリル重合体、(c)エポキシ樹脂、及び(d)有機溶剤を含有し、150℃でのゲルタイムが50秒以上200秒以下である液晶シール剤。
- 前記成分(b)のコア層がn-ブチルアクリレートの重合体であり、シェル層がメチルメタクリレートの重合体である請求項1に記載の液晶シール剤。
- 前記成分(d)が、プロピレングリコールジアセテート、二塩基酸ジメチルエステル、プロピレングリコールモノエチルエーテルアセテート、及びエチレングリコールジブチルエーテルからなる群から選択される1種以上の有機溶剤である請求項1又は2に記載の液晶シール剤。
- 前記成分(c)のエポキシ基1当量に対する前記成分(a)の水酸基の当量が0.2~1.4化学当量である請求項1乃至4のいずれか一項に記載の液晶シール剤。
- 前記成分(c)が、ビスフェノールA型エポキシ樹脂である請求項1乃至5のいずれか一項に記載の液晶シール剤。
- 更に、(e)硬化促進剤を含有する請求項1乃至6のいずれか一項に記載の液晶シール剤。
- 前記成分(e)が、2,4-ジアミノ-6-[2’-メチルイミダゾリル-(1’)]-エチル-s-トリアジンイソシアヌル酸付加物及びエポキシ樹脂アミンアダクトから選ばれる少なくとも1種である請求項7に記載の液晶シール剤。
- 更に、(f)カップリング剤を含有する請求項1乃至8のいずれか一項に記載の液晶シール剤。
- 前記成分(f)が、エポキシシランカップリング剤である請求項9に記載の液晶シール剤。
- 更に、(g)無機充填剤を含有する請求項1乃至10のいずれか一項に記載の液晶シール剤。
- 請求項1乃至11のいずれか一項に記載の液晶シール剤を硬化して得られる硬化物でシールされた液晶表示セル。
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018181849A1 (ja) * | 2017-03-31 | 2018-10-04 | 新日鉄住金化学株式会社 | 繊維強化複合材料用エポキシ樹脂組成物、繊維強化複合材料及び成形体 |
WO2021241129A1 (ja) * | 2020-05-29 | 2021-12-02 | 三井化学株式会社 | 表示装置用シール剤 |
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JP6283624B2 (ja) * | 2015-05-28 | 2018-02-21 | 日東電工株式会社 | 中空型電子デバイス封止用シート、中空型電子デバイスパッケージの製造方法、及び、中空型電子デバイスパッケージ |
WO2017073548A1 (ja) * | 2015-10-26 | 2017-05-04 | 積水化学工業株式会社 | 液晶表示素子用シール剤、上下導通材料及び液晶表示素子 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09302071A (ja) * | 1996-05-10 | 1997-11-25 | Mitsui Toatsu Chem Inc | 液晶封止用樹脂組成物 |
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 |
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 |
JP2011021050A (ja) * | 2009-07-13 | 2011-02-03 | Dic Corp | エポキシ樹脂組成物、その硬化物、回路基板、ビルドアップ材料、及び半導体封止材料 |
Family Cites Families (3)
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---|---|---|---|---|
JP5181218B2 (ja) * | 2007-11-30 | 2013-04-10 | 日立化成株式会社 | 誘電体ペースト用バインダー樹脂の製造法、樹脂及び誘電体ペースト |
KR101134635B1 (ko) * | 2009-10-12 | 2012-04-09 | 금호석유화학 주식회사 | 액정 표시 소자용 실란트 조성물 |
KR101860356B1 (ko) * | 2011-11-25 | 2018-05-24 | 금호석유화학 주식회사 | 액정 오염성을 개선한 표시소자용 실란트 조성물 및 그를 경화하여 형성된 실란트 |
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2012
- 2012-09-26 CN CN201280047436.5A patent/CN103827741B/zh not_active Expired - Fee Related
- 2012-09-26 JP JP2013536327A patent/JP6087824B2/ja not_active Expired - Fee Related
- 2012-09-26 WO PCT/JP2012/074681 patent/WO2013047579A1/ja active Application Filing
- 2012-09-26 SG SG11201400967YA patent/SG11201400967YA/en unknown
- 2012-09-26 KR KR1020147007853A patent/KR20140081806A/ko not_active Application Discontinuation
- 2012-09-27 TW TW101135536A patent/TWI550015B/zh not_active IP Right Cessation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09302071A (ja) * | 1996-05-10 | 1997-11-25 | Mitsui Toatsu Chem Inc | 液晶封止用樹脂組成物 |
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 |
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 |
JP2011021050A (ja) * | 2009-07-13 | 2011-02-03 | Dic Corp | エポキシ樹脂組成物、その硬化物、回路基板、ビルドアップ材料、及び半導体封止材料 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018181849A1 (ja) * | 2017-03-31 | 2018-10-04 | 新日鉄住金化学株式会社 | 繊維強化複合材料用エポキシ樹脂組成物、繊維強化複合材料及び成形体 |
WO2021241129A1 (ja) * | 2020-05-29 | 2021-12-02 | 三井化学株式会社 | 表示装置用シール剤 |
JP7391211B2 (ja) | 2020-05-29 | 2023-12-04 | 三井化学株式会社 | 表示装置用シール剤 |
Also Published As
Publication number | Publication date |
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TW201329153A (zh) | 2013-07-16 |
KR20140081806A (ko) | 2014-07-01 |
SG11201400967YA (en) | 2014-09-26 |
CN103827741A (zh) | 2014-05-28 |
CN103827741B (zh) | 2016-06-22 |
TWI550015B (zh) | 2016-09-21 |
JPWO2013047579A1 (ja) | 2015-03-26 |
JP6087824B2 (ja) | 2017-03-01 |
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