CN106978122A - Sealing material for liquid crystal display device and liquid crystal display cells - Google Patents
Sealing material for liquid crystal display device and liquid crystal display cells Download PDFInfo
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- CN106978122A CN106978122A CN201610857623.XA CN201610857623A CN106978122A CN 106978122 A CN106978122 A CN 106978122A CN 201610857623 A CN201610857623 A CN 201610857623A CN 106978122 A CN106978122 A CN 106978122A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
- C09J163/10—Epoxy resins modified by unsaturated compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
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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
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- 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
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- 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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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- 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
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- 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
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- C09K2200/0625—Polyacrylic esters or derivatives thereof
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1339—Gaskets; Spacers; Sealing of cells
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Abstract
It is an object of the present invention to provide the adhesivity to alignment films is excellent and does not produce the sealing material for liquid crystal display device of liquid crystal pollution substantially.In addition, it is an object of the present invention to provide the liquid crystal display cells being made using the sealing material for liquid crystal display device.The present invention is a kind of sealing material for liquid crystal display device；It contains：Curable resin with (methyl) acryloyl group; curing agent, and selected from least one of surface treatment hydrotalcite, surface treatment calcium carbonate, medlin particulate, nitrile rubber particulate, 3 alkoxysilyl propylsuccinic anhydrides, the compound by following formula (1) expression, the compound by following formula (2) expression and compound by following formula (3) expression.In formula (1), R1Represent methyl, methoxyl group or ethyoxyl, R2、R3Represent methoxy or ethoxy.In formula (2), R4Represent methyl, methoxyl group or ethyoxyl, R5、R6Represent methoxy or ethoxy.In formula (3), R7Represent methoxy or ethoxy.
Description
The international application no that the application is applicant to be proposed on the 8th in August in 2012 is 2012800114406, denomination of invention
For the division of the international application of " sealing material for liquid crystal display device and liquid crystal display cells ".
Technical field
The present invention relates to the adhesivity to alignment films is excellent and do not produce the used for liquid crystal display element of liquid crystal pollution substantially
Sealant.Moreover, it relates to the liquid crystal display cells being made using the sealing material for liquid crystal display device.
Background technology
Liquid crystal display cells have to be sealed in the cells by being coated with sealant on 2 plate bases and making formed by its laminating
Liquid crystal cells obtained by liquid crystal are entered.
Liquid crystal display is manufactured by following step, i.e. make 2 electroded transparency carriers across defined interval pair
Put, with sealant to being sealed around it, so as to form unit, from the liquid crystal injecting port set on one part by liquid crystal
It is injected into unit, the liquid crystal injecting port is sealed using sealant or sealing compound.
In addition, in recent years, be investigated as disclosed in Patent Document 1, used photocuring heat cure and sealed with type
Being referred to as of agent drip technique liquid crystal display cells manufacture method.
In technique of dripping, first, the seal pattern of frame-shaped is formed on a piece of in 2 electroded transparency carriers.Connect
, the droplet of liquid crystal, which drips, in the state of sealant is uncured is applied to the seal pattern inframe entire surface of transparency carrier,
Another transparency carrier is overlapped under reduced pressure, to sealing irradiation ultraviolet radiation, carries out precuring.Afterwards, heat and lead admittedly
Change, make liquid crystal display cells.
For conventional liquid crystal display cells, the allocation position of sealant is basic in inorganic material such as glass, ITO
On, and in view of for adhesive tension of these inorganic material etc., also being designed sealant.But, with recent years
The expansion of the purposes of liquid crystal display device, advances the straight hem frame of liquid crystal display part, sealant is configured with alignment films
Substrate is rapidly popularized, for conventional sealant, exist it is not enough to the adhesive tensions of alignment films so the problem of.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2001-133794 publications
The content of the invention
Invent problem to be solved
It is an object of the present invention to provide the adhesivity to alignment films is excellent and does not produce the liquid of liquid crystal pollution substantially
Crystal display element sealant.In addition, it is an object of the present invention to provide being made using the sealing material for liquid crystal display device
Liquid crystal display cells.
Method for solving problem
The present invention is a kind of sealing material for liquid crystal display device, it is characterised in that contained：With (methyl) acryloyl group
Curable resin, curing agent, and it is micro- selected from surface treatment hydrotalcite, surface treatment calcium carbonate, medlin particulate, nitrile rubber
Grain, 3- alkoxysilyls propylsuccinic anhydride, the compound represented by following formula (1), the chemical combination represented by following formula (2)
Thing and at least one of the compound represented by following formula (3).
In formula (1), R1Represent methyl, methoxyl group or ethyoxyl, R2、R3Represent methoxy or ethoxy.In formula (2),
R4Represent methyl, methoxyl group or ethyoxyl, R5、R6Represent methoxy or ethoxy.In formula (3), R7Represent methoxyl group or second
Epoxide.
Hereinafter, the present invention is described in detail.
The inventors discovered that, by using selected from surface treatment hydrotalcite, surface treatment calcium carbonate, medlin particulate,
Nitrile rubber particulate, by above-mentioned formula (1) represent compound, by above-mentioned formula (2) represent compound and by above-mentioned formula (3)
At least one of compound of expression, so as to significantly improve the sealing material for liquid crystal display device of gained to alignment films
Adhesive tension, so as to complete the present invention.
The sealing material for liquid crystal display device of the present invention contains selected from surface treatment hydrotalcite, surface treatment calcium carbonate, gathered
Imide particle, nitrile rubber particulate, by above-mentioned formula (1) represent compound, by above-mentioned formula (2) represent compound and by
At least one of compound that above-mentioned formula (3) represents.
By containing selected from surface treatment hydrotalcite, surface treatment calcium carbonate, medlin particulate, nitrile rubber particulate,
In the compound represented by above-mentioned formula (1), the compound represented by above-mentioned formula (2) and the compound represented by above-mentioned formula (3)
At least one so that the present invention sealing material for liquid crystal display device it is excellent to the adhesive tension of alignment films.
<It is surface-treated hydrotalcite>
Above-mentioned surface treatment hydrotalcite is implemented to be surface-treated and is made to hydrotalcite.
As the above-mentioned surface treatment implemented to hydrotalcite, fatty acid treatment, silane coupler processing can be included
Deng.Wherein, preferably hydrophobic treatment.
As the surface conditioning agent for implementing surface treatment to above-mentioned hydrotalcite, for example, it can include stearic acid, oil
The aliphatic acid such as acid, linoleic acid, dimethyldimethoxysil,ne, dimethyldiethoxysilane, MTMS, methyl
Triethoxysilane, n-hexyl trimethoxy silane, n-hexyl triethoxysilane, γ-glycidoxypropyl trimethoxy silicon
Silane couplers such as alkane etc..Wherein, from the sealing material for liquid crystal display device of gained it is particularly excellent to the adhesivity of alignment films go out
Hair, preferred fat acid treatment.
As commercially available above-mentioned surface treatment hydrotalcite, it (is consonanceization that can for example include DHT-4A, DHT-4A-2
Learn industrial group's system) etc..
The preferred upper limit of the average grain diameter of the secondary aggregation thing of above-mentioned surface treatment hydrotalcite is 5 μm.At above-mentioned surface
When the average grain diameter of the secondary aggregation thing of reason hydrotalcite is more than 5 μm, resulting sealing material for liquid crystal display device is being used
In the case of, the obstacle that the cell gap as liquid crystal display cells is controlled sometimes.The secondary aggregation of above-mentioned surface treatment hydrotalcite
The preferred upper limit of the average grain diameter of thing is 3 μm.
It should be noted that in this specification, above-mentioned average grain diameter refers to by using laser diffraction formula particle size distribution
The average grain diameter that device is measured and calculated.
The content of above-mentioned surface treatment hydrotalcite, relative to the above-mentioned parts by weight of curable resin 100, lower limit preferably is 3
Parts by weight, the upper limit preferably is 100 parts by weight.When the content of above-mentioned surface treatment hydrotalcite is less than 3 parts by weight, adhesive tension sometimes
It is insufficient.When the content of above-mentioned surface treatment hydrotalcite is more than 100 parts by weight, the viscosity of sometimes resulting sealant became
It is high.The preferred lower limit of the content of above-mentioned surface treatment hydrotalcite is 5 parts by weight, and the preferred upper limit is 50 parts by weight.
<It is surface-treated calcium carbonate>
Above-mentioned surface treatment calcium carbonate is implemented to be surface-treated and is made to calcium carbonate.
As the surface treatment implemented to above-mentioned calcium carbonate, fatty acid treatment, silane coupler processing etc. can be enumerated.
Wherein, preferably hydrophobic treatment.
As the above-mentioned surface conditioning agent for being used to implement calcium carbonate surface treatment, for example, it can include stearic acid, oil
The aliphatic acid such as acid, linoleic acid, dimethyldimethoxysil,ne, dimethyldiethoxysilane, MTMS, methyl
Triethoxysilane, n-hexyl trimethoxy silane, n-hexyl triethoxysilane, γ-glycidoxypropyl trimethoxy silicon
Silane couplers such as alkane etc..Wherein, from the sealing material for liquid crystal display device of gained it is particularly excellent to the adhesivity of alignment films go out
Hair, preferred fat acid treatment.
As commercially available above-mentioned surface treatment calcium carbonate, can for example include MSK-C, MSK-P, MSK-PO,
The レ Star Network ス 100 of Calfine100, Calfine200, Calfine200M, Calfine500, カ mono-, the レ Star Network ス 300 of カ mono-,
MS700, N-2, NC-5, NC-K, CUBE-18BHS (being ball tail calcium company system) etc..
The preferred upper limit of the average grain diameter of the secondary aggregation thing of above-mentioned surface treatment calcium carbonate is 5 μm.At above-mentioned surface
When the average grain diameter of the secondary aggregation thing of reason calcium carbonate is more than 5 μm, in the feelings using obtained sealing material for liquid crystal display device
Under condition, the obstacle that the cell gap as liquid crystal display cells is controlled sometimes.The secondary aggregation thing of above-mentioned surface treatment calcium carbonate
Average grain diameter the preferred upper limit be 3 μm.
The content of above-mentioned surface treatment calcium carbonate, relative to the above-mentioned parts by weight of curable resin 100, lower limit preferably is 3
Parts by weight, the upper limit preferably is 100 parts by weight.When the content of above-mentioned surface treatment calcium carbonate is less than 3 parts by weight, it can not fill sometimes
The effect for making sealant improve the adhesive tension of alignment films is waved in distribution.The content of above-mentioned surface treatment calcium carbonate is more than 100 weight
During part, the viscosity of the sealant obtained sometimes becomes too high.The preferred lower limit of the content of above-mentioned surface treatment calcium carbonate is 5
Parts by weight, the preferred upper limit is 50 parts by weight.
<Medlin particulate>
As the manufacture method of above-mentioned medlin particulate, for example, it can include and hot acyl Asia is carried out to polyamic acid solution
The method of amination treatment, the method for carrying out hot-imide processing to the polyamic acid particle after polyamic acid particle is made,
Method crushed, cut to the film after the film that is formed by polyimides is made etc. etc..
As commercially available above-mentioned medlin particulate, such as can include PI powder (Finetech company systems).
The preferred upper limit of the average grain diameter of the secondary aggregation thing of above-mentioned medlin particulate is 5 μm.Above-mentioned polyimides
When the average grain diameter of the secondary aggregation thing of particulate is more than 5 μm, in the case where using obtained sealing material for liquid crystal display device,
Sometimes the obstacle that the cell gap as liquid crystal display cells is controlled.The average grain of the secondary aggregation thing of above-mentioned medlin particulate
The preferred upper limit in footpath is 3 μm.
The content of above-mentioned medlin particulate, relative to the above-mentioned parts by weight of curable resin 100, lower limit preferably is 3 weights
Part is measured, the upper limit preferably is 100 parts by weight.When the content of above-mentioned medlin particulate is less than 3 parts by weight, make sealant to orientation
The effect that the adhesive tension of film is improved can not give full play to sometimes.When the content of above-mentioned medlin particulate is more than 100 parts by weight, have
When the obtained viscosity of sealant become too high.The preferred lower limit of the content of above-mentioned medlin particulate is 5 parts by weight, more
It is preferred that the upper limit be 50 parts by weight.
<Nitrile rubber particulate>
In this specification, above-mentioned " nitrile rubber (hereinafter also referred to NBR) " refers to the copolymer of acrylonitrile and butadiene.
In addition, above-mentioned NBR can also be carboxy-modified NBR (XNBR), a part for butadiene is replaced as into isoprene
Obtained by material (NBIR).
The content ratio of the segment from acrylonitrile in above-mentioned NBR particulates is preferably 20~50%.
As commercially available above-mentioned NBR particulates, it (is three that can for example include NarpowVP-401, NarpowVP-501
Foreign trading company's system) etc..
The preferred upper limit of the average grain diameter of the secondary aggregation thing of above-mentioned NBR particulates is 5 μm.Above-mentioned NBR particulates it is secondary
When the average grain diameter of condensation product is more than 5 μm, in the case where using obtained sealing material for liquid crystal display device, sometimes as liquid
The obstacle of the cell gap control of crystal display element.The average grain diameter of the secondary aggregation thing of above-mentioned NBR particulates it is preferred on
It is limited to 3 μm.
The content of above-mentioned NBR particulates, relative to the above-mentioned parts by weight of curable resin 100, lower limit preferably is 3 parts by weight,
It is preferred that the upper limit be 100 parts by weight.When the content of above-mentioned NBR particulates is less than 3 parts by weight, can not give full play to sometimes makes sealant
The effect that adhesive tension to alignment films is improved.When the content of above-mentioned NBR particulates is more than 100 parts by weight, the sealant obtained sometimes
Viscosity become too high.The preferred lower limit of the content of above-mentioned NBR particulates is 5 parts by weight, and the preferred upper limit is 50 weight
Part.
It should be noted that the sealing material for liquid crystal display device in the present invention contains selected from surface treatment hydrotalcite, table
In the case of at least one of face processing calcium carbonate, medlin particulate and nitrile rubber particulate, it can only contain these
In one kind, can also contain more than two kinds.The present invention sealing material for liquid crystal display device contain surface treatment hydrotalcite,
In the case of being surface-treated more than two kinds in calcium carbonate, medlin particulate and nitrile rubber particulate, its total content is relative
In the above-mentioned parts by weight of curable resin 100, lower limit preferably is 3 parts by weight, and the upper limit preferably is 100 parts by weight.
<3- alkoxysilyls propylsuccinic anhydride, the compound represented by formula (1), the chemical combination represented by formula (2)
Thing and the compound represented by formula (3)>
Hereinafter, by 3- alkoxysilyls propylsuccinic anhydride, by above-mentioned formula (1) represent compound, by above-mentioned formula
(2) compound represented and the compound represented by above-mentioned formula (3) are also referred to as " silane coupler of the invention ".
As above-mentioned 3- alkoxysilyls propylsuccinic anhydride, for example, it can include 3- trimethoxysilyls
Propylsuccinic anhydride, 3- triethoxysilylpropyltetrasulfides butanedioic acid, 3- methyl dimethoxy epoxide silylpropyls butanedioic acid, 3-
Methyl diethoxy silylpropyl butanedioic acid etc..
As commercially available above-mentioned 3- alkoxysilyls propylsuccinic anhydride, for example, it can include X-12-967C (letters
More chemical industrial company's system) etc..
In above-mentioned formula (1), R1Represent methyl, methoxyl group or ethyoxyl, R2、R3Represent methoxy or ethoxy.
As the commercially available compound represented by above-mentioned formula (1), for example, it can include X-12-987 (SHIN-ETSU HANTOTAI's chemical industry
Company system) etc..
In above-mentioned formula (2), R4Represent methyl, methoxyl group or ethyoxyl, R5、R6Represent methoxy or ethoxy.
As the commercially available compound represented by above-mentioned formula (2), for example, it can include X-12-989 (SHIN-ETSU HANTOTAI's chemical industry
Company system) etc..
In above-mentioned formula (3), R7Represent methoxy or ethoxy.
As the commercially available compound represented by above-mentioned formula (3), for example, it can include X-12-965 (SHIN-ETSU HANTOTAI's chemical industry
Company system) etc..
The content of the silane coupler of the present invention, relative to the parts by weight of curable resin 100, lower limit preferably is 0.2 weight
Part is measured, the upper limit preferably is 10 parts by weight.When the content of the silane coupler of the present invention is less than 0.2 parts by weight, adhesive tension sometimes
It is insufficient.When the content of the silane coupler of the present invention is more than 10 parts by weight, the storage stability of the sealant obtained sometimes becomes
Difference, or silane coupler into the liquid crystal dissolution of the invention when making liquid crystal display cells, produce display irregular.The present invention
Silane coupler content preferred lower limit be 0.5 parts by weight, the preferred upper limit be 7 parts by weight, further preferably
The upper limit be 5 parts by weight.
It should be noted that the sealing material for liquid crystal display device of the present invention contains selected from surface treatment hydrotalcite, surface
Handle calcium carbonate, medlin particulate, nitrile rubber particulate, 3- alkoxysilyls propylsuccinic anhydride, by formula (1) represent
Compound, the compound represented by formula (2) and at least one of the compound represented by formula (3)；It can also contain
Have selected from least one of surface treatment hydrotalcite, surface treatment calcium carbonate, medlin particulate and nitrile rubber particulate,
The chemical combination represented with the compound represented selected from 3- alkoxysilyls propylsuccinic anhydride, by above-mentioned formula (1), by formula (2)
Thing and at least one of the compound represented by formula (3).
Containing selected from surface treatment hydrotalcite, surface treatment calcium carbonate, medlin particulate and nitrile rubber particulate
At least one of and one or more of the silane coupler of the present invention in the case of, on its total content, be surface-treated water
Talcum, the total content for being surface-treated calcium carbonate, medlin particulate and nitrile rubber particulate, relative to above-mentioned curable resin
100 parts by weight, lower limit preferably is 3 parts by weight, and the upper limit preferably is 100 parts by weight, in addition, the silane coupler of the present invention
Total content, relative to the parts by weight of curable resin 100, lower limit preferably is 0.2 parts by weight, and the upper limit preferably is 10 parts by weight.
The 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, can for example include by make (methyl) acrylic acid with
Ester compounds obtained by compound reaction with hydroxyl, by making ring obtained by the reaction of (methyl) acrylic acid and epoxide
Oxygen (methyl) acrylate, by make isocyanates with hydroxyl (methyl) acrylic acid derivative reaction obtained by amino first
Acid esters (methyl) acrylate etc..
It should be noted that in this specification, above-mentioned (methyl) acryloyl group refers to acryloyl group or methylacryloyl,
Above-mentioned (methyl) acrylate refers to acrylate or methacrylate.In addition, in this specification, above-mentioned epoxy (methyl) third
Olefin(e) acid ester is to instigate all epoxy radicals in epoxide and compound obtained by (methyl) propylene acid reaction.
As above by making (methyl) acrylic acid and single official in ester compounds obtained by the compound reaction with hydroxyl
Can ester compounds, can for example include (methyl) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate,
(methyl) acrylic acid -4- hydroxybutyls, (methyl) acrylic acid -2- hydroxybutyls, (methyl) isobutyl acrylate, (methyl) propylene
Tert-butyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) dodecylacrylate, (methyl) octadecyl acrylate, (methyl)
Isobornyl acrylate, (methyl) cyclohexyl acrylate, (methyl) acrylic acid -2- methoxy acrylates, (methyl) acrylic acid-methoxy
Ethyl glycol ester, (methyl) acrylic acid -2- ethoxy ethyl esters, (methyl) acrylic acid tetrahydro furfuryl ester, (methyl) benzyl acrylate,
(methyl) acrylic acid ethyl carbitol ester, (methyl) acrylate, (methyl) acrylic acid phenoxy group binaryglycol ester,
(methyl) acrylic acid phenoxy group macrogol ester, (methyl) methoxyethyl macrogol ester, (methyl) acrylic acid -2,2,2-
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) third
Olefin(e) acid propyl ester, (methyl) n-butyl acrylate, (methyl) cyclohexyl acrylate, (methyl) acrylic acid-2-ethyl caproite, (methyl)
N-octyl, the different nonyl ester of (methyl) acrylic acid, the different tetradecane base ester of (methyl) acrylic acid, (methyl) acrylic acid -2- fourth oxygen
Base ethyl ester, (methyl) acrylic acid -2- phenoxy ethyls, (methyl) acrylic acid dicyclopentenyloxyethyl methacrylate, (methyl) isodecyl acrylate,
(methyl) acrylic acid diethylamino ethyl ester, (methyl) acrylate, butanedioic acid -2- (methyl) acryloyl-oxy
Base ethyl ester, hexahydrophthalic acid -2- (methyl) acryloyloxyethyl ester, phthalic acid -2- (methyl) acryloxy second
Base -2- hydroxypropyl acrylates, (methyl) glycidyl acrylate, phosphoric acid -2- (methyl) acryloyloxyethyl ester etc..
As above by making (methyl) acrylic acid and 2 functions in ester compounds obtained by the compound reaction with hydroxyl
Ester compounds, can for example include BDO two (methyl) acrylate, 1,3-BDO two (methyl) acrylic acid
Ester, 1,6- hexylene glycols two (methyl) acrylate, 1,9- nonanediols two (methyl) acrylate, 1,10- decanediols two (methyl)
Acrylate, 2- normal-butyls -2- ethyls -1,3-PD two (methyl) acrylate, DPG two (methyl) acrylate,
Tripropylene glycol two (methyl) acrylate, polypropylene glycol (methyl) acrylate, ethylene glycol two (methyl) acrylate, diethyl two
Alcohol two (methyl) acrylate, tetraethylene glycol two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, expoxy propane
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) propylene
Acid esters, neopentyl glycol two (methyl) acrylate, ethylene-oxide-modified isocyanuric acid two (methyl) acrylate, 2- hydroxyls -3-
(methyl) acryloxypropyl (methyl) acrylate, carbonate diol two (methyl) acrylate, (first of PTMEG two
Base) acrylate, polyester-diol two (methyl) acrylate, polycaprolactone glycol two (methyl) acrylate, polybutadiene two
Alcohol two (methyl) acrylate etc..
As above by making (methyl) acrylic acid and 3 functions in ester compounds obtained by the compound reaction with hydroxyl
Ester compounds, can for example include pentaerythrite three (methyl) acrylate, trimethylolpropane tris (methyl) acrylic acid
Ester, expoxy propane 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, expoxy propane addition
Glycerine three (methyl) acrylate, three (methyl) acryloyl-oxyethyl phosphates etc..
As above by (methyl) acrylic acid and epoxy (methyl) acrylate obtained by epoxide reaction is made, do not have
It is particularly limited to, for example, can includes by making epoxy resin with (methyl) acrylic acid according to conventional methods in base catalyst
In the presence of react obtained from epoxy (methyl) acrylate.
As the epoxide of the raw material for synthesizing above-mentioned epoxy (methyl) acrylate, it is not particularly limited, example
Bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, 2,2 '-diallyl bis-phenol can such as be included
A types epoxy resin, A Hydrogenated Bisphenol A type epoxy resin, expoxy propane addition bisphenol A type epoxy resin, resorcinol type asphalt mixtures modified by epoxy resin
Fat, biphenyl type epoxy resin, thioether-type epoxy resin, diphenyl ether type epoxy, dicyclopentadiene-type epoxy resin, naphthalene type
Epoxy resin, phenol novolak type epoxy resin, o-cresol phenolic epoxy varnish, dicyclopentadiene novolac type
Epoxy resin, biphenyl phenolic resin varnish type epoxy resin, naphthalene phenol novolak type epoxy resin, glycidyl amine type asphalt mixtures modified by epoxy resin
Fat, alkyl polyols type epoxy resin, modified rubber type epoxy resin, epihydric alcohol ester compound, bisphenol A-type episulfide tree
Fat etc..
As commercially available above-mentioned bisphenol A type epoxy resin, for example, it can include EPIKOTE 828EL, EPIKOTE
1004 (being Mitsubishi Chemical Ind's system), EPICLON 850-S (DIC company systems) etc..
As commercially available above-mentioned bisphenol f type epoxy resin, for example, it can include EPIKOTE 806, EPIKOTE 4004
(being Mitsubishi Chemical Ind's system) etc..
As commercially available above-mentioned bisphenol-s epoxy resin, for example, it can include (the DIC companies of EPICLON EXA 1514
System) etc..
As commercially available above-mentioned 2,2 '-diallyl bisphenol type epoxy resin can for example include RE-810NM (days
This chemical drug company system) etc..
As commercially available above-mentioned A Hydrogenated Bisphenol A type epoxy resin, can for example including EPICLON EXA 7015, (DIC is public
Department's system) etc..
As commercially available above-mentioned expoxy propane addition bisphenol A type epoxy resin, for example, it can include EP-4000S
(ADEKA company systems) etc..
As commercially available above-mentioned resorcinol type epoxy resin, for example, it can include EX-201 (Nagase Chemtex
Company system) etc..
As commercially available above-mentioned biphenyl type epoxy resin, for example, it can include EPIKOTE YX-4000H (Mitsubishi Chemicals
Company system) etc..
As commercially available above-mentioned thioether-type epoxy resin, for example, it can include YSLV-50TE (chemical companies of Nippon Steel
System) etc..
As commercially available above-mentioned diphenyl ether type epoxy, can for example including YSLV-80DE, (Nippon Steel's chemistry is public
Department's system) etc..
As commercially available above-mentioned dicyclopentadiene-type epoxy resin, for example, it can include EP-4088S (ADEKA companies
System) etc..
As commercially available above-mentioned naphthalene type epoxy resin, for example, it can include EPICLON HP4032, EPICLON EXA-
4700 (being DIC company systems) etc..
As commercially available above-mentioned phenol novolak type epoxy resin, for example, it can include EPICLON N-770 (DIC
Company system) etc..
As commercially available above-mentioned o-cresol phenolic epoxy varnish, for example, it can include EPICLON N-670-
EXP-S (DIC company systems) etc..
As commercially available above-mentioned dicyclopentadiene novolac type epoxy resin, for example, it can include EPICLON
HP7200 (DIC company systems) etc..
As commercially available above-mentioned biphenyl phenolic resin varnish type epoxy resin, for example, it can include NC-3000P (Japanese chemical drugs
Company system) etc..
As commercially available above-mentioned naphthalene phenol novolak type epoxy resin, for example, it can include ESN-165S (Nippon Steel
Chemical company's system) etc..
As commercially available above-mentioned glycidyl amine type epoxy resin, for example, it can include (the Mitsubishis of EPIKOTE 630
Learn company system), EPICLON 430 (DIC company systems), TETRAD-X (Mitsubishi Gas Chemical company system) etc..
As commercially available abovementioned alkyl polyol type epoxy resin, can for example including ZX-1542, (Nippon Steel's chemistry is public
Department system), EPICLON 726 (DIC company systems), EPOLIGHT 80MFA (chemical company of common prosperity society system), DENACOL EX-611
(Nagase Chemtex company systems) etc..
As commercially available above-mentioned modified rubber type epoxy resin, it (is new day that can for example include YR-450, YR-207
Iron chemical company system), EPOLEAD PB (Daicel chemical industrial companies system) etc..
As commercially available above-mentioned epihydric alcohol ester compound, for example, it can include DENACOL EX-147 (Nagase
Chemtex company systems) etc..
As commercially available above-mentioned bisphenol A-type episulfide resin, for example, it can include EPIKOTE YL-7000 (Mitsubishis
Chemical company's system) etc..
As other commercially available products in above-mentioned epoxy resin, for example, it can include YDC-1312, YSLV-80XY, YSLV-
90CR (being chemical company of Nippon Steel system), XAC4151 (Asahi Kasei Corporation's system), EPIKOTE 1031, EPIKOTE 1032 are (
For Mitsubishi Chemical Ind's system), EXA-7120 (DIC company systems), TEPIC (Nissan Chemical company system) etc..
For above by make (methyl) acrylic acid and epoxide react obtained by epoxy (methyl) acrylate and
Speech, specifically, for example by resorcinol type epoxy resin (Nagase Chemtex company systems, " EX-201 ") 360 parts by weight,
It is used as the parts by weight of p methoxy phenol 2 of polymerization inhibitor, the parts by weight of triethylamine 2 as catalysts, the weight of acrylic acid 210
Part, return stirring is carried out while air is sent at 90 DEG C, it is reacted 5 hours, thereby, it is possible to obtain resorcinol type ring
Oxypropylene acid esters.
As commercially available above-mentioned epoxy (methyl) acrylate, for example, it can include EBECRYL 860, EBECRYL
3200、EBECRYL 3201、EBECRYL 3412、EBECRYL 3600、EBECRYL 3700、EBECRYL 3701、EBECRYL
3702nd, EBECRYL 3703, EBECRYL 3800, EBECRYL 6040, EBECRYL RDX63182 (are Daicel cytec
Company system), EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (be that Xin Zhong villages chemical industry is public
Department 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 (are
Chemical company of common prosperity society system), DENACOL ACRYLATE DA-141, DENACOL ACRYLATE DA-314, DENACOL
ACRYLATE DA-911 (being Nagase Chemtex company systems) etc..
For above by make isocyanates with hydroxyl (methyl) acrylic acid derivative reaction obtained by amino first
Acid esters (methyl) acrylate, for example can be by making to have for the equivalent of compound 1 with 2 NCOs
The equivalent of (methyl) acrylic acid derivative 2 of hydroxyl reacts and obtained in the presence of the tin compound of catalytic amount.
As above by amino obtained from making isocyanates and there is the reaction of (methyl) acrylic acid derivative of hydroxyl
The isocyanates of the raw material of formic acid esters (methyl) acrylate, for example, can include IPDI, 2,4- first
Phenylene diisocyanate, 2,6- toluene di-isocyanate(TDI)s, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate,
Diphenyl methane -4,4 '-diisocyanate (MDI), hydrogenation MDI, polymeric MDI, 1,5- naphthalene diisocyanates, norbornane two are different
Cyanate, tolidine diisocyanate, XDI (XDI), hydrogenation XDI, lysine diisocyanate
(Japanese：The ト of リ ジ Application ジ ィ ソ シ ァ ネ mono-), triphenylmethane triisocyanate, tri o cresyl thiophosphate (4- phenyl isocyanates), four
Xylylene diisocyanate, 1,6,10- hendecane triisocyanates etc..
In addition, as above by make isocyanates with hydroxyl (methyl) acrylic acid derivative reaction obtained by ammonia
The isocyanates of the raw material of carbamate (methyl) acrylate, can also use by ethylene glycol, glycerine, D-sorbite,
Polyalcohol and the mistakes such as trimethylolpropane, (poly-) propane diols, carbonate diol, PTMEG, polyester-diol, polycaprolactone glycol
The isocyanate compound of chain elongation obtained by the reaction of the isocyanates of amount.
As above by make isocyanates with hydroxyl (methyl) acrylic acid derivative reaction obtained by amino first
Raw material, with hydroxyl (methyl) acrylic acid derivative of acid esters (methyl) acrylate, for example, can include (methyl)
2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate, (methyl) acrylic acid -4- hydroxybutyls, (methyl) propylene
The commercially available products such as acid -2- hydroxybutyls, ethylene glycol, propane diols, 1,3-PD, 1,3-BDO, BDO, polyethylene glycol
Deng list (methyl) acrylate of dihydric alcohol, the list (methyl) of the trihydroxylic alcohol such as trimethylolethane, trimethylolpropane, glycerine
Acrylate or two (methyl) acrylate, the epoxy acrylate such as bisphenol A modified epoxy acrylate etc..
As above by amino obtained from making isocyanates and there is the reaction of (methyl) acrylic acid derivative of hydroxyl
Formic acid esters (methyl) acrylate, specifically, for example, can be obtained by following step, i.e. add trimethylolpropane
134 parts by weight, the parts by weight of BHT 0.2 as polymerization inhibitor, the weight of dibutyl tin dilaurate 0.01 as catalysts
Part, the parts by weight of IPDI 666, carry out reacting while return stirring 2 hours at 60 DEG C, then, add
The parts by weight of 2-Hydroxy ethyl acrylate 51, carry out return stirring while air is sent at 90 DEG C, at the same time make its anti-
Answer 2 hours.
As commercially available above-mentioned carbamate (methyl) acrylate, for example, it can include M-1100, M-1200, M-
1210th, 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 systems), ArtresinUN-9000H, ArtresinUN-9000A,
ArtresinUN-7100、ArtresinUN-1255、ArtresinUN-330、ArtresinUN-3320HB、ArtresinUN-
1200TPK, ArtresinSH-500B (being Gen Shang industrial groups system), 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 chemical industrial company of Xin Zhong villages 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 the dysgenic side to liquid crystal
Face, it is however preferred to have-OH bases ,-NH- bases ,-NH2The curable resin of the unit of the hydrogen bonds such as base, goes out from easiness of synthesis etc.
Hair, particularly preferably epoxy (methyl) acrylate.
In addition, for the above-mentioned curable resin with (methyl) acryloyl group, from the height of reactivity, being preferably
There is the curable resin of (methyl) acryloyl group 2~3 in the molecule.
The sealing material for liquid crystal display device of the present invention preferably also coordinates the resin with epoxy radicals to be used as curable resin.
As the commercially available resin with epoxy radicals, it can include：It is used as the above-mentioned original for synthesizing epoxy (methyl) acrylate
The epoxide of material and resin for including etc..In addition, the resin with epoxy radicals can also be had in 1 molecule
The compound of (methyl) acryloyl group and epoxy radicals.As such compound, for example, it can include：By making that there are 2
The epoxy radicals of a part for the compound of epoxy radicals above and compound etc. obtained from (methyl) propylene acid reaction.So lead to
The epoxy radicals for the part for making the compound with epoxy radicals is crossed with compound etc. obtained from (methyl) propylene acid reaction also may be used
To be considered as the above-mentioned curable resin with (methyl) acryloyl group.
For the epoxy radicals above by the part for making the compound with the epoxy radicals of more than 2 and (methyl) propylene
, for example can be by making epoxy resin with (methyl) acrylic acid according to conventional methods in alkalescence for compound obtained by acid reaction
React and obtain in the presence of catalyst.Specifically, phenol novolak type epoxy resin N-770 (DIC companies are for example made
System) 190g dissolve in toluene 500mL, and addition triphenylphosphine 0.1g, obtains uniform solution, resulting in the solution
Acrylic acid 35g was added dropwise with 2 hours under return stirring in solution, return stirring is then further carried out 6 hours, first is removed
Benzene, thus, can obtain 50 moles of % epoxy radicals and part acrylic acid modified phenol phenolic varnish type obtained by propylene acid reaction
Epoxy resin (has carried out the modification of 50% part acrylic acid) in this case.
It is used as the commercially available epoxy radicals above by the part for making the compound with the epoxy radicals of more than 2 and (first
Base) compound obtained by propylene acid reaction, it can for example include EBECRYL 1561 (Daicel cytec systems).
For the sealing material for liquid crystal display device of the present invention, (methyl) acryloyl group is preferably set to be coexisted with epoxy radicals,
It is preferred that coordinating in the way of the mol ratio of (methyl) acryloyl group of curable resin and epoxy radicals reaches 50: 50~95: 5 has
The curable resin of (methyl) acryloyl group and the resin with epoxy radicals.
The sealing material for liquid crystal display device of the present invention contains curing agent.
As above-mentioned curing agent, it can include for making (methyl) acryloyl group be reacted by light such as ultraviolets
Optical free radical polymerization initiator, for making (methyl) acryloyl group, by heat, the hot radical that reacts polymerize and triggered
Agent, for making light cationic polymerization initiator that epoxy radicals reacted by UV, for making epoxy radicals occur by heat
The hot epoxy hardener of reaction.
Above-mentioned optical free radical polymerization initiator is not particularly limited, and as commercially available product, for example, can include
IRGACURE184、IRGACURE369、IRGACURE379、IRGACURE651、IRGACURE819、IRGACURE907、
IRGACURE2959, IRGACURE OXE01, Lucirin TPO (being Japanese BASF AG's system), benzoin methyl ether, benzene are even
Relation by marriage ethylether, benzoin isopropyl ether (being Tokyo chemical conversion industry company system above) etc., ADEKA CRUISE NCI 930
(ADEKA company systems) etc..
The content of above-mentioned optical free radical polymerization initiator is not particularly limited, and has (methyl) acryloyl group relative to above-mentioned
The parts by weight of curable resin 100 for, preferred lower limit is 0.1 parts by weight, and the upper limit preferably is 10 parts by weight.If above-mentioned light
The content of radical polymerization initiator is less than 0.1 parts by weight, then can not make the sealing material for liquid crystal display device of the present invention sometimes
Cure sufficiently.If the content of above-mentioned optical free radical polymerization initiator is more than 10 parts by weight, storage stability is reduced sometimes.
Above-mentioned hot radical polymerization initiator is not particularly limited, and can include peroxide and azo-compound, makees
For commercially available product, for example, it can include PERBUTYL O, PERHEXYL O, PERBUTYL PV (being day oily company system), V-
30th, V-501, V-601, VPE-0201, VPE-0401, VPE-0601 (being and Wako Pure Chemical Industries company system) etc..
The content of above-mentioned hot radical polymerization initiator is not particularly limited, and has (methyl) acryloyl group relative to above-mentioned
The parts by weight of curable resin 100 for, preferred lower limit is 0.01 parts by weight, and the upper limit preferably is 10 parts by weight.If above-mentioned
The content of hot radical polymerization initiator is less than 0.01 parts by weight, then can not make the sealing used for liquid crystal display element of the present invention sometimes
Agent is cured sufficiently.If the content of above-mentioned hot radical polymerization initiator is reduced more than 10 parts by weight, sometimes storage stability.
Above-mentioned light cationic polymerization initiator is not particularly limited, and as commercially available product, for example, can include ADEKA
OPTOMER SP-150, ADEKA OPTOMER SP-170 (being ADEKA company systems) etc..
The content of above-mentioned light cationic polymerization initiator is not particularly limited, relative to the above-mentioned resin with epoxy radicals
For 100 parts by weight, lower limit preferably is 0.1 parts by weight, and the upper limit preferably is 10 parts by weight.If above-mentioned smooth cationic polymerization draws
The content for sending out agent is less than 0.1 parts by weight, then can not cure sufficiently sometimes the sealing material for liquid crystal display device of the present invention.If
The content of above-mentioned light cationic polymerization initiator is more than 10 parts by weight, then storage stability is reduced sometimes.
As above-mentioned hot epoxy hardener, for example, it can include organic acid hydrazides, imdazole derivatives, amines, many
First phenolic compound, acid anhydrides etc..Wherein, the organic acid hydrazides of solid is preferably used.
The organic acid hydrazides of above-mentioned solid is not particularly limited, for example, can include sebacic dihydrazide, isophthalic diformazan
Acid dihydrazide, adipic dihydrazide, acid dihydrazide etc., as commercially available product, for example, can include SDH (Japan
Finechem company systems), ADH (great mound chemical company system) etc..In addition, in addition to this it is possible to using AMICURE VDH,
AMICURE VDH-J, AMICURE UDH (being AJINOMOTO FINE-TECHNO company systems) etc..
For the content of above-mentioned hot epoxy hardener, for the above-mentioned parts by weight of resin 100 with epoxy radicals,
It is preferred that lower limit be 1 parts by weight, the preferred upper limit is 50 parts by weight.If the content of above-mentioned hot epoxy hardener is less than 1 parts by weight,
Sometimes the sealing material for liquid crystal display device of the present invention can not then cured sufficiently.If the content of above-mentioned hot epoxy thermosetting agent
More than 50 parts by weight, then the viscosity of sealing material for liquid crystal display device of the invention increases, and coating etc. is damaged sometimes.Above-mentioned heat
The preferred upper limit of the content of epoxy hardener is 30 parts by weight.
Using the improvement of the adhesivity based on stress dispersion effect, improvement of linear expansivity etc. as purpose, liquid of the invention
Crystal display element sealant can also contain filler.
Above-mentioned filler is not particularly limited, for example, can include talcum, asbestos, silica, diatomite, illiteracy de-
Stone, bentonite, calcium carbonate, magnesium carbonate, aluminum oxide, montmorillonite, zinc oxide, iron oxide, magnesia, tin oxide, titanium oxide, hydrogen-oxygen
Change magnesium, aluminium hydroxide, bead, silicon nitride, barium sulfate, gypsum, calcium silicates, sericite atlapulgite, aluminium nitride etc. are inorganic to be filled out
Fill the organic fillers such as agent, and polyester micropartical, polyurethane particulate, polyvinyl particulate, acrylate copolymer particulate.
The sealing material for liquid crystal display device of the present invention can also be containing other silicon beyond silane coupler of the invention
Alkane coupling agent.Above-mentioned other silane couplers are not particularly limited, and preferably use such as gamma-amino propyl trimethoxy silicon
Alkane, γ mercaptopropyitrimethoxy silane, γ-glycidoxypropyltrimethoxy silane, γ-isocyanates propyl group trimethoxy
Base silane etc..These other silane couplers can be used alone, and can also use two or more.
The sealing material for liquid crystal display device of the present invention can also contain as needed：For adjusting the reactive dilute of viscosity
Release agent, the thixotropic thixotropic agent of regulation, for adjusting the polymeric beads of panel gap part, 3- rubigan -1,1- bis- at equal intervals
Other known additives such as the curing accelerators such as MU, defoamer, levelling agent, polymerization inhibitor.
The method for manufacturing the sealing material for liquid crystal display device of the present invention is not particularly limited, for example can the side of being listed below
Method etc.：Using mixers such as homogeneous dispersion machine, homogeneous mixer, universal mixer, planetary-type mixer, kneader, three rollers,
To the curable resin with (methyl) acryloyl group, curing agent, selected from surface treatment hydrotalcite, surface treatment calcium carbonate, gather
Imide particle, nitrile rubber particulate, 3- alkoxysilyls propylsuccinic anhydride, by formula (1) represent compound, by formula
(2) at least one of the compound represented and the compound by formula (3) expression and other silane being added as needed on are even
The additives such as connection agent are mixed.
The liquid crystal display cells being made using the sealing material for liquid crystal display device of the present invention are also one of present invention.
As the method for the liquid crystal display cells of the manufacture present invention, such as can enumerate the method including following process；
That is, by the sealing material for liquid crystal display device of the present invention on 1 that ito thin film etc. has electrode and the transparency carrier of alignment films
Deng the process for forming rectangular seal pattern by silk-screen printing, distributor coating etc., in the liquid crystal display cells of the present invention
The droplet of liquid crystal is dripped in the state of uncured with sealant etc. and overlapped at once after being coated on the inframe entire surface of transparency carrier
The process of another transparency carrier, to the seal pattern partial illumination ultraviolet of the sealing material for liquid crystal display device of the present invention etc.
Make the process of sealant precuring, and the work for being heated to the sealant after precuring and making it carry out main solidification Deng light
Sequence.
The effect of invention
According to the present invention it is possible to provide excellent to the adhesivities of alignment films and not produce the liquid crystal of liquid crystal pollution substantially
Show element sealant.In addition, according to the present invention it is possible to providing the liquid crystal being made using the sealing material for liquid crystal display device
Show element.
Embodiment
Hereinafter, embodiment is enumerated to give the account in greater detail to the mode of the present invention, but the present invention is not limited only to these
Embodiment.
(embodiment 1~54 and comparative example 1~5)
Match ratio according to described in table 1~10, uses planetary stirring machine (THINKY company systems, " あ わ と りToo
Youth ") by after the mixing of each material, reuse three rollers and mixed, thus, prepare embodiment 1~54 and comparative example 1~5
Sealing material for liquid crystal display device.
In the alignment films of the substrate with transparency electrode and alignment films (Nissan Chemical company system " SE7492 "), by gained
To sealing material for liquid crystal display device by depict square frame in the way of be coated with distributor.Then, by liquid crystal
The droplet of (Chisso company systems " JC-5004LA "), which drips, is applied to the inframe entire surface of substrate, and another is overlapped under vacuo
Substrate with transparency electrode and alignment films.After Vacuum solutions are removed, sealing material for liquid crystal display device is set to solidify and obtain liquid crystal
Show element.
It should be noted that the solidification of sealing material for liquid crystal display device by ultraviolet by carrying out 3000mJ/cm2Irradiation
Heat 1 hour and carry out at 120 DEG C again afterwards.
It should be noted that the partially modified things of N-770 in table 1~10 are prepared by following method.
That is, phenol novolak type epoxy resin (DIC company systems " N-770 ") 190g is made to be dissolved in toluene 500mL,
Triphenylphosphine 0.1g is added in the solution, uniform solution is obtained.By acrylic acid under return stirring in resulting solution
35g was added dropwise with 2 hours, then further carried out 6 hours return stirrings.Toluene is removed, thus, is obtained 50mol% epoxy
The part propylene that base is modified to acryloyl group is acylated epoxy resin (the partially modified things of N-770).
(evaluation)
For the sealing material for liquid crystal display device and liquid crystal display cells obtained in embodiment and comparative example, pass through
Following method is evaluated.
Show the result in table 1~10.
(1) evaluation of adhesive strength
In the resulting parts by weight of sealing material for liquid crystal display device 100, using planetary agitating device to average grain
The polymeric beads that 5 μm of footpath (ponding chemical industrial company system " Micropearl SP ") 3 parts by weight are disperseed, and obtain uniform
Liquid.The liquid of the gained of denier is placed in glass substrate (20mm × 50mm × 1.1mmt) central portion, overlapped thereon
The glass substrate of homotype, expands sealing material for liquid crystal display device.100mW/cm is irradiated in this condition2Ultraviolet 30
Second.Then, heated 1 hour at 120 DEG C, obtain adhesive test piece.
For resulting adhesive test piece, adhesive strength (comparative unit is determined using tensometer：N/cm2).As
Glass substrate, glass using blank glass (Coming 1737), with TN alignment films SE7492 (Nissan Chemical company systems),
This 3 kinds of the glass with VA alignment films JALS2021 (JSR company systems).
(2) the irregular evaluation of the display of liquid crystal display cells
For resulting liquid crystal display cells, sealant periphery is visually observed under "on" position and unpowered state
Liquid crystal produced by color spot.Situation without color spot completely is evaluated as " ◎ ", the almost situation without color spot is evaluated as
"○", " △ " is evaluated as by the situation for having a small amount of color spot, and the situation for having a large amount of color spots is evaluated as into "×".
(3) evaluation of the viscosity stability of sealant
It is dark at 25 DEG C for the sealing material for liquid crystal display device obtained in embodiment 23~47 and comparative example 1,5
Place is preserved 24 hours, and the viscosity before and after keeping is determined with E types viscosimeter, determine rate of viscosity increase (viscosity after keeping in 24 hours/
Viscosity before keeping).
Industrial applicability
According to the present invention it is possible to provide excellent to the adhesivities of alignment films and not produce the liquid crystal of liquid crystal pollution substantially
Display element sealant.In addition, according to the present invention it is possible to providing the liquid being made using the sealing material for liquid crystal display device
Crystal display element.
Claims (3)
1. a kind of sealing material for liquid crystal display device, it is characterised in that
Contain：Curable resin with (methyl) acryloyl group, curing agent, and selected from 3- alkoxysilyl propylsuccinics
Acid anhydrides, the compound represented by following formula (1), the compound represented by following formula (2) and the change represented by following formula (3)
At least one of compound,
Wherein, the 3- alkoxysilyls propylsuccinic anhydride, by following formula (1) represent compound, by following formula (2)
The compound of expression, the use level of the compound represented by following formula (3) are relative to the parts by weight of curable resin 100
0.2~10 parts by weight,
In formula (1), R1Represent methyl, methoxyl group or ethyoxyl, R2、R3Represent in methoxy or ethoxy, formula (2), R4Represent
Methyl, methoxyl group or ethyoxyl, R5、R6Represent in methoxy or ethoxy, formula (3), R7Represent methoxy or ethoxy.
2. sealing material for liquid crystal display device according to claim 1, it is characterised in that contain：With (methyl) propylene
The curable resin of acyl group, curing agent, selected from least one of fatty acid treatment calcium carbonate and medlin particulate, and choosing
The compound represented from 3- alkoxysilyls propylsuccinic anhydride, by formula (1), the compound represented by formula (2), Yi Jiyou
At least one of compound that formula (3) is represented.
3. a kind of liquid crystal display cells, it is characterised in that be the sealing used for liquid crystal display element described in usage right requirement 1 or 2
Agent and be made.
Applications Claiming Priority (11)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011178455 | 2011-08-17 | ||
| JP2011-178456 | 2011-08-17 | ||
| JP2011178454 | 2011-08-17 | ||
| JP2011178456 | 2011-08-17 | ||
| JP2011-178457 | 2011-08-17 | ||
| JP2011-178454 | 2011-08-17 | ||
| JP2011178457 | 2011-08-17 | ||
| JP2011-178455 | 2011-08-17 | ||
| JP2011-179023 | 2011-08-18 | ||
| JP2011179023 | 2011-08-18 | ||
| CN201280011440.6A CN103430086B (en) | 2011-08-17 | 2012-08-08 | Sealing agent for liquid crystal display element and liquid crystal display element |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280011440.6A Division CN103430086B (en) | 2011-08-17 | 2012-08-08 | Sealing agent for liquid crystal display element and liquid crystal display element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106978122A true CN106978122A (en) | 2017-07-25 |
Family
ID=47715088
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610857623.XA Pending CN106978122A (en) | 2011-08-17 | 2012-08-08 | Sealing material for liquid crystal display device and liquid crystal display cells |
| CN201310404377.9A Expired - Fee Related CN103487995B (en) | 2011-08-17 | 2012-08-08 | Sealing material for liquid crystal display device and liquid crystal display cells |
| CN201280011440.6A Active CN103430086B (en) | 2011-08-17 | 2012-08-08 | Sealing agent for liquid crystal display element and liquid crystal display element |
Family Applications After (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310404377.9A Expired - Fee Related CN103487995B (en) | 2011-08-17 | 2012-08-08 | Sealing material for liquid crystal display device and liquid crystal display cells |
| CN201280011440.6A Active CN103430086B (en) | 2011-08-17 | 2012-08-08 | Sealing agent for liquid crystal display element and liquid crystal display element |
Country Status (5)
| Country | Link |
|---|---|
| JP (2) | JP5281204B1 (en) |
| KR (2) | KR101357327B1 (en) |
| CN (3) | CN106978122A (en) |
| TW (2) | TWI544261B (en) |
| WO (1) | WO2013024768A1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102224443B1 (en) * | 2014-12-10 | 2021-03-09 | 엘지디스플레이 주식회사 | Liquid Crystal Display Device |
| KR20180042337A (en) * | 2015-08-21 | 2018-04-25 | 디아이씨 가부시끼가이샤 | Liquid crystal display element |
| JP6717005B2 (en) * | 2016-03-31 | 2020-07-01 | 日立化成株式会社 | Resin composition, cured product, resin film, sealing material and sealing structure |
| CN109072040B (en) * | 2016-08-09 | 2023-02-03 | 积水化学工业株式会社 | Adhesive composition, cured body, electronic component, and assembled component |
| JP6844271B2 (en) * | 2017-01-18 | 2021-03-17 | 日油株式会社 | A color filter comprising a thermosetting resin composition and a cured film thereof. |
| KR102267591B1 (en) | 2018-11-20 | 2021-06-18 | 주식회사 엘지화학 | Liquid crystal alignment composition, method of preparing liquid crystal alignment film, and liquid crystal alignment film, liquid crystal display using the same |
| KR102267590B1 (en) | 2018-11-20 | 2021-06-18 | 주식회사 엘지화학 | Liquid crystal alignment composition, method of preparing liquid crystal alignment film, and liquid crystal alignment film, liquid crystal display using the same |
| KR102410008B1 (en) | 2019-01-21 | 2022-06-16 | 주식회사 엘지화학 | Liquid crystal alignment composition, and liquid crystal alignment film, liquid crystal display using the same |
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- 2012-08-08 CN CN201310404377.9A patent/CN103487995B/en not_active Expired - Fee Related
- 2012-08-08 CN CN201280011440.6A patent/CN103430086B/en active Active
- 2012-08-08 KR KR1020137018415A patent/KR101357327B1/en active IP Right Grant
- 2012-08-08 WO PCT/JP2012/070223 patent/WO2013024768A1/en active Application Filing
- 2012-08-08 KR KR1020137018537A patent/KR101953925B1/en active IP Right Grant
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Also Published As
| Publication number | Publication date |
|---|---|
| TW201341911A (en) | 2013-10-16 |
| TW201312233A (en) | 2013-03-16 |
| CN103487995A (en) | 2014-01-01 |
| KR20130097805A (en) | 2013-09-03 |
| WO2013024768A1 (en) | 2013-02-21 |
| TWI425282B (en) | 2014-02-01 |
| JPWO2013024768A1 (en) | 2015-03-05 |
| CN103487995B (en) | 2018-01-09 |
| CN103430086A (en) | 2013-12-04 |
| KR101953925B1 (en) | 2019-03-04 |
| JP5960636B2 (en) | 2016-08-02 |
| KR20140037033A (en) | 2014-03-26 |
| KR101357327B1 (en) | 2014-02-03 |
| JP5281204B1 (en) | 2013-09-04 |
| TWI544261B (en) | 2016-08-01 |
| CN103430086B (en) | 2014-09-03 |
| JP2013167888A (en) | 2013-08-29 |
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