CN103487995A - Sealing agent for liquid crystal display element and liquid crystal display element - Google Patents

Sealing agent for liquid crystal display element and liquid crystal display element Download PDF

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CN103487995A
CN103487995A CN201310404377.9A CN201310404377A CN103487995A CN 103487995 A CN103487995 A CN 103487995A CN 201310404377 A CN201310404377 A CN 201310404377A CN 103487995 A CN103487995 A CN 103487995A
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methyl
liquid crystal
crystal display
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formula
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CN103487995B (en
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尾山雄一
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Sekisui Chemical Co Ltd
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    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
    • 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
    • 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
    • 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
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    • 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
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/544—Silicon-containing compounds containing nitrogen
    • C08K5/5477—Silicon-containing compounds containing nitrogen containing nitrogen in a heterocyclic ring
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    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
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    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
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    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0615—Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09K2200/0625—Polyacrylic esters or derivatives thereof
    • 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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  • Sealing Material Composition (AREA)
  • Liquid Crystal (AREA)
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Abstract

The present invention provides a sealing agent that is for a liquid crystal display element, has superior adhesion to an oriented film, and for the most part does not cause liquid crystal contamination to arise. Also, the objective of the present invention is to provide a liquid crystal display element obtained using the sealing agent for a liquid crystal display element. The sealing agent for a liquid crystal display element contains: a curable resin having a (meth)acrylate group; a curing agent; and at least one compound selected from the group consisting of a surface-treated hydrotalcite, a surface-treated calcium carbonate, polyimide microparticles, nitrile butadiene rubber microparticles, a 3-alkoxysilyl propyl succinate anhydride, the compound represented by formula (1), the compound represented by formula (2), and the compound represented by formula (3). In formula (1), R1 represents a methyl group, a methoxy group, or an ethoxy group, and R2 and R3 represent a methoxy group or an ethoxy group. In formula (2), R4 represents a methyl group, a methoxy group, or an ethoxy group, and R5 and R6 represent a methoxy group or an ethoxy group. In formula (3),R7 represents a methoxy group or an ethoxy group.

Description

Sealing material for liquid crystal display device and liquid crystal display cells
The application is that the international application no that the applicant proposed on August 8th, 2012 is the division that PCT/JP2012/070223, denomination of invention are the international application of " sealing material for liquid crystal display device and liquid crystal display cells ".
Technical field
The present invention relates to tackiness to alignment films good and substantially do not produce the sealing material for liquid crystal display device of liquid crystal pollution.In addition, the present invention relates to use this sealing material for liquid crystal display device and the liquid crystal display cells made.
Background technology
Liquid crystal display cells have by coating sealant on 2 plate bases and its laminating is formed enclosed the liquid crystal cells that liquid crystal obtains in unit.
Liquid crystal display is by following step manufacture,, make 2 electroded transparency carriers opposed across the interval of regulation, with sealant, to around it, sealed, thereby formation unit, from the liquid crystal injecting port that arranges in its part by Liquid crystal pour in unit, seal this liquid crystal injecting port with sealant or sealing compound.
In addition, in recent years, also studied as disclosed in Patent Document 1, used the photocuring heat curing and by the drip manufacture method of liquid crystal display cells of technique of being called as of type sealant.
In the technique of dripping, at first, form the seal pattern of frame shape on a slice in 2 electroded transparency carriers.Then, in the seal pattern frame that is applied to transparency carrier that under uncured state, the droplet of liquid crystal dripped at sealant whole, under reduced pressure overlap another sheet transparency carrier, to the sealing irradiation ultraviolet radiation, carry out precuring.Afterwards, heating and led curingly, make liquid crystal display cells.
For liquid crystal display cells in the past, the allocation position of sealant substantially on the inorganic material such as glass, ITO, and is considered adhesive power for these inorganic material etc., also sealant is designed.But, along with the expansion of the purposes of liquid crystal indicator in recent years, advanced the straight hem frame of liquid crystal display part, dispose the substrate of sealant and popularize rapidly on alignment films, for sealant in the past, there is the not enough such problem of adhesive power to alignment films.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2001-133794 communique
Summary of the invention
Invent problem to be solved
The object of the invention is to, provide tackiness to alignment films good and substantially do not produce the sealing material for liquid crystal display device of liquid crystal pollution.In addition, the object of the invention is to, the liquid crystal display cells that uses this sealing material for liquid crystal display device to make is provided.
For solving the method for problem
The present invention is a kind of sealing material for liquid crystal display device; it is characterized in that; contain: the curable resin with (methyl) acryloyl group; hardening agent, and be selected from surface treatment hydrotalcite, surface treatment calcium carbonate, medlin particulate, nitrile rubber particulate, 3-alkoxysilyl propyl group succinic anhydride, the compound meaned by following formula (1), the compound meaned by following formula (2) and the compound that meaned by following formula (3) at least one.
Figure BSA0000094883970000031
In formula (1), R 1mean methyl, methoxyl or ethoxy, R 2, R 3mean methoxy or ethoxy.In formula (2), R 4mean methyl, methoxyl or ethoxy, R 5, R 6mean methoxy or ethoxy.In formula (3), R 7mean methoxy or ethoxy.
Below, the present invention is described in detail in detail.
The inventor finds, by use be selected from surface treatment hydrotalcite, surface treatment calcium carbonate, medlin particulate, nitrile rubber particulate, the compound meaned by above-mentioned formula (1), the compound meaned by above-mentioned formula (2) and the compound that meaned by above-mentioned formula (3) at least one, thereby can significantly improve the adhesive power of the sealing material for liquid crystal display device of gained to alignment films, thereby complete the present invention.
Sealing material for liquid crystal display device of the present invention contains at least one in the compound that is selected from surface treatment hydrotalcite, surface treatment calcium carbonate, medlin particulate, nitrile rubber particulate, the compound meaned by above-mentioned formula (1), the compound meaned by above-mentioned formula (2) and is meaned by above-mentioned formula (3).
By containing at least one in the compound that is selected from surface treatment hydrotalcite, surface treatment calcium carbonate, medlin particulate, nitrile rubber particulate, the compound meaned by above-mentioned formula (1), the compound meaned by above-mentioned formula (2) and is meaned by above-mentioned formula (3), thereby make sealing material for liquid crystal display device of the present invention good to the adhesive power of alignment films.
<surface treatment hydrotalcite >
Above-mentioned surface treatment hydrotalcite is implemented surface treatment to hydrotalcite and is made.
As the above-mentioned surface treatment that hydrotalcite is implemented, can list fatty acid treatment, silane coupling agent processing etc.Wherein, be preferably hydrophobic treatments.
As for above-mentioned hydrotalcite is implemented to the surface-treated surface conditioning agent, such as listing the fatty acid such as stearic acid, oleic acid, linoleic acid, the silane coupling agents such as dimethyldimethoxysil,ne, dimethyldiethoxysilane, methyltrimethoxy silane, methyl triethoxysilane, n-hexyl trimethoxy silane, n-hexyl triethoxysilane, γ-glycidoxypropyltrimethoxy silane etc.Wherein, from the sealing material for liquid crystal display device of gained to the tackiness of alignment films good especially, preferred fat acid treatment.
As commercially available above-mentioned surface treatment hydrotalcite, such as listing DHT-4A, DHT-4A-2 (being consonance chemical industrial company system) etc.
Be limited to 5 μ m on the mean grain size of the secondary aggregation thing of above-mentioned surface treatment hydrotalcite preferred.When the mean grain size of the secondary aggregation thing of above-mentioned surface treatment hydrotalcite surpasses 5 μ m, in the situation that use resulting sealing material for liquid crystal display device, sometimes become the obstacle of the cell gap control of liquid crystal display cells.Be limited to 3 μ m on the mean grain size of the secondary aggregation thing of above-mentioned surface treatment hydrotalcite preferred.
It should be noted that, in this instructions, above-mentioned mean grain size refers to by with laser diffraction formula particle size distribution device, being measured the mean grain size of calculating.
The content of above-mentioned surface treatment hydrotalcite, with respect to above-mentioned curable resin 100 weight portions, be limited to 3 weight portions under preferred, is limited to 100 weight portions on preferred.The content of above-mentioned surface treatment hydrotalcite is during lower than 3 weight portion, and adhesive power is insufficient sometimes.When the content of above-mentioned surface treatment hydrotalcite surpasses 100 weight portion, the viscosity of resulting sealant becomes too high sometimes.Be limited to 5 weight portions under the content of above-mentioned surface treatment hydrotalcite preferred, be limited to 50 weight portions on preferred.
<surface treatment calcium carbonate >
Above-mentioned surface treatment calcium carbonate is implemented surface treatment to calcium carbonate and is made.
As the surface treatment that above-mentioned calcium carbonate is implemented, can enumerate fatty acid treatment, silane coupling agent processing etc.Wherein, be preferably hydrophobic treatments.
As above-mentioned for calcium carbonate being implemented to the surface-treated surface conditioning agent, such as listing the fatty acid such as stearic acid, oleic acid, linoleic acid, the silane coupling agents such as dimethyldimethoxysil,ne, dimethyldiethoxysilane, methyltrimethoxy silane, methyl triethoxysilane, n-hexyl trimethoxy silane, n-hexyl triethoxysilane, γ-glycidoxypropyltrimethoxy silane etc.Wherein, from the sealing material for liquid crystal display device of gained to the tackiness of alignment films good especially, preferred fat acid treatment.
As commercially available above-mentioned surface treatment calcium carbonate, such as listing MSK-C, MSK-P, MSK-PO, Calfine100, Calfine200, Calfine200M, Calfine500, カ mono-レ ッ Network ス 100, カ mono-レ Star Network ス 300, MS700, N-2, NC-5, NC-K, CUBE-18BHS (being ball tail calcium company system) etc.
Be limited to 5 μ m on the mean grain size of the secondary aggregation thing of above-mentioned surface treatment calcium carbonate preferred.When the mean grain size of the secondary aggregation thing of above-mentioned surface treatment calcium carbonate surpasses 5 μ m, in the situation that the sealing material for liquid crystal display device that use obtains, sometimes become the obstacle that the cell gap of liquid crystal display cells is controlled.Be limited to 3 μ m on the mean grain size of the secondary aggregation thing of above-mentioned surface treatment calcium carbonate preferred.
The content of above-mentioned surface treatment calcium carbonate, with respect to above-mentioned curable resin 100 weight portions, be limited to 3 weight portions under preferred, is limited to 100 weight portions on preferred.The content of above-mentioned surface treatment calcium carbonate is during lower than 3 weight portion, sometimes can not give full play to the effect that sealant is improved the adhesive power of alignment films.When the content of above-mentioned surface treatment calcium carbonate surpasses 100 weight portion, the viscosity of the sealant sometimes obtained becomes too high.Be limited to 5 weight portions under the content of above-mentioned surface treatment calcium carbonate preferred, be limited to 50 weight portions on preferred.
<medlin particulate >
Manufacture method as above-mentioned medlin particulate, for example can list the method for polyamic acid solution being carried out to the hot-imide processing, make the method for after the polyamic acid particle, this polyamic acid particle being carried out to the hot-imide processing, this film is being carried out the method etc. of fragmentation, cutting etc. after making the film formed by polyimide.
As commercially available above-mentioned medlin particulate, such as listing PI powder (Finetech company system) etc.
Be limited to 5 μ m on the mean grain size of the secondary aggregation thing of above-mentioned medlin particulate preferred.When the mean grain size of the secondary aggregation thing of above-mentioned medlin particulate surpasses 5 μ m, in the situation that the sealing material for liquid crystal display device that use obtains, sometimes become the obstacle that the cell gap of liquid crystal display cells is controlled.Be limited to 3 μ m on the mean grain size of the secondary aggregation thing of above-mentioned medlin particulate preferred.
The content of above-mentioned medlin particulate, with respect to above-mentioned curable resin 100 weight portions, be limited to 3 weight portions under preferred, is limited to 100 weight portions on preferred.The content of above-mentioned medlin particulate is during lower than 3 weight portion, and the effect that sealant is improved the adhesive power of alignment films can not be given full play to sometimes.When the content of above-mentioned medlin particulate surpasses 100 weight portion, the viscosity of the sealant sometimes obtained becomes too high.Be limited to 5 weight portions under the content of above-mentioned medlin particulate preferred, be limited to 50 weight portions on preferred.
<nitrile rubber particulate >
In this instructions, above-mentioned " nitrile rubber (following also referred to as NBR) " refers to the multipolymer of vinyl cyanide and butadiene.
In addition, above-mentioned NBR can be also carboxy-modified NBR (XNBR), the part of butadiene is replaced as to isoprene and material (NBIR).
The segment that derives from vinyl cyanide in above-mentioned NBR particulate be preferably 20～50% containing proportional.
As commercially available above-mentioned NBR particulate, such as listing NarpowVP-401, NarpowVP-501 (being Sanyo trading company system) etc.
Be limited to 5 μ m on the mean grain size of the secondary aggregation thing of above-mentioned NBR particulate preferred.When the mean grain size of the secondary aggregation thing of above-mentioned NBR particulate surpasses 5 μ m, in the situation that the sealing material for liquid crystal display device that use obtains, sometimes become the obstacle that the cell gap of liquid crystal display cells is controlled.Be limited to 3 μ m on the mean grain size of the secondary aggregation thing of above-mentioned NBR particulate preferred.
The content of above-mentioned NBR particulate, with respect to above-mentioned curable resin 100 weight portions, be limited to 3 weight portions under preferred, is limited to 100 weight portions on preferred.The content of above-mentioned NBR particulate is during lower than 3 weight portion, sometimes can not give full play to the effect that sealant is improved the adhesive power of alignment films.When the content of above-mentioned NBR particulate surpasses 100 weight portion, the viscosity of the sealant sometimes obtained becomes too high.Be limited to 5 weight portions under the content of above-mentioned NBR particulate preferred, be limited to 50 weight portions on preferred.
It should be noted that, in the situation that sealing material for liquid crystal display device of the present invention contains at least one in being selected from surface treatment hydrotalcite, surface treatment calcium carbonate, medlin particulate and nitrile rubber particulate, can only contain a kind of in these, also can contain more than two kinds.In the situation that sealing material for liquid crystal display device of the present invention in containing surface treatment hydrotalcite, surface treatment calcium carbonate, medlin particulate and nitrile rubber particulate more than two kinds, its total content is with respect to above-mentioned curable resin 100 weight portions, be limited to 3 weight portions under preferred, be limited to 100 weight portions on preferred.
<3-alkoxysilyl propyl group succinic anhydride, the compound meaned by formula (1), the compound meaned by formula (2) and the compound meaned by formula (3) >
Below, by 3-alkoxysilyl propyl group succinic anhydride, the compound meaned by above-mentioned formula (1), the compound meaned by above-mentioned formula (2) and the compound that meaned by above-mentioned formula (3) also referred to as " silane coupling agent of the present invention ".
As above-mentioned 3-alkoxysilyl propyl group succinic anhydride, such as listing 3-trimethoxy-silylpropyl succinic anhydride, 3-triethoxysilylpropyltetrasulfide succinic acid, 3-methyl dimethoxy oxygen base silicyl propyl group succinic acid, 3-methyl diethoxy silicyl propyl group succinic acid etc.
As commercially available above-mentioned 3-alkoxysilyl propyl group succinic anhydride, such as listing X-12-967C (chemical industrial company of SHIN-ETSU HANTOTAI system) etc.
In above-mentioned formula (1), R 1mean methyl, methoxyl or ethoxy, R 2, R 3mean methoxy or ethoxy.
As the commercially available compound meaned by above-mentioned formula (1), such as listing X-12-987 (chemical industrial company of SHIN-ETSU HANTOTAI system) etc.
In above-mentioned formula (2), R 4mean methyl, methoxyl or ethoxy, R 5, R 6mean methoxy or ethoxy.
As the commercially available compound meaned by above-mentioned formula (2), such as listing X-12-989 (chemical industrial company of SHIN-ETSU HANTOTAI system) etc.
In above-mentioned formula (3), R 7mean methoxy or ethoxy.
As the commercially available compound meaned by above-mentioned formula (3), such as listing X-12-965 (chemical industrial company of SHIN-ETSU HANTOTAI system) etc.
The content of silane coupling agent of the present invention, with respect to curable resin 100 weight portions, be limited to 0.2 weight portion under preferred, is limited to 10 weight portions on preferred.The content of silane coupling agent of the present invention is during lower than 0.2 weight portion, and adhesive power is insufficient sometimes.When the content of silane coupling agent of the present invention surpasses 10 weight portion, the storage stability variation of the sealant sometimes obtained, or when making liquid crystal display cells silane coupling agent of the present invention to stripping in liquid crystal, produce show irregular.Be limited to 0.5 weight portion under the content of silane coupling agent of the present invention preferred, be limited to 7 weight portions on preferred, be limited to 5 weight portions on further preferred.
It should be noted that, sealing material for liquid crystal display device of the present invention contain in the compound that is selected from surface treatment hydrotalcite, surface treatment calcium carbonate, medlin particulate, nitrile rubber particulate, 3-alkoxysilyl propyl group succinic anhydride, the compound meaned by formula (1), the compound meaned by formula (2) and is meaned by formula (3) at least one get final product; Also can contain at least one being selected from surface treatment hydrotalcite, surface treatment calcium carbonate, medlin particulate and nitrile rubber particulate, and be selected from 3-alkoxysilyl propyl group succinic anhydride, the compound meaned by above-mentioned formula (1), the compound meaned by formula (2) and the compound that meaned by formula (3) at least one.
Be selected from the surface treatment hydrotalcite containing, surface treatment calcium carbonate, at least one in medlin particulate and nitrile rubber particulate, in more than one situation in silane coupling agent of the present invention, about its total content, the surface treatment hydrotalcite, surface treatment calcium carbonate, the total content of medlin particulate and nitrile rubber particulate, with respect to above-mentioned curable resin 100 weight portions, be limited to 3 weight portions under preferred, be limited to 100 weight portions on preferred, in addition, the total content of silane coupling agent of the present invention, with respect to curable resin 100 weight portions, be limited to 0.2 weight portion under preferred, be limited to 10 weight portions on preferred.
Sealing material for liquid crystal display device of the present invention contains the curable resin with (methyl) acryloyl group.
The above-mentioned curable resin with (methyl) acryloyl group, such as can list ester compounds by (methyl) acrylic acid being reacted with the compound with hydroxyl obtain, epoxy (methyl) acrylate by (methyl) acrylic acid being reacted with epoxy compound obtain, by carbamate (methyl) acrylate of isocyanates being reacted with (methyl) acrylic acid derivative with hydroxyl obtain etc.
It should be noted that, in this instructions, above-mentioned (methyl) acryloyl group refers to acryloyl group or methacryl, and above-mentioned (methyl) acrylate refers to acrylate or methacrylate.In addition, in this instructions, above-mentioned epoxy (methyl) acrylate be instigate all epoxy radicals in epoxy compound with (methyl) acrylic acid, react and compound.
By making (methyl) acrylic acid react the ester compounds of simple function in the ester compounds obtained with the compound with hydroxyl, for example can list (methyl) 2-Hydroxy ethyl acrylate as above-mentioned, (methyl) 2-hydroxypropyl acrylate, (methyl) acrylic acid-4-hydroxyl butyl ester, (methyl) acrylic acid-2-hydroxyl butyl ester, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) dodecylacrylate, (methyl) octadecyl acrylate, (methyl) isobornyl acrylate, (methyl) cyclohexyl acrylate, (methyl) acrylic acid-2-methoxyl ethyl ester, (methyl) acrylic acid-methoxyl glycol ester, (methyl) acrylic acid-2-ethoxy ethyl ester, (methyl) acrylic acid tetrahydro furfuryl ester, (methyl) benzyl acrylate, (methyl) acrylic acid ethyl carbitol ester, (methyl) acrylic acid phenoxy ethyl, (methyl) acrylic acid phenoxy group binaryglycol ester, (methyl) acrylic acid phenoxy group macrogol ester, (methyl) acrylic acid methoxy poly (ethylene glycol) ester, (methyl) acrylic acid-2,2, the 2-trifluoro ethyl ester, (methyl) acrylic acid-2,2,3,3-tetrafluoro propyl ester, (methyl) acrylic acid-1H, 1H, 5H-octafluoro pentyl ester, (methyl) acrylic acid imide ester, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) propyl acrylate, (methyl) n-butyl acrylate, (methyl) cyclohexyl acrylate, (methyl) acrylic acid-2-ethyl caproite, (methyl) acrylic acid n-octyl, (methyl) acrylic acid ester in the different ninth of the ten Heavenly Stems, the different myristyl ester of (methyl) acrylic acid, (methyl) acrylic acid-2-butoxyethyl, (methyl) acrylic acid-2-phenoxy ethyl, (methyl) acrylic acid dicyclopentenyloxyethyl methacrylate, (methyl) isodecyl acrylate, (methyl) acrylic acid diethylamino ethyl ester, (methyl) acrylic acid dimethylamino ethyl ester, succinic acid-2-(methyl) acryloxy ethyl ester, hexahydrophthalic acid-2-(methyl) acryloxy ethyl ester, phthalic acid-2-(methyl) acryloxy ethyl-2-hydroxypropyl acrylate, (methyl) glycidyl acrylate, phosphoric acid-2-(methyl) acryloxy ethyl ester etc.
By making (methyl) acrylic acid react the ester compounds of 2 officials' energy in the ester compounds obtained with the compound with hydroxyl, for example can list BDO two (methyl) acrylate as above-mentioned, 1,3-BDO two (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, 1,10-decanediol two (methyl) acrylate, 2-normal-butyl-2-ethyl-1,3-PD two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, polypropylene glycol (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, diethylene glycol two (methyl) acrylate, TEG two (methyl) acrylate, polyglycol two (methyl) acrylate, epoxypropane addition bisphenol-A two (methyl) acrylate, ethyleneoxide addition bisphenol-A two (methyl) acrylate, ethyleneoxide addition Bisphenol F two (methyl) acrylate, dihydroxymethyl dicyclopentadienyl two (methyl) acrylate, 1,3-BDO two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, oxirane modification isocyanuric acid two (methyl) acrylate, 2-hydroxyl-3-(methyl) acryloxy propyl group (methyl) acrylate, carbonic ester glycol two (methyl) acrylate, PTMEG two (methyl) acrylate, polyester-diol two (methyl) acrylate, polycaprolactone glycol two (methyl) acrylate, polybutadiene diol two (methyl) acrylate etc.
As above-mentioned by make (methyl) acrylic acid with the compound with hydroxyl, react in the ester compounds obtained 3 officials can ester compounds, for example can list pentaerythrite three (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, epoxypropane addition trimethylolpropane tris (methyl) acrylate, ethyleneoxide addition trimethylolpropane tris (methyl) acrylate, caprolactone modification trimethylolpropane tris (methyl) acrylate, ethyleneoxide addition isocyanuric acid three (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, double trimethylolpropane four (methyl) acrylate, pentaerythrite four (methyl) acrylate, glycerine three (methyl) acrylate, epoxypropane addition glycerine three (methyl) acrylate, three (methyl) acryloxy ethyl phosphonic acid ester etc.
As above-mentioned epoxy (methyl) acrylate obtained by (methyl) acrylic acid is reacted with epoxy compound, be not particularly limited, for example can list by making epoxy resin and (methyl) acrylic acid react according to conventional methods epoxy (methyl) acrylate obtained under the existence of base catalyst.
Epoxy compound as the raw material for the synthesis of above-mentioned epoxy (methyl) acrylate, be not particularly limited, for example can list bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, 2, 2 '-diallyl bisphenol type epoxy resin, A Hydrogenated Bisphenol A type epoxy resin, epoxypropane addition bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, thioether-type epoxy resin, the diphenyl ether type epoxy, dicyclopentadiene-type epoxy resin, naphthalene type epoxy resin, phenol novolak type epoxy resin, o-cresol phenolic epoxy varnish, the bicyclopentadiene phenolic resin varnish type epoxy resin, the biphenyl phenolic resin varnish type epoxy resin, the naphthalene phenol novolak type epoxy resin, glycidyl group amine type epoxy resin, alkyl polyols type epoxy resin, modified rubber type epoxy resin, epihydric alcohol ester compound, bisphenol A-type episulfide resin etc.
As commercially available above-mentioned bisphenol A type epoxy resin, for example can list EPIKOTE828EL, EPIKOTE1004 (being Mitsubishi Chemical Ind's system), EPICLON850-S (DIC company system) etc.
As commercially available above-mentioned bisphenol f type epoxy resin, such as listing EPIKOTE806, EPIKOTE4004 (being Mitsubishi Chemical Ind's system) etc.
As commercially available above-mentioned bisphenol-s epoxy resin, such as listing EPICLON EXA1514 (DIC company system) etc.
As commercially available above-mentioned 2,2 '-diallyl bisphenol type epoxy resin, such as listing RE-810NM (Japanese chemical drug company system) etc.
As commercially available above-mentioned A Hydrogenated Bisphenol A type epoxy resin, such as listing EPICLON EXA7015 (DIC company system) etc.
As commercially available above-mentioned epoxypropane addition bisphenol A type epoxy resin, such as listing EP-4000S (ADEKA company system) etc.
As commercially available above-mentioned resorcinol type epoxy resin, such as listing EX-201 (Nagase Chemtex company system) etc.
As commercially available above-mentioned biphenyl type epoxy resin, such as listing EPIKOTE YX-4000H (Mitsubishi Chemical Ind's system) etc.
As commercially available above-mentioned thioether-type epoxy resin, such as listing YSLV-50TE (chemical company of Nippon Steel system) etc.
As commercially available above-mentioned diphenyl ether type epoxy, such as listing YSLV-80DE (chemical company of Nippon Steel system) etc.
As commercially available above-mentioned dicyclopentadiene-type epoxy resin, such as listing EP-4088S (ADEKA company system) etc.
As commercially available above-mentioned naphthalene type epoxy resin, such as listing EPICLON HP4032, EPICLON EXA-4700 (being DIC company system) etc.
As commercially available above-mentioned phenol novolak type epoxy resin, such as listing EPICLON N-770 (DIC company system) etc.
As commercially available above-mentioned o-cresol phenolic epoxy varnish, such as listing EPICLONN-670-EXP-S (DIC company system) etc.
As commercially available above-mentioned bicyclopentadiene phenolic resin varnish type epoxy resin, such as listing EPICLON HP7200 (DIC company system) etc.
As commercially available above-mentioned biphenyl phenolic resin varnish type epoxy resin, such as listing NC-3000P (Japanese chemical drug company system) etc.
As commercially available above-mentioned naphthalene phenol novolak type epoxy resin, such as listing ESN-165S (chemical company of Nippon Steel system) etc.
As commercially available above-mentioned glycidyl group amine type epoxy resin, such as listing EPIKOTE630 (Mitsubishi Chemical Ind's system), EPICLON430 (DIC company system), TETRAD-X (aerochemistry company of Mitsubishi system) etc.
As commercially available abovementioned alkyl polyvalent alcohol type epoxy resin, such as listing ZX-1542 (chemical company of Nippon Steel system), EPICLON726 (DIC company system), EPOLIGHT80MFA (chemical company of common prosperity society system), DENACOL EX-611 (Nagase Chemtex company system) etc.
As commercially available above-mentioned modified rubber type epoxy resin, such as listing YR-450, YR-207 (being chemical company of Nippon Steel system), EPOLEAD PB (Daicel chemical industrial company system) etc.
As commercially available above-mentioned epihydric alcohol ester compound, such as listing DENACOL EX-147 (Nagase Chemtex company system) etc.
As commercially available above-mentioned bisphenol A-type episulfide resin, such as listing EPIKOTE YL-7000 (Mitsubishi Chemical Ind's system) etc.
As other commercially available products in above-mentioned epoxy resin, for example can list YDC-1312, YSLV-80XY, YSLV-90CR (being chemical company of Nippon Steel system), XAC4151 (Asahi Kasei Corporation system), EPIKOTE1031, EPIKOTE1032 (being Mitsubishi Chemical Ind's system), EXA-7120 (DIC company system), TEPIC (daily output chemical company system) etc.
For above-mentioned for epoxy (methyl) acrylate that (methyl) acrylic acid is reacted with epoxy compound obtain, specifically, for example, using resorcinol type epoxy resin (Nagase Chemtex company system, " EX-201 ") 360 weight portions, p methoxy phenol 2 weight portions as polymerization inhibitor, triethylamine 2 weight portions as catalysts, acrylic acid 210 weight portions, carry out return stirring when under 90 ℃, sending into air, make its reaction 5 hours, thus, can access resorcinol type epoxy acrylate.
As commercially available above-mentioned epoxy (methyl) acrylate, for example can list EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3800, EBECRYL6040, EBECRYL RDX63182 (being Daicel cytec company system), EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (being Xin Zhong village chemical industrial company system), epoxy-ester M-600A, epoxy-ester 40EM, epoxy-ester 70PA, epoxy-ester 200PA, epoxy-ester 80MFA, epoxy-ester 3002M, epoxy-ester 3002A, epoxy-ester 1600A, epoxy-ester 3000M, epoxy-ester 3000A, epoxy-ester 200EA, epoxy-ester 400EA (being chemical company of common prosperity society system), DENACOL ACRYLATE DA-141, DENACOL ACRYLATE DA-314, DENACOL ACRYLATE DA-911 (being Nagase Chemtex company system) etc.
For above-mentioned, by making isocyanates react carbamate (methyl) acrylate obtained with (methyl) acrylic acid derivative with hydroxyl, for example can for compound 1 equivalent with respect to thering are 2 isocyanate group, make (methyl) acrylic acid derivative 2 equivalents with hydroxyl react and obtain under the existence of the tin compound of catalytic amount.
As above-mentioned by making isocyanates react the isocyanates of the raw material of carbamate (methyl) acrylate obtained with (methyl) acrylic acid derivative with hydroxyl, for example can list isophorone diisocyanate, 2, the 4-toluene diisocyanate, 2, the 6-toluene diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, diphenyl methane-4, 4 '-diisocyanate (MDI), hydrogenation MDI, polymeric MDI, 1, the 5-naphthalene diisocyanate, norbornene alkyl diisocyanate, the tolidine diisocyanate, XDI (XDI), hydrogenation XDI, lysinediisocyanate (Japanese: リ ジ Application ジ ィ ソ シ ァ ネ mono-ト), triphenylmethane triisocyanate, tri o cresyl thiophosphate (4-phenyl isocyanate), tetramethylbenzene dimethyl diisocyanate, 1, 6, 10-undecane triisocyanate etc.
In addition, as above-mentioned by making isocyanates react the isocyanates of the raw material of carbamate (methyl) acrylate obtained with (methyl) acrylic acid derivative with hydroxyl, can also use the chain elongation that obtains with reacting of excessive isocyanates by polyvalent alcohols such as ethylene glycol, glycerine, D-sorbite, trimethylolpropane, (gathering) propylene glycol, carbonic ester glycol, PTMEG, polyester-diol, polycaprolactone glycols isocyanate compound.
As above-mentioned by making isocyanates react the raw material of carbamate (methyl) acrylate obtained with (methyl) acrylic acid derivative with hydroxyl, (methyl) acrylic acid derivative with hydroxyl, for example can list (methyl) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate, (methyl) acrylic acid-4-hydroxyl butyl ester, (methyl) acrylic acid-commercially available products such as 2-hydroxyl butyl ester, ethylene glycol, propylene glycol, 1, ammediol, 1, the 3-butylene glycol, 1, the 4-butylene glycol, the list of the dibasic alcohol such as polyglycol (methyl) acrylate, trimethylolethane, trimethylolpropane, the list of the trihydroxy alcohols such as glycerine (methyl) acrylate or two (methyl) acrylate, the epoxy acrylates such as bisphenol A modified epoxy acrylate etc.
As above-mentioned by making isocyanates react carbamate (methyl) acrylate obtained with (methyl) acrylic acid derivative with hydroxyl, particularly, for example can obtain by following step, , add trimethylolpropane 134 weight portions, BHT0.2 weight portion as polymerization inhibitor, dibutyl tin dilaurate 0.01 weight portion as catalysts, isophorone diisocyanate 666 weight portions, carry out the simultaneous reactions 2 hours of return stirring under 60 ℃, then, add 2-Hydroxy ethyl acrylate 51 weight portions, carry out return stirring under 90 ℃ when sending into air, meanwhile make its reaction 2 hours.
Above-mentioned carbamate (methyl) acrylate as commercially available, for example can list M-1100, M-1200, M-1210, M-1600 (being East Asia Synesis Company system), EBECRYL230, EBECRYL270, EBECRYL4858, EBECRYL8402, EBECRYL8804, EBECRYL8803, EBECRYL8807, EBECRYL9260, EBECRYL1290, EBECRYL5129, EBECRYL4842, EBECRYL210, EBECRYL4827, EBECRYL6700, EBECRYL220, EBECRYL2220 (being Daicel-UCB company system), ArtresinUN-9000H, ArtresinUN-9000A, ArtresinUN-71OO, ArtresinUN-1255, ArtresinUN-330, ArtresinUN-3320HB, ArtresinUN-1200TPK, ArtresinSH-500B (being industrial group's system on root), U-122P, U-108A, U-340P, U-4HA, U-6HA, U-324A, U-15HA, UA-5201P, UA-W2A, U-1084A, U-6LPA, U-2HA, U-2PHA, UA-4100, UA-7100, UA-4200, UA-4400, UA-340P, U-3HA, UA-7200, U-2061BA, U-10H, U-122A, U-340A, U-108, U-6H, UA-4000 (being Xin Zhong village chemical industrial company system), AH-600, AT-600, UA-306H, AI-600, UA-101T, UA-101I, UA-306T, UA-306I (being chemical company of common prosperity society system) etc.
For the above-mentioned curable resin with (methyl) acryloyl group, suppressing aspect liquid crystal dysgenic, be preferably have-OH base ,-the NH-base ,-NH 2the curable resin of the unit of the hydrogen bonds such as base, from synthetic easiness grade, be particularly preferably epoxy (methyl) acrylate.
In addition, for the above-mentioned curable resin with (methyl) acryloyl group, from reactive height, be preferably in molecule the curable resin with 2～3 of (methyl) acryloyl groups.
Sealing material for liquid crystal display device of the present invention preferably also coordinates and has the resin of epoxy radicals as curable resin.The resin with epoxy radicals as commercially available can list: as the epoxy compound of the above-mentioned raw material for the synthesis of epoxy (methyl) acrylate and resin listed etc.In addition, the resin that has an epoxy radicals can be also for example to have the compound of (methyl) acryloyl group and epoxy radicals in 1 molecule.As such compound, such as listing: the epoxy radicals of the part of the compound by making to have the epoxy radicals more than 2 is reacted compound obtained etc. with (methyl) acrylic acid.The epoxy radicals of the part of the compound by making to have epoxy radicals is reacted compound of obtaining etc. and also can be considered as the above-mentioned curable resin with (methyl) acryloyl group with (methyl) acrylic acid like this.
, for example can react and obtain under the existence of base catalyst according to conventional methods with (methyl) acrylic acid by making epoxy resin for (methyl) acrylic acid reacts the compound obtained for the epoxy radicals of the part of the above-mentioned compound by making to have the epoxy radicals more than 2.Particularly, for example make phenol novolak type epoxy resin N-770 (DIC company system) 190g dissolve in toluene 500mL, add triphenylphosphine 0.1g in this solution, obtain uniform solution, in resulting solution, under return stirring, acrylic acid 35g was dripped with 2 hours, then further carry out return stirring 6 hours, remove toluene, thus, can obtain that the epoxy radicals of 50 % by mole is reacted with acrylic acid and part acrylic acid modified phenol phenolic resin varnish type epoxy resin (having carried out in this case 50% part acrylic acid modification).
Epoxy radicals as the part of the commercially available above-mentioned compound by making to have the epoxy radicals more than 2 reacts with (methyl) acrylic acid the compound obtained, and for example can list EBECRYL1561 (Daicel cytec system).
With regard to sealing material for liquid crystal display device of the present invention; preferably make (methyl) acryloyl group and epoxy radicals coexist, preferably (methyl) acryloyl group with curable resin reach 50: 50 with the mol ratio of epoxy radicals～mode of 95: 5 coordinates the curable resin with (methyl) acryloyl group and the resin with epoxy radicals.
Sealing material for liquid crystal display device of the present invention contains hardening agent.
As above-mentioned hardening agent, can list optical free radical polymerization initiator for (methyl) acryloyl group is reacted by light such as ultraviolet rays, the hot radical polymerization initiator for (methyl) acryloyl group is reacted by heat, the light cationic polymerization initiators for epoxy radicals is reacted by UV, the hot epoxy hardener for epoxy radicals is reacted by heat.
Above-mentioned optical free radical polymerization initiator is not particularly limited, as commercially available product, such as listing IRGACURE184, IRGACURE369, IRGACURE379, IRGACURE651, IRGACURE819, IRGACURE907, IRGACURE2959, IRGACURE OXE01, Lucirin TPO (being Japanese BASF AG system), benzoin methyl ether, benzoin ethylether, benzoin isopropyl ether (more than be Tokyo change into industrial group's system) etc., ADEKA CRUISE NCI930 (ADEKA company system) etc.
The content of above-mentioned optical free radical polymerization initiator is not particularly limited, and for above-mentioned curable resin 100 weight portions with (methyl) acryloyl group, is limited to 0.1 weight portion under preferred, is limited to 10 weight portions on preferred.If the content of above-mentioned optical free radical polymerization initiator lower than 0.1 weight portion, can't make sealing material for liquid crystal display device of the present invention solidify fully sometimes.When if the content of above-mentioned optical free radical polymerization initiator surpasses 10 weight portion, storage stability reduces sometimes.
Above-mentioned hot radical polymerization initiator is not particularly limited, can list superoxide and azo-compound, as commercially available product, such as listing PERBUTYL O, PERHEXYL O, PERBUTYL PV (being a day oily company system), V-30, V-501, V-601, VPE-0201, VPE-0401, VPE-0601 (being the system with the pure pharmaceutical worker's industry of light company) etc.
The content of above-mentioned hot radical polymerization initiator is not particularly limited, and for above-mentioned curable resin 100 weight portions with (methyl) acryloyl group, is limited to 0.01 weight portion under preferred, is limited to 10 weight portions on preferred.If the content of above-mentioned hot radical polymerization initiator lower than 0.01 weight portion, can't make sealing material for liquid crystal display device of the present invention solidify fully sometimes.If the content of above-mentioned hot radical polymerization initiator surpasses 10 weight portions, storage stability reduces sometimes.
Above-mentioned smooth cationic polymerization initiators is not particularly limited, as commercially available product, such as listing ADEKA OPTOMER SP-150, ADEKA OPTOMER SP-170 (being ADEKA company system) etc.
The content of above-mentioned smooth cationic polymerization initiators is not particularly limited, and for above-mentioned resin 100 weight portions with epoxy radicals, is limited to 0.1 weight portion under preferred, is limited to 10 weight portions on preferred.If the content of above-mentioned smooth cationic polymerization initiators lower than 0.1 weight portion, can't make sealing material for liquid crystal display device of the present invention solidify fully sometimes.If the content of above-mentioned smooth cationic polymerization initiators surpasses 10 weight portions, storage stability reduces sometimes.
As above-mentioned hot epoxy hardener, such as listing organic acid hydrazides, imdazole derivatives, amines, polyhydric phenols, acid anhydrides etc.Wherein, preferably use the organic acid hydrazides of solid.
The organic acid hydrazides of above-mentioned solid is not particularly limited, such as listing sebacic dihydrazide, isophthalic dihydrazide, adipic dihydrazide, malonic acid two hydrazides etc., as commercially available product, such as listing SDH (Japanese Finechem company system), ADH (great mound chemical company system) etc.In addition, in addition, can also use AMICURE VDH, AMICURE VDH-J, AMICURE UDH (being AJINOMOTO FINE-TECHNO company system) etc.
With regard to the content of above-mentioned hot epoxy hardener, for above-mentioned resin 100 weight portions with epoxy radicals, be limited to 1 weight portion under preferred, be limited to 50 weight portions on preferred.If the content of above-mentioned hot epoxy hardener lower than 1 weight portion, can't make sealing material for liquid crystal display device of the present invention solidify fully sometimes.If the content of above-mentioned hot epoxy thermosetting agent surpasses 50 weight portions, the viscosity increased of sealing material for liquid crystal display device of the present invention, damage coating etc. sometimes.Be limited to 30 weight portions on the content of above-mentioned hot epoxy hardener preferred.
Using the improvement of the tackiness based on the stress dispersion effect, the improvement of linear expansivity etc. as purpose, and sealing material for liquid crystal display device of the present invention can also contain filling agent.
Above-mentioned filling agent is not particularly limited, such as listing the inorganic fillers such as talcum, asbestos, silicon dioxide, zeyssatite, smectite, bentonitic clay, calcium carbonate, magnesium carbonate, aluminium oxide, polynite, zinc paste, iron oxide, magnesium oxide, tin oxide, titanium dioxide, magnesium hydroxide, aluminium hydroxide, beaded glass, silicon nitride, barium sulphate, gypsum, calcium silicate, sericite atlapulgite, aluminium nitride, and the organic filler such as polyester micropartical, polyurethane particulate, polyvinyl particulate, acrylate copolymer particulate.
Sealing material for liquid crystal display device of the present invention can also contain other silane coupling agents beyond silane coupling agent of the present invention.Above-mentioned other silane coupling agent is not particularly limited, and preferably uses such as gamma-amino propyl trimethoxy silicane, γ mercaptopropyitrimethoxy silane, γ-glycidoxypropyltrimethoxy silane, γ-isocyanates propyl trimethoxy silicane etc.These other silane coupling agent can be used separately, and also two or more kinds may be used.
Sealing material for liquid crystal display device of the present invention can also contain as required: for the reactive diluent of adjusting viscosity, regulate thixotropic thixotropic agent, for the polymeric beads of adjusting range sheet separation uniformly-spaced part, 3-rubigan-1, other known adjuvants such as the curing accelerators such as 1-dimethyl urea, defoamer, levelling agent, polymerization inhibitor.
The method of manufacturing sealing material for liquid crystal display device of the present invention is not particularly limited, such as being listed below method etc.: use homogeneous dispersion machine, homogeneous stirring machine, universal mixer, planetary-type mixer, kneader, the mixers such as three rollers, to thering is the curable resin of (methyl) acryloyl group, hardening agent, be selected from the surface treatment hydrotalcite, surface treatment calcium carbonate, medlin particulate, the nitrile rubber particulate, 3-alkoxysilyl propyl group succinic anhydride, the compound meaned by formula (1), at least one in the compound meaned by formula (2) and the compound that meaned by formula (3), the adjuvants such as other silane coupling agents that add are as required mixed.
Using the liquid crystal display cells that sealing material for liquid crystal display device of the present invention is made is also one of the present invention.
As the method for manufacturing liquid crystal display cells of the present invention, such as enumerating the method that comprises following operation etc., , at ito thin film etc., have on 1 of transparency carrier of electrode and alignment films sealing material for liquid crystal display device of the present invention etc. by serigraphy, divider coatings etc. form the operation of rectangular seal pattern, the droplet of liquid crystal is dripped under uncured state at sealing material for liquid crystal display device of the present invention etc. and overlap at once the operation of another sheet transparency carrier in the frame that is coated on transparency carrier after whole, to light such as the seal pattern part irradiation ultraviolet radiations of sealing material for liquid crystal display device of the present invention etc. and make the operation of sealant precuring, and the sealant after precuring is heated and makes it be led curing operation.
The effect of invention
According to the present invention, can provide tackiness to alignment films good and substantially do not produce the sealing material for liquid crystal display device of liquid crystal pollution.In addition, according to the present invention, can provide the liquid crystal display cells that uses this sealing material for liquid crystal display device to make.
Embodiment
Below, enumerate embodiment mode of the present invention is given the account in greater detail, but the present invention is not limited only to these embodiment.
(embodiment 1～54 and comparative example 1～5)
According to the match ratio of record in table 1～10, use planetary stirring machine (THINKY company system, " あ ゎ と り
Figure BSA0000094883970000181
youth too ") each material is mixed after, re-use three rollers and mixed, thus, prepare the sealing material for liquid crystal display device of embodiment 1～54 and comparative example 1～5.
On the alignment films of the substrate with transparency electrode and alignment films (daily output chemical company's system " SE7492 "), resulting sealing material for liquid crystal display device is coated with divider in the mode of depicting foursquare frame.Then, the droplet of liquid crystal (Chisso company system " JC-5004LA ") is dripped in the frame that is applied to substrate to whole, overlap the substrate that another sheet has transparency electrode and alignment films under vacuum.After Vacuum solutions is removed, sealing material for liquid crystal display device is solidified and obtain liquid crystal display cells.
It should be noted that the solidifying by ultraviolet ray is carried out to 3000mJ/cm of sealing material for liquid crystal display device 2heat and carry out in 1 hour under 120 ℃ again after irradiation.
It should be noted that, the partially modified thing of the N-770 in table 1～10 is by following method preparation.
That is, phenol novolak type epoxy resin (DIC company system " N-770 ") 190g is dissolved in toluene 500mL, add triphenylphosphine 0.1g in this solution, obtain uniform solution.Under return stirring, acrylic acid 35g was dripped with 2 hours in resulting solution, then further carry out 6 hours return stirrings.Remove toluene, thus, obtain the epoxy radicals modification of 50mo1% is become the part propylene acidylate epoxy resin (the partially modified thing of N-770) of acryloyl group.
(evaluation)
For the sealing material for liquid crystal display device obtained in embodiment and comparative example and liquid crystal display cells, by following method, estimated.
Show the result in table 1～10.
(1) evaluation of adhesive strength
In resulting sealing material for liquid crystal display device 100 weight portions, utilize planetary stirring apparatus to be disperseed polymeric beads (ponding chemical industrial company system " Micropearl SP ") 3 weight portions of mean grain size 5 μ m, obtain uniform liquid.The liquid of the gained of denier is placed in to the central portion of glass substrate (20mm * 50mm * 1.1mmt), overlaps the glass substrate of homotype thereon, make the sealing material for liquid crystal display device expansion.Irradiate 100mW/cm under this state 2ultraviolet ray 30 seconds.Then, under 120 ℃, heating is 1 hour, obtains the adhesive test sheet.
For resulting adhesive test sheet, with tensiometer, measure adhesive strength (comparative unit: N/cm 2).As glass substrate, these 3 kinds, the glass of use blank glass (Corning1737), band alignment films SE7492 (daily output chemical company system) for TN, the glass that band VA uses alignment films JALS2021 (JSR company system).
(2) the irregular evaluation of the demonstration of liquid crystal display cells
For resulting liquid crystal display cells, at "on" position and color spot that liquid crystal of visualization sealant periphery does not produce under "on" position.By the average evaluation that there is no color spot fully, being " ◎ ", is " zero " by almost there is no the average evaluation of color spot, and it is " △ " that the average evaluation of a small amount of color spot will be arranged, and the average evaluation that a large amount of color spots will be arranged is " * ".
(3) evaluation of the viscosity stability of sealant
For the sealing material for liquid crystal display device obtained in embodiment 23～47 and comparative example 1,5, the dark places of 25 ℃, preserve 24 hours, by the viscosity before and after the keeping of E type viscometer determining, measure viscosity increment rate (viscosity before the viscosity after keeping in 24 hours/keeping).
Figure BSA0000094883970000211
Figure BSA0000094883970000221
Figure BSA0000094883970000231
Figure BSA0000094883970000241
Figure BSA0000094883970000251
Figure BSA0000094883970000261
Figure BSA0000094883970000271
Figure BSA0000094883970000281
Figure BSA0000094883970000291
Utilizability on industry
According to the present invention, can provide tackiness to alignment films good and substantially do not produce the sealing material for liquid crystal display device of liquid crystal pollution.In addition, according to the present invention, can provide the liquid crystal display cells that uses this sealing material for liquid crystal display device and make.

Claims (3)

1. a sealing material for liquid crystal display device, is characterized in that,
Contain: the curable resin with (methyl) acryloyl group; hardening agent; with at least one in the compound that is selected from surface treatment calcium carbonate, medlin particulate, nitrile rubber particulate, 3-alkoxysilyl propyl group succinic anhydride, the compound meaned by following formula (1), the compound meaned by following formula (2) and is meaned by following formula (3)
Wherein, the use level of described surface treatment calcium carbonate, described medlin particulate, described nitrile rubber particulate is 3～100 weight portions with respect to described curable resin 100 weight portions, the use level of described 3-alkoxysilyl propyl group succinic anhydride, the compound meaned by following formula (1), the compound meaned by following formula (2), the compound that meaned by following formula (3) is 0.2～10 weight portion with respect to described curable resin 100 weight portions
In formula (1), R 1mean methyl, methoxyl or ethoxy, R 2, R 3mean methoxy or ethoxy, in formula (2), R 4mean methyl, methoxyl or ethoxy, R 5, R 6mean methoxy or ethoxy, in formula (3), R 7mean methoxy or ethoxy.
2. sealing material for liquid crystal display device according to claim 1; it is characterized in that; contain: the curable resin with (methyl) acryloyl group; hardening agent; be selected from least one in surface treatment calcium carbonate, medlin particulate and nitrile rubber particulate, and be selected from 3-alkoxysilyl propyl group succinic anhydride, the compound meaned by formula (1), the compound meaned by formula (2) and the compound that meaned by formula (3) at least one.
3. a liquid crystal display cells, is characterized in that, right to use requires 1 or 2 described sealing material for liquid crystal display device to make.
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