WO2018139210A1 - Liquid crystal display element sealant, vertical conduction material, liquid crystal display element, and cured product - Google Patents
Liquid crystal display element sealant, vertical conduction material, liquid crystal display element, and cured product Download PDFInfo
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- WO2018139210A1 WO2018139210A1 PCT/JP2018/000572 JP2018000572W WO2018139210A1 WO 2018139210 A1 WO2018139210 A1 WO 2018139210A1 JP 2018000572 W JP2018000572 W JP 2018000572W WO 2018139210 A1 WO2018139210 A1 WO 2018139210A1
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- 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
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- 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
- C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
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- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- 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
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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
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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
- G02F1/1341—Filling or closing of cells
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- 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
- C09K2003/1034—Materials or components characterised by specific properties
- C09K2003/1059—Heat-curable materials
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- 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
- C09K2003/1034—Materials or components characterised by specific properties
- C09K2003/1062—UV-curable materials
Definitions
- the present invention relates to a sealant for a liquid crystal display element that is difficult to cause cracks and cracks in a substrate even in a liquid crystal display element with a narrow frame design. Moreover, this invention relates to the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal display elements. Furthermore, this invention relates to the hardened
- a liquid crystal dropping method called a dropping method using a photothermal combined curing type sealing agent containing a polymerization initiator and a thermosetting agent is used.
- a rectangular seal pattern is formed on one of the two substrates with electrodes by dispensing.
- liquid crystal microdrops are dropped into the sealing frame of the substrate in a state where the sealing agent is uncured, the other substrate is superposed under vacuum, and the sealing portion is irradiated with light such as ultraviolet rays to perform temporary curing. Thereafter, heating is performed to perform main curing, and a liquid crystal display element is manufactured.
- this dripping method has become the mainstream method for manufacturing liquid crystal display elements.
- the present invention relates to a sealant for a liquid crystal display element that is difficult to cause cracks and cracks in a substrate even in a liquid crystal display element with a narrow frame design.
- Another object of the present invention is to provide a vertical conduction material and a liquid crystal display element using the sealing agent for a liquid crystal display element. Furthermore, this invention aims at providing the hardened
- the present invention is a sealing agent for liquid crystal display elements containing a curable resin and a polymerization initiator and / or a thermosetting agent, and the cured product according to JIS K 5600-5-4 has a pencil hardness of 3H or less.
- a sealing agent for a liquid crystal display element. The present invention is described in detail below.
- FIG. 1A is a schematic diagram showing a panel dividing position in a conventional liquid crystal display element not having a narrow frame design
- FIG. 1B is a schematic diagram showing a panel dividing position in a liquid crystal display element having a narrow frame design.
- the present inventor uses a hardened material having a pencil hardness of 3H or less as a sealing agent, thereby making it difficult to cause cracks or cracks in the substrate even in a liquid crystal display element with a narrow frame design. As a result, the present invention has been completed.
- the sealing agent for liquid crystal display elements of the present invention has a pencil hardness of 3H or less in a cured product according to JIS K 5600-5-4.
- the cured product has a pencil hardness of 3H or less, even a liquid crystal display element having a narrow frame design can hardly cause cracks or cracks in the substrate.
- cured material is 3B or more from viewpoints, such as moisture-permeable prevention property.
- the pencil hardness of “3H or less” means that the pencil hardness is 3H or softer than 3H, and the pencil hardness is “3B”. “It is above” means that the pencil hardness is 3B or is harder than 3B.
- the cured product for measuring the pencil hardness can be obtained by irradiating a sealing agent for liquid crystal display elements with 100 mW / cm 2 of ultraviolet rays (wavelength 365 nm) for 30 seconds and then heating at 120 ° C. for 1 hour.
- cured material means the sealing agent hardened
- the sealing agent for liquid crystal display elements of this invention contains curable resin, a polymerization initiator, and / or a thermosetting agent.
- a method using a polymerizable compound having a flexible skeleton as the curable resin, or a sealing agent has flexibility. Examples thereof include a method of blending a polymer and flexible particles. Among these, a method using a polymerizable compound having a flexible skeleton is preferable, and a method using a polymerizable compound having a flexible skeleton and flexible particles in combination is more preferable.
- Examples of the polymerizable compound having a flexible skeleton include a (meth) acrylic compound having a flexible skeleton and an epoxy compound having a flexible skeleton.
- the curable resin preferably contains a (meth) acrylic compound having the flexible skeleton and / or an epoxy compound having the flexible skeleton.
- the “(meth) acryl” means acryl or methacryl
- the “(meth) acryl compound” means a compound having a (meth) acryloyl group
- Examples of the (meth) acrylic compound having a flexible skeleton include a long-chain (meth) acrylic compound, a (meth) acrylic compound having a rubber structure, and a urethane-modified (meth) acrylic compound.
- Examples of the long chain (meth) acrylic compound include alkylene oxide-modified (meth) acrylic compounds and caprolactone-modified (meth) acrylic compounds.
- Examples of commercially available long chain (meth) acrylic compounds include, for example, long chain (meth) acrylic compounds manufactured by Kyoeisha Chemical Co., Ltd., long chain (meth) acrylic compounds manufactured by Nagase ChemteX Corporation, Toagosei Co., Ltd. Examples include long-chain (meth) acrylic compounds manufactured by Shin-Nakamura Chemical Co., Ltd., long-chain (meth) acrylic compounds manufactured by Daicel Ornex. Examples of the long-chain (meth) acrylic compound manufactured by Kyoeisha Chemical Co., Ltd.
- Examples of the long chain (meth) acrylic compound manufactured by Nagase ChemteX Corporation include DA-911M, DA-920, DA-931, DM-811, DM-832, DM-851, and the like.
- Examples of the long-chain (meth) acrylic compound manufactured by Toagosei Co., Ltd. include M-327.
- Examples of the long chain (meth) acrylic compound manufactured by Shin-Nakamura Chemical Co., Ltd. include A-9300-1CL, A-GLY-9E, A-GLY-20E and the like.
- Examples of the long-chain (meth) acrylic compound manufactured by Daicel Ornex Corporation include EBECRYL 3708.
- Examples of the (meth) acrylic compound having the rubber structure include (meth) acryl-modified butadiene rubber, (meth) acryl-modified isoprene rubber, and the like.
- Examples of commercially available (meth) acrylic compounds having the rubber structure include (meth) acrylic compounds having a rubber structure manufactured by Nippon Soda Co., Ltd., and (meth) acrylic compounds having a rubber structure manufactured by Kuraray Co., Ltd. Etc.
- Examples of the (meth) acrylic compound having a rubber structure manufactured by Nippon Soda Co., Ltd. include NISSO-TE.
- Examples of the (meth) acrylic compound having a rubber structure manufactured by Kuraray Co., Ltd. include UC-102 and UC-203.
- Examples of the urethane-modified (meth) acrylic compound include aliphatic urethane (meth) acrylate and aromatic urethane (meth) acrylate.
- Examples of commercially available urethane-modified (meth) acrylic compounds include, for example, urethane-modified (meth) acrylic compounds manufactured by Daicel Ornex, urethane-modified (meth) acrylic compounds manufactured by Arakawa Chemical Industries, Ltd., and Negami Chemical. Examples include urethane-modified (meth) acrylic compounds manufactured by Kogyo Co., Ltd.
- Examples of the urethane-modified (meth) acrylic compound manufactured by Daicel Ornex include EBECRYL 230, EBECRYL 4491, EBECRYL 210, and the like.
- Examples of the urethane-modified (meth) acrylic compound manufactured by Arakawa Chemical Industries, Ltd. include 551B.
- Examples of the urethane-modified (meth) acrylic compound manufactured by Negami Chemical Industry Co., Ltd. include UN-350 and UN-1255.
- the (meth) acrylic compound having the flexible skeleton a long chain (meth) acrylic compound is preferable because the pencil hardness of the cured product can be easily adjusted, and an alkylene oxide modified (meth) acrylic compound is more preferable.
- an alkylene oxide-modified epoxy (meth) acrylate is more preferable, an epoxy (meth) acrylate having a polypropylene glycol skeleton is particularly preferable, and an acrylic acid adduct of tripropylene glycol diglycidyl ether is most preferable.
- the “(meth) acrylate” means acrylate or methacrylate, and the “epoxy (meth) acrylate” means that all epoxy groups in the epoxy compound react with (meth) acrylic acid. Represents the compound.
- Examples of the epoxy compound having the flexible skeleton include a long-chain epoxy compound and an epoxy compound having a rubber structure.
- Examples of the long-chain epoxy compound include alkylene oxide-modified epoxy resins and alkylene-modified epoxies.
- Examples of commercially available long-chain epoxy compounds include, for example, long-chain epoxy compounds manufactured by Kyoeisha Chemical Co., Ltd., long-chain epoxy compounds manufactured by DIC, long-chain epoxy compounds manufactured by Daicel-Ornex, and Sanwa Synthesis Examples include long-chain epoxy compounds manufactured by Kagaku Co., Ltd., long-chain epoxy compounds manufactured by Shin Nippon Rika Co., Ltd., long-chain epoxy compounds manufactured by ADEKA, and long-chain epoxy compounds manufactured by Mitsubishi Chemical Corporation. Examples of the long-chain epoxy compound manufactured by Kyoeisha Chemical Co., Ltd.
- Examples of the long-chain epoxy compound manufactured by DIC include EPICLON EXA-4816, EPICLON EXA-4850, and the like.
- Examples of the long-chain epoxy compound manufactured by Daicel Ornex include Celoxide 2081, Epolide GT-401, and the like.
- Examples of the long-chain epoxy compound manufactured by Sanwa Synthetic Chemical Co., Ltd. include Chemisizer series.
- Examples of the long-chain epoxy compound manufactured by Shin Nippon Rika Co., Ltd. include Sansosizer E-2000H.
- Examples of the long-chain epoxy compound manufactured by ADEKA include ED-503, ED-503G, ED-506, EP-4000, EP-4005, EP-7001, and the like.
- Examples of the long-chain epoxy compound manufactured by Mitsubishi Chemical Corporation include YL-7410, YL-7175-500, YL-7175-1000, jER 871, jER 872, and the like.
- Examples of the epoxy compound having the rubber structure include a butadiene-modified epoxy resin, a terminal carboxyl group-containing polybutadiene-acrylonitrile (CTBN) -modified epoxy resin, and an epoxy group-containing acrylic rubber.
- CBN polybutadiene-acrylonitrile
- epoxy compound which has another flexible skeleton among the epoxy compounds which have the said flexible skeleton examples include, for example, epoxy compounds having other flexible skeletons manufactured by ADEKA, and epoxy compounds having other flexible skeletons manufactured by Nippon Shokubai Co., Ltd. And other epoxy compounds having a flexible skeleton manufactured by Asahi Kasei.
- examples of the epoxy compound having another flexible skeleton manufactured by ADEKA include EPU-7N.
- Examples of the epoxy compound having another flexible skeleton manufactured by Nippon Shokubai Co., Ltd. examples include Acryset BP series.
- Examples of the epoxy compound having other flexible skeleton manufactured by Asahi Kasei Co., Ltd. include AER9000.
- Examples of commercially available polymerizable compounds having other flexible skeletons other than the (meth) acrylic compound having the flexible skeleton and the epoxy compound having the flexible skeleton include, for example, others manufactured by Sakai Kogyo Co., Ltd. Polymerizable compounds having other flexible skeletons, polymerizable compounds having other flexible skeletons manufactured by Idemitsu Kosan Co., Ltd., polymerizable compounds having other flexible skeletons manufactured by Kaneka Corporation, and other flexibility manufactured by Toagosei Co., Ltd.
- Examples thereof include a polymerizable compound having a skeleton, a polymerizable compound having another flexible skeleton manufactured by Soken Chemical Co., and a polymerizable compound having another flexible skeleton manufactured by Shin-Etsu Chemical Co., Ltd.
- Examples of the polymerizable compound having another flexible skeleton manufactured by Sakai Kogyo Co., Ltd. include Ricon 130MA8.
- Examples of the polymerizable compound having another flexible skeleton manufactured by Idemitsu Kosan Co., Ltd. include Poly bd.
- Examples of the polymerizable compound having another flexible skeleton manufactured by Kaneka Corporation include the EPION series. Examples of other polymerizable compounds having a flexible skeleton manufactured by Toagosei Co., Ltd.
- Examples of the polymerizable compound having another flexible skeleton manufactured by Soken Chemical Co., Ltd. include Actflow series.
- Examples of the polymerizable compound having another flexible skeleton manufactured by Shin-Etsu Chemical Co., Ltd. include modified silicone oil.
- the polymerizable compound having the flexible skeleton may be used alone, or two or more kinds may be used in combination.
- a preferable lower limit of the content of the polymerizable compound having the flexible skeleton in 100 parts by weight of the curable resin is 20 parts by weight.
- the content of the polymerizable compound having the flexible skeleton is within this range, it becomes easy to set the pencil hardness of the cured liquid crystal display element sealant to 3H or less.
- the minimum with more preferable content of the polymeric compound which has the said flexible skeleton is 30 weight part, Furthermore, a preferable minimum is 60 weight part.
- the upper limit of the content of the polymerizable compound having the flexible skeleton in 100 parts by weight of the curable resin is 80 parts by weight.
- the said curable resin contains other curable resins other than the polymeric compound which has the said flexible skeleton for the objective of improving the adhesiveness of the sealing compound for liquid crystal display elements obtained, and a low liquid-crystal stain
- said other curable resin other (meth) acryl compounds other than the epoxy compound other than the epoxy compound which has the said flexible skeleton, and the (meth) acryl compound which has the said flexible skeleton are used suitably.
- Examples of the other epoxy compounds include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, 2,2′-diallyl bisphenol A type epoxy resin, and hydrogenated bisphenol type.
- the said curable resin may contain the compound which has an epoxy group and a (meth) acryloyl group in 1 molecule as said other epoxy compound.
- a compound for example, a moiety obtained by reacting an epoxy group of a part of an epoxy compound having two or more epoxy groups in one molecule and not having a flexible skeleton with (meth) acrylic acid. (Meth) acryl-modified epoxy resin and the like.
- Examples of the other (meth) acrylic compounds include, for example, epoxy (meth) acrylate obtained by reacting (meth) acrylic acid with an epoxy compound having no flexible skeleton, (meth) acrylic acid, and a hydroxyl group. And (meth) acrylic acid ester compounds obtained by reacting with a compound having a flexible skeleton. Of these, epoxy (meth) acrylate is preferable.
- the other (meth) acrylic compounds are preferably those having two or more (meth) acryloyl groups in the molecule because of their high reactivity.
- an epoxy (meth) acrylate which is said other (meth) acryl compound for example, an epoxy compound having no flexible skeleton and (meth) acrylic acid are reacted in the presence of a basic catalyst according to a conventional method. Can be obtained.
- Said other curable resin may be used independently and 2 or more types may be used in combination.
- Examples of the flexible polymer include (meth) acrylic polymers.
- Examples of commercially available polymers having the flexibility described above include Alfon UG-4000 (manufactured by Toagosei Co., Ltd.).
- flexibility may be used independently, and 2 or more types may be used in combination.
- flexibility in 100 weight part of whole sealing compound for liquid crystal display elements of this invention is 5 weight part.
- the content of the polymer having flexibility is within this range, it becomes easy to set the pencil hardness of the obtained cured product of the sealing agent for liquid crystal display elements to 3H or less.
- a more preferable lower limit of the content of the polymer having flexibility is 10 parts by weight.
- Examples of the flexible particles include rubber particles and urethane particles.
- the flexible particles may have a core-shell structure.
- Examples of the rubber particles include acrylic rubber particles, butadiene rubber particles, isoprene rubber particles, nitrile rubber particles, silicone rubber particles, sulfide rubber particles, and fluorine rubber particles.
- Examples of commercially available rubber particles include Kaneka's rubber particles, Nippon Zeon's rubber particles, Aika Industry's rubber particles, Toray Finechem's rubber particles, and the like.
- Examples of the rubber particles manufactured by Kaneka Corporation include Kane Ace B series and Kane Ace FM series.
- Examples of the rubber particles manufactured by Zeon Corporation include Nipol series.
- Examples of the rubber particles manufactured by Aika Kogyo include Zefiac F351.
- Examples of the rubber particles manufactured by Toray Finechem Co., Ltd. include Thiocol LP-282.
- Examples of commercially available urethane particles include those manufactured by Negami Chemical Industry Co., Ltd. and those manufactured by Dainichi Seika Kogyo Co., Ltd.
- Examples of the urethane particles manufactured by Negami Chemical Industry Co., Ltd. include Art Pearl.
- Examples of the urethane particles manufactured by Dainichi Seika Kogyo Co., Ltd. include dimic beads.
- grain may be used independently and 2 or more types may be used in combination.
- the minimum with preferable content of the said flexible particle in 100 weight part of sealing compounds for liquid crystal display elements of this invention is 20 weight part.
- grain is 30 weight part.
- the minimum with preferable content of the said flexible particle is 10 weight part with respect to 100 weight part of said curable resins.
- a more preferable lower limit of the content of the flexible particles when the polymerizable compound having the flexible skeleton and the flexible particles are used in combination is 15 parts by weight.
- the sealing agent for liquid crystal display elements of this invention contains a polymerization initiator and / or a thermosetting agent. It is preferable that the sealing agent for liquid crystal display elements of this invention contains radical photopolymerization initiator and a thermosetting agent.
- photo radical polymerization initiator examples include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, thioxanthones, and the like.
- the radical photopolymerization initiator by BASF As what is marketed among the said radical photopolymerization initiators, the radical photopolymerization initiator by BASF, the radical photopolymerization initiator by Tokyo Chemical Industry, etc. are mentioned, for example.
- the radical photopolymerization initiator manufactured by BASF include IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, and Lucillin TPO.
- the photo radical polymerization initiator manufactured by Tokyo Chemical Industry Co., Ltd. include benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.
- the sealing agent for liquid crystal display elements of the present invention may use a thermal radical polymerization initiator as the polymerization initiator.
- a thermal radical polymerization initiator what consists of an azo compound, an organic peroxide, etc. is mentioned, for example.
- a polymer azo initiator composed of a polymer azo compound is preferable.
- the polymer azo compound means a compound having an azo group and generating a radical capable of curing a (meth) acryloyloxy group by heat and having a number average molecular weight of 300 or more.
- the preferable lower limit of the number average molecular weight of the polymer azo compound is 1000, and the preferable upper limit is 300,000.
- the more preferable lower limit of the number average molecular weight of the polymer azo compound is 5000, the more preferable upper limit is 100,000, the still more preferable lower limit is 10,000, and the still more preferable upper limit is 90,000.
- the said number average molecular weight is a value calculated
- Examples of the polymer azo compound include those having a structure in which a plurality of units such as polyalkylene oxide and polydimethylsiloxane are bonded via an azo group.
- the polymer azo compound having a structure in which a plurality of units such as polyalkylene oxide are bonded via the azo group those having a polyethylene oxide structure are preferable.
- Specific examples of the polymer azo compound include, for example, a polycondensate of 4,4′-azobis (4-cyanopentanoic acid) and polyalkylene glycol, and 4,4′-azobis (4-cyanopentanoic acid). And a polycondensate of polydimethylsiloxane having a terminal amino group.
- Examples of commercially available polymer azo compounds include VPE-0201, VPE-0401, VPE-0601, VPS-0501, and VPS-1001 (all manufactured by Wako Pure Chemical Industries, Ltd.). .
- Examples of commercially available azo compounds that are not polymers include V-65 and V-501 (both manufactured by Wako Pure Chemical Industries, Ltd.).
- organic peroxide examples include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, peroxyester, diacyl peroxide, and peroxydicarbonate.
- the said polymerization initiator may be used independently and 2 or more types may be used in combination.
- the content of the polymerization initiator is preferably 0.1 parts by weight and preferably 30 parts by weight with respect to 100 parts by weight of the curable resin.
- the content of the polymerization initiator is 0.1 parts by weight or more, the obtained sealing agent for liquid crystal display elements is more excellent in curability.
- the content of the polymerization initiator is 30 parts by weight or less, the obtained sealing agent for liquid crystal display elements is more excellent in storage stability.
- a more preferable lower limit of the content of the polymerization initiator is 1 part by weight, a more preferable upper limit is 10 parts by weight, and a still more preferable upper limit is 5 parts by weight.
- an imidazole thermosetting agent is preferable.
- the imidazole thermosetting agent include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4 -Diamino-6- (2'-methylimidazolyl- (1 '))-ethyl-s-triazine, 2,4-diamino-6- (2'-methylimidazolyl- (1'))-ethyl-s-triazine
- Examples include isocyanuric acid adducts.
- curing agent as said imidazole series thermosetting agent.
- the adduct-type curing agent include adducts obtained by a reaction between an imidazole compound and an epoxy compound.
- the adduct-type curing agents that are commercially available, for example, an adduct-type curing agent manufactured by Ajinomoto Fine Techno Co., an adduct-type curing agent manufactured by Shikoku Kasei Kogyo Co., and an adduct-type curing agent manufactured by Mitsubishi Chemical Corporation Examples thereof include a curing agent.
- Examples of the adduct-type curing agent manufactured by Ajinomoto Fine Techno Co., Ltd. include Amicure PN-23, Amicure PN-23J, Amicure PN-H, Amicure PN-31, Amicure PN-31J, Amicure PN-40, Amicure PN- 40J, Amicure PN-50, Amicure PN-F, Amicure MY-24, Amicure MY-H, and the like.
- Examples of the adduct type curing agent manufactured by Shikoku Kasei Kogyo Co., Ltd. include P-0505.
- Examples of the adduct-type curing agent manufactured by Mitsubishi Chemical Corporation include P-200.
- thermosetting agent other thermosetting agents other than the imidazole thermosetting agent may be used.
- thermosetting agent organic acid hydrazide, an amine compound, a polyhydric phenol type compound, an acid anhydride etc. are mentioned, for example. Of these, organic acid hydrazide is preferably used.
- Examples of the organic acid hydrazide include sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide, and the like.
- Examples of commercially available organic acid hydrazides include organic acid hydrazides manufactured by Otsuka Chemical Co., Ltd., organic acid hydrazides manufactured by Ajinomoto Fine Techno Co., and the like.
- Examples of the organic acid hydrazide manufactured by Otsuka Chemical Co., Ltd. include SDH and ADH.
- Examples of the organic acid hydrazide manufactured by Ajinomoto Fine Techno Co. include Amicure VDH, Amicure VDH-J, Amicure UDH, Amicure UDH-J, and the like.
- thermosetting agent may be used independently and 2 or more types may be used in combination.
- the content of the thermosetting agent is preferably 1 part by weight with respect to 100 parts by weight of the curable resin, and 50 parts by weight with respect to the preferable upper limit.
- the upper limit with more preferable content of the said thermosetting agent is 30 weight part.
- the sealing agent for liquid crystal display elements of the present invention contains an inorganic filler for the purpose of improving the viscosity, further improving the adhesion due to the stress dispersion effect, improving the linear expansion coefficient, and improving the moisture resistance of the cured product. Is preferred.
- examples of the inorganic filler include silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, smectite, bentonite, montmorillonite, sericite, activated clay, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, and titanium oxide. , Calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate, calcium silicate and the like.
- the lower limit of the content of the inorganic filler is preferably 15 parts by weight with respect to 100 parts by weight of the curable resin.
- the content of the inorganic filler is 15 parts by weight or more, the heat shock resistance when the environmental change between low and high temperatures is repeated is excellent.
- the minimum with more preferable content of the said inorganic filler is 25 weight part.
- the upper limit of the content of the inorganic filler is preferably 60 parts by weight with respect to 100 parts by weight of the curable resin.
- the sealing agent for liquid crystal display elements of the present invention preferably contains an ion scavenger.
- the ion scavenger has a role of suppressing the occurrence of liquid crystal contamination by capturing water-soluble ions in the liquid crystal display element sealing agent.
- the ion trapping agent examples include a cation trapping agent that traps cations, an anion trapping agent that traps anions, and both ion trapping agents that trap cations and anions. Since it is excellent in the inhibitory effect, what capture
- Examples of the ion scavenger include zirconium compounds, antimony compounds, bismuth compounds, magnesium compounds, aluminum compounds, and the like. Especially, since it is excellent by the effect which suppresses generation
- zirconium compounds examples include IXE-100 (manufactured by Toagosei Co., Ltd.).
- antimony compounds examples include antimony compounds manufactured by Wako Pure Chemical Industries, Ltd., antimony compounds manufactured by Toagosei Co., Ltd., and the like.
- antimony compound manufactured by Wako Pure Chemical Industries, Ltd. examples include antimony pentoxide.
- antimony compound manufactured by Toagosei Co., Ltd. examples include IXE-300, IXE-600, and IXE-633.
- Examples of commercially available bismuth compounds include IXE-500, IXE-530, and IXE-550 (all manufactured by Toagosei Co., Ltd.).
- Examples of commercially available magnesium compounds include IXE-700F (manufactured by Toagosei Co., Ltd.).
- the said ion trapping agent may be used independently and 2 or more types may be used in combination.
- the preferable lower limit of the content of the ion scavenger in 100 parts by weight of the sealant for liquid crystal display elements of the present invention is 2 parts by weight, and the preferable upper limit is 30 parts by weight.
- the content of the ion scavenger is within this range, the effect of suppressing the occurrence of liquid crystal contamination is improved without deteriorating applicability and the like.
- the more preferable lower limit of the content of the ion scavenger is 5 parts by weight, and the more preferable upper limit is 20 parts by weight.
- the sealing agent for liquid crystal display elements of the present invention preferably contains a silane coupling agent for the purpose of further improving the adhesiveness.
- the silane coupling agent mainly has a role as an adhesion assistant for favorably bonding the sealing agent and the substrate.
- the silane coupling agent for example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane and the like are preferably used.
- the said silane coupling agent may be used independently and 2 or more types may be used in combination.
- the minimum with preferable content of the said silane coupling agent in 100 weight part of sealing agents for liquid crystal display elements of this invention is 0.1 weight part, and a preferable upper limit is 20 weight part.
- a preferable upper limit is 20 weight part.
- the minimum with more preferable content of the said silane coupling agent is 0.5 weight part, and a more preferable upper limit is 10 weight part.
- the sealing agent for liquid crystal display elements of the present invention may contain a light shielding agent.
- the sealing compound for liquid crystal display elements of this invention can be used suitably as a light shielding sealing agent.
- Examples of the light-shielding agent include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. Of these, titanium black is preferable.
- Titanium black is a substance having higher transmittance for light in the vicinity of the ultraviolet region, particularly for light with a wavelength of 370 nm to 450 nm, compared to the average transmittance for light with a wavelength of 300 nm to 800 nm. That is, the above-described titanium black sufficiently shields light having a wavelength in the visible light region, thereby providing a light shielding property to the sealing agent for liquid crystal display elements of the present invention, while transmitting light having a wavelength in the vicinity of the ultraviolet region.
- the light shielding agent contained in the liquid crystal display element sealant of the present invention is preferably a highly insulating material, and titanium black is also preferred as the highly insulating light shielding agent.
- the above-mentioned titanium black exhibits a sufficient effect even if it is not surface-treated, but the surface is treated with an organic component such as a coupling agent, silicon oxide, titanium oxide, germanium oxide, aluminum oxide, oxidized Surface-treated titanium black such as those coated with an inorganic component such as zirconium or magnesium oxide can also be used. Especially, what is processed with the organic component is preferable at the point which can improve insulation more.
- the liquid crystal display element produced using the sealing agent for liquid crystal display elements of the present invention containing the above-described titanium black as a light-shielding agent has a sufficient light-shielding property, and thus has high contrast without light leakage. A liquid crystal display element having excellent image display quality can be realized.
- Examples of commercially available titanium black include titanium black manufactured by Mitsubishi Materials Corporation and titanium black manufactured by Ako Kasei Co., Ltd. Examples of the titanium black manufactured by Mitsubishi Materials include 12S, 13M, 13M-C, 13R-N, and 14M-C. Examples of the titanium black manufactured by Ako Kasei Co., Ltd. include Tilac D.
- the preferable lower limit of the specific surface area of the titanium black is 13 m 2 / g, the preferable upper limit is 30 m 2 / g, the more preferable lower limit is 15 m 2 / g, and the more preferable upper limit is 25 m 2 / g.
- the preferred lower limit of the volume resistance of the titanium black is 0.5 ⁇ ⁇ cm, the preferred upper limit is 3 ⁇ ⁇ cm, the more preferred lower limit is 1 ⁇ ⁇ cm, and the more preferred upper limit is 2.5 ⁇ ⁇ cm.
- the primary particle diameter of the light-shielding agent is not particularly limited as long as it is not more than the distance between the substrates of the liquid crystal display element, but the preferred lower limit is 1 nm and the preferred upper limit is 5 ⁇ m. When the primary particle diameter of the light-shielding agent is within this range, the viscosity and thixotropy of the obtained sealing agent for liquid crystal display elements are not greatly increased, and the coating property is excellent.
- the more preferable lower limit of the primary particle diameter of the light shielding agent is 5 nm
- the more preferable upper limit is 200 nm
- the still more preferable lower limit is 10 nm
- the still more preferable upper limit is 100 nm.
- the primary particle size of the light-shielding agent can be measured using a particle size distribution meter (for example, “NICOMP 380ZLS” manufactured by PARTICLE SIZING SYSTEMS).
- the preferable lower limit of the content of the light-shielding agent in 100 parts by weight of the sealant for liquid crystal display elements of the present invention is 5 parts by weight, and the preferable upper limit is 80 parts by weight.
- the content of the light-shielding agent is within this range, the effect of improving the light-shielding property can be improved without significantly reducing the adhesiveness, strength after curing, and drawing property of the obtained sealing agent for liquid crystal display elements.
- the more preferable lower limit of the content of the light shielding agent is 10 parts by weight, the more preferable upper limit is 70 parts by weight, the still more preferable lower limit is 30 parts by weight, and the still more preferable upper limit is 60 parts by weight.
- the sealing agent for liquid crystal display elements of the present invention is further added with a stress relaxation agent, reactive diluent, thixotropic agent, spacer, curing accelerator, antifoaming agent, leveling agent, polymerization inhibitor, etc., if necessary.
- An agent may be contained.
- the sealing agent for liquid crystal display elements of the present invention for example, using a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, a three roll, a curable resin, and a polymerization
- a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, a three roll, a curable resin, and a polymerization
- a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, a three roll, a curable resin, and a polymerization
- a vertical conducting material can be produced by blending conductive fine particles with the liquid crystal display element sealant of the present invention.
- Such a vertical conduction material containing the sealing agent for liquid crystal display elements of the present invention and conductive fine particles is also one aspect of the present invention.
- the conductive fine particles a metal ball, a resin fine particle formed with a conductive metal layer on the surface, or the like can be used.
- the one in which the conductive metal layer is formed on the surface of the resin fine particles is preferable because the conductive connection is possible without damaging the transparent substrate due to the excellent elasticity of the resin fine particles.
- the liquid crystal display element using the sealing agent for liquid crystal display elements of this invention or the vertical conduction material of this invention is also one of this invention.
- a liquid crystal display element having a narrow frame design is preferable.
- the width of the frame portion around the liquid crystal display unit is preferably 2 mm or less.
- variety of the sealing compound for liquid crystal display elements of this invention at the time of manufacturing the liquid crystal display element of this invention is 1 mm or less.
- the sealing agent for liquid crystal display elements of this invention can be used suitably for manufacture of the liquid crystal display element by a liquid crystal dropping method.
- Examples of the method for producing the liquid crystal display element of the present invention by the liquid crystal dropping method include the following methods. First, a step of forming a rectangular seal pattern on the substrate by screen printing, dispenser application, or the like with the sealing agent for liquid crystal display elements of the present invention is performed. Next, the liquid crystal display element sealant or the like of the present invention is applied in an uncured state by applying liquid crystal microdroplets onto the entire surface of the transparent substrate and immediately stacking another substrate.
- a liquid crystal display element can be obtained by performing the method.
- a cured product obtained by curing the sealant for liquid crystal display elements of the present invention that is, a cured product obtained by curing a sealant for liquid crystal display elements containing a curable resin and a polymerization initiator and / or a thermosetting agent.
- a cured product having a pencil hardness of 3H or less in accordance with JIS K 5600-5-4 is also one aspect of the present invention.
- the sealing compound for liquid crystal display elements which is hard to produce a crack and a crack in a board
- the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal display elements can be provided.
- curing this sealing compound for liquid crystal display elements can be provided.
- FIG. 1A is a schematic diagram showing a panel dividing position in a conventional liquid crystal display element not having a narrow frame design
- FIG. 1B is a schematic diagram showing a panel dividing position in a liquid crystal display element having a narrow frame design.
- Examples 1 to 5 and Comparative Examples 1 and 2 Each material having a blending ratio shown in Table 1 was mixed using a planetary stirrer (“Shinky Co., Ltd.,“ Awatori Netaro ”), and then further mixed using three rolls.
- the sealants for liquid crystal display elements 1 to 5 and Comparative Examples 1 and 2 were prepared.
- the liquid crystal display element was produced using each sealing compound for liquid crystal display elements obtained by the Example and the comparative example.
- a cured product obtained by irradiating with 100 mW / cm 2 ultraviolet rays (wavelength 365 nm) for 30 seconds using a metal halide lamp and then heating and curing at 120 ° C. for 1 hour.
- the pencil hardness was measured according to K 5600-5-4. The results are shown in Table 1.
- a pattern was formed on the substrate so that adjacent drawing portions of the sealing agent contacted between the cells.
- the sealant part was irradiated with 100 mW / cm 2 of ultraviolet rays for 30 seconds using a metal halide lamp, and then heated at 120 ° C. for 1 hour to cure the sealant, so that the cured product of the sealant was placed at the cutting position.
- a total of 100 liquid crystal display elements were manufactured by cutting with a cut. Confirm the divided substrate of each liquid crystal display element, and if no cracks or cracks are confirmed in all the liquid crystal display elements, “ ⁇ ” indicates that no cracks are found on the substrate in one or more than five liquid crystal display elements. The case where cracks were confirmed was evaluated as “ ⁇ ”, and the case where cracks or cracks were confirmed in the substrate in five or more liquid crystal display elements was evaluated as “x”, and the splitting stability of the panel was evaluated.
- the sealing compound for liquid crystal display elements which is hard to produce a crack and a crack in a board
- the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal display elements can be provided.
- curing this sealing compound for liquid crystal display elements can be provided.
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Abstract
Description
滴下工法では、まず、2枚の電極付き基板の一方に、ディスペンスにより長方形状のシールパターンを形成する。次いで、シール剤が未硬化の状態で液晶の微小滴を基板のシール枠内に滴下し、真空下で他方の基板を重ね合わせ、シール部に紫外線等の光を照射して仮硬化を行う。その後、加熱して本硬化を行い、液晶表示素子を作製する。現在この滴下工法が液晶表示素子の製造方法の主流となっている。 In recent years, as a method of manufacturing a liquid crystal display element such as a liquid crystal display cell, a curable resin and a light as disclosed in
In the dropping method, first, a rectangular seal pattern is formed on one of the two substrates with electrodes by dispensing. Next, liquid crystal microdrops are dropped into the sealing frame of the substrate in a state where the sealing agent is uncured, the other substrate is superposed under vacuum, and the sealing portion is irradiated with light such as ultraviolet rays to perform temporary curing. Thereafter, heating is performed to perform main curing, and a liquid crystal display element is manufactured. At present, this dripping method has become the mainstream method for manufacturing liquid crystal display elements.
以下に本発明を詳述する。 The present invention is a sealing agent for liquid crystal display elements containing a curable resin and a polymerization initiator and / or a thermosetting agent, and the cured product according to JIS K 5600-5-4 has a pencil hardness of 3H or less. A sealing agent for a liquid crystal display element.
The present invention is described in detail below.
また、透湿防止性等の観点から、上記硬化物の鉛筆硬度は、3B以上であることが好ましい。
なお、本明細書において上記鉛筆硬度が「3H以下である」とは、鉛筆硬度が3Hとなる硬さである、又は、3Hとなる硬さよりも柔らかいことを意味し、上記鉛筆硬度が「3B以上である」とは、鉛筆硬度が3Bとなる硬さである、又は、3Bとなる硬さよりも硬いことを意味する。
上記鉛筆硬度を測定する硬化物は、液晶表示素子用シール剤に100mW/cm2の紫外線(波長365nm)を30秒照射した後、120℃で1時間加熱することにより得ることができる。また、該硬化物は、液晶表示素子中においては基板等の貼り合わせや封止に用いられているシール剤硬化物を意味する。 The sealing agent for liquid crystal display elements of the present invention has a pencil hardness of 3H or less in a cured product according to JIS K 5600-5-4. When the cured product has a pencil hardness of 3H or less, even a liquid crystal display element having a narrow frame design can hardly cause cracks or cracks in the substrate.
Moreover, it is preferable that pencil hardness of the said hardened | cured material is 3B or more from viewpoints, such as moisture-permeable prevention property.
In the present specification, the pencil hardness of “3H or less” means that the pencil hardness is 3H or softer than 3H, and the pencil hardness is “3B”. “It is above” means that the pencil hardness is 3B or is harder than 3B.
The cured product for measuring the pencil hardness can be obtained by irradiating a sealing agent for liquid crystal display elements with 100 mW / cm 2 of ultraviolet rays (wavelength 365 nm) for 30 seconds and then heating at 120 ° C. for 1 hour. Moreover, this hardened | cured material means the sealing agent hardened | cured material used for bonding and sealing of a board | substrate etc. in a liquid crystal display element.
本発明の液晶表示素子用シール剤において、硬化物の鉛筆硬度を3H以下とする方法としては、上記硬化性樹脂として柔軟性骨格を有する重合性化合物を用いる方法や、シール剤に柔軟性を有するポリマーや柔軟粒子を配合する方法等が挙げられる。なかでも、柔軟性骨格を有する重合性化合物を用いる方法が好ましく、柔軟性骨格を有する重合性化合物と柔軟粒子とを併用する方法がより好ましい。 The sealing agent for liquid crystal display elements of this invention contains curable resin, a polymerization initiator, and / or a thermosetting agent.
In the sealing agent for liquid crystal display elements of the present invention, as a method of setting the pencil hardness of the cured product to 3H or less, a method using a polymerizable compound having a flexible skeleton as the curable resin, or a sealing agent has flexibility. Examples thereof include a method of blending a polymer and flexible particles. Among these, a method using a polymerizable compound having a flexible skeleton is preferable, and a method using a polymerizable compound having a flexible skeleton and flexible particles in combination is more preferable.
なお、本明細書において上記「(メタ)アクリル」は、アクリル又はメタクリルを意味し、上記「(メタ)アクリル化合物」は、(メタ)アクリロイル基を有する化合物を意味し、上記「(メタ)アクリロイル」は、アクリロイル又はメタクリロイルを意味する。 Examples of the polymerizable compound having a flexible skeleton include a (meth) acrylic compound having a flexible skeleton and an epoxy compound having a flexible skeleton. The curable resin preferably contains a (meth) acrylic compound having the flexible skeleton and / or an epoxy compound having the flexible skeleton.
In the present specification, the “(meth) acryl” means acryl or methacryl, the “(meth) acryl compound” means a compound having a (meth) acryloyl group, and the above “(meth) acryloyl”. "Means acryloyl or methacryloyl.
上記長鎖(メタ)アクリル化合物のうち市販されているものとしては、例えば、共栄社化学社製の長鎖(メタ)アクリル化合物、ナガセケムテックス社製の長鎖(メタ)アクリル化合物、東亞合成社製の長鎖(メタ)アクリル化合物、新中村化学工業社製の長鎖(メタ)アクリル化合物、ダイセル・オルネクス社製の長鎖(メタ)アクリル化合物等が挙げられる。
上記共栄社化学社製の長鎖(メタ)アクリル化合物としては、例えば、エポキシエステル40EM、70PA、200PA、80FMA、3002M、3002A等が挙げられる。
上記ナガセケムテックス社製の長鎖(メタ)アクリル化合物としては、例えば、DA-911M、DA-920、DA-931、DM-811、DM-832、DM-851等が挙げられる。
上記東亞合成社製の長鎖(メタ)アクリル化合物としては、例えば、M-327等が挙げられる。
上記新中村化学工業社製の長鎖(メタ)アクリル化合物としては、例えば、A-9300-1CL、A-GLY-9E、A-GLY-20E等が挙げられる。
上記ダイセル・オルネクス社製の長鎖(メタ)アクリル化合物としては、例えば、EBECRYL 3708等が挙げられる。 Examples of the long chain (meth) acrylic compound include alkylene oxide-modified (meth) acrylic compounds and caprolactone-modified (meth) acrylic compounds.
Examples of commercially available long chain (meth) acrylic compounds include, for example, long chain (meth) acrylic compounds manufactured by Kyoeisha Chemical Co., Ltd., long chain (meth) acrylic compounds manufactured by Nagase ChemteX Corporation, Toagosei Co., Ltd. Examples include long-chain (meth) acrylic compounds manufactured by Shin-Nakamura Chemical Co., Ltd., long-chain (meth) acrylic compounds manufactured by Daicel Ornex.
Examples of the long-chain (meth) acrylic compound manufactured by Kyoeisha Chemical Co., Ltd. include epoxy esters 40EM, 70PA, 200PA, 80FMA, 3002M, and 3002A.
Examples of the long chain (meth) acrylic compound manufactured by Nagase ChemteX Corporation include DA-911M, DA-920, DA-931, DM-811, DM-832, DM-851, and the like.
Examples of the long-chain (meth) acrylic compound manufactured by Toagosei Co., Ltd. include M-327.
Examples of the long chain (meth) acrylic compound manufactured by Shin-Nakamura Chemical Co., Ltd. include A-9300-1CL, A-GLY-9E, A-GLY-20E and the like.
Examples of the long-chain (meth) acrylic compound manufactured by Daicel Ornex Corporation include EBECRYL 3708.
上記ゴム構造を有する(メタ)アクリル化合物のうち市販されているものとしては、例えば、日本曹達社製のゴム構造を有する(メタ)アクリル化合物、クラレ社製のゴム構造を有する(メタ)アクリル化合物等が挙げられる。
上記日本曹達社製のゴム構造を有する(メタ)アクリル化合物としては、例えば、NISSO-TE等が挙げられる。
上記クラレ社製のゴム構造を有する(メタ)アクリル化合物としては、例えば、UC-102、UC-203等が挙げられる。 Examples of the (meth) acrylic compound having the rubber structure include (meth) acryl-modified butadiene rubber, (meth) acryl-modified isoprene rubber, and the like.
Examples of commercially available (meth) acrylic compounds having the rubber structure include (meth) acrylic compounds having a rubber structure manufactured by Nippon Soda Co., Ltd., and (meth) acrylic compounds having a rubber structure manufactured by Kuraray Co., Ltd. Etc.
Examples of the (meth) acrylic compound having a rubber structure manufactured by Nippon Soda Co., Ltd. include NISSO-TE.
Examples of the (meth) acrylic compound having a rubber structure manufactured by Kuraray Co., Ltd. include UC-102 and UC-203.
上記ウレタン変性(メタ)アクリル化合物のうち市販されているものとしては、例えば、ダイセル・オルネクス社製のウレタン変性(メタ)アクリル化合物、荒川化学工業社製のウレタン変性(メタ)アクリル化合物、根上化学工業社製のウレタン変性(メタ)アクリル化合物等が挙げられる。
上記ダイセル・オルネクス社製のウレタン変性(メタ)アクリル化合物としては、例えば、EBECRYL 230、EBECRYL 4491、EBECRYL 210等が挙げられる。
上記荒川化学工業社製のウレタン変性(メタ)アクリル化合物としては、例えば、551B等が挙げられる。
上記根上化学工業社製のウレタン変性(メタ)アクリル化合物としては、例えば、UN-350、UN-1255等が挙げられる。 Examples of the urethane-modified (meth) acrylic compound include aliphatic urethane (meth) acrylate and aromatic urethane (meth) acrylate.
Examples of commercially available urethane-modified (meth) acrylic compounds include, for example, urethane-modified (meth) acrylic compounds manufactured by Daicel Ornex, urethane-modified (meth) acrylic compounds manufactured by Arakawa Chemical Industries, Ltd., and Negami Chemical. Examples include urethane-modified (meth) acrylic compounds manufactured by Kogyo Co., Ltd.
Examples of the urethane-modified (meth) acrylic compound manufactured by Daicel Ornex include EBECRYL 230, EBECRYL 4491, EBECRYL 210, and the like.
Examples of the urethane-modified (meth) acrylic compound manufactured by Arakawa Chemical Industries, Ltd. include 551B.
Examples of the urethane-modified (meth) acrylic compound manufactured by Negami Chemical Industry Co., Ltd. include UN-350 and UN-1255.
なお、本明細書において上記「(メタ)アクリレート」とは、アクリレート又はメタクリレートを意味し、上記「エポキシ(メタ)アクリレート」とは、エポキシ化合物中の全てのエポキシ基を(メタ)アクリル酸と反応させた化合物のことを表す。 Among them, as the (meth) acrylic compound having the flexible skeleton, a long chain (meth) acrylic compound is preferable because the pencil hardness of the cured product can be easily adjusted, and an alkylene oxide modified (meth) acrylic compound is more preferable. Preferably, an alkylene oxide-modified epoxy (meth) acrylate is more preferable, an epoxy (meth) acrylate having a polypropylene glycol skeleton is particularly preferable, and an acrylic acid adduct of tripropylene glycol diglycidyl ether is most preferable.
In the present specification, the “(meth) acrylate” means acrylate or methacrylate, and the “epoxy (meth) acrylate” means that all epoxy groups in the epoxy compound react with (meth) acrylic acid. Represents the compound.
上記長鎖エポキシ化合物のうち市販されているものとしては、例えば、共栄社化学社製の長鎖エポキシ化合物、DIC社製の長鎖エポキシ化合物、ダイセル・オルネクス社製の長鎖エポキシ化合物、三和合成化学社製の長鎖エポキシ化合物、新日本理化社製の長鎖エポキシ化合物、ADEKA社製の長鎖エポキシ化合物、三菱化学社製の長鎖エポキシ化合物等が挙げられる。
上記共栄社化学社製の長鎖エポキシ化合物としては、例えば、エポライト40E、100E、200E、400E、70P,200P、400P、1500NP、1600、80MF、100MF、4000、3002等が挙げられる。
上記DIC社製の長鎖エポキシ化合物としては、例えば、EPICLON EXA-4816、EPICLON EXA-4850等が挙げられる。
上記ダイセル・オルネクス社製の長鎖エポキシ化合物としては、例えば、セロキサイド2081、エポリードGT-401等が挙げられる。
上記三和合成化学社製の長鎖エポキシ化合物としては、例えば、ケミサイザーシリーズ等が挙げられる。
上記新日本理化社製の長鎖エポキシ化合物としては、例えば、サンソサイザー E-2000H等が挙げられる。
上記ADEKA社製の長鎖エポキシ化合物としては、例えば、ED-503、ED-503G、ED-506、EP-4000、EP-4005、EP-7001等が挙げられる。
上記三菱化学社製の長鎖エポキシ化合物としては、例えば、YL-7410、YL-7175-500 、YL-7175-1000、jER 871、jER 872等が挙げられる。 Examples of the long-chain epoxy compound include alkylene oxide-modified epoxy resins and alkylene-modified epoxies.
Examples of commercially available long-chain epoxy compounds include, for example, long-chain epoxy compounds manufactured by Kyoeisha Chemical Co., Ltd., long-chain epoxy compounds manufactured by DIC, long-chain epoxy compounds manufactured by Daicel-Ornex, and Sanwa Synthesis Examples include long-chain epoxy compounds manufactured by Kagaku Co., Ltd., long-chain epoxy compounds manufactured by Shin Nippon Rika Co., Ltd., long-chain epoxy compounds manufactured by ADEKA, and long-chain epoxy compounds manufactured by Mitsubishi Chemical Corporation.
Examples of the long-chain epoxy compound manufactured by Kyoeisha Chemical Co., Ltd. include Epolite 40E, 100E, 200E, 400E, 70P, 200P, 400P, 1500NP, 1600, 80MF, 100MF, 4000, 3002, and the like.
Examples of the long-chain epoxy compound manufactured by DIC include EPICLON EXA-4816, EPICLON EXA-4850, and the like.
Examples of the long-chain epoxy compound manufactured by Daicel Ornex include Celoxide 2081, Epolide GT-401, and the like.
Examples of the long-chain epoxy compound manufactured by Sanwa Synthetic Chemical Co., Ltd. include Chemisizer series.
Examples of the long-chain epoxy compound manufactured by Shin Nippon Rika Co., Ltd. include Sansosizer E-2000H.
Examples of the long-chain epoxy compound manufactured by ADEKA include ED-503, ED-503G, ED-506, EP-4000, EP-4005, EP-7001, and the like.
Examples of the long-chain epoxy compound manufactured by Mitsubishi Chemical Corporation include YL-7410, YL-7175-500, YL-7175-1000, jER 871, jER 872, and the like.
上記その他の柔軟性骨格を有するエポキシ化合物のうち市販されているものとしては、例えば、ADEKA社製のその他の柔軟性骨格を有するエポキシ化合物、日本触媒社製のその他の柔軟性骨格を有するエポキシ化合物、旭化成社製のその他の柔軟性骨格を有するエポキシ化合物等が挙げられる。
上記ADEKA社製のその他の柔軟性骨格を有するエポキシ化合物としては、例えば、EPU-7N等が挙げられる。
上記日本触媒社製のその他の柔軟性骨格を有するエポキシ化合物としては、例えば、アクリセットBPシリーズ等が挙げられる。
上記旭化成社製のその他の柔軟性骨格を有するエポキシ化合物としては、例えば、AER9000等が挙げられる。 Moreover, as an epoxy compound which has another flexible skeleton among the epoxy compounds which have the said flexible skeleton, a urethane modified epoxy compound, a rubber particle dispersion | distribution epoxy compound, etc. are mentioned, for example.
Examples of commercially available epoxy compounds having other flexible skeletons include, for example, epoxy compounds having other flexible skeletons manufactured by ADEKA, and epoxy compounds having other flexible skeletons manufactured by Nippon Shokubai Co., Ltd. And other epoxy compounds having a flexible skeleton manufactured by Asahi Kasei.
Examples of the epoxy compound having another flexible skeleton manufactured by ADEKA include EPU-7N.
Examples of the epoxy compound having another flexible skeleton manufactured by Nippon Shokubai Co., Ltd. include Acryset BP series.
Examples of the epoxy compound having other flexible skeleton manufactured by Asahi Kasei Co., Ltd. include AER9000.
上記巴工業社製のその他の柔軟性骨格を有する重合性化合物としては、例えば、Ricon 130MA8等が挙げられる。
上記出光興産社製のその他の柔軟性骨格を有する重合性化合物としては、例えば、Poly bd等が挙げられる。
上記カネカ社製のその他の柔軟性骨格を有する重合性化合物としては、例えば、エピオンシリーズ等が挙げられる。
上記東亞合成社製のその他の柔軟性骨格を有する重合性化合物としては、例えば、アルフオンUS-6000、マクロモノマーシリーズ等が挙げられる。
上記綜研化学社製のその他の柔軟性骨格を有する重合性化合物としては、例えば、アクトフローシリーズ等が挙げられる。
上記信越化学工業社製のその他の柔軟性骨格を有する重合性化合物としては、例えば、変性シリコーンオイル等が挙げられる。 Examples of commercially available polymerizable compounds having other flexible skeletons other than the (meth) acrylic compound having the flexible skeleton and the epoxy compound having the flexible skeleton include, for example, others manufactured by Sakai Kogyo Co., Ltd. Polymerizable compounds having other flexible skeletons, polymerizable compounds having other flexible skeletons manufactured by Idemitsu Kosan Co., Ltd., polymerizable compounds having other flexible skeletons manufactured by Kaneka Corporation, and other flexibility manufactured by Toagosei Co., Ltd. Examples thereof include a polymerizable compound having a skeleton, a polymerizable compound having another flexible skeleton manufactured by Soken Chemical Co., and a polymerizable compound having another flexible skeleton manufactured by Shin-Etsu Chemical Co., Ltd.
Examples of the polymerizable compound having another flexible skeleton manufactured by Sakai Kogyo Co., Ltd. include Ricon 130MA8.
Examples of the polymerizable compound having another flexible skeleton manufactured by Idemitsu Kosan Co., Ltd. include Poly bd.
Examples of the polymerizable compound having another flexible skeleton manufactured by Kaneka Corporation include the EPION series.
Examples of other polymerizable compounds having a flexible skeleton manufactured by Toagosei Co., Ltd. include Alfon US-6000, Macromonomer Series, and the like.
Examples of the polymerizable compound having another flexible skeleton manufactured by Soken Chemical Co., Ltd. include Actflow series.
Examples of the polymerizable compound having another flexible skeleton manufactured by Shin-Etsu Chemical Co., Ltd. include modified silicone oil.
また、透湿防止性等の観点から、上記硬化性樹脂100重量部中における上記柔軟性骨格を有する重合性化合物の含有量の好ましい上限は80重量部である。 A preferable lower limit of the content of the polymerizable compound having the flexible skeleton in 100 parts by weight of the curable resin is 20 parts by weight. When the content of the polymerizable compound having the flexible skeleton is within this range, it becomes easy to set the pencil hardness of the cured liquid crystal display element sealant to 3H or less. The minimum with more preferable content of the polymeric compound which has the said flexible skeleton is 30 weight part, Furthermore, a preferable minimum is 60 weight part.
In addition, from the viewpoint of moisture permeation prevention property and the like, the upper limit of the content of the polymerizable compound having the flexible skeleton in 100 parts by weight of the curable resin is 80 parts by weight.
上記柔軟性を有するポリマーのうち市販されているものとしては、例えば、アルフオン UG-4000(東亞合成社製)等が挙げられる。
上記柔軟性を有するポリマーは、単独で用いられてもよいし、2種以上が組み合わせて用いられてもよい。 Examples of the flexible polymer include (meth) acrylic polymers.
Examples of commercially available polymers having the flexibility described above include Alfon UG-4000 (manufactured by Toagosei Co., Ltd.).
The said polymer which has the said softness | flexibility may be used independently, and 2 or more types may be used in combination.
また、上記柔軟粒子は、コアシェル構造を有していてもよい。 Examples of the flexible particles include rubber particles and urethane particles.
The flexible particles may have a core-shell structure.
上記ゴム粒子のうち市販されているもとしては、例えば、カネカ社製のゴム粒子、日本ゼオン社製のゴム粒子、アイカ工業社製のゴム粒子、東レ・ファインケム社製のゴム粒子等が挙げられる。
上記カネカ社製のゴム粒子としては、例えば、カネエースBシリーズ、カネエースFMシリーズ等が挙げられる。
上記日本ゼオン社製のゴム粒子としては、例えば、Nipolシリーズ等が挙げられる。
上記アイカ工業社製のゴム粒子としては、例えば、ゼフィアックF351等が挙げられる。
上記東レ・ファインケム社製のゴム粒子としては、例えば、チオコールLP-282等が挙げられる。 Examples of the rubber particles include acrylic rubber particles, butadiene rubber particles, isoprene rubber particles, nitrile rubber particles, silicone rubber particles, sulfide rubber particles, and fluorine rubber particles.
Examples of commercially available rubber particles include Kaneka's rubber particles, Nippon Zeon's rubber particles, Aika Industry's rubber particles, Toray Finechem's rubber particles, and the like. .
Examples of the rubber particles manufactured by Kaneka Corporation include Kane Ace B series and Kane Ace FM series.
Examples of the rubber particles manufactured by Zeon Corporation include Nipol series.
Examples of the rubber particles manufactured by Aika Kogyo include Zefiac F351.
Examples of the rubber particles manufactured by Toray Finechem Co., Ltd. include Thiocol LP-282.
上記根上化学工業社製のウレタン粒子としては、例えば、アートパール等が挙げられる。上記大日精化工業社製のウレタン粒子としては、例えば、ダイミックビーズ等が挙げられる。 Examples of commercially available urethane particles include those manufactured by Negami Chemical Industry Co., Ltd. and those manufactured by Dainichi Seika Kogyo Co., Ltd.
Examples of the urethane particles manufactured by Negami Chemical Industry Co., Ltd. include Art Pearl. Examples of the urethane particles manufactured by Dainichi Seika Kogyo Co., Ltd. include dimic beads.
また、上記柔軟性骨格を有する重合性化合物と上記柔軟粒子とを併用する場合、上記柔軟粒子の含有量は、上記硬化性樹脂100重量部に対して、好ましい下限が10重量部である。上記柔軟粒子の含有量がこの範囲であることにより、得られる液晶表示素子用シール剤の硬化物の鉛筆硬度を3H以下とすることが容易となる。上記柔軟性骨格を有する重合性化合物と上記柔軟粒子とを併用する場合の上記柔軟粒子の含有量のより好ましい下限は15重量部である。 The minimum with preferable content of the said flexible particle in 100 weight part of sealing compounds for liquid crystal display elements of this invention is 20 weight part. When the content of the flexible particles is within this range, it becomes easy to set the pencil hardness of the obtained cured product of the sealing agent for liquid crystal display elements to 3H or less. The minimum with more preferable content of the said flexible particle | grain is 30 weight part.
Moreover, when using together the polymeric compound which has the said flexible skeleton, and the said flexible particle, the minimum with preferable content of the said flexible particle is 10 weight part with respect to 100 weight part of said curable resins. When the content of the flexible particles is within this range, it becomes easy to set the pencil hardness of the obtained cured product of the sealing agent for liquid crystal display elements to 3H or less. A more preferable lower limit of the content of the flexible particles when the polymerizable compound having the flexible skeleton and the flexible particles are used in combination is 15 parts by weight.
本発明の液晶表示素子用シール剤は、光ラジカル重合開始剤及び熱硬化剤を含有することが好ましい。 The sealing agent for liquid crystal display elements of this invention contains a polymerization initiator and / or a thermosetting agent.
It is preferable that the sealing agent for liquid crystal display elements of this invention contains radical photopolymerization initiator and a thermosetting agent.
上記BASF社製の光ラジカル重合開始剤としては、例えば、IRGACURE 184、IRGACURE 369、IRGACURE 379、IRGACURE 651、IRGACURE 819、IRGACURE 907、IRGACURE 2959、IRGACURE OXE01、ルシリンTPO等が挙げられる。
上記東京化成工業社製の光ラジカル重合開始剤としては、例えば、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル等が挙げられる。 As what is marketed among the said radical photopolymerization initiators, the radical photopolymerization initiator by BASF, the radical photopolymerization initiator by Tokyo Chemical Industry, etc. are mentioned, for example.
Examples of the radical photopolymerization initiator manufactured by BASF include IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, and Lucillin TPO.
Examples of the photo radical polymerization initiator manufactured by Tokyo Chemical Industry Co., Ltd. include benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.
上記熱ラジカル重合開始剤としては、例えば、アゾ化合物、有機過酸化物等からなるものが挙げられる。なかでも、高分子アゾ化合物からなる高分子アゾ開始剤が好ましい。
なお、本明細書において高分子アゾ化合物とは、アゾ基を有し、熱によって(メタ)アクリロイルオキシ基を硬化させることができるラジカルを生成する、数平均分子量が300以上の化合物を意味する。 The sealing agent for liquid crystal display elements of the present invention may use a thermal radical polymerization initiator as the polymerization initiator.
As said thermal radical polymerization initiator, what consists of an azo compound, an organic peroxide, etc. is mentioned, for example. Among these, a polymer azo initiator composed of a polymer azo compound is preferable.
In the present specification, the polymer azo compound means a compound having an azo group and generating a radical capable of curing a (meth) acryloyloxy group by heat and having a number average molecular weight of 300 or more.
なお、本明細書において、上記数平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)で溶媒としてテトラヒドロフランを用いて測定を行い、ポリスチレン換算により求められる値である。GPCによってポリスチレン換算による数平均分子量を測定する際のカラムとしては、例えば、Shodex LF-804(昭和電工社製)等が挙げられる。 The preferable lower limit of the number average molecular weight of the polymer azo compound is 1000, and the preferable upper limit is 300,000. When the number average molecular weight of the polymer azo compound is within this range, it can be easily mixed into the curable resin while preventing adverse effects on the liquid crystal. The more preferable lower limit of the number average molecular weight of the polymer azo compound is 5000, the more preferable upper limit is 100,000, the still more preferable lower limit is 10,000, and the still more preferable upper limit is 90,000.
In addition, in this specification, the said number average molecular weight is a value calculated | required by polystyrene conversion, measuring using tetrahydrofuran as a solvent by gel permeation chromatography (GPC). Examples of the column for measuring the number average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko KK).
上記アゾ基を介してポリアルキレンオキサイド等のユニットが複数結合した構造を有する高分子アゾ化合物としては、ポリエチレンオキサイド構造を有するものが好ましい。
上記高分子アゾ化合物としては、具体的には例えば、4,4’-アゾビス(4-シアノペンタン酸)とポリアルキレングリコールの重縮合物や、4,4’-アゾビス(4-シアノペンタン酸)と末端アミノ基を有するポリジメチルシロキサンの重縮合物等が挙げられる。
上記高分子アゾ化合物のうち市販されているものとしては、例えば、VPE-0201、VPE-0401、VPE-0601、VPS-0501、VPS-1001(いずれも和光純薬工業社製)等が挙げられる。
また、高分子ではないアゾ化合物として市販されているものとしては、例えば、V-65、V-501(いずれも和光純薬工業社製)等が挙げられる。 Examples of the polymer azo compound include those having a structure in which a plurality of units such as polyalkylene oxide and polydimethylsiloxane are bonded via an azo group.
As the polymer azo compound having a structure in which a plurality of units such as polyalkylene oxide are bonded via the azo group, those having a polyethylene oxide structure are preferable.
Specific examples of the polymer azo compound include, for example, a polycondensate of 4,4′-azobis (4-cyanopentanoic acid) and polyalkylene glycol, and 4,4′-azobis (4-cyanopentanoic acid). And a polycondensate of polydimethylsiloxane having a terminal amino group.
Examples of commercially available polymer azo compounds include VPE-0201, VPE-0401, VPE-0601, VPS-0501, and VPS-1001 (all manufactured by Wako Pure Chemical Industries, Ltd.). .
Examples of commercially available azo compounds that are not polymers include V-65 and V-501 (both manufactured by Wako Pure Chemical Industries, Ltd.).
上記イミダゾール系熱硬化剤としては、例えば、2-メチルイミダゾール、2-エチル-4-メチルイミダゾール、1-シアノエチル-2-フェニルイミダゾール、1-シアノエチル-2-フェニルイミダゾリウムトリメリテート、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、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等が挙げられる。 As the thermosetting agent, an imidazole thermosetting agent is preferable.
Examples of the imidazole thermosetting agent include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4 -Diamino-6- (2'-methylimidazolyl- (1 '))-ethyl-s-triazine, 2,4-diamino-6- (2'-methylimidazolyl- (1'))-ethyl-s-triazine Examples include isocyanuric acid adducts.
上記アダクト型の硬化剤としては、例えば、イミダゾール化合物とエポキシ化合物等との反応により得られるアダクト体が挙げられる。
上記アダクト型の硬化剤のうち市販されているものとしては、例えば、味の素ファインテクノ社製のアダクト型の硬化剤、四国化成工業社製のアダクト型の硬化剤、三菱化学社製のアダクト型の硬化剤等が挙げられる。
上記味の素ファインテクノ社製のアダクト型の硬化剤としては、例えば、アミキュアPN-23、アミキュアPN-23J、アミキュアPN-H、アミキュアPN-31、アミキュアPN-31J、アミキュアPN-40、アミキュアPN-40J、アミキュアPN-50、アミキュアPN-F、アミキュアMY-24、アミキュアMY-H等が挙げられる。
上記四国化成工業社製のアダクト型の硬化剤としては、例えば、P-0505等が挙げられる。
上記三菱化学社製のアダクト型の硬化剤としては、例えば、P-200等が挙げられる。 Moreover, you may use an adduct type hardening | curing agent as said imidazole series thermosetting agent. By using the above adduct type curing agent, excessive thickening of the sealing agent can be suppressed.
Examples of the adduct-type curing agent include adducts obtained by a reaction between an imidazole compound and an epoxy compound.
Among the adduct-type curing agents that are commercially available, for example, an adduct-type curing agent manufactured by Ajinomoto Fine Techno Co., an adduct-type curing agent manufactured by Shikoku Kasei Kogyo Co., and an adduct-type curing agent manufactured by Mitsubishi Chemical Corporation Examples thereof include a curing agent.
Examples of the adduct-type curing agent manufactured by Ajinomoto Fine Techno Co., Ltd. include Amicure PN-23, Amicure PN-23J, Amicure PN-H, Amicure PN-31, Amicure PN-31J, Amicure PN-40, Amicure PN- 40J, Amicure PN-50, Amicure PN-F, Amicure MY-24, Amicure MY-H, and the like.
Examples of the adduct type curing agent manufactured by Shikoku Kasei Kogyo Co., Ltd. include P-0505.
Examples of the adduct-type curing agent manufactured by Mitsubishi Chemical Corporation include P-200.
上記その他の熱硬化剤としては、例えば、有機酸ヒドラジド、アミン化合物、多価フェノール系化合物、酸無水物等が挙げられる。なかでも、有機酸ヒドラジドが好適に用いられる。 As the thermosetting agent, other thermosetting agents other than the imidazole thermosetting agent may be used.
As said other thermosetting agent, organic acid hydrazide, an amine compound, a polyhydric phenol type compound, an acid anhydride etc. are mentioned, for example. Of these, organic acid hydrazide is preferably used.
上記有機酸ヒドラジドのうち市販されているものとしては、例えば、大塚化学社製の有機酸ヒドラジド、味の素ファインテクノ社製の有機酸ヒドラジド等が挙げられる。
上記大塚化学社製の有機酸ヒドラジドとしては、例えば、SDH、ADH等が挙げられる。
上記味の素ファインテクノ社製の有機酸ヒドラジドとしては、例えば、アミキュアVDH、アミキュアVDH-J、アミキュアUDH、アミキュアUDH-J等が挙げられる。 Examples of the organic acid hydrazide include sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide, and the like.
Examples of commercially available organic acid hydrazides include organic acid hydrazides manufactured by Otsuka Chemical Co., Ltd., organic acid hydrazides manufactured by Ajinomoto Fine Techno Co., and the like.
Examples of the organic acid hydrazide manufactured by Otsuka Chemical Co., Ltd. include SDH and ADH.
Examples of the organic acid hydrazide manufactured by Ajinomoto Fine Techno Co. include Amicure VDH, Amicure VDH-J, Amicure UDH, Amicure UDH-J, and the like.
また、塗布性等の観点から、上記無機充填剤の含有量は、上記硬化性樹脂100重量部に対して、好ましい上限が60重量部である。 The lower limit of the content of the inorganic filler is preferably 15 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the inorganic filler is 15 parts by weight or more, the heat shock resistance when the environmental change between low and high temperatures is repeated is excellent. The minimum with more preferable content of the said inorganic filler is 25 weight part.
From the viewpoint of applicability and the like, the upper limit of the content of the inorganic filler is preferably 60 parts by weight with respect to 100 parts by weight of the curable resin.
上記イオン捕捉剤は、上記液晶表示素子用シール剤中の水溶性イオンを捕捉することで液晶汚染の発生を抑制する役割を有する。 The sealing agent for liquid crystal display elements of the present invention preferably contains an ion scavenger.
The ion scavenger has a role of suppressing the occurrence of liquid crystal contamination by capturing water-soluble ions in the liquid crystal display element sealing agent.
上記和光純薬工業社製のアンチモン系化合物としては、例えば、五酸化アンチモン等が挙げられる。
上記東亞合成社製のアンチモン系化合物としては、例えば、IXE-300、IXE-600、IXE-633等が挙げられる。 Examples of commercially available antimony compounds include antimony compounds manufactured by Wako Pure Chemical Industries, Ltd., antimony compounds manufactured by Toagosei Co., Ltd., and the like.
Examples of the antimony compound manufactured by Wako Pure Chemical Industries, Ltd. include antimony pentoxide.
Examples of the antimony compound manufactured by Toagosei Co., Ltd. include IXE-300, IXE-600, and IXE-633.
上記シランカップリング剤としては、例えば、3-アミノプロピルトリメトキシシラン、3-メルカプトプロピルトリメトキシシラン、3-グリシドキシプロピルトリメトキシシラン等が好適に用いられる。
上記シランカップリング剤は、単独で用いられてもよいし、2種以上が組み合わせて用いられてもよい。 The sealing agent for liquid crystal display elements of the present invention preferably contains a silane coupling agent for the purpose of further improving the adhesiveness. The silane coupling agent mainly has a role as an adhesion assistant for favorably bonding the sealing agent and the substrate.
As the silane coupling agent, for example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane and the like are preferably used.
The said silane coupling agent may be used independently and 2 or more types may be used in combination.
また、遮光剤として上記チタンブラックを含有する本発明の液晶表示素子用シール剤を用いて製造した液晶表示素子は、充分な遮光性を有するため、光の漏れ出しがなく高いコントラストを有し、優れた画像表示品質を有する液晶表示素子を実現することができる。 The above-mentioned titanium black exhibits a sufficient effect even if it is not surface-treated, but the surface is treated with an organic component such as a coupling agent, silicon oxide, titanium oxide, germanium oxide, aluminum oxide, oxidized Surface-treated titanium black such as those coated with an inorganic component such as zirconium or magnesium oxide can also be used. Especially, what is processed with the organic component is preferable at the point which can improve insulation more.
In addition, the liquid crystal display element produced using the sealing agent for liquid crystal display elements of the present invention containing the above-described titanium black as a light-shielding agent has a sufficient light-shielding property, and thus has high contrast without light leakage. A liquid crystal display element having excellent image display quality can be realized.
上記三菱マテリアル社製のチタンブラックとしては、例えば、12S、13M、13M-C、13R-N、14M-C等が挙げられる。
上記赤穂化成社製のチタンブラックとしては、例えば、ティラックD等が挙げられる。 Examples of commercially available titanium black include titanium black manufactured by Mitsubishi Materials Corporation and titanium black manufactured by Ako Kasei Co., Ltd.
Examples of the titanium black manufactured by Mitsubishi Materials include 12S, 13M, 13M-C, 13R-N, and 14M-C.
Examples of the titanium black manufactured by Ako Kasei Co., Ltd. include Tilac D.
また、上記チタンブラックの体積抵抗の好ましい下限は0.5Ω・cm、好ましい上限は3Ω・cmであり、より好ましい下限は1Ω・cm、より好ましい上限は2.5Ω・cmである。 The preferable lower limit of the specific surface area of the titanium black is 13 m 2 / g, the preferable upper limit is 30 m 2 / g, the more preferable lower limit is 15 m 2 / g, and the more preferable upper limit is 25 m 2 / g.
Further, the preferred lower limit of the volume resistance of the titanium black is 0.5 Ω · cm, the preferred upper limit is 3 Ω · cm, the more preferred lower limit is 1 Ω · cm, and the more preferred upper limit is 2.5 Ω · cm.
なお、上記遮光剤の一次粒子径は、粒度分布計(例えば、PARTICLE SIZING SYSTEMS社製、「NICOMP 380ZLS」)を用いて測定することができる。 The primary particle diameter of the light-shielding agent is not particularly limited as long as it is not more than the distance between the substrates of the liquid crystal display element, but the preferred lower limit is 1 nm and the preferred upper limit is 5 μm. When the primary particle diameter of the light-shielding agent is within this range, the viscosity and thixotropy of the obtained sealing agent for liquid crystal display elements are not greatly increased, and the coating property is excellent. The more preferable lower limit of the primary particle diameter of the light shielding agent is 5 nm, the more preferable upper limit is 200 nm, the still more preferable lower limit is 10 nm, and the still more preferable upper limit is 100 nm.
The primary particle size of the light-shielding agent can be measured using a particle size distribution meter (for example, “NICOMP 380ZLS” manufactured by PARTICLE SIZING SYSTEMS).
本発明の液晶表示素子としては、狭額縁設計の液晶表示素子が好ましい。具体的には、液晶表示部の周囲の枠部分の幅が2mm以下であることが好ましい。
また、本発明の液晶表示素子を製造する際の本発明の液晶表示素子用シール剤の塗布幅は1mm以下であることが好ましい。 The liquid crystal display element using the sealing agent for liquid crystal display elements of this invention or the vertical conduction material of this invention is also one of this invention.
As the liquid crystal display element of the present invention, a liquid crystal display element having a narrow frame design is preferable. Specifically, the width of the frame portion around the liquid crystal display unit is preferably 2 mm or less.
Moreover, it is preferable that the application | coating width | variety of the sealing compound for liquid crystal display elements of this invention at the time of manufacturing the liquid crystal display element of this invention is 1 mm or less.
液晶滴下工法によって本発明の液晶表示素子を製造する方法としては、例えば、以下の方法等が挙げられる。
まず、基板に本発明の液晶表示素子用シール剤等をスクリーン印刷、ディスペンサー塗布等により長方形状のシールパターンを形成する工程を行う。次いで、本発明の液晶表示素子用シール剤等が未硬化の状態で液晶の微小滴を透明基板の枠内全面に滴下塗布し、すぐに別の基板を重ね合わせる工程を行う。その後、本発明の液晶表示素子用シール剤等のシールパターン部分に紫外線等の光を照射してシール剤を仮硬化させる工程、及び、仮硬化させたシール剤を加熱して本硬化させる工程を行う方法により、液晶表示素子を得ることができる。 The sealing agent for liquid crystal display elements of this invention can be used suitably for manufacture of the liquid crystal display element by a liquid crystal dropping method.
Examples of the method for producing the liquid crystal display element of the present invention by the liquid crystal dropping method include the following methods.
First, a step of forming a rectangular seal pattern on the substrate by screen printing, dispenser application, or the like with the sealing agent for liquid crystal display elements of the present invention is performed. Next, the liquid crystal display element sealant or the like of the present invention is applied in an uncured state by applying liquid crystal microdroplets onto the entire surface of the transparent substrate and immediately stacking another substrate. Thereafter, a step of irradiating the seal pattern portion of the sealant for the liquid crystal display element of the present invention with light such as ultraviolet rays to temporarily cure the sealant, and a step of heating and temporarily curing the temporarily cured sealant A liquid crystal display element can be obtained by performing the method.
表1に記載された配合比の各材料を、遊星式撹拌機(シンキー社製、「あわとり練太郎」)を用いて混合した後、更に3本ロールを用いて混合することにより、実施例1~5、及び、比較例1、2の各液晶表示素子用シール剤を調製した。また、実施例及び比較例で得られた各液晶表示素子用シール剤を用いて液晶表示素子を作製した。
得られた各液晶表示素子用シール剤について、メタルハライドランプを用いて100mW/cm2の紫外線(波長365nm)を30秒照射した後、120℃で1時間加熱して硬化させた硬化物について、JIS K 5600-5-4に準拠して鉛筆硬度を測定した。結果を表1に示した。 (Examples 1 to 5 and Comparative Examples 1 and 2)
Each material having a blending ratio shown in Table 1 was mixed using a planetary stirrer (“Shinky Co., Ltd.,“ Awatori Netaro ”), and then further mixed using three rolls. The sealants for liquid
About each obtained liquid crystal display element sealant, a cured product obtained by irradiating with 100 mW / cm 2 ultraviolet rays (wavelength 365 nm) for 30 seconds using a metal halide lamp and then heating and curing at 120 ° C. for 1 hour. The pencil hardness was measured according to K 5600-5-4. The results are shown in Table 1.
実施例及び比較例で得られた液晶表示素子用シール剤について以下の評価を行った。結果を表1に示した。 <Evaluation>
The following evaluation was performed about the sealing compound for liquid crystal display elements obtained by the Example and the comparative example. The results are shown in Table 1.
実施例及び比較例で得られた各液晶表示素子用シール剤100重量部にスペーサー微粒子(積水化学工業社製、「ミクロパールSI-H050」)1重量部を分散させ、2枚のラビング済み配向膜及び透明電極付き基板の一方にシール剤の線幅が0.8mmになるようにディスペンサーで塗布した。
続いて液晶(チッソ社製、「JC-5004LA」)の微小滴を透明電極付き基板のシール剤の枠内全面に滴下塗布し、すぐにもう一方の透明電極付き基板を貼り合わせた。この際、図1(b)のように各セル間で隣接するシール剤の描画箇所が接触するように基板上にパターンを作成した。シール剤部分にメタルハライドランプを用いて100mW/cm2の紫外線を30秒照射した後、120℃で1時間加熱してシール剤を硬化させ、シール剤の硬化物上が分断位置となるようにスクライバを用いて切り込みを入れてカッティングし、合計100個の液晶表示素子を作製した。
各液晶表示素子の分断された基板を確認し、全ての液晶表示素子において基板にひびや割れが確認されなかった場合を「○」、1個以上5個未満の液晶表示素子において基板にひびや割れが確認された場合を「△」、5個以上の液晶表示素子において基板にひびや割れが確認された場合を「×」としてパネルの分断安定性を評価した。 (Panel division stability)
1 part by weight of spacer fine particles (“Micropearl SI-H050” manufactured by Sekisui Chemical Co., Ltd.) is dispersed in 100 parts by weight of the sealant for each liquid crystal display element obtained in Examples and Comparative Examples, and two rubbed orientations are obtained. It applied with a dispenser so that the line width of a sealing agent might be set to 0.8 mm to one of a film | membrane and a board | substrate with a transparent electrode.
Subsequently, fine droplets of liquid crystal (manufactured by Chisso Corporation, “JC-5004LA”) were dropped onto the entire surface of the sealing agent frame of the substrate with transparent electrode, and the other substrate with transparent electrode was immediately bonded. At this time, as shown in FIG. 1B, a pattern was formed on the substrate so that adjacent drawing portions of the sealing agent contacted between the cells. The sealant part was irradiated with 100 mW / cm 2 of ultraviolet rays for 30 seconds using a metal halide lamp, and then heated at 120 ° C. for 1 hour to cure the sealant, so that the cured product of the sealant was placed at the cutting position. A total of 100 liquid crystal display elements were manufactured by cutting with a cut.
Confirm the divided substrate of each liquid crystal display element, and if no cracks or cracks are confirmed in all the liquid crystal display elements, “○” indicates that no cracks are found on the substrate in one or more than five liquid crystal display elements. The case where cracks were confirmed was evaluated as “Δ”, and the case where cracks or cracks were confirmed in the substrate in five or more liquid crystal display elements was evaluated as “x”, and the splitting stability of the panel was evaluated.
上記「(パネルの分断安定性)」で得られた液晶表示素子60個について、冷熱サイクル試験機を用いて、-30℃で保持した後85℃まで昇温し、85℃で保持した後-30℃まで降温する過程を1サイクルとし、これを1000サイクル行う冷熱サイクル試験を行った。
試験後、全ての液晶表示素子において液晶漏れが確認されなかった場合を「◎」、1個又は2個の液晶表示素子において液晶漏れが確認された場合を「○」、3個又は4個の液晶表示素子において液晶漏れが確認された場合を「△」、5個以上の液晶表示素子において液晶漏れが確認された場合を「×」として耐ヒートショック性を評価した。 (Heat shock resistance)
About 60 liquid crystal display elements obtained in the above-mentioned “(Partitioning stability of panel)”, after holding at −30 ° C., raising the temperature to 85 ° C. and holding at 85 ° C. using a thermal cycle tester— The process of lowering the temperature to 30 ° C. was defined as one cycle, and a thermal cycle test was performed in which the cycle was 1000 cycles.
After the test, the case where no liquid crystal leak was confirmed in all the liquid crystal display elements was “◎”, and the case where liquid crystal leak was confirmed in one or two liquid crystal display elements was “◯”, three or four When the liquid crystal leak was confirmed in the liquid crystal display element as “Δ”, the case where the liquid crystal leak was confirmed in five or more liquid crystal display elements was evaluated as “x”, and the heat shock resistance was evaluated.
2 シール剤の硬化物
3 パネルの分断位置 1
Claims (7)
- 硬化性樹脂と重合開始剤及び/又は熱硬化剤とを含有する液晶表示素子用シール剤であって、JIS K 5600-5-4に準拠した硬化物の鉛筆硬度が3H以下であることを特徴とする液晶表示素子用シール剤。 A sealing agent for a liquid crystal display element containing a curable resin and a polymerization initiator and / or a thermosetting agent, wherein the pencil hardness of the cured product according to JIS K 5600-5-4 is 3H or less. A sealing agent for liquid crystal display elements.
- 前記硬化性樹脂は、柔軟性骨格を有する(メタ)アクリル化合物及び/又は柔軟性骨格を有するエポキシ化合物を含有する請求項1記載の液晶表示素子用シール剤。 The sealing agent for liquid crystal display elements according to claim 1, wherein the curable resin contains a (meth) acrylic compound having a flexible skeleton and / or an epoxy compound having a flexible skeleton.
- 光ラジカル重合開始剤及び熱硬化剤を含有する請求項1又は2記載の液晶表示素子用シール剤。 The sealing agent for liquid crystal display elements of Claim 1 or 2 containing radical photopolymerization initiator and a thermosetting agent.
- 無機充填剤を含有し、前記硬化性樹脂100重量部に対して前記無機充填剤を15重量部以上60重量部以下含有する請求項1、2又は3記載の液晶表示素子用シール剤。 The sealing agent for liquid crystal display elements of Claim 1, 2, or 3 containing an inorganic filler and containing 15 to 60 parts by weight of the inorganic filler with respect to 100 parts by weight of the curable resin.
- 請求項1、2、3又は4記載の液晶表示素子用シール剤と導電性微粒子とを含有する上下導通材料。 A vertical conduction material containing the sealing agent for liquid crystal display elements according to claim 1, and conductive fine particles.
- 請求項1、2、3若しくは4記載の液晶表示素子用シール剤又は請求項5記載の上下導通材料を用いてなる液晶表示素子。 A liquid crystal display element using the sealing agent for a liquid crystal display element according to claim 1, 2, 3, or 4, or the vertical conduction material according to claim 5.
- 硬化性樹脂と重合開始剤及び/又は熱硬化剤とを含有する液晶表示素子用シール剤を硬化してなる硬化物であって、JIS K 5600-5-4に準拠した鉛筆硬度が3H以下であることを特徴とする硬化物。 A cured product obtained by curing a sealing agent for a liquid crystal display element containing a curable resin and a polymerization initiator and / or a thermosetting agent, and having a pencil hardness of 3H or less according to JIS K 5600-5-4 A cured product characterized by being.
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Publication number | Priority date | Publication date | Assignee | Title |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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