CN110325904B - Sealing agent for liquid crystal display element, vertical conduction material, and liquid crystal display element - Google Patents

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

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CN110325904B
CN110325904B CN201880014052.0A CN201880014052A CN110325904B CN 110325904 B CN110325904 B CN 110325904B CN 201880014052 A CN201880014052 A CN 201880014052A CN 110325904 B CN110325904 B CN 110325904B
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acrylate
liquid crystal
weight
crystal display
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CN110325904A (en
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松井庆枝
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
    • C08G59/1461—Unsaturated monoacids
    • C08G59/1466—Acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • 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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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Nonlinear Science (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Optics & Photonics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Emergency Medicine (AREA)
  • General Chemical & Material Sciences (AREA)
  • Liquid Crystal (AREA)
  • Sealing Material Composition (AREA)
  • Epoxy Resins (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)

Abstract

The purpose of the present invention is to provide a sealing agent for a liquid crystal display element, which has excellent coatability, curability, and low liquid crystal contamination. 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. The present invention is a sealant for a liquid crystal display element, which contains a curable resin and a polymerization initiator, wherein the curable resin contains a partially (meth) acrylic-modified novolac epoxy resin (a), a partially (meth) acrylic-modified non-novolac epoxy resin (B), and a non-novolac epoxy (meth) acrylate (C), the content of the partially (meth) acrylic-modified novolac epoxy resin (a) is 3 parts by weight or more and 9 parts by weight or less in 100 parts by weight of the curable resin, the content of the partially (meth) acrylic-modified non-novolac epoxy resin (B) is 25 parts by weight or less in 100 parts by weight of the curable resin, the ratio of the partially (meth) acrylic-modified non-novolac epoxy resin (B) to the partially (meth) acrylic-modified novolac epoxy resin (a) is 1 or more, the content of the non-novolac epoxy (meth) acrylate (C) is 10 parts by weight or more and 45 parts by weight or less in 100 parts by weight of the curable resin, and the weight average molecular weight of the partially (meth) acrylic-modified novolac epoxy resin (a) is 700 or more and 2000 or less.

Description

Sealing agent for liquid crystal display element, vertical conduction material, and liquid crystal display element
Technical Field
The present invention relates to a sealant for a liquid crystal display element, which is excellent in coatability, curability, and low liquid crystal contamination. 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.
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 process using a photo-thermal curable sealant has been used as disclosed in patent documents 1 and 2 from the viewpoint of shortening the tact time and optimizing the amount of liquid crystal used.
In the one drop fill process, first, a rectangular seal pattern is formed on one of two electrode-carrying substrates by dispensing. Next, in a state where the sealant is not cured, droplets of liquid crystal are dropped into a sealing frame of the substrate, another substrate is stacked under vacuum, and the sealing portion is irradiated with light such as ultraviolet rays to perform precuring. Thereafter, the resultant was subjected to main curing by heating to produce a liquid crystal display element. This one drop fill process is currently the mainstream of a method for manufacturing a liquid crystal display element.
However, in the modern day in which various mobile devices with liquid crystal panels such as mobile phones and portable game machines are increasingly widespread, miniaturization of the devices is the most demanding issue. As a method for downsizing, narrowing of the liquid crystal display portion can be mentioned, and for example, an operation of disposing the position of the sealing portion under the black matrix (hereinafter, also referred to as narrow frame design) is performed.
With such a narrow bezel design, the distance from the pixel region to the sealant becomes shorter in the liquid crystal display element, and there is a problem that display unevenness is likely to occur due to contamination of the liquid crystal by the sealant.
Documents of the prior art
Patent literature
Patent document 1: japanese patent laid-open No. 2001-133794
Patent document 2: international publication No. 02/092718
Disclosure of Invention
Problems to be solved by the invention
The purpose of the present invention is to provide a sealing agent for a liquid crystal display element, which has excellent coatability, curability, and low liquid crystal contamination. 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.
Means for solving the problems
The present invention is a sealant for a liquid crystal display element, which contains a curable resin and a polymerization initiator, wherein the curable resin contains a partially (meth) acrylic-modified novolac epoxy resin (a), a partially (meth) acrylic-modified non-novolac epoxy resin (B), and a non-novolac epoxy (meth) acrylate (C), the content of the partially (meth) acrylic-modified novolac epoxy resin (a) is 3 parts by weight or more and 9 parts by weight or less in 100 parts by weight of the curable resin, the content of the partially (meth) acrylic-modified non-novolac epoxy resin (B) is 25 parts by weight or less in 100 parts by weight of the curable resin, the ratio of the partially (meth) acrylic-modified non-novolac epoxy resin (B) to the partially (meth) acrylic-modified novolac epoxy resin (a) is 1 or more, the content of the non-novolac epoxy (meth) acrylate (C) is 10 parts by weight or more and 45 parts by weight or less in 100 parts by weight of the curable resin, and the weight average molecular weight of the partially (meth) acrylic-modified novolac epoxy resin (a) is 700 or more and 2000 or less.
The present invention is described in detail below.
The present inventors have studied using a partially (meth) acrylic-modified epoxy resin having a relatively high molecular weight as a curable resin in order to improve low liquid crystal contamination of a sealing agent for a liquid crystal display element. However, when such a curable resin is used, the resulting sealant for a liquid crystal display element may have poor coatability and curability. Thus, the present inventors have studied to use a combination of a partially (meth) acrylic acid-modified novolak-type epoxy resin, a partially (meth) acrylic acid-modified non-novolak-type epoxy resin, and a non-novolak-type epoxy (meth) acrylate in such a manner that the respective contents are in specific proportions. As a result, they found that: the present inventors have completed the present invention by obtaining a sealant for a liquid crystal display element which is excellent in coatability, curability, and low liquid crystal contamination.
The sealant for a liquid crystal display element of the present invention contains a curable resin.
The curable resin contains a part of (meth) acrylic-modified novolac epoxy resin (a) (hereinafter also referred to as "component (a)"), a part of (meth) acrylic-modified non-novolac epoxy resin (B) (hereinafter also referred to as "component (B)"), and a non-novolac epoxy (meth) acrylate (C) (hereinafter also referred to as "component (C)"). By containing the component (a), the component (B), and the component (C) in such a manner that the content ratios thereof fall within the ranges described below, the sealant for a liquid crystal display element of the present invention is excellent in coatability, curability, and low liquid crystal contamination.
In the present specification, the term "partially (meth) acrylic-modified novolac epoxy resin" means: a resin in which a part of epoxy groups of a novolac epoxy resin are reacted with (meth) acrylic acid to introduce (meth) acryloyl groups.
The above-mentioned "partially (meth) acrylic-modified non-novolac epoxy resin" means: a resin in which a part of epoxy groups other than a novolac type epoxy resin (hereinafter also referred to as a "non-novolac type epoxy resin") are reacted with (meth) acrylic acid to introduce a (meth) acryloyl group.
The above-mentioned "non-novolac type epoxy (meth) acrylate" means: a non-novolac epoxy resin in which all epoxy groups are reacted with (meth) acrylic acid to introduce (meth) acryloyl groups.
The above "(meth) acrylic" means acrylic or methacrylic, "(meth) acrylate" means acrylate or methacrylate, and "(meth) acryloyl" means acryloyl or methacryloyl.
Since the component (a) is a phenol type, the viscosity increases slowly even if the molecular weight is increased to a high level from the viewpoint of low liquid crystal contamination, and the coatability is not easily deteriorated.
The lower limit of the weight average molecular weight of the component (A) is 700 and the upper limit thereof is 2000. When the weight average molecular weight of the component (a) is 700 or more, the resultant sealant for a liquid crystal display element is excellent in low liquid crystal contamination. When the weight average molecular weight of the component (a) is 2000 or less, the resulting sealant for a liquid crystal display element has excellent coatability. The lower limit of the weight average molecular weight of the component (a) is preferably 750, the upper limit thereof is preferably 1500, the lower limit thereof is more preferably 800, and the upper limit thereof is more preferably 1200.
In the present specification, the weight average molecular weight is a value obtained by measuring the weight average molecular weight by Gel Permeation Chromatography (GPC) using tetrahydrofuran as a solvent and converting the weight average molecular weight into polystyrene. Examples of the column for measuring the weight average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko K.K.).
Examples of the component (a) include partially (meth) acrylic acid-modified phenol novolac type epoxy resins, partially (meth) acrylic acid-modified o-cresol novolac type epoxy resins, partially (meth) acrylic acid-modified dicyclopentadiene novolac type epoxy resins, partially (meth) acrylic acid-modified diphenol novolac type epoxy resins, and partially (meth) acrylic acid-modified naphthol novolac type epoxy resins. Among these, a partially (meth) acrylic-modified phenol novolac epoxy resin is preferable.
The component (a) can be obtained in a mixture of the component (a), the novolac epoxy resin, and the novolac epoxy (meth) acrylate by reacting a part of the epoxy groups of the novolac epoxy resin with (meth) acrylic acid in the presence of a basic catalyst according to a conventional method.
In the present specification, the term "novolac-type epoxy (meth) acrylate" refers to: a substance in which all epoxy groups of the novolac epoxy resin are reacted with (meth) acrylic acid to introduce (meth) acryloyl groups.
Examples of the novolac epoxy resin which is a raw material of the component (a) include phenol novolac epoxy resins, o-cresol novolac epoxy resins, dicyclopentadiene novolac epoxy resins, biphenyl novolac epoxy resins, and naphthol novolac epoxy resins.
The lower limit of the content of the component (a) in 100 parts by weight of the curable resin is 3 parts by weight and the upper limit thereof is 9 parts by weight. When the content of the component (a) is 3 parts by weight or more, the obtained sealant for a liquid crystal display element is excellent in low liquid crystal contamination. When the content of the component (a) is 9 parts by weight or less, the obtained sealant for a liquid crystal display element has excellent coatability. The lower limit of the content of the component (a) is preferably 4 parts by weight, the upper limit is preferably 8 parts by weight, and the upper limit is more preferably 7 parts by weight.
Examples of the component (B) include partially (meth) acrylic-modified bisphenol a type epoxy resin, partially (meth) acrylic-modified bisphenol F type epoxy resin, partially (meth) acrylic-modified bisphenol E type epoxy resin, partially (meth) acrylic-modified bisphenol S type epoxy resin, partially (meth) acrylic-modified 2,2' -diallylbisphenol a type epoxy resin, partially (meth) acrylic-modified hydrogenated bisphenol type epoxy resin, partially (meth) acrylic-modified propylene oxide adduct bisphenol a type epoxy resin, partially (meth) acrylic-modified resorcinol type epoxy resin, partially (meth) acrylic-modified biphenyl type epoxy resin, partially (meth) acrylic-modified sulfide type epoxy resin, partially (meth) acrylic-modified diphenyl ether type epoxy resin, partially (meth) acrylic-modified dicyclopentadiene type epoxy resin, partially (meth) acrylic-modified naphthalene type epoxy resin, partially (meth) acrylic-modified glycidyl amine type epoxy resin, partially (meth) acrylic-modified alkyl polyhydric alcohol type epoxy resin, partially (meth) acrylic-modified epoxy resin, and partially (meth) acrylic-modified rubber. Among these, partially (meth) acrylic acid-modified bisphenol a epoxy resins are preferable.
The component (B) can be obtained in a mixture of the component (B), the non-novolac epoxy resin, and the non-novolac epoxy (meth) acrylate by reacting a part of the epoxy groups of the non-novolac epoxy resin with (meth) acrylic acid in the presence of a basic catalyst according to a conventional method.
Examples of the non-phenol type epoxy resin which is a raw material of the component (B) 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-added bisphenol a type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, sulfide type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, glycidylamine type epoxy resin, alkyl polyhydric alcohol type epoxy resin, rubber-modified type epoxy resin and the like.
The upper limit of the content of the component (B) in 100 parts by weight of the curable resin is 25 parts by weight. When the content of the component (B) in 100 parts by weight of the curable resin is 25 parts by weight or less, the obtained sealant for a liquid crystal display element is excellent in low liquid crystal contamination. The upper limit of the content of the component (B) in 100 parts by weight of the curable resin is preferably 22 parts by weight, and the upper limit is more preferably 20 parts by weight.
The ratio of the component (B) to the component (a) is 1 or more. When the ratio of the component (B) to the component (a) is 1 or more, the obtained sealant for a liquid crystal display element has excellent coatability. The lower limit of the ratio of the component (B) to the component (a) is preferably 1.2, and the lower limit is more preferably 1.5.
The "ratio of the component (B) to the component (a)" means the content of the component (B)/the content of the component (a).
Examples of the component (C) include bisphenol a type epoxy (meth) acrylate, bisphenol F type epoxy (meth) acrylate, bisphenol E type epoxy (meth) acrylate, bisphenol S type epoxy (meth) acrylate, 2' -diallylbisphenol a type epoxy (meth) acrylate, hydrogenated bisphenol type epoxy (meth) acrylate, propylene oxide addition type bisphenol a type epoxy (meth) acrylate, resorcinol type epoxy (meth) acrylate, biphenyl type epoxy (meth) acrylate, sulfide type epoxy (meth) acrylate, diphenyl ether type epoxy (meth) acrylate, dicyclopentadiene type epoxy (meth) acrylate, naphthalene type epoxy (meth) acrylate, glycidyl amine type epoxy (meth) acrylate, alkyl polyhydric alcohol type epoxy (meth) acrylate, rubber modified type epoxy (meth) acrylate, and the like. Among them, bisphenol a type epoxy (meth) acrylate is preferable.
The component (C) can be obtained by reacting all epoxy groups of the non-novolac epoxy resin with (meth) acrylic acid in the presence of a basic catalyst according to a conventional method.
Examples of the non-phenolic epoxy resin which is a raw material of the component (C) include the same resins as those of the non-phenolic epoxy resin which is a raw material of the component (B).
The lower limit of the content of the component (C) in 100 parts by weight of the curable resin is 10 parts by weight and the upper limit thereof is 45 parts by weight. When the content of the component (C) in 100 parts by weight of the curable resin is 10 parts by weight or more, the obtained sealant for a liquid crystal display element has excellent photocurability. When the content of the component (C) is 45 parts by weight or less, the obtained sealant for a liquid crystal display element has excellent adhesiveness. The lower limit of the content of the component (C) in 100 parts by weight of the curable resin is preferably 14 parts by weight, and the lower limit is more preferably 18 parts by weight.
The sealant for a liquid crystal display element of the present invention may further contain another polymerizable compound as the curable resin within a range not impairing the object of the present invention.
Examples of the other polymerizable compound include the above-mentioned novolac epoxy resin, the above-mentioned non-novolac epoxy resin, the above-mentioned novolac epoxy (meth) acrylate, and other (meth) acrylic compounds.
Examples of the other (meth) acrylic compounds include (meth) acrylate compounds obtained by reacting a compound having a hydroxyl group with (meth) acrylic acid, urethane (meth) acrylates obtained by reacting a (meth) acrylic acid derivative having a hydroxyl group with an isocyanate compound, and the like.
From the viewpoint of reactivity, the other (meth) acrylic compound preferably has 2 or more (meth) acryloyl groups in 1 molecule.
Examples of the monofunctional compound among the above-mentioned (meth) acrylate compounds include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, methoxyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxy diethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ethyl carbitol (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1h, 5h-octafluoropentyl (meth) acrylate, imide (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxyethyl 2-hydroxypropyl phthalate, 2- (meth) acryloyloxyethyl phosphate, glycidyl (meth) acrylate, and the like.
Examples of the difunctional compound among the (meth) acrylate compounds include 1, 3-butanediol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 2-n-butyl-2-ethyl-1, 3-propanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide addition bisphenol A di (meth) acrylate, propylene oxide addition bisphenol A di (meth) acrylate, ethylene oxide addition bisphenol F di (meth) acrylate, dimethylol dicyclopentadiene di (meth) acrylate, ethylene oxide-modified isocyanurate di (meth) acrylate, 2-hydroxy-3- (meth) acrylate, acryloxypropyl) acrylate, and ethylene oxide addition bisphenol F di (meth) acrylate, polyether diol di (meth) acrylate, polyester diol di (meth) acrylate, polycaprolactone diol di (meth) acrylate, polybutadiene diol di (meth) acrylate, and the like.
Examples of the trifunctional or higher-functional compound among the (meth) acrylate compounds include trimethylolpropane tri (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) acrylate, propylene oxide-added trimethylolpropane tri (meth) acrylate, caprolactone-modified trimethylolpropane tri (meth) acrylate, ethylene oxide-added isocyanuric acid tri (meth) acrylate, glycerol tri (meth) acrylate, propylene oxide-added glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri (meth) acryloyloxyethyl phosphate, bis (trimethylolpropane) tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.
The urethane (meth) acrylate can be obtained, for example, by reacting a (meth) acrylic acid derivative having a hydroxyl group with an isocyanate compound in the presence of a catalytic amount of a tin compound.
Examples of the isocyanate compound include isophorone diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4, 4' -diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1, 5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene Diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate, tetramethylxylylene diisocyanate, 1,6, 11-undecane triisocyanate, and the like.
Further, as the above isocyanate compound, a chain-extended isocyanate compound obtained by a reaction of a polyol with an excess of the isocyanate compound may also be used.
Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, and polycaprolactone diol.
Examples of the (meth) acrylic acid derivative having a hydroxyl group include hydroxyalkyl mono (meth) acrylates, mono (meth) acrylates of diols, mono (meth) acrylates or di (meth) acrylates of triols, and the like.
Examples of the hydroxyalkyl mono (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.
Examples of the diol include ethylene glycol, propylene glycol, 1, 3-propanediol, 1, 3-butanediol, 1, 4-butanediol, and polyethylene glycol.
Examples of the trihydric alcohol include trimethylolethane, trimethylolpropane, glycerol, and the like.
From the viewpoint of suppressing the contamination of the liquid crystal, the other (meth) acrylic compounds preferably have-OH, -NH-group, -NH2And hydrogen-bonding units.
The sealant for a liquid crystal display element of the present invention contains a polymerization initiator.
Examples of the polymerization initiator include a radical polymerization initiator and a cationic polymerization initiator.
As the radical polymerization initiator, a photo radical polymerization initiator which generates radicals by light irradiation, and a thermal radical polymerization initiator which generates radicals by heating can be used.
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.
Specific examples of the photo radical polymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 1,2- (dimethylamino) -2- ((4-methylphenyl) methyl) -1- (4- (4-morpholino) phenyl) -1-butanone, 2-dimethoxy-1, 2-diphenylethan-1-one, bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 1- (4- (2-hydroxyethoxy) -phenyl) -2-hydroxy-2-methyl-1-propan-1-one, 1- (4- (phenylthio) phenyl) -1, 2-octanedione 2- (O-benzoyloxime), 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.
The photo radical polymerization initiator may be used alone, or 2 or more kinds may be used in combination.
Examples of the thermal radical polymerization initiator include thermal radical polymerization initiators containing azo compounds, organic peroxides, and the like. Among them, an initiator containing a macromolecular azo compound (hereinafter, also referred to as "macromolecular azo initiator") is preferable.
The thermal radical polymerization initiator may be used alone, or 2 or more kinds may be used in combination.
In the present specification, the macromolecular azo compound means: a compound having an azo group, which generates a radical capable of curing a (meth) acryloyl group by heat, and which has a number average molecular weight of 300 or more.
The lower limit of the number average molecular weight of the macromolecular azo compound is preferably 1000, and the upper limit thereof is preferably 30 ten thousand. When the number average molecular weight of the macromolecular azo compound is in this range, the azo compound can be easily mixed with the curable resin while suppressing liquid crystal contamination. The number average molecular weight of the macromolecular azo compound has a lower limit of preferably 5000 and an upper limit of preferably 10 ten thousand, a lower limit of more preferably 1 ten thousand, and an upper limit of more preferably 9 ten thousand.
In the present specification, the number average molecular weight is a value obtained by measuring by Gel Permeation Chromatography (GPC) using tetrahydrofuran as a solvent and converting into 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 units such as polyalkylene oxide are bonded via an azo group preferably has 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 among the above-mentioned macromolecular azo compounds include VPE-0201, VPE-0401, VPE-0601, VPS-0501, and VPS-1001 (all manufactured by Fuji film & Wako pure chemical industries, ltd.).
Further, examples of commercially available products other than the macromolecular azo compound include V-65 and V-501 (both manufactured by Fuji film and Wako pure chemical industries, ltd.).
Examples of the organic peroxide include ketone peroxide, peroxyketal, hydrogen peroxide, dialkyl peroxide, peroxyester, diacyl peroxide, and peroxydicarbonate.
As the cationic polymerization initiator, a photo cationic polymerization initiator can be suitably used.
The photo cation polymerization initiator is not particularly limited as long as it generates a protonic acid or a lewis acid by light irradiation, and may be a photo cation polymerization initiator of an ionic photo acid-generating group or a photo cation polymerization initiator of a nonionic photo acid-generating group.
Examples of the photo cation polymerization initiator include onium salts such as aromatic diazonium salts, aromatic halonium salts, and aromatic sulfonium salts; and organic metal complexes such as iron-allene complexes, titanocene complexes, and aryl silanol-aluminum complexes.
Examples of commercially available products among the above-mentioned photo cation polymerization initiators include ADEKAOPTOMER SP-150 and ADEKAOPTOMER SP-170 (both manufactured by ADEKA Co., ltd.).
The lower limit of the content of the polymerization initiator is preferably 0.01 part by weight and the upper limit is preferably 10 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the polymerization initiator is in this range, the obtained sealant for a liquid crystal display element suppresses liquid crystal contamination and has more excellent storage stability and curability. The lower limit of the content of the polymerization initiator is more preferably 0.1 part by weight, and the upper limit is more preferably 5 parts by weight.
The sealant for a liquid crystal display element of the present invention preferably contains a thermosetting agent.
Examples of the heat-curing agent include organic acid hydrazides, imidazole derivatives, amine compounds, polyphenol compounds, and acid anhydrides. Among them, solid organic acid hydrazides are suitably used.
The thermosetting agent may be used alone, or 2 or more of them may be used in combination.
Examples of the solid organic acid hydrazide include 1, 3-bis (hydrazinocarbonylethyl) -5-isopropylhydantoin, sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide and malonic acid dihydrazide.
Examples of commercially available products among the solid organic acid hydrazides include an organic acid hydrazide manufactured by Otsuka chemical company, an organic acid hydrazide manufactured by Nippon Fine chemical company, an organic acid hydrazide manufactured by Ajinomoto Fine science and technology 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 japan fine chemical company include MDH.
Examples of the organic acid hydrazide manufactured by Ajinomoto Fine science and technology include AMICURE VDH, AMICURE VDH-J, and AMICURE UDH.
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 entire curable resin. When the content of the heat curing agent is within this range, the obtained sealant for a liquid crystal display element maintains excellent coatability and storage stability, and has more excellent curability. The upper limit of the content of the thermosetting agent is more preferably 30 parts by weight.
The sealant for a liquid crystal display element of the present invention preferably contains a filler for the purpose of increasing viscosity, further improving adhesiveness by a stress dispersion effect, improving a linear expansion coefficient, improving moisture resistance of a cured product, and the like.
As the filler, an inorganic filler or an organic filler can be used.
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.
Examples of the organic filler include polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, and acrylic polymer fine particles.
The fillers may be used alone, or 2 or more of them may be used in combination.
The lower limit of the content of the filler in 100 parts by weight of the sealant for a liquid crystal display element of the present invention is preferably 10 parts by weight, and the upper limit is preferably 70 parts by weight. When the content of the filler is within this range, the effect of improving the adhesiveness and the like can be further exhibited while suppressing deterioration of the coatability and the like. The lower limit of the content of the filler is more preferably 20 parts by weight, and the upper limit is more preferably 60 parts by weight.
The sealant for a liquid crystal display element of the present invention preferably contains soft particles from the viewpoint of improving the flexibility, adhesiveness, and the like of a cured product, suppressing the insertion of a liquid crystal into the sealant, and suppressing the elution of the sealant into the liquid crystal.
Examples of the soft particles include silicone particles, vinyl particles, urethane particles, fluorine particles, nitrile particles, and the like. Among them, silicone particles and vinyl particles are preferable.
The soft particles may be used alone, or 2 or more kinds may be used in combination.
The silicone particles are preferably silicone rubber particles from the viewpoint of dispersibility in a resin.
As the vinyl particles, (meth) acrylic particles can be suitably used.
The (meth) acrylic particles can be obtained by polymerizing a monomer to be a raw material by a known method. Specifically, for example, a method of suspension polymerization of a monomer in the presence of a radical polymerization initiator, a method of swelling seed particles by allowing non-crosslinked seed particles to absorb a monomer in the presence of a radical polymerization initiator and performing seed polymerization, and the like can be cited.
Examples of the monomer to be used as a raw material for forming the (meth) acrylic particles include monofunctional monomers such as alkyl (meth) acrylates, oxygen atom-containing (meth) acrylates, nitrile-containing monomers, and fluorine-containing (meth) acrylates.
Examples of the alkyl (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate.
Examples of the (meth) acrylic esters containing an oxygen atom include 2-hydroxyethyl (meth) acrylate, glycerol (meth) acrylate, polyoxyethylene (meth) acrylate, and glycidyl (meth) acrylate.
Examples of the nitrile-containing monomer include (meth) acrylonitrile.
Examples of the fluorine-containing (meth) acrylates include trifluoromethyl (meth) acrylate, pentafluoroethyl (meth) acrylate, and the like.
Among them, alkyl (meth) acrylates are preferable because the homopolymer has a low Tg and the amount of deformation when a load of 1g is applied can be increased.
In order to have a crosslinked structure, a polyfunctional monomer may be used as a monomer to be a raw material for forming the (meth) acrylic particles.
Examples of the polyfunctional monomer include tetramethylolmethane tetra (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, glycerol tri (meth) acrylate, glycerol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, (poly) tetramethylene di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, and isocyanuric acid skeleton tri (meth) acrylate. Among them, preferred are (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, (poly) tetramethylene di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, and 1, 6-hexanediol di (meth) acrylate, from the viewpoint that the molecular weight between crosslinking points is large and the deformation amount can be increased when a load of 1g is applied.
The amount of the crosslinkable monomer used is preferably 1% by weight in the lower limit and 90% by weight in the total amount of the monomers to be used as the raw material for forming the (meth) acrylic particles. When the amount of the crosslinkable monomer is 1% by weight or more, the solvent resistance is improved, and the crosslinking monomer is easily uniformly dispersed without causing problems such as swelling when kneaded with other sealant components. By setting the amount of the crosslinkable monomer to 90% by weight or less, the recovery rate can be reduced. The lower limit of the amount of the crosslinkable monomer is more preferably 3% by weight, and the upper limit is more preferably 80% by weight.
Further, in addition to these acrylic monomers, monomers such as styrene monomers, vinyl ethers, vinyl carboxylates, unsaturated hydrocarbons, halogen-containing monomers, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, divinylbenzene, diallyl phthalate, diallyl acrylamide, diallyl ether, γ - (meth) acryloyloxypropyltrimethoxysilane, and vinyltrimethoxysilane can be used.
Examples of the styrene monomer include styrene, α -methylstyrene, trimethoxysilylstyrene and the like.
Examples of the vinyl ethers include methyl vinyl ether, ethyl vinyl ether, and propyl vinyl ether.
Examples of the vinyl carboxylate esters include vinyl acetate, vinyl butyrate, vinyl laurate, and vinyl stearate.
Examples of the unsaturated hydrocarbon include ethylene, propylene, isoprene, and butadiene.
Examples of the halogen-containing monomer include vinyl chloride, vinyl fluoride, and chlorinated styrene.
As the (meth) acrylic particles, core-shell (meth) acrylate copolymer fine particles can also be suitably used.
Examples of commercially available products among the core-shell (meth) acrylate copolymer microparticles include F351 (manufactured by AICA industries, inc.).
As the vinyl particles, for example, polydivinylbenzene particles, polychloroprene particles, butadiene rubber particles, and the like can be used.
The lower limit of the average particle diameter of the soft particles is preferably 0.01 μm, and the upper limit thereof is preferably 10 μm. By setting the average particle diameter of the soft particles to this range, the effect of improving the flexibility and adhesiveness of the cured product of the obtained sealant for a liquid crystal display element is further enhanced. The lower limit of the average particle size of the soft particles is more preferably 0.1 μm, and the upper limit thereof is more preferably 8 μm.
In the present specification, the average particle size of the soft particles is: a value obtained by measurement using a laser diffraction particle size distribution measuring apparatus. As the laser diffraction type particle size distribution measuring apparatus, MASTERSIZER 2000 (manufactured by Malvern Instruments ltd) or the like can be used.
The lower limit of the hardness of the soft particles is preferably 10, and the upper limit thereof is preferably 50. By setting the hardness of the soft particles to this range, the effect of improving the flexibility and adhesiveness of the cured product of the obtained sealant for a liquid crystal display element is further enhanced. The lower limit of the hardness of the soft particles is more preferably 20, and the upper limit thereof is more preferably 40.
In the present specification, the hardness of the soft particles means: durometer a hardness measured by a method according to JIS K6253.
The 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 preferably 5 parts by weight, and the upper limit is preferably 50 parts by weight. When the content of the soft particles is in this range, the effect of improving the flexibility and adhesiveness of the cured product of the obtained sealant for a liquid crystal display element is further excellent. The lower limit of the content of the soft particles is more preferably 10 parts by weight, and the upper limit is more preferably 30 parts by weight.
The sealant for a liquid crystal display element of the present invention preferably contains a silane coupling agent for the purpose of further improving the adhesiveness. 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 can be suitably used.
The silane coupling agents may be used alone, or 2 or more kinds thereof may be used in combination.
The lower limit of 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 is preferably 0.1 part by weight, and the upper limit is preferably 10 parts by weight. When the content of the silane coupling agent is in this range, the effect of further improving the adhesiveness can be exerted while suppressing the occurrence of liquid crystal contamination. The lower limit of the content of the silane coupling agent is more preferably 0.3 parts by weight, and the upper limit is more preferably 5 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 light-shading agent can be used alone, or can be used in combination of 2 or more.
The titanium black has a higher transmittance for light in the vicinity of the ultraviolet region, particularly for light having a wavelength of 370nm to 450nm, than the average transmittance for light having a wavelength of 300nm to 800 nm. 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 exerts a sufficient effect even without being surface-treated, but a titanium black surface-treated with an organic component such as a coupling agent may be used; surface-treated titanium black such as titanium black coated with an inorganic component such as silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide, or magnesium oxide. Among them, titanium black treated with an organic component is preferable from the viewpoint of further improving the insulation properties.
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, it is possible to realize a liquid crystal display element having high contrast without light leakage and having excellent image display quality.
Examples of commercially available products among the above-mentioned titanium blacks include titanium black manufactured by Mitsubishi corporation, titanium black manufactured by Chiba Kasei-Kasei Co., ltd, 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 corporation include titanium black 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 the lower limit is preferably 1nm and the upper limit is preferably 5 μm. When the primary particle size of the light-shading agent is in this range, the coatability can be further improved without significantly increasing the viscosity or thixotropy of the obtained sealant for a liquid crystal display element. The lower limit of the primary particle size 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 100nm.
The primary PARTICLE size of the light-shading agent can be measured by dispersing the light-shading agent in a solvent (such as water or an organic solvent) using a PARTICLE size distribution meter (for example, "NICOMP 380ZLS" manufactured by parathicle SIZING SYSTEMS).
The 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 preferably 5 parts by weight, and the upper limit is preferably 80 parts by weight. By setting the content of the light-shielding agent within this range, the effect of improving the light-shielding property can be further exerted without significantly reducing the adhesiveness, strength after curing, and drawing property of the obtained sealant for a liquid crystal display element. The lower limit of the content of the light-screening agent is more preferably 10 parts by weight, the upper limit is more preferably 70 parts by weight, the lower limit is more preferably 30 parts by weight, and the upper limit is more preferably 60 parts by weight.
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 a 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, a heat curing agent, and additives such as a silane coupling agent, which are added as needed, using a mixer such as a homogenizer, a homomixer, a universal mixer, a planetary mixer, a kneader, or a triple roll mill.
The lower limit of the viscosity of the sealant for a liquid crystal display element of the present invention measured at 25 ℃ and 1rpm with an E-type viscometer is preferably 100Pa · s, and the upper limit thereof is preferably 800Pa · s. When the viscosity is within this range, the resulting sealant for a liquid crystal display element has excellent coatability. The lower limit of the viscosity is more preferably 200 pas and the upper limit is more preferably 700 pas.
By adding conductive fine particles to the sealant for a liquid crystal display element of the present invention, a vertical conduction material can be produced. Further, a vertical conduction material containing the sealant for a 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 fine particles can be electrically connected without damaging the transparent substrate or the like due to the excellent elasticity of the resin fine particles.
Further, 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.
As a method for manufacturing the liquid crystal display element of the present invention, a liquid crystal dropping method is suitably used, and specifically, a method having the following steps, for example, is exemplified.
A liquid crystal display element can be obtained by a method which first performs the steps of: the sealant for a liquid crystal display element of the present invention is applied by screen printing, dispenser application, or the like to one of two substrates such as a glass substrate with an electrode such as an ITO film attached thereto and a polyethylene terephthalate substrate to form a frame-shaped seal pattern; then, the following steps are carried out: applying droplets of liquid crystal to a frame of a seal pattern of a substrate in a state where the sealant for a liquid crystal display element of the present invention is not cured, and stacking the other substrate under vacuum; thereafter, a step of pre-curing the sealant by irradiating the seal pattern portion of the sealant for liquid crystal display element of the present invention with light such as ultraviolet rays and a step of main-curing the pre-cured sealant by heating are performed.
ADVANTAGEOUS EFFECTS OF INVENTION
The present invention can provide a sealant for a liquid crystal display element, which has excellent coatability, curability, and low liquid crystal contamination. 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.
Detailed Description
The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.
(preparation of phenol-aldehyde type curable resin mixture (A1))
557 parts by weight of phenol novolac epoxy resin (product of DIC Co., ltd., "EPICLON-740") was dissolved in 900mL of toluene, and 0.3g of triphenylphosphine was added thereto to prepare a uniform solution. After 122 parts by weight of acrylic acid was added dropwise to the resulting solution with reflux stirring over 2 hours, reflux stirring was further carried out for 6 hours. Subsequently, toluene was removed under reduced pressure to obtain a phenol-based curable resin mixture (A1).
By passing1H-NMR、13C-NMR and FT-IR confirmed that: the phenol-novolac curable resin mixture (A1) was a mixture containing 11.8 wt% of a partially acrylic-modified phenol-novolac epoxy resin, 68.6 wt% of a phenol-novolac epoxy resin, and 19.6 wt% of a phenol-novolac epoxy acrylate.
Further, the weight average molecular weight of the obtained partially acrylic-modified phenol novolac type epoxy resin was 1200.
(preparation of phenol-aldehyde type curable resin mixture (A2))
395 parts by weight of phenol novolac epoxy resin (available from DIC corporation, "EPICLON-730S") was dissolved in 900mL of toluene, and 0.3g of triphenylphosphine was added to the solution to prepare a uniform solution. After 94 parts by weight of acrylic acid was added dropwise to the resulting solution with stirring at reflux over 2 hours, stirring at reflux was further carried out for 6 hours. Subsequently, toluene was removed under reduced pressure to obtain a phenol-formaldehyde curable resin mixture (A2).
By passing1H-NMR、13C-NMR and FT-IR confirmed that: the phenol-novolac curable resin mixture (A2) was a mixture containing 11.8 wt% of a partially acrylic-modified phenol-novolac epoxy resin, 68.6 wt% of a phenol-novolac epoxy resin, and 19.6 wt% of a phenol-novolac epoxy acrylate.
Further, the weight average molecular weight of the obtained partially acrylic-modified phenol novolac epoxy resin was 800.
(preparation of phenol-aldehyde type curable resin mixture (A3))
965 parts by weight of phenol novolac epoxy resin (available from DIC corporation, "EPICLON-770") were dissolved in 1800mL of toluene, and 0.3g of triphenylphosphine was added thereto to prepare a homogeneous solution. After 216 parts by weight of acrylic acid was added dropwise to the resulting solution with stirring at reflux over 2 hours, stirring at reflux was further carried out for 6 hours. Subsequently, toluene was removed under reduced pressure to obtain a phenol-formaldehyde curable resin mixture (A3).
By passing1H-NMR、13C-NMR and FT-IR confirmed that: phenolic curable resin mixture (A3)) The epoxy resin composition was a mixture containing 11.8 wt% of a partially acrylic-modified phenol novolac epoxy resin, 68.6 wt% of a phenol novolac epoxy resin, and 19.6 wt% of a phenol novolac epoxy acrylate.
Further, the weight average molecular weight of the obtained partially acrylic-modified phenol novolac epoxy resin was 2500.
(preparation of non-phenolic curable resin mixture (B1))
326 parts by weight of bisphenol A epoxy resin (product of Mitsubishi chemical corporation, "jER 828 EL") was dissolved in 900mL of toluene, and 0.3g of triphenylphosphine was added to prepare a uniform solution. After 72 parts by weight of acrylic acid was added dropwise to the resulting solution with stirring at reflux over 2 hours, stirring at reflux was further carried out for 6 hours. Subsequently, toluene was removed under reduced pressure to obtain a non-phenol-based curable resin mixture (B1).
By passing1H-NMR、13C-NMR and FT-IR, confirmed that: the non-phenol type curable resin mixture (B1) is a mixture containing 50 wt% of a partially acrylic-modified bisphenol a type epoxy resin, 25 wt% of a bisphenol a type epoxy resin, and 25 wt% of a bisphenol a type epoxy acrylate.
(examples 1 to 10 and comparative examples 1 to 8)
The materials were stirred by a planetary stirring apparatus (e.g., jinky corporation, the name "1235454\ 1243012392263224464,") at the mixing ratios described in tables 1 and 2, and then uniformly mixed by a ceramic triple roll mill to obtain the liquid crystal display element sealants of examples 1 to 10 and comparative examples 1 to 8.
< evaluation >
The following evaluations were made for the respective liquid crystal display element sealants obtained in examples and comparative examples. The results are shown in tables 1 and 2.
(viscosity)
The respective sealants for liquid crystal display elements obtained in examples and comparative examples were measured for viscosity at 25 ℃ and 1rpm using an E-type viscometer (manufactured by BROOKFIELD, "DV-III").
(coatability)
Each of the liquid crystal display elements obtained in examples and comparative examples was coated on a glass substrate using a dispenser (manufactured by Musashi Engineering, "SHOTMASTER 300"). When the dispensing nozzle was fixed to 400 μm, the nozzle gap was fixed to 30 μm, and the coating pressure was fixed to 300kPa to perform coating, the case where coating was possible without white splash or sagging was marked as "o", the case where coating was not broken but white splash or sagging occurred was marked as "Δ", and the case where coating was broken or was not possible at all was marked as "x", and the coatability was evaluated.
(curing Property)
The sealing agent for liquid crystal display elements obtained in examples and comparative examples was applied to a glass substrate to a thickness of about 5 μm, and then glass substrates having the same size were stacked. Next, using a metal halide lamp, 3000mJ/cm of irradiation was performed2365 nm. The amount of change (reduction rate) of the peak derived from the (meth) acryloyl group before and after light irradiation was measured using an infrared spectrometer (FTS 3000, manufactured by BIORAD).
Curability was evaluated by designating the rate of decrease in the peak derived from a (meth) acryloyl group after light irradiation as "excellent", the rate of decrease in the peak derived from a (meth) acryloyl group after light irradiation as "o", the rate of decrease in the peak derived from a (meth) acryloyl group after light irradiation as 85% or more and less than 95% as "o", the rate of decrease in the peak derived from a (meth) acryloyl group after light irradiation as "Δ", and the rate of decrease in the peak derived from a (meth) acryloyl group after light irradiation as "75% or more and less than 85% as" x ".
(Low liquid Crystal contamination)
The sealants for liquid crystal display elements obtained in examples and comparative examples were mixed with 1 wt% of a silica spacer (SI-H055, manufactured by hydrophytic chemical industries), defoamed to remove bubbles in the sealant, filled into a syringe for dispensing (PSY-10E, manufactured by Musashi Engineering), and defoamed again. Next, a sealant was applied to one of the two ITO-film-attached glass substrates by drawing a frame using a dispenser (manufactured by Musashi Engineering, "SHOTMASTER 300"). Next, droplets of TN liquid crystal (JC-5001 LA, manufactured by CHISSO Co., ltd.) were applied dropwise into the frame of the sealant by a liquid crystal dropping device, and another glass substrate with an ITO film was stacked and applied by a vacuum bonding device under a reduced pressure of 5PaAnd bonding the two substrates. Irradiating the bonded unit with a metal halide lamp at 3000mJ/cm2After the ultraviolet ray, the sealant was thermally cured by heating at 120 ℃ for 60 minutes, thereby producing a liquid crystal display element. The obtained liquid crystal display element was stored at 80 ℃ and 90% RH for 100 hours, and then voltage-driven at AC3.5V, and the presence or absence of display unevenness (color unevenness) was visually observed. The low liquid crystal contamination was evaluated by marking "o" when no display unevenness was observed, marking "Δ" when there was display unevenness in the peripheral portion of the liquid crystal display element, and marking "x" when the display unevenness was not only present in the peripheral portion but also diffused in the central portion of the liquid crystal display element.
[ Table 1]
Figure BDA0002179402910000221
[ Table 2]
Figure BDA0002179402910000231
Industrial applicability
The present invention can provide a sealant for a liquid crystal display element, which has excellent coatability, curability, and low liquid crystal contamination. 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.

Claims (3)

1. A sealant for a liquid crystal display element, comprising a curable resin and a polymerization initiator, wherein,
the curable resin contains a partially (meth) acrylic-modified novolac epoxy resin A, a partially (meth) acrylic-modified non-novolac epoxy resin B, and a non-novolac epoxy (meth) acrylate C,
the content of the partially (meth) acrylic-modified novolac epoxy resin A is 3 parts by weight or more and 9 parts by weight or less based on 100 parts by weight of the curable resin,
the content of the partially (meth) acrylic-modified non-phenol-novolac epoxy resin B is 25 parts by weight or less in 100 parts by weight of the curable resin, and the ratio of the partially (meth) acrylic-modified non-phenol-novolac epoxy resin B to the partially (meth) acrylic-modified phenol-novolac epoxy resin A is 1 or more,
the content of the non-phenolic epoxy (meth) acrylate C is 10 to 45 parts by weight based on 100 parts by weight of the curable resin,
the weight average molecular weight of the partial (meth) acrylic acid-modified novolac epoxy resin a is 700 or more and 2000 or less.
2. A vertically conducting material comprising the sealing agent for a liquid crystal display element according to claim 1 and conductive fine particles.
3. A liquid crystal display element produced by using the sealant for a liquid crystal display element according to claim 1 or the vertically conducting material according to claim 2.
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