CN104471470A - Liquid-crystal sealing material and liquid-crystal display cell obtained using same - Google Patents
Liquid-crystal sealing material and liquid-crystal display cell obtained using same Download PDFInfo
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- CN104471470A CN104471470A CN201380037808.0A CN201380037808A CN104471470A CN 104471470 A CN104471470 A CN 104471470A CN 201380037808 A CN201380037808 A CN 201380037808A CN 104471470 A CN104471470 A CN 104471470A
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- 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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- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/10—Epoxy resins modified by unsaturated compounds
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Abstract
Proposed is a liquid-crystal sealing material for liquid-crystal dropping methods which has excellent resistance to liquid-crystal penetration thereinto and is also excellent in terms of general properties required of liquid-crystal sealing materials, such as adhesion strength, and which facilitates the production of a liquid-crystal display cell having excellent long-term reliability. This liquid-crystal sealing material for liquid-crystal dropping methods contains a solid ingredient (I), wherein in cases when the specific gravity of the solid ingredient (I) is expressed by A [g/cm3], the content of the ingredient (I) in the liquid-crystal sealing material by B [g], and the volume of the liquid-crystal sealing material by C [cm3], the A, B, and C satisfy numerical expression (a). In viscosity examination with an E-type viscometer at 25 Degree Centigrate under the conditions of 5 rpm and 0.5 rpm, the sealing material has a thixotropic ratio, shown by (viscosity at 0.5 rpm)/(viscosity at 5 rpm), of 1.1-3.0. 0.2<=B/(A*C)<=0.4 (a).
Description
Technical field
The present invention relates to the liquid crystal sealing agent used in liquid crystal dripping process and the liquid crystal display using it.More specifically, relate to liquid crystal excellent to the insertion patience of liquid crystal sealing agent, and as bonding strength etc. as liquid crystal dripping process liquid crystal sealing agent also excellent in the general characteristic of liquid crystal sealing agent and the liquid crystal display using it.
Background technology
Along with the maximization of liquid crystal display in recent years, as the manufacture method of liquid crystal display, propose the higher so-called liquid crystal dripping process of production (patent documentation 1,2).This liquid crystal dripping process is more particularly by a substrate of fitting again after dripping liquid crystal to the inner side forming the weir be made up of liquid crystal sealing agent on one substrate, the manufacture method of solidifying the liquid crystal display of liquid crystal sealing agent afterwards.
But, in liquid crystal dripping process, before liquid crystal sealing agent solidification, liquid crystal contacts with liquid crystal sealing agent, generation is inserted into the phenomenon in liquid crystal sealing agent because of the pressure of liquid crystal, in the worst case, the weir be sometimes made up of liquid crystal sealing agent can crumble and have problems.This problem and use up and heat liquid crystal dripping process in, also when exist as distribution etc. shadow and do not irradiate sufficient ultraviolet part produce.In addition, Ultraviolet radiation is not being carried out, only by particularly large problem when heat curing liquid crystal sealing agent.In order to solve this problem, need the precision of the amount of dripping improving liquid crystal, even if but like this, when the heating of the curing process as liquid crystal sealing agent, liquid crystal also expands, therefore be difficult to suppress above-mentioned insertion phenomenon completely.
In addition, in liquid crystal dripping process liquid crystal sealing agent, the various problem of the operability of the general characteristic or storage stability etc. solving low liquid crystal pollution, high-adhesive-strength, high moisture-proof, high-fire resistance etc. and so on is needed.
In order to solve this problem, propose various technology.
In patent documentation 3, organobentonite is used to realize the solution of above-mentioned problem.The method is inserted with certain achievement to liquid crystal, but is difficult to be enough.
In patent documentation 4, describe use have employed forging silica, polymercaptan liquid crystal sealing agent, carry out the method for the B-stage process of liquid crystal sealing agent.But, in the method, there is the shortcoming that operation is elongated, need the device and so on for this operation.
In patent documentation 5, disclose the liquid crystal dripping process liquid crystal sealing agent preventing from inserting by using hot radical polymerization initiator to improve curing rate.
As previously discussed, although hanker after very much the exploitation carrying out liquid crystal sealing agent, there is excellent insertion patience and not yet complete exploitation as the sealant that the general characteristic of the liquid crystal sealing agent of low liquid crystal pollution, high-adhesive-strength etc. is also excellent.
Prior art document
Patent documentation
Patent documentation 1: Japanese Laid-Open Patent Publication 63-179323 publication
Patent documentation 2: Japanese Unexamined Patent Publication 10-239694 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2010-14771 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2011-150181 publication
Patent documentation 5: No. 2011/061910th, International Publication
Summary of the invention
The problem that invention will solve
The present invention relates to the liquid crystal sealing agent used in liquid crystal dripping process and the liquid crystal display using it, more specifically, liquid crystal is proposed to the excellent and liquid crystal dripping process liquid crystal sealing agent that the general characteristic as liquid crystal sealing agent of bonding strength etc. is also excellent of the insertion patience of liquid crystal sealing agent and the liquid crystal display using it.
The means of technical solution problem
The present inventor is the liquid crystal sealing agent containing solid composition (I) through the result studied with keen determination, finds the proportion A (g/cm of the solid composition (I) in liquid crystal sealing agent
3), the volume C (cm of content B (g) in the liquid crystal sealing agent of this solid composition (I), liquid crystal sealing agent
3) between when having certain relation, there is very excellent insertion characteristic, made the present invention.
In addition; in this instructions; " (methyl) acrylic acid ((metha) acryl) " means " acrylic acid (acryl) and/or methacrylic acid (methaacryl) ", and " (methyl) acryloyl group ((metha) acryloyl) " means " acryloyl group and/or methacryl ".In addition, also have " liquid crystal dripping process liquid crystal sealing agent " situation referred to as " liquid crystal sealing agent ".
Namely the present invention relates to following 1) ~ 12).
1) a liquid crystal dripping process liquid crystal sealing agent, containing solid composition (I), is A (g/cm at the proportion of the above-mentioned solid composition (I) of definition
3), the content in liquid crystal sealing agent is B (g), and the volume of definition liquid crystal sealing agent is C (cm
3) time, above-mentioned A, B and C meet following numerical expression (a), further, measure in the value of the viscosity obtained at use E type viscosity meter under the condition of 5rpm and 0.5rpm of 25 DEG C, the thixotropic ratio represented with the viscosity of the viscosity under 0.5rpm/under 5rpm is for 1.1 ~ 3.0:
0.2≦B/(A×C)≦0.4……(a)。
2) according to above-mentioned 1) described in liquid crystal dripping process liquid crystal sealing agent, wherein, above-mentioned A (g/cm
3) be 0.85 ~ 1.10g/cm
3.
3) according to above-mentioned 1) or 2) described in liquid crystal dripping process liquid crystal sealing agent, wherein, in the total amount of above-mentioned solid composition (I), the Shore A hardness containing more than 85 quality % is the solid composition (I-1) of 10 ~ 70.
4) according to above-mentioned 3) described in liquid crystal dripping process liquid crystal sealing agent, wherein, above-mentioned solid composition (I-1) is the one kind or two or more solid composition being selected from silicon rubber, styrene rubber, styrene olefinic rubber, acrylic acid (ester) rubber.
5) according to above-mentioned 1) to 4) according to any one of liquid crystal dripping process liquid crystal sealing agent, also containing (methyl) acrylated epoxy resins (II), thermal curing agents (III) and hot radical polymerization initiator (IV).
6) according to above-mentioned 5) described in liquid crystal dripping process liquid crystal sealing agent, wherein, above-mentioned (methyl) acrylated epoxy resins (II) is (methyl) acrylate compound of resorcinolformaldehyde resin (resorcin diglycidylether).
7) according to above-mentioned 5) or 6) described in liquid crystal dripping process liquid crystal sealing agent, wherein, above-mentioned thermal curing agents (III) is multivalence hydrazides (hydrazide) compound.
8) according to above-mentioned 5) to 7) according to any one of liquid crystal dripping process liquid crystal sealing agent, wherein, above-mentioned hot radical polymerization initiator (IV) is two (trimethylsiloxane group)-1,1 of 1,2-, 2,2-tetraphenyl ethane (1,2-bis (trimethylsiloxy)-1,1,2,2-tetraphenyl ethane).
9) according to above-mentioned 1) to 8) according to any one of liquid crystal dripping process liquid crystal sealing agent, also containing silane coupling agent (V).
10) according to above-mentioned 1) to 9) according to any one of liquid crystal dripping process liquid crystal sealing agent, also containing epoxy resin (VI).
11) a kind of manufacture method of liquid crystal display, wherein, in the liquid crystal display be made up of two pieces of substrates, to formed on one substrate by above-mentioned 1) to 10) and according to any one of the inner side on weir that forms of liquid crystal dripping process liquid crystal sealing agent drip after liquid crystal, to fit another substrate, utilize the above-mentioned liquid crystal dripping process liquid crystal sealing agent of heat curing afterwards.
12) liquid crystal display, it is by solidifying above-mentioned 1) to 10) according to any one of liquid crystal dripping process liquid crystal sealing agent and the solidfied material sealing that obtains.
The effect of invention
Liquid crystal sealing agent of the present invention is very excellent in the patience of the insertion to liquid crystal.Therefore, the manufacture of liquid crystal display is simplified.In addition, the general characteristic as the liquid crystal sealing agent of bonding strength etc. is also excellent, therefore the liquid crystal display long-term reliability completed is high.Namely the present invention easily can manufacture excellent liquid crystal display.
Embodiment
Liquid crystal sealing agent of the present invention contains solid composition (I), it is characterized in that, this solid composition (I) is A (g/cm at definition proportion
3), the content in liquid crystal sealing agent is B (g), and the volume of liquid crystal sealing agent is C (cm
3) time, above-mentioned A, B and C meet following formula (a):
0.2≦B/(A×C)≦0.4……(a)。
Utilize above-mentioned formula, the volume occupation rate in the liquid crystal sealing agent of solid composition (I) can be calculated.That is, the volume occupation rate in liquid crystal sealing agent is crossed and is reduced partition characteristic at most, can not get inserting patience fully time very few.Here, the upper limit of above-mentioned volume occupation rate is 0.4, and lower limit is 0.2.With this numerical value for border, effect has clear and definite difference.That is, when volume occupation rate is more than 0.4, thixotropic ratio rises, and rectilinearity during sealing coating is deteriorated, and produces the insertion of liquid crystal when then fitting time less than 0.2.In addition, in the proportion A energy water of solid composition (I), method of substitution (JISK7112) is measured.
In addition, the feature of liquid crystal sealing agent of the present invention is, in the value of the viscosity using E type viscosity meter to measure under the condition of 5rpm and 0.5rpm of 25 DEG C, the thixotropic ratio represented with the viscosity of the viscosity under 0.5rpm/under 5rpm is for 1.1 ~ 3.0.When thixotropic ratio is more than 3.0, rectilinearity during sealing coating is deteriorated, and when thixotropic ratio is less than 1.1, the cutting of sealant is deteriorated.When the cutting of sealant is deteriorated, the terminal when sealing coating, produces the state of extension line, produces the problem that can not perfect draw.
In this manual, solid composition (I) means the composition that organic filler, inorganic filler etc. do not participate in chemical reaction.That is, the solid composition except the curing accelerator, the epoxy resin of solid, the Epocryl of solid etc. of thermal curing agents (III), hot radical polymerization initiator (IV), solid is meant.
In addition, to above-mentioned proportion A, method of substitution in water is not used can to calculate according to manufacturer's Directory Value yet.Such as, the proportion A when mixing organic filler and inorganic filler can calculate in order to lower formula.
A (g/cm
3inorganic filler containing ratio in the proportion × solid composition (I) of the organic filler containing ratio+inorganic filler in the proportion × solid composition (I) of)=organic filler
Even if the method is that the potpourri of more than 3 compositions is also applicable at solid composition (I).
Volume C (the cm of content B (g) in liquid crystal sealing agent, liquid crystal sealing agent
3) be the numerical value determined according to the sample size taked arbitrarily, can make to use graduated cylinder, electronics Libra etc. to measure from the liquid crystal sealing agent from the deaeration fully such as revolution type vacuum defoamation machine.
As above-mentioned solid composition (I), mean organic filler, inorganic filler.
As the example of organic filler, natural rubber (NR) can be exemplified, isoprene rubber (IR), butadiene rubber (BR), styrene butadiene ribber (SBR), butyl rubber (IIR), nitrile rubber (NBR), ethylene propylene rubber (EPM, EP), chloroprene rubber (CR), acrylic acid (ester) rubber (ACM, ANM), chlorosulfonated polyethylene rubber (CSM), urethane rubber (PUR), silicon rubber (SI, SR), fluororubber (FKM, FPM), polysulfide rubber (thiokol (thiokol)) etc.These solid compositions (I) can mix two or more and use.Wherein, silicon rubber, styrene rubber, styrene olefinic rubber, acrylic acid (ester) rubber is preferably.
As above-mentioned silicon rubber, preferred KMP-594, KMP-597, KMP-598 (more than, SHIN-ETSU HANTOTAI's chemical industry system), TREFIL
rTMe-5500,9701, EP-2001 (more than, Dow CorningToray Co., Ltd. system), as the preferred RABALON of styrene rubber
rTMt320C, T331C, SJ4400, SJ5400, SJ6400, SJ4300C, SJ5300C, SJ6300C (more than, Mitsubishi Chemical's system), as styrene olefinic rubber, preferred SEPTON
rTMsEPS2004, SEPS2063.In addition, in this instructions, above with " RTM " mean registered trademark.
In addition, when using aforesaid propylene acid (ester) rubber, the situation of acrylic acid (ester) rubber of the core-shell construction be preferably made up of two kinds of acrylic acid (ester) rubber, particularly preferably stratum nucleare is n-butyl acrylate, and shell is methyl methacrylate.This is as ZEFIAC
rTMf-351 is sold by Aica Industry Stock Company.
When the mean grain size of organic filler is excessive, gap when becoming lower glass substrate in laminating when the liquid crystal cells of narrow gap manufactures forms the undesirable element having some setbacks and wait, and less than 20 μm is suitable, preferably less than 10 μm.Particle diameter can be measured with electron microscope method.
As the example of the inorganic filler of above-mentioned solid composition (I), fused silica can be exemplified, crystalline silica, silit, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, barium sulphate, calcium sulphate, mica, talcum, clay, aluminium oxide, magnesium oxide, zirconia, aluminium hydroxide, magnesium hydroxide, calcium silicate, alumina silicate, lithium aluminium silicate, zirconium silicate, barium titanate, glass fibre, carbon fiber, molybdenum disulfide, asbestos etc., be preferably fused silica, crystalline silica, silicon nitride, boron nitride, calcium carbonate, barium sulphate, calcium sulphate, mica, talcum, clay, aluminium oxide, aluminium hydroxide, calcium silicate, alumina silicate, be more preferably fused silica, crystalline silica, aluminium oxide, talcum.These inorganic fillers can mix two or more use.Gap when becoming lower glass substrate in laminating when the liquid crystal cells of narrow gap manufactures when its mean grain size is excessive forms the undesirable element having some setbacks and wait, and is suitable below 3 μm, preferably less than 2 μm.Particle diameter is by laser diffraction and scattering formula particle size distribution measurement device (dry type) (SEISHIN enterprise of joint-stock company system; LMS-30) measure.
In addition, the proportion A (g/cm of preferred above-mentioned solid composition (I)
3) be 0.85 ~ 1.10.In this case, the impact of inserting patience is become more remarkable.
And in the total amount of above-mentioned solid composition (I), the solid composition (I-1) being preferably 10 ~ 70 containing Shore A hardness is the situation of more than 85 quality %.Situation again further preferably containing more than 90 quality %.In addition, Shore A hardness can be measured with JISK6253.Here, be the solid composition (I-1) of 10 ~ 70 as Shore A hardness, be equivalent to above-mentioned silicon rubber, styrene rubber, styrene olefinic rubber, acrylic acid (ester) rubber etc.
The volume occupation rate of the above-mentioned solid composition (I) of liquid crystal sealing agent of the present invention meets above-mentioned mathematical expression (a) and thixotropic ratio is included in above-mentioned given area, other compositions are not particularly limited, preferably containing (methyl) acrylated epoxy resins (II), thermal curing agents (III), hot radical polymerization initiator (IV).
(methyl) acrylated epoxy resins (II) obtains by epoxy resin and (methyl) acrylic acid well-known reaction.Such as, by adding (methyl) acrylic acid of set equivalent proportion and catalyzer to epoxy resin (such as, benzyl dimethylamine, triethylamine, benzyltrimethylammonium chloride, triphenylphosphine hydrogen, triphenyl antimonous hydride etc.) and polymerization preventing agent (such as first quinone (methoquinone), quinhydrones, methyl hydroquinone (methylhydroquinone), phenothiazine, dibutyl hydroxy toluene etc.), and carry out such as 80 ~ 110 DEG C of esterifications and obtain.As the epoxy resin of raw material, be not particularly limited, preferably 2 officials can above epoxy resin, such as can enumerate the diglycidyl ether of resorcinol, bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F phenolic type epoxy resin, alicyclic epoxy resin, aliphatics chain epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hydantoins type epoxy resin, isocyanuric acid ester type epoxy resin, there is the phenol novolak type epoxy resin of tris-phenol skeleton, in addition, the 2-glycidyl etherate of two trifunctional phenol classes, the 2-glycidyl etherate of two sense alcohols and halogenide thereof, hydride etc.Wherein, from the viewpoint of liquid crystal pollution, the more preferably diglycidyl ether of bisphenol-type epoxy resin, phenolic resin varnish type epoxy resin, resorcinol.
The content of above-mentioned (methyl) acrylated epoxy resins (II) considers the operability of the liquid crystal sealing agent that can obtain, physical property suitably determines, usually, is about 25 ~ 80 quality % in liquid crystal sealing agent, is preferably 25 ~ 75 quality %.
Thermal curing agents (III), as being not particularly limited, can be polyamines class, polyatomic phenol, hydrazide compound etc., particularly preferably uses multivalence hydrazide compound.Such as, as terephthaldehyde's acid dihydrazide (terephthalic dihydrazide), the isophthalic dihydrazide, 2 of aromatic hydrazide, 6-naphthoic acid two hydrazides (2,6-naphthoic acid dihydrazide), 2,6-pyridine two hydrazides, 1,2,4-benzene three hydrazides (benzenetrihydrazide), 1,4,5,8-naphthoic acid four hydrazides (Isosorbide-5-Nitrae, 5,8-naphthoic acidtetrahydrazide), Pyromellitic Acid four hydrazides (pyromellitic acid tetrahydrazide) etc.In addition, if aliphatics hydrazide compound, such as, can be formylhydrazine (formic acidhydrazide), acethydrazide, propionic acid hydrazides (propanoic acid hydrazide), grass acid dihydrazide, acid dihydrazide, amber acid dihydrazide, glutaric, adipic dihydrazide, heptandioic acid two hydrazides, Isosorbide-5-Nitrae-cyclohexane two hydrazides, winestone acid dihydrazide, apple acid dihydrazide, iminodiacetic acid two hydrazides, N, N ' the two semicarbazides of-hexa-methylene, citric acid three hydrazides, nitriloacetic acids three hydrazides, cyclohexanetricarboxylic acid three hydrazides, two (Hydrazinocarbonyl the ethyl)-5-isopropyl hydantoins of 1,3-etc. have hydantoins skeleton, preferably there is the dihydrazide compound of valine hydantoins skeleton (carbon atom of hydantoins ring is the skeleton replaced with isopropyl), three (1-Hydrazinocarbonyl methyl) isocyanuric acid ester, three (2-Hydrazinocarbonyl ethyl) isocyanuric acid ester, three (2-Hydrazinocarbonyl propyl group) isocyanuric acid ester, two (2-Hydrazinocarbonyl ethyl) isocyanuric acid ester.From the balance of solidification reactivity and potentiality, preferred isophthalic dihydrazide, acid dihydrazide, adipic dihydrazide, three (1-Hydrazinocarbonyl methyl) isocyanuric acid ester, three (2-Hydrazinocarbonyl ethyl) isocyanuric acid ester, three (3-Hydrazinocarbonyl propyl group) isocyanuric acid ester, particularly preferably (2-Hydrazinocarbonyl ethyl) isocyanuric acid ester.As the content of situation using relevant thermal curing agents (III), when setting the total amount of (methyl) acrylated epoxy resins (II) as 100 mass parts, situation preferably containing 30 ~ 50 mass parts, be more preferably 35 ~ 45 mass parts, also can mix two or more to use.
Hot radical polymerization initiator (IV) is as long as generate free radical by heating and start the compound of chain type polyreaction, be not particularly limited, organic peroxide, azo-compound, styrax compound, benzoin ether compound, aceotphenone compound, benzo pinacol etc. can be exemplified, preferably use benzo pinacol.Such as, as organic peroxide, KAYAMEK
rTMa, M, R, L, LH, SP-30C, PERKADOX CH-50L, BC-FF, CADOX B-40ES, PERKADOX 14, TRIGONOX
rTM22-70E, 23-C70,121,121-50E, 121-LS50E, 21-LS50E, 42,42LS, KAYAESTER
rTMp-70, TMPO-70, CND-C70, OO-50E, AN, KAYABUTYL
rTMb, PERKADOX 16, KAYACARBON
rTMbIC-75, AIC-75 (above, chemical drug Akzo joint-stock company), PERMEK
rTMn, H, S, F, D, G, PERHEXA
rTMh, HC, PER TMH, C, V, 22, MC, PERCURE
rTMaH, AL, HB, PERBUTYL
rTMh, C, ND, L, PERCUMYL
rTMh, D, PEROYL
rTMiB, IPP, PEROCTA
rTMnD (above, You joint-stock company) etc. can be used as commercially available product and starts with.In addition, as azo-compound, VA-044, V-070, VPE-0201, VSP-1001 etc. (more than, and light pure pharmaceutical worker's industry joint-stock company) etc. can be used as commercially available product and obtain.In addition, and, according to reactive and to liquid crystal deliquescent angle, be particularly suitable for the compound using following general expression (1) to express.
[changing 1]
(in formula (1), Y
1, Y
2represent hydrogen atom, phenyl or silicon atom independently of one another, R
1~ R
6represent the straight or branched alkyl of hydrogen atom or carbon number 1 ~ 4 independently of one another, X
1~ X
4represent hydrogen atom, methyl, ethyl, methoxyl, ethoxy, phenoxy group or halogen atom independently of one another.Wherein, with Y
1or Y
2the R combined respectively
1~ R
3or R
4~ R
6, at Y
1or Y
2be the situation of hydrogen atom be non-existent.)
In above-mentioned formula (1), Y
1and Y
2separately represent hydrogen atom, phenyl or silicon atom, preferably at least one is the situation of silicon atom, and particularly preferably both sides are situations of silicon atom.In above-mentioned formula (1), as R
1~ R
6in the straight or branched alkyl (hereinafter referred to as C1 ~ C4 alkyl) of carbon number 1 ~ 4, such as can exemplified by methyl, ethyl, n-pro-pyl, isopropyl, the tert-butyl group etc.In addition, as X
1~ X
4in halogen atom, fluorine atom, chlorine atom, bromine atoms etc. can be exemplified.
The Y of formula (1)
1or Y
2for beyond hydrogen atom when, R
1r
2r
3y
1-or R
4r
5r
6y
2the phenyl of-preferably phenyl or the C1 ~ C4 alkyl replacement with 1 ~ 3, or, preferably two C1 ~ C4 alkyl tin groups, alkyl silane groups or three C1 ~ C4 alkyl tin groups, alkyl silane groups, are more preferably two C1 ~ C4 alkyl tin groups, alkyl silane groups or three C1 ~ C4 alkyl tin groups, alkyl silane groups, are more preferably three C1 ~ C4 alkyl tin groups, alkyl silane groups.
At the R of formula (1)
1r
2r
3y
1-, R
4r
5r
6y
2-in two or three C1 ~ C4 straight or branched alkyl tin groups, alkyl silane groups in, C1 ~ C4 alkyl of 2 or 3 can identical can be different, as this silylation, two C1 ~ C4 alkyl tin groups, alkyl silane groups such as dimethylsilyl, diethylsilyl, Methylethyl silylation can be exemplified; Three C1 ~ C4 alkyl tin groups, alkyl silane groups such as TMS, triethyl silyl, dimethylethylsilyl, t-butyldimethylsilyi; Deng.Wherein, most preferably three C1 ~ C4 alkyl tin groups, alkyl silane groups, more preferably TMSs.
The X of formula (1)
1~ X
4represent hydrogen atom, methyl, ethyl, methoxyl, ethoxy, phenoxy group or halogen atom independently of one another, preferred X
1~ X
4for the situation of whole hydrogen atom.
As the compound represented by formula (1), specifically, benzo pinacol can be exemplified, 1,2-dimethoxy-1,1,2,2-tetraphenyl ethane, 1,2-diethoxy-1,1,2,2-tetraphenyl ethane, 1,2-hexichol Oxy-1,1,2,2-tetraphenyl ethane, 1,2-dimethoxy-1,1,2,2-tetra-(4-aminomethyl phenyl) ethane, 1,2-hexichol Oxy-1,1,2,2-tetra-(4-methoxyphenyl) ethane, 1,2-two (trimethylsiloxy group)-1,1,2,2-tetraphenyl ethane, 1,2-two (triethyl siloxy)-1,1,2,2-tetraphenyl ethane, 1,2-two (tertiary butyl dimethyl Si base)-1,1,2,2-tetraphenyl ethane, 1-hydroxyl-2-trimethylsiloxy group-1,1,2,2-tetraphenyl ethane, 1-hydroxyl-2-triethyl siloxy-1,1,2,2-tetraphenyl ethane, 1-hydroxyl-2-tertiary butyl dimethyl Si base-1,1,2,2-tetraphenyl ethane etc., are preferably 1-hydroxyl-2-trimethylsiloxy group-1,1,2,2-tetraphenyl ethane, 1-hydroxyl-2-triethyl siloxy-1,1,2,2-tetraphenyl ethane, 1-hydroxyl-2-tertiary butyl dimethyl Si base-1,1,2,2-tetraphenyl ethane, 1,2-two (trimethylsiloxy group)-1,1,2,2-tetraphenyl ethane, is more preferably 1-hydroxyl-2-trimethylsiloxy group-1,1,2,2-tetraphenyl ethane, 1,2-two (trimethylsiloxy group)-1,1,2,2-tetraphenyl ethane.But, as long as have the structure of formula (1), be not limited to these compounds.In addition can and with two or more.
It is commercially available that benzo pinacol in above-mentioned hot radical polymerization initiator (IV) changes into industry (strain) and light pure pharmaceutical worker industry (strain) etc. by Tokyo.In addition, the method for using well known easily synthesizes the hydroxyl of benzo pinacol by etherfied compound.In addition, the hydroxyl of benzo pinacol, by the etherfied compound of silylation, is synthesized into by the method heating corresponding benzo pinacol and various silane-based agent under the base catalyst of pyridine etc.As silane-based agent, the generally known trimethyl chlorosilane as TMS agent (TMCS), hexamethyldisilazane (HMDS), two (TMS) trifluoroacetamide (BSTFA) of N, O-or the chlorotriethyl silane (TECS) as triethyl silyl agent, the t-butyldimethylsilyl (TBMS) etc. as t-butyldimethylsilyi agent can be exemplified.These reagent easily can obtain from the market of silicon derivative manufacturer etc.As the reacting dose of silane-based agent, it is preferably 1.0 ~ 5.0 times moles to the hydroxyl 1 mole of subject compound.Be more preferably 1.5 ~ 3.0 times moles.Time fewer than 1.0 times moles, reaction efficiency is deteriorated, the reaction time is elongated, therefore promotes thermal decomposition.Than more than 5.0 times moles time, be separated during recovery and be deteriorated, refining become difficulty.
As base catalyst, pyridine, triethylamine etc. can be exemplified.The hydrogen chloride that base catalyst produces when having capture reaction under reactive system is remained on alkalescence, or the hydrogen deviating from hydroxyl promotes the effect of reacting more.As content, the hydroxyl of object is more than 0.5 times mole, also can be used as solvent.
As solvent, the non-polar organic solvent of normal hexane, ether, toluene etc. does not participate in reaction, therefore more excellent.In addition, the polar solvent of also preferred pyridine, dimethyl formamide (DMF), dimethyl sulfoxide (DMSO) (DMSO), tetrahydrofuran (THF), acetonitrile etc.As content, the weight concentration of preferred solute is about 5 ~ 40%.Be more preferably 10 ~ 30%.React slack-off time fewer than 5%, the decomposition caused because of thermal conductance is promoted, production declining.Than more than 40% time, secondary product is many, production declining.
Above-mentioned hot radical polymerization initiator (IV) preferably makes particle diameter thin and dispersed.Gap when becoming lower glass substrate in laminating when the liquid crystal display of narrow gap manufactures when its mean grain size is excessive forms the undesirable element having some setbacks and wait, and preferably less than 5 μm, is more preferably less than 3 μm.In addition, also have no relations although infinitely attenuate, lower limit is about 0.1 μm usually.Particle diameter is by laser diffraction and scattering formula particle size distribution measurement device (dry type) (SEISHIN enterprise of joint-stock company system; LMS-30) measure.
As the content of this hot radical polymerization initiator (IV), when setting the total amount of liquid crystal sealing agent of the present invention as 100 mass parts, be preferably 0.0001 ~ 10 mass parts, be more preferably 0.0005 ~ 7 mass parts, be particularly preferably 0.001 ~ 3 mass parts.
Silane coupling agent (V) can be used in liquid crystal sealing agent of the present invention to realize bonding strength improve or the raising of moisture-proof reliability.As silane coupling agent, 3-(2 can be exemplified, 3-epoxy third oxygen) propyl trimethoxy silicane (3-glycidoxypropyltrimethoxysilane), 3-(2, 3-epoxy third oxygen) hydroxypropyl methyl dimethoxysilane, 3-(2, 3-epoxy third oxygen) hydroxypropyl methyl diethoxy silane, 2-(3, 4-epoxycyclohexyl) ethyl trimethoxy silane, N-phenyl-gamma-amino propyl trimethoxy silicane, N-(2-amino-ethyl) 3-amino propyl methyl dimethoxysilane, N-(2-amino-ethyl) 3-amino propyl methyl trimethoxy silane, APTES, 3-mercaptopropyi trimethoxy silane, vinyltrimethoxy silane, N-(2-(vinyl-benzylamino) ethyl) 3-TSL 8330 hydrochloride, 3-methyl allyl acyloxypropyl trimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-r-chloropropyl trimethoxyl silane etc.These silane coupling agent is serial etc. by sale such as chemical industry joint-stock companies of SHIN-ETSU HANTOTAI as KBM series, KBE, easily can obtain from market.The content that silane coupling agent (V) is shared in liquid crystal sealing agent, when setting the entirety of liquid crystal sealing agent of the present invention as 100 quality %, be 0.05 ~ 3 quality % is suitable.
Liquid crystal sealing agent of the present invention can also use epoxy resin (VI) to realize the raising of bonding strength.As this epoxy resin (VI), be not particularly limited, preferably low to the contaminative of liquid crystal, dissolubility.As the example of suitable epoxy resin, bisphenol A type epoxy resin can be exemplified, bisphenol f type epoxy resin, bisphenol-s epoxy resin, the diglycidyl ether of resorcinol (resorcinol), phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F phenolic type epoxy resin, alicyclic epoxy resin, aliphatics chain epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hydantoins type epoxy resin, isocyanuric acid ester type epoxy resin, there is the phenol novolak type epoxy resin of tris-phenol skeleton, in addition, the 2-glycidyl etherate of two trifunctional phenol classes, the 2-glycidyl etherate of two sense alcohols and chloride thereof, hydride etc.
The content of epoxy resin (VI) considers the operability of liquid crystal sealing agent, physical property and suitably determining, usually, is about 25 ~ 80 quality % in liquid crystal sealing agent, is preferably 25 ~ 75 quality %.
In liquid crystal sealing agent of the present invention, monomer and/or the oligomer of (methyl) acrylate can be used as required.As such monomer, oligomer, can exemplify dipentaerythritol and (methyl) acrylic acid reactant, dipentaerythritol caprolactone and (methyl) acrylic acid reactant etc., as long as low to the contaminative of liquid crystal, there is no particular restriction.
In liquid crystal sealing agent of the present invention, the curing accelerator of optical free radical polymerization initiator, organic acid or imidazoles etc. or the adjuvant of pigment, levelling agent, defoamer, solvent etc. can also be coordinated as required.
As the example of method obtaining liquid crystal sealing agent of the present invention, there is method as follows.First, to (methyl) acrylated epoxy resins (II) heating for dissolving epoxy resin (VI) after cool to room temperature as required, add solid composition (I), and add thermal curing agents (III), hot radical polymerization initiator (IV), silane coupling agent (V), defoamer and levelling agent, solvent etc. as required, by using the Homogeneous phase mixing such as known mixing arrangement such as three-roll grinder, sand mill, bowl mill and filtering with metallic screen, liquid crystal sealing agent of the present invention can be manufactured.
Liquid crystal display of the present invention is by set interval a pair substrate forming set electrode at substrate arranged opposite, and around liquid crystal sealing agent sealing of the present invention, and gap encloses liquid crystal betwixt.The kind of the liquid crystal enclosed is not particularly limited.Here, the substrate of the combination of transmitance that has at least one that substrate is made up of glass, quartz, plastics, silicon etc. is formed.As its method for making, add the sept (clearance control material) of glass fibre etc. to liquid crystal sealing agent of the present invention after, after a side of this pair substrate uses this liquid crystal sealing agent of the coating such as divider, silk-screen printing device, carry out puppet solidification at 80 DEG C ~ 120 DEG C as required.Thereafter, drip the inner side to the weir be made up of this liquid crystal sealing agent liquid crystal, and another glass substrate superimposed, carries out gap formation in a vacuum.After gap is formed, 90 ~ 130 DEG C of solidifications 1 ~ 2 hour, liquid crystal display of the present invention can be obtained.The liquid crystal display of the present invention obtained in this wise, the display not having liquid crystal pollution to cause is bad, also excellent in cementability, moisture-proof reliability.As sept, glass fibre, silica beads, polymeric beads etc. can be exemplified.Its diameter is different with object, is generally 2 ~ 8 μm, is preferably 4 ~ 7 μm.Its content is generally 0.1 ~ 4 quality % to liquid crystal sealing agent 100 quality % of the present invention, is preferably 0.5 ~ 2 quality %, is more preferably about 0.9 ~ 1.5 quality %.
Liquid crystal sealing agent of the present invention is very good to the patience of the insertion of liquid crystal, under the bonding process of the substrate in liquid crystal dripping process, heating process, liquid crystal can not occur and insert or seal the phenomenon crumbled.Therefore, stable liquid crystal display can be generated.In addition, the volume occupation rate of solid composition (I) is high, therefore constituent is few to the stripping of liquid crystal, and the display that can reduce liquid crystal display is bad.In addition, also excellent on storage stability, therefore be suitable for the manufacture of liquid crystal display.And this solidfied material is excellent in the various solidfied material characteristics of bonding strength, thermotolerance, moisture-proof etc., the liquid crystal sealing agent of the application of the invention can be created on liquid crystal display excellent in reliability.In addition, the characteristic needed for liquid crystal display that the liquid crystal display using liquid crystal sealing agent of the present invention to generate is high as voltage retention, ion concentration is low is also sufficient.
Embodiment
Below, utilize experimental example, embodiment illustrates in greater detail the present invention, but the present invention is not limited to embodiment.In addition, as recorded without special, herein " part " and " % " be quality criteria.
[synthesis example 1]
[synthesis of the full acrylate of resorcinol diglycidyl ether]
Resorcinol diglycidyl ether 181.2g (EX-201:nagase chemtex joint-stock company) is dissolved into toluene 266.8g, adds dibutyl hydroxy toluene 0.8g to it and forbid agent as polymerization, be warmed up to 60 DEG C.Thereafter, add the acrylic acid 117.5g of 100% equivalent of epoxy radicals, be warmed up to 80 DEG C further, add the trimethyl ammonium chloride 0.6g as catalysts to it, 98 DEG C of stir abouts 30 hours, obtain reactant liquor.By washing this reactant liquor and removing toluene, obtain the epoxy acrylate 293g of the resorcinol diglycidyl ether as target.The theoretical value of the reactive base equivalent of the epoxy acrylate obtained is 183.
[synthesis example 2]
[synthesis of 1,2-two (trimethylsiloxane group)-1,1,2,2-tetraphenyl ethane]
Commercially available benzo pinacol (Tokyo changes into system) 100 parts (0.28 mole) is dissolved into dimethyl formamide 350 parts.Add pyridine 32 parts (0.4 mole) as base catalyst to it, add BSTFA (SHIN-ETSU HANTOTAI's chemical industry system) 150 parts (0.58 moles) and, as silane-based agent, be warmed up to 70 DEG C and stir 2 hours.Cool the reactant liquor obtained, add 200 parts, water while stirring, precipitation product also makes unreacted silicon alkylating agent inactivation.After the product of isolated by filtration precipitation, wash fully.The product obtained subsequently is dissolved in acetone, adds water and make its recrystallization, refine.Obtain 105.6 (output 88.3%) 1,2-two (trimethylsiloxane group)-1,1,2,2-tetraphenyl ethane as target.
By the result that HPLC (high-speed liquid chromatography) analyzes, purity is 99.0% (area percentage).
[embodiment 1 ~ 4, comparative example 1]
The heating mixing acrylated epoxy resins (II) of the amount shown in following table 1 and epoxy resin (VI) after cooling, after interpolation solid composition (I), thermal curing agents (III), hot radical polymerization initiator (IV), silane coupling agent (V), curing accelerator also stir, disperse with three-roll grinder mill and use metallic screen (635 order) to filter, modulating the liquid crystal sealing agent of embodiment 1 ~ 4.In addition, by the material shown in same coordination of processes table 1, the liquid crystal sealing agent of modulation comparative example 1.
In addition, the proportion of solid composition (I) is calculated by said method as the proportion of mixed system.In addition, C (cm
3) liquid crystal sealing agent in the content of solid composition (I) by taking C (cm
3) liquid crystal sealing agent after measure its weight, and the containing ratio being multiplied by solid composition (I) calculates.In addition, C (cm
3) all unify for 100cm
3measure.
In addition, the thixotropic ratio of each liquid crystal sealing agent is obtained as follows: use E type viscosity meter (Dong Ji industry joint-stock company) to measure the viscosity of 5rpm and 0.5rpm at 25 DEG C of liquid crystal sealing agent, calculates the value of the viscosity of viscosity under 0.5rpm/under 5rpm according to this value.
[table 1]
1. KMP-594 (chemical industry joint-stock company of SHIN-ETSU HANTOTAI, a mean grain size: 3 μm)
2. T320C (Industrial Co., Ltd of Mitsubishi Chemical uses after being ground into mean grain size 3 μm)
3. SEPS2063 (Clea joint-stock company uses after being ground into mean grain size 3 μm)
4. ZEFIAC F-351S (Aica Industry Stock Company, a mean grain size: 0.3 μm)
5. X-24-9163A (chemical industry joint-stock company of SHIN-ETSU HANTOTAI, a mean grain size: 0.11 μm)
6. KMP-701 (chemical industry joint-stock company of SHIN-ETSU HANTOTAI, a mean grain size: 3.5 μm)
7. synthesized by synthesis example 1
8. HCIC (Japanese fine chemistry industry joint-stock company uses after being ground into mean grain size 1.5 μm)
9. by the 2-in-1 one-tenth of synthesis example
10. Sila-Ace S-510 (CHISSO joint-stock company)
kBM-603 (chemical industry joint-stock company of SHIN-ETSU HANTOTAI)
eX-201 (nagase chemtex joint-stock company)
cIC (four countries change into Industry Stock Company's system, use after being ground into mean grain size 1.5 μm)
Following evaluation is carried out to the liquid crystal sealing agent of modulation in embodiment 1 ~ 4, comparative example 1.Result is summed up in table 2.
[cell gap evaluation]
Add the glass fibre (PF-50S: NEG joint-stock company) of diameter 5 μm to each 100g of liquid crystal sealing agent 1g is as sept and carry out mix and blend deaeration, being filled into syringe.The liquid crystal sealing agent of this syringe will be filled into, use divider (SHOTMASTER300: Wu KURA Engineering Shares Co., Ltd system) is coated to the glass substrate (470 × 370 × 0.7SP30ITO:Geomatec joint-stock company) with ito transparent electrode, forms seal pattern and pseudo-seal pattern.Next, by liquid crystal (JC-5015LA; Nitrogen joint-stock company) tiny droplets drip in the frame of seal pattern.Sept (Natoco sept KSEB-525F in the glass substrate pattern that another block friction treatment is complete; Natoco joint-stock company; Gap width after laminating 5 μm) and carry out thermosetting and connect, use laminating apparatus in a vacuum with complete baseplate-laminating under liquid crystal drop before.Open into air and after forming gap, place after 10 minutes, the baking oven dropping into 120 DEG C is heating and curing 1 hour, is formed with polarizing microscope observation unit gap.
To evaluate according to benchmark below.
Zero: the cell gap in unit being 3 μm equably
△: the place having the gap not occurring about 4 μm in unit
×: sealing crumbles, can not forming unit
[sealing shape]
Observe and use that the liquid crystal sealing agent being filled into syringe is gone out to press 400kPa, coating speed 20mm/sec An Zhao Tu by divider (SHOTMASTER300: Wu KURA Engineering Shares Co., Ltd system), linear when carrying out straight line coating of headroom 50 μm, nozzle diameter 200 μm, evaluate based on following benchmark.
Zero: the deviation of sealed width is less than 5%
△: the deviation of sealed width is less than 10%
×: the deviation of sealed width is more than 10%
[test of liquid crystal sealing agent bonding strength]
To add the glass fibre 1g of diameter 3 μm as sept to liquid crystal sealing agent 100g and carry out mix and blend.On the glass substrate of 50mm × 50mm, apply this liquid crystal sealing agent, the glass sheet of the 1.5mm × 1.5mm that fits on this liquid crystal sealing agent also drops into the baking oven 1 hour of 120 DEG C and solidifies.Bond's tester (SS-30WD: Xi Jin business joint-stock company) is used to measure the cut-out bonding strength of this glass sheet.Its result is as shown in table 2.
[table 2]
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | |
| Sealing shape | ○ | ○ | ○ | △ | × |
| Cell gap | ○ | ○ | ○ | △ | × |
| Bonding strength (MPa) | 55 | 56 | 58 | 31 | 23 |
As the result of table 2, the liquid crystal sealing agent of embodiments of the invention, confirm that sealing shape is good, therefore operability is good, forms the cell gap expected and excellent in adhesion.Particularly the liquid crystal sealing agent of embodiment 1 ~ 3 demonstrates excellent result in all evaluations.In the liquid crystal sealing agent of embodiment 4, the proportion A (g/cm of solid composition (I)
3) be 1.31, in the total amount of solid composition (I) in addition, the Shore A hardness not containing more than 85 quality % is the solid composition (I-1) of 10 ~ 70, and result is slightly poor.
[utilizability in industry]
Liquid crystal sealing agent of the present invention is excellent to the patience of the insertion of liquid crystal sealing agent to liquid crystal, and the general characteristic as liquid crystal sealing agent of bonding strength etc. is also excellent, therefore can simplify the manufacture of the liquid crystal display of long-term reliability excellence.
Claims (12)
1. a liquid crystal dripping process liquid crystal sealing agent, wherein, described liquid crystal dripping process liquid crystal sealing agent is the liquid crystal sealing agent containing solid composition (I), is setting the proportion of described solid composition (I) as A (g/cm
3), the content in liquid crystal sealing agent is B (g), and the volume of definition liquid crystal sealing agent is C (cm
3) time, described A, B and C meet following mathematical expression (a), further, measuring in the value of the viscosity obtained at use E type viscosity meter under the condition of 5rpm and 0.5rpm of 25 DEG C, is 1.1 ~ 3.0 with the thixotropic ratio that the viscosity of the viscosity under 0.5rpm/under 5rpm represents:
0.2≦B/(A×C)≦0.4……(a)。
2. liquid crystal dripping process liquid crystal sealing agent according to claim 1, wherein, described A (g/cm
3) be 0.85g/cm
3~ 1.10g/cm
3.
3. liquid crystal dripping process liquid crystal sealing agent according to claim 1 and 2, wherein, in the total amount of described solid composition (I), the Shore A hardness containing more than 85 quality % is the solid composition (I-1) of 10 ~ 70.
4. liquid crystal dripping process liquid crystal sealing agent according to claim 3, wherein, described solid composition (I-1) is the one kind or two or more solid composition being selected from silicon rubber, styrene rubber, styrene olefinic rubber, acrylic rubber.
5. liquid crystal dripping process liquid crystal sealing agent according to any one of claim 1 to 4, also containing (methyl) acrylated epoxy resins (II), thermal curing agents (III) and hot radical polymerization initiator (IV).
6. liquid crystal dripping process liquid crystal sealing agent according to claim 5, wherein, described (methyl) acrylated epoxy resins (II) is resorcinolformaldehyde resin (methyl) acrylate compound.
7. the liquid crystal dripping process liquid crystal sealing agent according to claim 5 or 6, wherein, described thermal curing agents (III) is multivalence hydrazide compound.
8. the liquid crystal dripping process liquid crystal sealing agent according to any one of claim 5 to 7, wherein, described hot radical polymerization initiator (IV) is 1,2-two (trimethylsiloxane group)-1,1,2,2-tetraphenyl ethane.
9. liquid crystal dripping process liquid crystal sealing agent according to any one of claim 1 to 8, also containing silane coupling agent (V).
10. liquid crystal dripping process liquid crystal sealing agent according to any one of claim 1 to 9, also containing epoxy resin (VI).
The manufacture method of 11. 1 kinds of liquid crystal displays, wherein, in the liquid crystal display be made up of two pieces of substrates, after liquid crystal is dripped in the inner side on the weir formed to the liquid crystal dripping process liquid crystal sealing agent according to any one of claim 1 to 10 be formed on a substrate, to fit another substrate, utilize liquid crystal dripping process liquid crystal sealing agent described in heat curing afterwards.
12. 1 kinds of liquid crystal displays, wherein, the solidfied material sealing that described liquid crystal display is obtained by the liquid crystal dripping process liquid crystal sealing agent solidified according to any one of claim 1 to 10.
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| JP2012158480 | 2012-07-17 | ||
| JP2012-158480 | 2012-07-17 | ||
| PCT/JP2013/069384 WO2014014015A1 (en) | 2012-07-17 | 2013-07-17 | Liquid-crystal sealing material and liquid-crystal display cell obtained using same |
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| CN104471470A true CN104471470A (en) | 2015-03-25 |
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|---|---|
| JP (1) | JP5543035B1 (en) |
| KR (1) | KR20150036198A (en) |
| CN (1) | CN104471470A (en) |
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| WO (1) | WO2014014015A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1711300A (en) * | 2002-11-06 | 2005-12-21 | 日本化药株式会社 | Sealing material for liquid crystal and liquid crystal display cell using same |
| JP2007079588A (en) * | 2006-10-11 | 2007-03-29 | Nippon Kayaku Co Ltd | Liquid crystal sealant and liquid crystal cell |
| JP2009229722A (en) * | 2008-03-21 | 2009-10-08 | Sekisui Chem Co Ltd | Sealant for liquid crystal display element, vertical conduction material and liquid crystal display element |
| CN101617267A (en) * | 2007-02-20 | 2009-12-30 | 三井化学株式会社 | Sealing liquid crystal is with hardening resin composition and use the manufacture method of the display panels of said composition |
| JP2010014771A (en) * | 2008-07-01 | 2010-01-21 | Nippon Kayaku Co Ltd | Thermosetting liquid crystal sealing material for liquid crystal dropping method and liquid crystal display cell using the same |
| CN102472928A (en) * | 2009-07-01 | 2012-05-23 | 日本化药株式会社 | Liquid crystal sealing agent for liquid crystal dropping method and liquid crystal display cell using same |
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| JP5388091B2 (en) * | 2007-11-16 | 2014-01-15 | 日本化薬株式会社 | Liquid crystal sealant and liquid crystal display cell using the same |
-
2013
- 2013-07-15 TW TW102125249A patent/TW201410853A/en unknown
- 2013-07-17 WO PCT/JP2013/069384 patent/WO2014014015A1/en active Application Filing
- 2013-07-17 KR KR1020157002012A patent/KR20150036198A/en not_active Application Discontinuation
- 2013-07-17 JP JP2013541117A patent/JP5543035B1/en active Active
- 2013-07-17 CN CN201380037808.0A patent/CN104471470A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1711300A (en) * | 2002-11-06 | 2005-12-21 | 日本化药株式会社 | Sealing material for liquid crystal and liquid crystal display cell using same |
| JP2007079588A (en) * | 2006-10-11 | 2007-03-29 | Nippon Kayaku Co Ltd | Liquid crystal sealant and liquid crystal cell |
| CN101617267A (en) * | 2007-02-20 | 2009-12-30 | 三井化学株式会社 | Sealing liquid crystal is with hardening resin composition and use the manufacture method of the display panels of said composition |
| JP2009229722A (en) * | 2008-03-21 | 2009-10-08 | Sekisui Chem Co Ltd | Sealant for liquid crystal display element, vertical conduction material and liquid crystal display element |
| JP2010014771A (en) * | 2008-07-01 | 2010-01-21 | Nippon Kayaku Co Ltd | Thermosetting liquid crystal sealing material for liquid crystal dropping method and liquid crystal display cell using the same |
| CN102472928A (en) * | 2009-07-01 | 2012-05-23 | 日本化药株式会社 | Liquid crystal sealing agent for liquid crystal dropping method and liquid crystal display cell using same |
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| JP5543035B1 (en) | 2014-07-09 |
| JPWO2014014015A1 (en) | 2016-07-07 |
| TW201410853A (en) | 2014-03-16 |
| KR20150036198A (en) | 2015-04-07 |
| WO2014014015A1 (en) | 2014-01-23 |
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