CN109219773B - Sealing agent for liquid crystal display element, vertical conduction material, liquid crystal display element, and cured product - Google Patents

Sealing agent for liquid crystal display element, vertical conduction material, liquid crystal display element, and cured product Download PDF

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CN109219773B
CN109219773B CN201880002243.5A CN201880002243A CN109219773B CN 109219773 B CN109219773 B CN 109219773B CN 201880002243 A CN201880002243 A CN 201880002243A CN 109219773 B CN109219773 B CN 109219773B
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liquid crystal
crystal display
display element
sealant
examples
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CN109219773A (en
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小林洋
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Sekisui Chemical Co Ltd
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Sekisui Chemical Co Ltd
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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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Nonlinear Science (AREA)
  • Organic Chemistry (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Liquid Crystal (AREA)
  • Sealing Material Composition (AREA)
  • Polymerisation Methods In General (AREA)
  • Epoxy Resins (AREA)

Abstract

The invention aims to provide a sealant for a liquid crystal display element, which can prevent a substrate from cracking or breaking even for a liquid crystal display element with a narrow frame design. Further, another object of the present invention is to provide a vertical conduction material and a liquid crystal display element, each of which is produced using the sealant for a liquid crystal display element. Further, another object of the present invention is to provide a cured product obtained by curing the sealant for a liquid crystal display element. The present invention is a sealant for a liquid crystal display element, which contains a curable resin and further contains a polymerization initiator and/or a thermal curing agent, wherein the pencil hardness of a cured product of the sealant for a liquid crystal display element is 3H or less according to JIS K5600-5-4.

Description

Sealing agent for liquid crystal display element, vertical conduction material, liquid crystal display element, and cured product
Technical Field
The present invention relates to a sealant for a liquid crystal display element, which is less likely to cause cracking or breaking of a substrate even in a liquid crystal display element designed with a narrow frame. The present invention also relates to a vertical conduction material and a liquid crystal display element, which are produced using the sealant for a liquid crystal display element. The present invention also relates to a cured product obtained by curing the sealant for a liquid crystal display element.
Background
In recent years, as a method for manufacturing a liquid crystal display element such as a liquid crystal display unit, a liquid crystal dropping method called a dropping method using a photo-thermal curing type sealing agent containing a curable resin, a photopolymerization initiator, and a thermal curing agent as disclosed in patent document 1 and patent document 2 has been used from the viewpoint of shortening the tact time and optimizing the amount of liquid crystal used.
In the dropping process, first, a rectangular seal pattern is formed on one of two substrates with electrodes by a dispenser. Next, in a state where the sealant is not cured, fine droplets of liquid crystal are dropped into a sealing frame of the substrate, another substrate is stacked under vacuum, and light such as ultraviolet rays is irradiated to the sealing portion to perform precuring. Thereafter, the resultant was subjected to heat treatment to perform main curing, thereby producing a liquid crystal display element. This one drop fill process is now the mainstream of a method for manufacturing a liquid crystal display element.
In addition, in recent years in which various mobile devices with liquid crystal panels such as mobile phones and portable game machines are widespread, miniaturization of the devices is the most demanded issue. As a method for downsizing, a narrow frame of a liquid crystal display portion is given, and for example, a position of a sealing portion is disposed below a black matrix (hereinafter, also referred to as a narrow frame design).
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2001-133794
Patent document 2: japanese laid-open patent publication No. 5-295087
Disclosure of Invention
Problems to be solved by the invention
The present invention relates to a sealant for a liquid crystal display element, which is less likely to cause cracking or breaking of a substrate even in a liquid crystal display element designed with a narrow frame. Further, an object of the present invention is to provide a vertical conduction material and a liquid crystal display element, each of which is produced using the sealant for a liquid crystal display element. Further, another object of the present invention is to provide a cured product obtained by curing the sealant for a liquid crystal display element.
Means for solving the problems
The present invention is a sealant for a liquid crystal display element, which contains a curable resin and further contains a polymerization initiator and/or a thermal curing agent, wherein the pencil hardness of a cured product of the sealant for a liquid crystal display element is 3H or less according to JIS K5600-5-4.
The present invention will be described in detail below.
In general, a liquid crystal display element is manufactured by cutting a panel from mother glass, but in the case of manufacturing a liquid crystal display element of narrow frame design in which the width of a frame portion around a liquid crystal display unit is 2mm or less, there is a problem that cracks or breaks are likely to occur in a substrate particularly in a step of cutting the panel. Fig. 1(a) is a schematic diagram showing a panel cut-off position of a conventional liquid crystal display element not designed with a narrow frame, and fig. 1(b) is a schematic diagram showing a panel cut-off position of a liquid crystal display element not designed with a narrow frame. As shown in fig. 1(a), in the conventional liquid crystal display device which is not designed to have a narrow frame, since drawing positions of the sealant are spaced apart from each other at a constant interval, a cut-off position of the panel is not located on the cured product of the sealant. On the other hand, as shown in fig. 1(b), in the liquid crystal display element of narrow frame design, the drawing positions of the sealant are in contact with each other between the adjacent panels, and the panel cutting position is on the cured product of the sealant. The inventor considers that: the reason why the substrate is likely to crack or break when the panel is cut in the liquid crystal display device having a narrow frame design is that the cured product of the sealant at the cut position of the panel is too hard. Therefore, the present inventors have conducted intensive studies and, as a result, have found that: the present inventors have found that, by using a sealant in which a cured product of the sealant has a pencil hardness of 3H or less, a substrate is less likely to crack or break even in a liquid crystal display element designed to have a narrow frame, and have completed the present invention.
The cured product of the sealant for a liquid crystal display element of the present invention has a pencil hardness of 3H or less in accordance with JIS K5600-5-4. By setting the pencil hardness of the cured product to 3H or less, the substrate is less likely to crack or break even in a liquid crystal display element designed with a narrow frame.
In addition, from the viewpoint of moisture permeability resistance, etc., the pencil hardness of the cured product is preferably 3B or more.
In the present specification, the pencil hardness of "3H or less" means a hardness of 3H or softer than 3H, and the pencil hardness of "3B or more" means a hardness of 3B or harder than 3B.
The cured product for measuring the pencil hardness can be obtained by: the sealant for liquid crystal display element was irradiated for 30 seconds with 100mW/cm2After the UV ray (wavelength: 365nm), the mixture was heated at 120 ℃ for 1 hour. The cured product means a sealant for bonding and sealing substrates and the like in a liquid crystal display deviceAnd (4) melting the mixture.
The sealant for a liquid crystal display element of the present invention contains a curable resin, and further contains a polymerization initiator and/or a thermal curing agent.
The sealant for a liquid crystal display element of the present invention is prepared by setting the pencil hardness of a cured product to 3H or less, and includes: a method of using a polymerizable compound having a flexible skeleton as the curable resin, a method of blending a polymer having flexibility and flexible particles in a sealant, and the like. 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, an epoxy compound having a flexible skeleton, and the like. The curable resin preferably contains the (meth) acrylic compound having a flexible skeleton and/or the epoxy compound having a flexible skeleton.
In the present specification, the "(meth) acrylic" refers to an acrylic or methacrylic, the "(meth) acrylic compound" refers to a compound having a (meth) acryloyl group, and the "(meth) acryloyl group" refers to an acryloyl group or a methacryloyl 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 an alkylene oxide-modified (meth) acrylic compound, a caprolactone-modified (meth) acrylic compound, and the like.
Examples of commercially available products of the long-chain (meth) acrylic compound include a long-chain (meth) acrylic compound manufactured by Kyoeisha chemical company, a long-chain (meth) acrylic compound manufactured by Nagase ChemteX Corporation, a long-chain (meth) acrylic compound manufactured by Toya Synthesis Co., Ltd., a long-chain (meth) acrylic compound manufactured by Xinzhou chemical industry Co., Ltd., a long-chain (meth) acrylic compound manufactured by Daicel-Allnex Corporation, and the like.
Examples of the long-chain (meth) acrylic compound manufactured by Kyoeisha chemical company include EpoxyEster 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, and DM-851.
Examples of the long-chain (meth) acrylic compound manufactured by east Asia Synthesis Co., Ltd include M-327 and the like.
Examples of the long-chain (meth) acrylic compound manufactured by Nippon Komura chemical industries include A-9300-1CL and A-GLY-9E, A-GLY-20E.
Examples of the long-chain (meth) acrylic compound manufactured by Daicel-Allnex Corporation include EBECRYL 3708.
Examples of the (meth) acrylic compound having a rubber structure include (meth) acrylic-modified butadiene rubber and (meth) acrylic-modified isoprene rubber.
Examples of commercially available products of the above-mentioned (meth) acrylic compound having a rubber structure include (meth) acrylic compounds having a rubber structure manufactured by kojida, japan, and (meth) acrylic compounds having a rubber structure manufactured by korea.
Examples of the (meth) acrylic compound having a rubber structure manufactured by Nissan corporation include NISSO-TE.
Examples of the (meth) acrylic compound having a rubber structure manufactured by the above-mentioned Coly company include UC-102 and UC-203.
Examples of the urethane-modified (meth) acrylic compound include aliphatic urethane (meth) acrylate and aromatic urethane (meth) acrylate.
Commercially available products of the urethane-modified (meth) acrylic compound include, for example, urethane-modified (meth) acrylic compounds manufactured by Daicel-Allnex Corporation, urethane-modified (meth) acrylic compounds manufactured by Daichuan chemical industry, and the like.
Examples of the urethane-modified (meth) acrylic compound manufactured by Daicel-Allnex Corporation include EBECRYL 230, EBECRYL 4491, and EBECRYL 210.
Examples of the urethane-modified (meth) acrylic compound manufactured by seikagawa chemical industry include 551B.
Examples of the urethane-modified (meth) acrylic compound manufactured by Kokusho chemical industries include UN-350 and UN-1255.
Among these, the (meth) acrylic compound having a flexible skeleton is preferably a long-chain (meth) acrylic compound, more preferably an alkylene oxide-modified (meth) acrylic compound, still more preferably an alkylene oxide-modified epoxy (meth) acrylate, particularly preferably an epoxy (meth) acrylate having a polypropylene glycol skeleton, and most preferably an acrylic acid adduct of tripropylene glycol diglycidyl ether, from the viewpoint of the ease with which the pencil hardness of a cured product can be adjusted.
In the present specification, the "(meth) acrylate" means an acrylate or a methacrylate, and the "epoxy (meth) acrylate" means a compound obtained by reacting all epoxy groups in an epoxy compound with (meth) acrylic acid.
Examples of the epoxy compound having a flexible skeleton include long-chain epoxy compounds, epoxy compounds having a rubber structure, and the like.
Examples of the long-chain epoxy compound include alkylene oxide-modified epoxy resins, alkylene modified epoxy resins, and the like.
Examples of commercially available products of the long-chain epoxy compound include long-chain epoxy compounds manufactured by Kyoeisha chemical Co., Ltd, long-chain epoxy compounds manufactured by DIC Co., Ltd, long-chain epoxy compounds manufactured by Daicel-Allnex Corporation, long-chain epoxy compounds manufactured by Sanyo chemical Co., Ltd, long-chain epoxy compounds manufactured by Nissan chemical Co., Ltd, long-chain epoxy compounds manufactured by ADEKA Co., Ltd, and long-chain epoxy compounds manufactured by Mitsubishi chemical Co., Ltd.
Examples of the above-mentioned long chain epoxy compound manufactured by Kyoeisha chemical company include Eplight 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 and EPICLONEXA-4850.
Examples of the long chain epoxy compound manufactured by Daicel-Allnex Corporation include Celoxide 2081 and Epolead GT-401.
Examples of the above-mentioned long chain epoxy compound manufactured by Sanhe Kagaku K.K. include ケミサイザ series.
Examples of the long chain epoxy compound manufactured by Nippon chemical Co., Ltd include Sansocizer E-2000H and the like.
Examples of the long chain epoxy compound manufactured by the ADEKA company 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 company include YL-7410, YL-7175-500, YL-7175-1000, jER 871 and jER 872.
Examples of the epoxy compound having a rubber structure include a butadiene-modified epoxy resin, a polybutadiene-acrylonitrile (CTBN) modified epoxy resin having a carboxyl group at a terminal thereof, and an epoxy-containing acrylic rubber.
Among the epoxy compounds having a flexible skeleton, examples of other epoxy compounds having a flexible skeleton include urethane-modified epoxy compounds, rubber particle-dispersed epoxy compounds, and the like.
Examples of commercially available products of the other epoxy compounds having a flexible skeleton include other epoxy compounds having a flexible skeleton manufactured by ADEKA corporation, other epoxy compounds having a flexible skeleton manufactured by japan catalyst corporation, and other epoxy compounds having a flexible skeleton manufactured by asahi chemical corporation.
Examples of the epoxy compound having a flexible skeleton manufactured by the ADEKA company include EPU-7N.
Examples of the epoxy compound having a flexible skeleton manufactured by the above japanese catalyst company include acryst BP series and the like.
Examples of the epoxy compound having a flexible skeleton manufactured by Asahi Kasei corporation include AER 9000.
Examples of commercially available products of polymerizable compounds having a flexible skeleton other than the (meth) acrylic compound having a flexible skeleton and the epoxy compound having a flexible skeleton include other polymerizable compounds having a flexible skeleton manufactured by barns industries, other polymerizable compounds having a flexible skeleton manufactured by shinning industries, other polymerizable compounds having a flexible skeleton manufactured by Kaneka Corporation, other polymerizable compounds having a flexible skeleton manufactured by east asia synthesis, other polymerizable compounds having a flexible skeleton manufactured by seikagaku Corporation, and other polymerizable compounds having a flexible skeleton manufactured by shin-behind chemical industries.
Examples of other polymerizable compounds having a flexible skeleton manufactured by the above-mentioned barns industries include Ricon 130MA8 and the like.
Examples of the other polymerizable compounds having a flexible skeleton manufactured by the aforementioned prosperous company include Poly bd.
Examples of the other polymerizable compounds having a flexible skeleton manufactured by Kaneka Corporation include epon series and the like.
Examples of the other polymerizable compounds having a flexible skeleton manufactured by Toyo Synthesis Co., Ltd include Arufon US-6000 and Macro Monomer series.
Examples of other polymerizable compounds having a flexible skeleton manufactured by the above-mentioned seikagaku corporation include the Actflow series.
Examples of other polymerizable compounds having a flexible skeleton manufactured by shin-Etsu chemical industries include modified silicone oil and the like.
The polymerizable compounds having a flexible skeleton may be used alone, or 2 or more kinds thereof may be used in combination.
The lower limit of the content of the polymerizable compound having a flexible skeleton in 100 parts by weight of the curable resin is preferably 20 parts by weight. When the content of the polymerizable compound having a flexible skeleton is in this range, the pencil hardness of the cured product of the obtained sealant for a liquid crystal display element can be easily set to 3H or less. The lower limit of the content of the polymerizable compound having a flexible skeleton is more preferably 30 parts by weight, and still more preferably 60 parts by weight.
In addition, from the viewpoint of moisture permeability resistance and the like, the preferable upper limit of the content of the polymerizable compound having a flexible skeleton in 100 parts by weight of the curable resin is 80 parts by weight.
For the purpose of improving the adhesiveness, reducing liquid crystal contamination, and the like of the obtained sealant for a liquid crystal display element, it is preferable that the curable resin contains a curable resin other than the polymerizable compound having a flexible skeleton. As the other curable resin, an epoxy compound other than the epoxy compound having a flexible skeleton, or a (meth) acrylic compound other than the (meth) acrylic compound having a flexible skeleton can be suitably used.
Examples of the other epoxy compound include bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, 2' -diallylbisphenol a type epoxy resin, hydrogenated bisphenol type epoxy resin, propylene oxide adduct bisphenol a type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, o-cresol novolac type epoxy resin, dicyclopentadiene novolac type epoxy resin, biphenol novolac type epoxy resin, naphthol novolac type epoxy resin, glycidyl amine type epoxy resin, alkyl polyhydric alcohol type epoxy resin, glycidyl ester compound, and the like.
The curable resin may contain, as the other epoxy compound, a compound having an epoxy group and a (meth) acryloyl group in 1 molecule. Examples of such a compound include a partially (meth) acrylic-modified epoxy resin obtained by reacting a part of epoxy groups of an epoxy compound having 2 or more epoxy groups in 1 molecule and having no flexible skeleton with (meth) acrylic acid.
Examples of the other (meth) acrylic compounds include epoxy (meth) acrylates obtained by reacting (meth) acrylic acid with epoxy compounds having no flexible skeleton, and (meth) acrylate compounds obtained by reacting (meth) acrylic acid with compounds having hydroxyl groups and having no flexible skeleton. Among them, epoxy (meth) acrylates are preferred. In addition, from the viewpoint of high reactivity, the other (meth) acrylic compound preferably has 2 or more (meth) acryloyl groups in the molecule.
Examples of the epoxy (meth) acrylate which is the other (meth) acrylic compound include those obtained by reacting an epoxy compound having no flexible skeleton with (meth) acrylic acid by a conventional method in the presence of a basic catalyst.
Examples of the epoxy compound having no flexible skeleton, which is a raw material for synthesizing the epoxy (meth) acrylate, include the same epoxy compounds as the other epoxy compounds.
The other curable resins may be used alone or in combination of 2 or more.
Examples of the polymer having flexibility include (meth) acrylic polymers.
As a commercially available product of the above-mentioned polymer having flexibility, for example, Arufon UG-4000 (manufactured by Toyo Seisaku-Sho Co., Ltd.) is exemplified.
The above-mentioned polymers having flexibility may be used alone, or 2 or more thereof may be used in combination.
The preferable lower limit of the content of the flexible polymer in 100 parts by weight of the entire sealant for a liquid crystal display element of the present invention is 5 parts by weight. When the content of the polymer having flexibility is in this range, the pencil hardness of the cured product of the obtained sealant for a liquid crystal display element can be easily set 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 soft particles include rubber particles and polyurethane particles.
The soft 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 fluororubber particles.
Examples of commercially available products of the rubber particles include rubber particles manufactured by Kaneka Corporation, rubber particles manufactured by ZEON Corporation, rubber particles manufactured by アイカ chemical , and rubber particles manufactured by Toray Finechem co.
Examples of the rubber particles manufactured by the Kaneka Corporation include Kane Ace B series and Kaneace FM series.
Examples of the rubber particles manufactured by the ZEON Corporation include Nipol series.
Examples of the rubber particles manufactured by アイカ chemical include ゼフィアツク F351 and the like.
Examples of the rubber particles produced by Toray Finechem Co., Ltd. include Thiokol LP-282.
Examples of commercially available products of the polyurethane particles include polyurethane particles manufactured by chemical industries, and polyurethane particles manufactured by DAHI chemical industries.
Examples of the polyurethane particles manufactured by the above-mentioned chemical industry company include Art Pearl and the like. Examples of the polyurethane particles manufactured by DAHI industries include Dimic beads and the like.
The soft particles may be used alone, or 2 or more kinds may be used in combination.
The preferable lower limit of the content of the soft particles in 100 parts by weight of the sealant for a liquid crystal display element of the present invention is 20 parts by weight. When the content of the soft particles is in this range, the pencil hardness of the cured product of the obtained sealant for a liquid crystal display element can be easily set to 3H or less. A more preferable lower limit of the content of the soft particles is 30 parts by weight.
When the polymerizable compound having a flexible skeleton and the soft particles are used in combination, the lower limit of the content of the soft particles is preferably 10 parts by weight based on 100 parts by weight of the curable resin. When the content of the soft particles is in this range, the pencil hardness of the cured product of the obtained sealant for a liquid crystal display element can be easily set to 3H or less. When the polymerizable compound having a flexible skeleton and the flexible particles are used in combination, the more preferable lower limit of the content of the flexible particles is 15 parts by weight.
The sealant for a liquid crystal display element of the present invention contains a polymerization initiator and/or a thermal curing agent.
The sealant for a liquid crystal display element of the present invention preferably contains a photo radical polymerization initiator and a thermal curing agent.
Examples of the photo radical polymerization initiator include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, and thioxanthone compounds.
Examples of commercially available products of the photo radical polymerization initiator include a photo radical polymerization initiator manufactured by BASF corporation, a photo radical polymerization initiator manufactured by tokyo chemical industry corporation, and the like.
Examples of the photoradical polymerization initiator manufactured by BASF include IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE2959, IRGACURE OXE01, and Lucirin TPO.
Examples of the photo radical polymerization initiator manufactured by tokyo chemical industry include benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.
The sealant for a liquid crystal display element of the present invention may use a thermal radical polymerization initiator as the polymerization initiator.
Examples of the thermal radical polymerization initiator include initiators formed from azo compounds, organic peroxides, and the like. Among them, a polymeric azo initiator formed from a polymeric azo compound is preferable.
In the present specification, the macromolecular azo compound refers to a compound having an azo group, which generates a radical capable of curing a (meth) acryloyloxy group by heat, and has a number average molecular weight of 300 or more.
The number average molecular weight of the macromolecular azo compound preferably has a lower limit of 1000 and an upper limit of 30 ten thousand. When the number average molecular weight of the macromolecular azo compound is in the above range, adverse effects on the liquid crystal can be prevented, and the compound can be easily mixed with the curable resin. The number average molecular weight of the macromolecular azo compound is preferably 5000 as a lower limit, more preferably 10 ten thousand as an upper limit, still more preferably 1 ten thousand as a lower limit, and still more preferably 9 ten thousand as an upper limit.
In the present specification, the number average molecular weight is a value determined by Gel Permeation Chromatography (GPC) using tetrahydrofuran as a solvent and converted to polystyrene. 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 K.K.).
Examples of the macromolecular azo compound include compounds 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 polyalkylene oxide units and the like are bonded to each other via an azo group is preferably a compound having a polyethylene oxide structure.
Specific examples of the macromolecular azo compound include a polycondensate of 4, 4 '-azobis (4-cyanovaleric acid) and a polyalkylene glycol, and a polycondensate of 4, 4' -azobis (4-cyanovaleric acid) and a polydimethylsiloxane having a terminal amino group.
Examples of commercially available products of the polymer azo compounds include VPE-0201, VPE-0401, VPE-0601, VPS-0501 and VPS-1001 (all manufactured by Wako pure chemical industries, Ltd.).
Further, examples of commercially available azo compounds which are not polymers include V-65 and V-501 (both manufactured by Wako pure chemical industries, Ltd.).
Examples of the organic peroxide include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, peroxyesters, diacylperoxides, and peroxydicarbonates.
The polymerization initiators may be used alone or in combination of 2 or more.
The lower limit of the content of the polymerization initiator is preferably 0.1 part by weight and the upper limit is preferably 30 parts by weight with respect to 100 parts by weight of the curable resin. By setting the content of the polymerization initiator to 0.1 parts by weight or more, the obtained sealant for a liquid crystal display element is more excellent in curability. By setting the content of the polymerization initiator to 30 parts by weight or less, the storage stability of the obtained sealant for a liquid crystal display element is further improved. The lower limit of the content of the polymerization initiator is more preferably 1 part by weight, the upper limit is more preferably 10 parts by weight, and the upper limit is further preferably 5 parts by weight.
The thermosetting agent is preferably an imidazole thermosetting agent.
Examples of the imidazole-based heat-curing agent include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitic acid, 2, 4-diamino-6- (2 '-methylimidazolyl- (1')) -ethyl-s-triazine, and 2, 4-diamino-6- (2 '-methylimidazolyl- (1')) -ethyl-s-triazine isocyanuric acid adduct.
Further, as the imidazole-based heat curing agent, a combination type curing agent may be used. By using the above-mentioned addition type curing agent, excessive thickening of the sealant can be suppressed.
Examples of the above-mentioned addition type curing agent include an adduct obtained by a reaction of an imidazole compound with an epoxy compound or the like.
Examples of commercially available products of the addition-type curing agent include addition-type curing agents manufactured by Aomoto Fine science and technology, addition-type curing agents manufactured by Sizhou chemical industries, and addition-type curing agents manufactured by Mitsubishi chemical corporation.
Examples of the addition-type curing agent manufactured by the aforementioned Shinylorine Fine science and technology company include Amicure PN-23, Amicure PN-23J, Amicure PN-H, Amicure PN-31J, Amicure PN-40J, Amicure PN-50, Amicure PN-F, Amicure MY-24, and Amicure MY-H.
Examples of the addition type curing agent manufactured by the above four national chemical industry Co., Ltd include P-0505 and the like.
Examples of the addition type curing agent manufactured by Mitsubishi chemical company include P-200.
As the heat curing agent, a heat curing agent other than the imidazole heat curing agent may be used.
Examples of the other thermal curing agent include organic acid hydrazides, amine compounds, polyphenol compounds, and acid anhydrides. Among them, organic acid hydrazide is preferably used.
Examples of the organic acid hydrazide include sebacic dihydrazide, isophthalic dihydrazide, adipic dihydrazide, malonic dihydrazide, and the like.
Examples of commercially available products of the organic acid hydrazide include an organic acid hydrazide available from Otsuka chemical company, an organic acid hydrazide available from Aomoto optical science company, and the like.
Examples of the organic acid hydrazide available from Otsuka chemical company include SDH and ADH.
Examples of the organic acid hydrazide manufactured by the aforementioned Aomoto essence Fine science and technology company include Amicure VDH, Amicure VDH-J, Amicure UDH, and Amicure UDH-J.
The thermosetting agent may be used alone, or 2 or more of them may be used in combination.
The lower limit of the content of the thermosetting agent is preferably 1 part by weight and the upper limit is preferably 50 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the thermosetting agent is in this range, the thermosetting property can be further improved without deteriorating the coating property and the like of the obtained sealant for a liquid crystal display element. A more preferable upper limit of the content of the thermosetting agent is 30 parts by weight.
The sealant for a liquid crystal display element of the present invention preferably contains an inorganic filler for the purpose of improving viscosity, further improving adhesiveness by a stress dispersion effect, improving a linear expansion coefficient, improving moisture resistance of a cured product, and the like.
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, titanium oxide, calcium carbonate, magnesium hydroxide, aluminum nitride, silicon nitride, barium sulfate, calcium silicate, and the like.
The preferable lower limit of the content of the inorganic filler is 15 parts by weight with respect to 100 parts by weight of the curable resin. By setting the content of the inorganic filler to 15 parts by weight or more, the thermal shock resistance when the environmental change at low temperature and high temperature is repeated is excellent. A more preferable lower limit of the content of the inorganic filler is 25 parts by weight.
From the viewpoint of coatability and the like, the content of the inorganic filler is preferably 60 parts by weight per 100 parts by weight of the curable resin.
The sealant for a liquid crystal display element of the present invention preferably contains an ion scavenger.
The ion scavenger has a function of suppressing the occurrence of liquid crystal contamination by trapping water-soluble ions in the sealant for a liquid crystal display element.
Examples of the ion scavenger include a cation scavenger for trapping cations, an anion scavenger for trapping anions, and a zwitterion scavenger for trapping cations and anions, and from the viewpoint of further improving the effect of suppressing the occurrence of liquid crystal contamination, a cation scavenger, a zwitterion scavenger, which are cations, are preferable, and a cation scavenger is more preferable.
Examples of the ion scavenger include zirconium compounds, antimony compounds, bismuth compounds, magnesium compounds, and aluminum compounds. Among these, a zirconium compound or an antimony compound having a cation capturing effect is preferable, and a zirconium compound is more preferable, because the effect of suppressing the occurrence of liquid crystal contamination is more excellent.
Examples of commercially available products of the above-mentioned zirconium-based compounds include IXE-100 (manufactured by Toyo Seisaku-sho Co., Ltd.).
Examples of commercially available antimony compounds include antimony compounds manufactured by Wako pure chemical industries, and antimony compounds manufactured by Toyata industries.
Examples of the antimony compound manufactured by Wako pure chemical industries include antimony pentoxide and the like.
Examples of the antimony-based compound manufactured by Toyo Synthesis Co., Ltd include IXE-300, IXE-600, and IXE-633.
Examples of commercially available products of the bismuth-based compounds include IXE-500, IXE-530 and IXE-550 (all manufactured by Toyo Seisaku-sho Co., Ltd.).
Examples of commercially available magnesium compounds include IXE-700F (manufactured by Toyo Seisaku-sho Co., Ltd.).
The ion scavenger may be used alone or in combination of 2 or more.
The lower limit of the content of the ion scavenger is preferably 2 parts by weight, and the upper limit is preferably 30 parts by weight, in 100 parts by weight of the sealant for a liquid crystal display element of the present invention. When the content of the ion scavenger is within this range, the effect of suppressing the occurrence of liquid crystal contamination is further excellent without deteriorating coatability and the like. The lower limit of the content of the ion scavenger is more preferably 5 parts by weight, and the upper limit is more preferably 20 parts by weight.
For the purpose of further improving the adhesiveness, the sealant for a liquid crystal display element of the present invention preferably contains a silane coupling agent. The silane coupling agent mainly functions as an adhesion aid for satisfactorily adhering the sealant to a substrate or the like.
As the silane coupling agent, for example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane and the like are suitably used.
The silane coupling agents may be used alone, or 2 or more of them may be used in combination.
The content of the silane coupling agent in 100 parts by weight of the sealant for a liquid crystal display element of the present invention preferably has a lower limit of 0.1 part by weight and an upper limit of 20 parts by weight. When the content of the silane coupling agent is within this range, the effects of suppressing the occurrence of liquid crystal contamination and improving the adhesion can be further exhibited. A more preferable lower limit of the content of the silane coupling agent is 0.5 parts by weight, and a more preferable upper limit is 10 parts by weight.
The sealant for a liquid crystal display element of the present invention may contain a light-shading agent. By containing the light-shading agent, the sealant for a liquid crystal display element of the present invention can be suitably used as a light-shielding sealant.
Examples of the light-shading agent include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. Among them, titanium black is preferable.
The titanium black is a substance having a higher transmittance for light in the vicinity of the ultraviolet region, particularly for light having a wavelength of 370nm or more and 450nm or less, than the average transmittance for light having a wavelength of 300nm or more and 800nm or less. That is, the titanium black is a light-shading agent having the following properties: the sealant for a liquid crystal display element of the present invention is provided with light-shielding properties by sufficiently shielding light having a wavelength in the visible light region, while transmitting light having a wavelength in the vicinity of the ultraviolet region. The light-shading agent contained in the sealant for a liquid crystal display element of the present invention is preferably a high-insulating material, and titanium black is also suitable as a high-insulating light-shading agent.
The above titanium black exhibits a sufficient effect without being surface-treated, and a surface-treated titanium black such as a titanium black surface-treated with an organic component such as a coupling agent, or a titanium black surface-treated with an inorganic component such as silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide, or magnesium oxide may be used. Among them, titanium black treated with an organic component is preferable in that the insulating property can be further improved.
Further, since the liquid crystal display element produced using the sealant for a liquid crystal display element of the present invention containing the titanium black as a light-shielding agent has sufficient light-shielding properties, a liquid crystal display element having high contrast without light leakage and having excellent image display quality can be realized.
Examples of commercially available products of the titanium black include titanium black manufactured by mitsubishi integrated materials corporation, titanium black manufactured by gibberella chemical corporation, and the like.
Examples of the titanium black manufactured by Mitsubishi Integrated materials include 12S, 13M-C, 13R-N and 14M-C.
Examples of the titanium black manufactured by red spike formation company include Tilack D.
The lower limit of the specific surface area of the titanium black is preferably 13m2A preferred upper limit of 30m2A more preferred lower limit is 15m2A more preferable upper limit of 25m2/g。
The volume resistance of the titanium black is preferably 0.5 Ω · cm at the lower limit and 3 Ω · cm at the upper limit, more preferably 1 Ω · cm at the lower limit and 2.5 Ω · cm at the upper limit.
The primary particle size of the light-shading agent is not particularly limited as long as it is not more than the distance between the substrates of the liquid crystal display element, and a preferable lower limit is 1nm and a preferable upper limit is 5 μm. By setting the primary particle size of the light-shading agent to the above range, the coatability can be further improved without significantly increasing the viscosity and thixotropy of the obtained sealant for a liquid crystal display element. The lower limit of the primary particle diameter of the light-shading agent is more preferably 5nm, the upper limit is more preferably 200nm, the lower limit is more preferably 10nm, and the upper limit is more preferably 100 nm.
The primary particle size of the light-shading agent can be measured using a particle size distribution meter (for example, "NICOMP 380 ZLS" manufactured by paraticlesizing SYSTEMS).
The preferable lower limit of the content of the light-shading agent in 100 parts by weight of the sealant for a liquid crystal display element of the present invention is 5 parts by weight, and the preferable upper limit is 80 parts by weight. By setting the content of the light-shielding agent within this range, the effect of further improving the light-shielding property can be exerted without significantly reducing the adhesiveness, strength after curing, and drawing property of the obtained sealant for a liquid crystal display element. The content of the light-shading agent is more preferably 10 parts by weight at the lower limit, more preferably 70 parts by weight at the upper limit, still more preferably 30 parts by weight at the lower limit, and still more preferably 60 parts by weight at the upper limit.
The sealant for a liquid crystal display element of the present invention may further contain additives such as a stress relaxation agent, a reactive diluent, a thixotropic agent, a spacer, a curing accelerator, an antifoaming agent, a leveling agent, and a polymerization inhibitor, as required.
Examples of the method for producing the sealant for a liquid crystal display element of the present invention include a method of mixing a curable resin, a polymerization initiator and/or a heat-curing agent, and an inorganic filler, etc., using a mixer such as a homomixer, a universal mixer, a planetary mixer, a kneader, or a 3-roll machine.
The sealant for a liquid crystal display element of the present invention can be blended with conductive fine particles to produce a vertical conduction material. The vertical conduction material comprising the sealant for liquid crystal display element of the present invention and conductive fine particles is also one aspect of the present invention.
As the conductive fine particles, metal balls, fine particles in which a conductive metal layer is formed on the surface of resin fine particles, or the like can be used. Among these, fine particles having a conductive metal layer formed on the surface of the resin fine particles are preferable because the resin fine particles have excellent elasticity and can be electrically connected without damaging the transparent substrate or the like.
A liquid crystal display element produced using the sealant for a liquid crystal display element of the present invention or the vertical conduction material of the present invention is also one aspect of the present invention.
The liquid crystal display element of the present invention is preferably a liquid crystal display element of narrow frame design. Specifically, the width of the frame portion around the liquid crystal display unit is preferably 2mm or less.
The coating width of the sealant for a liquid crystal display element of the present invention when the liquid crystal display element of the present invention is manufactured is preferably 1mm or less.
The sealant for a liquid crystal display element of the present invention can be suitably used for manufacturing a liquid crystal display element by a one drop fill process.
Examples of a method for manufacturing the liquid crystal display element of the present invention by a liquid crystal dropping method include the following methods.
First, the following steps are performed: a step of forming the sealant for a liquid crystal display element of the present invention into a rectangular seal pattern on a substrate by screen printing, dispenser application, or the like. Next, the following steps are performed: and a step of applying a liquid crystal in a dropwise manner onto the entire inner surface of the frame of the transparent substrate in an uncured state of the sealant for a liquid crystal display element of the present invention, and immediately superposing the other substrate thereon. Then, a step of pre-curing the sealant by irradiating a seal pattern portion of the sealant for a liquid crystal display element or the like of the present invention with light such as ultraviolet rays and a step of heating the pre-cured sealant to primarily cure the sealant are performed. By the above method, a liquid crystal display element can be obtained.
A cured product obtained by curing the sealant for a liquid crystal display element of the present invention, that is, a cured product obtained by curing a sealant for a liquid crystal display element which contains a curable resin and further contains a polymerization initiator and/or a thermal curing agent, wherein the pencil hardness of the cured product is 3H or less according to JIS K5600-5-4 is also one aspect of the present invention.
Effects of the invention
According to the present invention, it is possible to provide a sealant for a liquid crystal display element, in which a substrate is less likely to be cracked or broken even in a liquid crystal display element designed to have a narrow frame. Further, according to the present invention, a vertical conduction material and a liquid crystal display element, which are produced using the sealant for a liquid crystal display element, can be provided. Further, the present invention can provide a cured product obtained by curing the sealant for a liquid crystal display element.
Drawings
Fig. 1(a) is a schematic diagram showing a panel cut-off position of a conventional liquid crystal display element not designed with a narrow frame, and fig. 1(b) is a schematic diagram showing a panel cut-off position of a liquid crystal display element designed with a narrow frame.
Detailed Description
The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
Examples 1 to 5 and comparative examples 1 and 2
The respective materials having the compounding ratios described in table 1 were mixed by a planetary mixer (manufactured by Thinky, "あわとり tylan"), and then mixed by a 3-roll mill, thereby preparing the sealants for liquid crystal display elements of examples 1 to 5 and comparative examples 1 and 2. Further, the liquid crystal display elements were produced using the respective sealants for liquid crystal display elements obtained in examples and comparative examples.
Each of the obtained sealants for liquid crystal display elements was irradiated with a metal halide lamp for 30 seconds at a rate of 100mW/cm2After the curing by heating at 120 ℃ for 1 hour, the pencil hardness of the obtained cured product was measured in accordance with JIS K5600-5-4. The results are shown in Table 1.
< evaluation >
The following evaluations were made for the liquid crystal display element sealants obtained in the examples and comparative examples. The results are shown in Table 1.
(stability of panel at cut)
In 100 parts by weight of each of the sealants for liquid crystal display elements obtained in examples and comparative examples, 1 part by weight of spacer particles (Micropearl SI-H050, manufactured by waterlogging chemical industries, Ltd.) was dispersed, and the resultant was coated on one of 2 substrates each having a rubbed alignment film and a transparent electrode by a dispenser so that the line width of the sealant became 0.8 mm.
Then, minute droplets of liquid crystal (JC-5004 LA, manufactured by Chisso corporation) were applied dropwise to the entire surface of the sealant of the substrate with a transparent electrode, and another substrate with a transparent electrode was bonded immediately. At this time, as shown in fig. 1(b), a pattern is formed on the substrate so that drawing positions of the adjacent sealing agent are in contact with each other between the cells. The sealant portion was irradiated with a metal halide lamp for 30 seconds at 100mW/cm2After the ultraviolet light, the sealant was cured by heating at 120 ℃ for 1 hour, and a total of 100 liquid crystal display elements were produced by making cuts using a scriber so that the cured product of the sealant became cut positions.
The cut substrates of the liquid crystal display elements were checked, and the panel cut stability was evaluated by marking "o" as the case where no cracks or fractures were observed in the substrates in all of the liquid crystal display elements, marking "Δ" as the case where cracks or fractures were observed in the substrates in 1 or more and less than 5 liquid crystal display elements, and marking "x" as the case where cracks or fractures were observed in the substrates in 5 or more liquid crystal display elements.
(thermal shock resistance)
60 liquid crystal display elements obtained in the above "(panel cut stability)" were subjected to a 1000-cycle cold-heat cycle test using a cold-heat cycle tester, holding at-30 ℃ and then raising the temperature to 85 ℃, holding at 85 ℃ and then lowering the temperature to-30 ℃, with the above procedure set to 1 cycle.
After the test, the heat shock resistance was evaluated by designating the case where no liquid crystal leakage was observed in all the liquid crystal display elements as "excellent", the case where liquid crystal leakage was observed in 1 or 2 liquid crystal display elements as "o", the case where liquid crystal leakage was observed in 3 or 4 liquid crystal display elements as "Δ", and the case where liquid crystal leakage was observed in 5 or more liquid crystal display elements as "x".
[ Table 1]
Figure BDA0001887309990000201
Industrial applicability
According to the present invention, it is possible to provide a sealant for a liquid crystal display element, which is less likely to cause cracking or breaking of a substrate even in a liquid crystal display element designed with a narrow frame. Further, according to the present invention, a vertical conduction material and a liquid crystal display element, which are produced using the sealant for a liquid crystal display element, can be provided. Further, the present invention can provide a cured product obtained by curing the sealant for a liquid crystal display element.
Description of the symbols
1 mother glass
2 cured product of sealing agent
3 panel cutting position

Claims (5)

1. A sealing agent for a liquid crystal display element, characterized by comprising a curable resin, a photo radical polymerization initiator and a thermal curing agent,
the cured product of the sealant for the liquid crystal display element has a pencil hardness of 3H or less according to JIS K5600-5-4.
2. The sealant for a liquid crystal display element 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.
3. The sealant for a liquid crystal display element according to claim 1 or 2, which contains an inorganic filler, and the inorganic filler is contained in an amount of 15 parts by weight or more and 60 parts by weight or less based on 100 parts by weight of the curable resin.
4. A vertically conducting material comprising the sealant for liquid crystal display element according to claim 1, 2 or 3 and conductive fine particles.
5. A liquid crystal display element using the sealant for a liquid crystal display element according to claim 1, 2 or 3 or the vertically conducting material according to claim 4.
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