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
  • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
  • C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
• • 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
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • 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
  • C08L63/10—Epoxy resins modified by unsaturated compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
  • C09J163/10—Epoxy resins modified by unsaturated compounds
• • 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 used for a liquid crystal dropping method. More specifically, the present invention relates to a liquid crystal sealant that is extremely excellent in adhesion to an organic film such as an alignment film, and a liquid crystal display cell using the same.
• this liquid crystal dropping method is a manufacturing method in which a liquid crystal is dropped inside a weir made of a liquid crystal sealing agent formed on one substrate, and then the other substrate is bonded, and then the liquid crystal sealing agent is cured. It is.
• the liquid crystal sealant comes into contact with the liquid crystal sealant before the liquid crystal sealant is cured, so that an insertion phenomenon occurs in the liquid crystal sealant due to the pressure of the liquid crystal. It is a problem that the weir made of may break down. In order to solve this problem, it is necessary to improve the accuracy of the liquid crystal dripping amount, but it is still difficult to completely suppress the above-mentioned insertion phenomenon because the liquid crystal expands during heating, which is the curing process of the liquid crystal sealant. It is.
• liquid crystal display elements are used in a wide variety of things. Therefore, it is necessary not to cause a problem with respect to a large change in temperature or high humidity. This property is equally applicable to liquid crystal sealants, and does not cause separation between substrates due to changes in temperature, and has resistance under high humidity and prevents water from entering. Characteristics are required.
• Patent Document 5 use of a partially (meth) acrylated epoxy resin having specific properties has been proposed (Patent Document 5). However, it is still not enough.
• the line width of the liquid crystal sealant becomes narrower, so the problem of adhesive strength is more serious than before. That is, the narrow line width of the liquid crystal sealant causes a problem that the upper and lower substrates peel off after normal temperature and humidity resistance reliability tests with the conventional adhesive strength.
• liquid crystal display cells in which a liquid crystal sealant is disposed on an alignment film or the like.
• the conventional liquid crystal sealant cannot be said to have sufficient adhesion to such an organic film, and is regarded as a problem to be solved.
• liquid crystal sealing agent for the liquid crystal dropping method needs to be excellent in general properties such as low liquid crystal contamination and high adhesive strength.
• the present invention is a liquid crystal sealant used in a liquid crystal dropping method, and is particularly excellent in adhesion to an organic film such as an alignment film.
• the liquid crystal sealing agent which is excellent also in the basic characteristics as liquid crystal sealing agents, such as property and heat resistance, and a liquid crystal display cell using the same are proposed.
• the inventors have determined that the adhesive strength with respect to an ITO (indium tin oxide) substrate at 25 ° C. after being cured in an atmosphere of 120 ° C. for 1 hour after being irradiated with 3000 mJ / cm 2 of ultraviolet light is A [ MPa], when the adhesive strength at 120 ° C. after curing is B [MPa], and when the adhesive strength to an ITO (indium tin oxide) substrate at 25 ° C. after curing with only 3000 mJ / cm 2 ultraviolet rays is C [MPa]
• the liquid crystal sealing agent in which A, B, and C have a certain relationship was found to have very good adhesion strength to an organic film, and the present invention was achieved.
• “(meth) acryl” means “acryl and / or methacryl”.
• the present invention relates to the following 1) to 13).
• 1) Adhesion strength to ITO (indium tin oxide) substrate at 25 ° C. after curing for 1 hour in an atmosphere of 120 ° C. after irradiation with 3000 mJ / cm 2 ultraviolet rays, and adhesion at 120 ° C. after the curing When the strength is B [MPa] and the adhesive strength to an ITO (indium tin oxide) substrate at 25 ° C. after curing with only ultraviolet rays of 3000 mJ / cm 2 is C [MPa], the above A, B, and C are the following formulas: A liquid crystal sealant for a liquid crystal dropping method that satisfies the relational expressions represented by (1) and (2).
• liquid-crystal sealing compound for liquid crystal dropping methods as described in any one of said 3) thru
• liquid-crystal sealing compound for liquid crystal dropping methods as described in any one of said 3) thru
• liquid-crystal sealing compound for liquid crystal dropping methods as described in any one of said 3) thru
• liquid crystal display cell constituted by two substrates, liquid crystal is dropped inside a weir formed of the liquid crystal sealing agent for a liquid crystal dropping method according to any one of 1) to 11) formed on one substrate. Then, the other substrate is bonded, and then the liquid crystal sealing agent for the liquid crystal dropping method is cured by ultraviolet rays and / or heat. 13) The liquid crystal display cell adhere
• the liquid crystal sealant for the liquid crystal dropping method of the present invention is particularly excellent in adhesiveness with an organic film such as an alignment film, and hardly peels even in various environments. Therefore, it is possible to realize a liquid crystal display cell that can be used in various environments. Moreover, since it is excellent also in general characteristics, such as low liquid-crystal stain
• liquid crystal sealing agent for liquid crystal dropping method of the present invention
• liquid crystal sealing agent is irradiated with ultraviolet rays of 3000 mJ / cm 2 and then cured at 120 ° C. for 1 hour at 25 ° C.
• the adhesive strength to an ITO (indium tin oxide) substrate is A [MPa]
• the adhesive strength at 120 ° C. after curing is B [MPa]
• the adhesive strength to the substrate is C [MPa]
• the above A, B, and C satisfy the relational expressions represented by the following formulas (1) and (2).
• the adhesive strength in the 120 ° C. atmosphere after curing for 1 hour in the 120 ° C. atmosphere after irradiation with 3000 mJ / cm 2 of ultraviolet light is 5 as the adhesive strength in the 25 ° C. atmosphere. It means that it is over 20%.
• the liquid crystal sealant having this characteristic enables stable production without causing separation of the upper and lower substrates in the heating step in the production of the liquid crystal display cell. Moreover, even when exposed alternately to high and low temperatures, such as a heat cycle test, it is stable without causing substrate peeling. Further, the formula (2), the adhesive strength under 25 ° C.
• the liquid crystal sealant having this characteristic has small curing shrinkage in the ultraviolet irradiation step in the production of a liquid crystal display cell, that is, the stress applied to the organic film is reduced even on the organic film, and excellent adhesiveness can be realized. .
• the adhesive strength to an ITO (indium tin oxide) substrate at 25 ° C. means the adhesive strength in an atmosphere at 25 ° C.
• the measuring method of the adhesive strength uses the adhesive strength in the shear direction. For example, a small amount of liquid crystal sealant is applied on a 5 cm square ITO (indium tin oxide) substrate, and a 1.5 mm square glass chip (EAGLE XG: CORNING made by cutting 1.5 mm square) with tweezers. Use together. After irradiating this test piece with ultraviolet rays of 3000 mJ / cm 2 , the test piece is placed in a hot air oven set at 120 ° C. for 1 hour to perform heat curing.
• the adhesive strength of this test piece (laminated glass chip) can be measured using a bond tester (SS-30WD: Seishin Shoji Co., Ltd.). The value of the adhesive strength thus obtained is defined as A [MPa] in the present application.
• the adhesive strength at 120 ° C. is an adhesive strength measured in a state where the cured test piece is heated to 120 ° C., and the measuring method itself is the same as described above.
• a method of heating to 120 ° C. a method of heating the measurement stage of the adhesive strength measuring device to 120 ° C. is simple.
• the value of the adhesive strength thus obtained is defined as B [MPa] in the present application.
• the adhesive strength to an ITO (indium tin oxide) substrate at 25 ° C. after curing with only 3000 mJ / cm 2 ultraviolet light is the adhesive strength measured for a test piece prepared without performing heat curing in the test piece preparation process. Yes, it is a value measured in an atmosphere of 25 ° C. The measurement itself is performed in the same manner as described above. In this application, the value of the adhesive strength thus obtained is defined as C [MPa].
• the adhesive strength to an ITO (indium tin oxide) substrate at 120 ° C. after curing with only 3000 mJ / cm 2 ultraviolet rays is the adhesive strength measured for a test piece prepared without performing heat curing in the test piece preparation process. Yes, it is a value measured in an atmosphere of 120 ° C. The measurement itself is performed in the same manner as described above. The value of the adhesive strength thus obtained is defined as D [MPa] in the present application.
• the present invention is a liquid crystal sealant for a liquid crystal dropping method.
• the process of manufacturing a liquid crystal display cell generally has an ultraviolet irradiation step, and a large stress is accumulated between the liquid crystal sealant cured in this step and an organic film such as an alignment film. Is done. Therefore, it is very effective to use the liquid crystal sealant of the present invention in such a liquid crystal dropping method.
• the liquid crystal sealant of the present invention is not particularly limited as long as it is a liquid crystal sealant for the liquid crystal dropping method having the above characteristics, but component (a) (meth) acrylated epoxy resin, component (b) photopolymerization initiator, component The case of containing (c) an inorganic filler and component (d) an organic acid hydrazide compound is a particularly preferred embodiment.
• the liquid crystal sealing agent containing these components has low contamination with respect to the liquid crystal and has excellent characteristics in the liquid crystal dropping method.
• Component (a) (meth) acrylated epoxy resin can be obtained by a well-known reaction between an epoxy resin and (meth) acrylic acid.
• (meth) acrylic acid in a predetermined equivalent ratio to an epoxy resin and a catalyst (for example, benzyldimethylamine, triethylamine, benzyltrimethylammonium chloride, triphenylphosphine, triphenylstibine, etc.) and a polymerization inhibitor (for example, methoquinone, For example, hydroquinone, methylhydroquinone, phenothiazine, dibutylhydroxytoluene) and the like, and an esterification reaction is performed at 80 to 110 ° C., for example.
• a catalyst for example, benzyldimethylamine, triethylamine, benzyltrimethylammonium chloride, triphenylphosphine, triphenylstibine, etc.
• a polymerization inhibitor for example, meth
• the epoxy resin used as a raw material is not particularly limited, but a bifunctional or higher epoxy resin is preferable.
• resorcinol (resorcin) diglycidyl ether bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S Type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F novolac type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester type epoxy resin, glycidyl Amine type epoxy resin, hydantoin type epoxy resin, isocyanurate type epoxy resin, phenol novolac type epoxy resin having triphenolmethane skeleton, other bifunctional phenol Diglycidyl ethers of Le acids, difunctional alcohols diglycidyl ethers of, and their halides, hydrogenated product and the like.
• bisphenol-type epoxy resin, novolac-type epoxy resin and diglycidyl ether digly
• the content of the component (a) (meth) acrylated epoxy resin is appropriately determined in consideration of workability and physical properties of the obtained liquid crystal sealant, and is usually about 25 to 80% by mass in the liquid crystal sealant. The amount is preferably 25 to 75% by mass.
• the component (b) photopolymerization initiator is not particularly limited as long as it is a compound that generates a radical upon irradiation with ultraviolet rays or visible light and initiates a chain polymerization reaction.
• benzyl dimethyl ketal 1-hydroxycyclohexyl phenyl ketone, Diethylthioxanthone, benzophenone, 2-ethylanthraquinone, 2-hydroxy-2-methylpropiophenone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propane, 2,4,6-trimethyl
• the superscript “RTM” means a registered trademark. From the viewpoint of liquid crystal contamination, it is preferable to use those having a (meth) acryl group in the molecule.
• 2-methacryloyloxyethyl isocyanate and 1- [4- (2-hydroxyethoxy) -phenyl]- The reaction product with 2-hydroxy-2-methyl-1-propan-1-one is preferably used.
• This compound can be obtained by the method described in International Publication No. 2006/027982.
• the content of the above-mentioned component (b) photopolymerization initiator that can be used in the liquid crystal sealant of the present invention is usually 0.01 to 15% by mass, preferably 0.8%, based on the total amount of the liquid crystal sealant. 02 to 10% by mass.
• Component (c) inorganic filler includes 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 fused silica, crystalline silica, Lumina is a talc.
• Two or more of these inorganic fillers may be mixed and used.
• the average particle size when used as an adhesive for the following liquid crystal display cell, if the average particle size is too large, it becomes a cause of defects such as inability to form a gap when laminating the upper and lower glass substrates when manufacturing a narrow gap liquid crystal display cell. Therefore, 3 ⁇ m or less is appropriate, and preferably 2 ⁇ m or less.
• 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 above-mentioned component (c) inorganic filler is usually 1 to 60% by mass, preferably 5 to 50% by mass, when the total liquid crystal sealant of the present invention is 100% by mass.
• the content of the component (c) inorganic filler is too little, since adhesive strength falls and moisture resistance reliability is also inferior, the fall of the adhesive strength after moisture absorption may also become large.
• the content of the component (c) inorganic filler is too large, cell gap formation may not be possible when used as an adhesive for liquid crystal display cells.
• the component (d) organic acid hydrazide compound is an aromatic or aliphatic compound having a functional group of —NHNH 2 so as to be obtained by reacting hydrazine with an organic acid.
• Aromatic hydrazides include terephthalic acid dihydrazide, isophthalic acid dihydrazide, 2,6-naphthoic acid dihydrazide, 2,6-pyridinedihydrazide, 1,2,4-benzenetrihydrazide, 1,4,5,8-naphthoic acid tetrahydride. Examples thereof include hydrazide and pyromellitic acid tetrahydrazide.
• Examples of the aliphatic hydrazide compound include form hydrazide, acetohydrazide, propionic acid hydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, pimelic acid dihydrazide, sebacic acid dihydride.
• Examples of the compound having an isocyanuric acid skeleton include tris (1-hydrazinocarbonylmethyl) isocyanurate, tris (2-hydrazinocarbonylethyl) isocyanurate, tris (2-hydrazinocarbonylethyl) isocyanurate, tris (3 -Hydrazinocarbonylpropyl) isocyanurate, bis (2-hydrazinocarbonylethyl) isocyanurate and the like.
• isophthalic acid dihydrazide isophthalic acid dihydrazide, malonic acid dihydrazide, adipic acid dihydrazide, tris (1-hydrazinocarbonylmethyl) isocyanurate, tris (2-hydrazinocarbonylethyl) isocyanurate, tris ( 2-hydrazinocarbonylethyl) isocyanurate and tris (3-hydrazinocarbonylpropyl) isocyanurate, particularly preferably malonic acid dihydrazide, sebacic acid dihydrazide and tris (2-hydrazinocarbonylethyl) isocyanurate.
• the content when the component (d) organic acid hydrazide compound is used may be 1 to 20 parts by mass when the total amount of the component (a) (meth) acrylated epoxy resin is 100 parts by mass. More preferably, it is 2 to 10 parts by mass, and two or more kinds may be mixed and used.
• the liquid-crystal sealing compound of this invention may contain a component (e) thermal radical polymerization initiator as needed.
• the component (e) thermal radical polymerization initiator is not particularly limited as long as it is a compound that generates radicals by heating and initiates a chain polymerization reaction.
• an organic peroxide, an azo compound, a benzoin compound, a benzoin ether compound, an acetophenone compound, A benzopinacol etc. are mentioned, A benzopinacol is used suitably.
• examples of the organic peroxide include Kayamek RTM A, M, R, L, LH, SP-30C, Perdox CH-50L, BC-FF, Kadox B-40ES, Pardox 14, Trigonox RTM 22-70E, 23- C70,121,121-50E, 121-LS50E, 21- LS50E, 42,42LS, Kayaester RTM P-70, TMPO-70 , CND-C70, OO-50E, AN, Kayabutyl RTM B, Padokkusu 16, Kayakarubon RTM BIC-75, AIC-75 (above, manufactured by Kayaku Akzo Co., Ltd.), Permec RTM N, H, S, F, D, G, Perhexa RTM H, HC, Pa TMH, C, V, 22, MC, Percure RTM AH, AL, HB, Perbutyl RTM H, C, ND, L , Percumyl R M H, D, PEROYL RTM
• thermal radical polymerization initiator is a benzopinacol-based thermal radical polymerization initiator (including those obtained by chemically modifying benzopinacol).
• benzopinacol 1,2-dimethoxy-1,1,2,2-tetraphenylethane, 1,2-diethoxy-1,1,2,2-tetraphenylethane, 1,2-diphenoxy- 1,1,2,2-tetraphenylethane, 1,2-dimethoxy-1,1,2,2-tetra (4-methylphenyl) ethane, 1,2-diphenoxy-1,1,2,2-tetra (4-methoxyphenyl) ethane, 1,2-bis (trimethylsiloxy) -1,1,2,2-tetraphenylethane, 1,2-bis (triethylsiloxy) -1,1,2,2-tetraphenyl Ethane, 1,2-bis (t-butyldimethylsiloxy) -1,1,2,2-tetraphenylethane, 1-hydroxy-2-trimethylsiloxy-1,1,2,2-tetraphenylethane, 1- Dorokishi 2-triethylsiloxy-1,1,2,2-phenylethane, 1-hydroxy
• 1-hydroxy-2-trimethylsiloxy-1,1,2,2-tetraphenylethane 1-hydroxy-2-triethylsiloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2- t-butyldimethylsiloxy-1,1,2,2-tetraphenylethane, 1,2-bis (trimethylsiloxy) -1,1,2,2-tetraphenylethane, more preferably 1-hydroxy-2 -Trimethylsiloxy-1,1,2,2-tetraphenylethane, 1,2-bis (trimethylsiloxy) -1,1,2,2-tetraphenylethane, particularly preferably 1,2-bis (trimethyl) Siloxy) -1,1,2,2-tetraphenylethane.
• the benzopinacol is commercially available from Tokyo Chemical Industry Co., Ltd., Wako Pure Chemical Industries, Ltd.
• a compound obtained by etherifying the hydroxy group of benzopinacol can be easily synthesized by a known method.
• a compound in which the hydroxy group of benzopinacol is converted to a silyl ether can be obtained by synthesizing the corresponding benzopinacol and various silylating agents by heating under a basic catalyst such as pyridine.
• silylating agents examples include trimethylchlorosilane (TMCS), hexamethyldisilazane (HMDS), N, O-bis (trimethylsilyl) trifluoroacetamide (BSTFA), which are generally known trimethylsilylating agents, and triethylsilylating agents. And triethylchlorosilane (TECS), and t-butylmethylsilane (TBMS), which is a t-butyldimethylsilylating agent. These reagents can be easily obtained from markets such as silicon derivative manufacturers.
• the reaction amount of the silylating agent is preferably 1.0 to 5.0 times mol for 1 mol of the hydroxyl group of the target compound.
• the amount is less than 1.0 times mol, the reaction efficiency is poor and the reaction time is prolonged, so that thermal decomposition is promoted.
• the amount is more than 5.0 times mol, separation may be deteriorated during collection or purification may be difficult.
• the thermal radical polymerization initiator preferably has a fine particle size and is uniformly dispersed.
• the average particle size is preferably 5 ⁇ m or less, more preferably 3 ⁇ m or less, because if the average particle size is too large, it becomes a cause of defects such as inability to successfully form a gap when the upper and lower glass substrates are bonded together during the production of a narrow gap liquid crystal display cell. .
• a minimum is about 0.1 micrometer.
• 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 (e) thermal radical polymerization initiator is preferably about 0.001 to 0.5% by mass when the entire liquid crystal sealant of the present invention is 100% by mass.
• the liquid-crystal sealing compound of this invention may contain a component (f) epoxy resin as needed.
• the component (f) epoxy resin is not particularly limited, but preferably has low contamination and solubility in liquid crystals.
• suitable epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, diglycidyl ether of resorcinol (resorcin), phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A Novolac type epoxy resin, bisphenol F novolac type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hydantoin type epoxy resin, isocyanurate type epoxy resin, triphenol Phenol novolac type epoxy resin having methane skeleton, diglycidyl etherified product of bifunctional phenols, diglycidyl ether of difunctional alcohols Products, and their halides,
• the content of the component (f) epoxy resin is appropriately determined in consideration of the workability and physical properties of the liquid crystal sealant, and is usually about 25 to 80% by mass, preferably 25 to 75% by mass in the liquid crystal sealant. It is. In one preferred embodiment of the present invention, the component (f) epoxy resin accounts for 1 to 30% by mass of the sum of the component (a) (meth) acrylated epoxy resin and the component (f) epoxy resin. More preferably, it is 5 to 15% by mass.
• the liquid crystal sealing agent of the present invention can further improve the adhesive strength by using the component (g) silane coupling agent.
• silane coupling agent aminosilane coupling agent, epoxy silane coupling agent, mercaptosilane coupling agent, vinyl silane coupling agent, acrylic silane coupling agent, methacrylic silane coupling agent, ureido silane coupling agent Etc.
• an aminosilane coupling agent and an epoxysilane coupling agent are preferable, and when the aminosilane coupling agent and the epoxysilane coupling agent are used in combination, the effects of the present invention are more remarkably exhibited.
• silane coupling agent examples include an epoxy silane coupling agent such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc.
• aminosilane coupling agents N-phenyl- ⁇ -aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2- (vinylbenzylamino) Ethyl) 3-aminopropyltri Toxisilane hydrochloride, etc., 3-mercaptopropyltrimethoxysilane as a mercaptosilane coupling agent, vinyltrimethoxysilane as a vinylsilane coupling agent, 3-acryloxypropyltrimethoxysilane, etc.
• methacrylsilane examples include 3-methacryloxypropyltrimethoxysilane, and examples of the ureidosilane coupling agent include 3-ureidopropyltriethoxysilane. Since these silane coupling agents are sold by Shin-Etsu Chemical Co., Ltd. as KBM series, KBE series, etc., they are easily available from the market.
• silane coupling agents are N-2- (aminoethyl) -3-aminopropyltrimethoxysilane (KBM-603, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-glycidoxypropyltrimethoxysilane (S -510 manufactured by Chisso Corporation, and the combination of both is most preferable.
• the content of the component (g) silane coupling agent is preferably 0.05 to 3% by mass when the entire liquid crystal sealant of the present invention is 100% by mass.
• the liquid crystal sealant of the present invention can further improve the adhesive strength by using a component (h) a compound having a phenolic hydroxyl group.
• the compound having a phenolic hydroxyl group 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, fluorene skeletons such as 1,1-di-4-hydroxyphenylfluorene Phenols, polyphenol compounds such as phenolized polybutadiene, phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, allylphenols, brominated bisphenol A, bipheny
• a monomer and / or oligomer of (meth) acrylic acid ester may be used as necessary.
• Such monomers and oligomers include, for example, a reaction product of dipentaerythritol and (meth) acrylic acid, a reaction product of dipentaerythritol / caprolactone and (meth) acrylic acid, etc., but has a contamination property to liquid crystals. If it is low, it will not be restricted in particular.
• the liquid crystal sealant of the present invention may further contain additives such as curing accelerators such as organic acids and imidazoles, organic fillers, pigments, leveling agents, antifoaming agents, solvents and the like, if necessary.
• curing accelerators such as organic acids and imidazoles
• organic fillers such as organic fillers, pigments, leveling agents, antifoaming agents, solvents and the like, if necessary.
• An example of a method for obtaining the liquid crystal sealant of the present invention is the following method. First, the component (a) (meth) acrylated epoxy resin is dissolved by heating the component (b) photopolymerization initiator, if necessary, the component (f) epoxy resin, and the component (h) a compound having a phenolic hydroxyl group. After cooling to room temperature, component (c) inorganic filler, component (d) organic acid hydrazide compound, component (e) thermal radical polymerization initiator, component (g) silane coupling agent are added as necessary, and organic Filler, antifoaming agent, leveling agent, solvent, etc. are added, mixed uniformly by a known mixing device such as a three-roll, sand mill, ball mill, etc., and filtered through a metal mesh, thereby the liquid crystal sealing agent of the present invention Can be manufactured.
• a known mixing device such as a three-roll, sand mill, ball mill, etc.
• 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 curing at 90 to 130 ° C. for 1 to 2 hours.
• the liquid crystal sealant part is irradiated with ultraviolet rays by an ultraviolet irradiator and photocured.
• the amount of ultraviolet irradiation is preferably 500 to 6000 mJ / cm 2 , more preferably 1000 to 4000 mJ / cm 2 .
• the liquid crystal display cell of the present invention can be obtained by curing at 90 to 130 ° C. for 1 to 2 hours.
• the liquid crystal display cell of the present invention thus obtained has no display defects due to liquid crystal contamination, and has excellent adhesion and 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% by mass, preferably about 0.5 to 2% by mass, and more preferably about 0.9 to 1.5% by mass with respect to the liquid crystal sealant of the present invention.
• the liquid crystal sealant of the present invention has high adhesive strength after curing with ultraviolet rays, and since the difference between the adhesive strength at room temperature and the adhesive strength in a heated atmosphere is small, it has excellent adhesion to organic films such as alignment films. It is possible to manufacture an excellent and stable liquid crystal display cell and to realize a liquid crystal display cell excellent in long-term reliability. Moreover, since the cured product of the liquid crystal sealant of the present invention is stable with respect to a heat cycle test, and further excellent in heat resistance and moisture resistance, a liquid crystal display cell excellent in reliability can be realized. The heat resistance can be confirmed by measuring the glass transition temperature, and the moisture resistance can be confirmed by measuring the adhesive strength after being placed in a high humidity environment.
• the liquid crystal sealant of the present invention has very little elution of the constituent components into the liquid crystal, and can reduce display defects of the liquid crystal display cell. Moreover, since it is excellent also in storage stability, it is suitable for manufacture of a liquid crystal display cell. In addition, 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.
• Examples 1 to 3, Comparative Examples 1 and 2 The component (a) (meth) acrylated epoxy resin is heated and dissolved in the component (a) (meth) acrylated epoxy resin with the component (b) photopolymerization initiator, the component (f) epoxy resin, the component (h) a compound having a phenolic hydroxyl group, as shown in Table 1 below. After cooling to room temperature, add component (c) inorganic filler, component (d) organic acid hydrazide compound, component (e) thermal radical polymerization initiator, component (h) compound having phenolic hydroxyl group, Mix evenly. Next, the liquid crystal sealants of Examples 1 to 3 were prepared by filtering through a metal mesh. Further, the liquid crystal sealants of Comparative Examples 1 and 2 were prepared by mixing the materials shown in Table 1 by the same process.
• An alignment film solution (PIA-5540-05A; manufactured by Chisso Corporation) was applied to a glass substrate with a spin coater, calcined for 90 seconds on a 60 ° C. hot plate, and baked in a 220 ° C. oven for 1 hour.
• This glass substrate with an alignment film was cut into two types of 25 mm ⁇ 25 mm and 25 mm ⁇ 30 mm, and cleaned for 80 seconds with a UV ozone cleaning device (UVD-25U03: manufactured by Japan UV Machine Co., Ltd.).
• a liquid crystal sealant is applied to a glass substrate with a 25 mm ⁇ 25 mm alignment film with a dispenser or a screen printing machine, the glass substrate with a 25 mm ⁇ 30 mm alignment film is bonded, and ultraviolet rays of 3000 mJ / cm 2 are irradiated with a UV irradiation machine. Then, it was put into an oven and thermally cured at 120 ° C. for 1 hour. The obtained test piece was measured with a bond tester (SS-30WD: Seishin Shoji Co., Ltd.) to measure the adhesive strength by pushing a position 2 mm straight from the seal end with a pin. The results are shown in Table 1.
• the liquid crystal sealants of Examples 1 to 3 had very strong adhesive strength to the alignment film, that is, the organic film. Therefore, the liquid crystal sealant of the present invention enables the realization of a liquid crystal display cell having excellent reliability even when the liquid crystal display cell is applied on the alignment film.
• the liquid crystal sealant of the present invention is particularly excellent in adhesiveness with an organic film such as an alignment film, and hardly peels off under various environments. Therefore, it is possible to realize a liquid crystal display cell that can be used in various environments. Moreover, since it is excellent also in general characteristics, such as low liquid-crystal stain

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
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• Physics & Mathematics (AREA)
• Nonlinear Science (AREA)
• Crystallography & Structural Chemistry (AREA)
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• General Physics & Mathematics (AREA)
• Optics & Photonics (AREA)
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• 2013
  • 2013-07-11 TW TW102124978A patent/TW201420735A/zh unknown
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