CN105209969A - Liquid crystal sealing agent and liquid crystal display cell using same - Google Patents

Liquid crystal sealing agent and liquid crystal display cell using same Download PDF

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Publication number
CN105209969A
CN105209969A CN201480016635.9A CN201480016635A CN105209969A CN 105209969 A CN105209969 A CN 105209969A CN 201480016635 A CN201480016635 A CN 201480016635A CN 105209969 A CN105209969 A CN 105209969A
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liquid crystal
sealing agent
crystal sealing
agent under
organic filler
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CN105209969B (en
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木村早纪
坂野常俊
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Nippon Kayaku Co Ltd
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Nippon Kayaku Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1339—Gaskets; Spacers; Sealing of cells
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1341—Filling or closing of cells
    • G02F1/13415—Drop filling process

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Nonlinear Science (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mathematical Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Sealing Material Composition (AREA)
  • Liquid Crystal (AREA)
  • Epoxy Resins (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Proposed is a liquid crystal sealing agent for liquid crystal dropping methods, which has excellent resistance to liquid crystal penetration thereinto and extremely low water vapor permeability, while being also excellent in terms of general characteristics required for liquid crystal sealing agents such as adhesion strength and low possibility of contaminating liquid crystals. By using a liquid crystal sealing agent of the present invention, a liquid crystal display cell having extremely excellent long-term reliability can be produced easily. A liquid crystal sealing agent of the present invention contains an organic filler (I) and a curable compound (II) that has a (meth)acryloyl group. The organic filler (I) has a 10% displacement force of 2.0 MPa or less and a water vapor transmission rate of less than 100 cc/m2*24h*atm. The content of the organic filler (I) is 20 parts by mass or more if the total amount of the curable compound (II) is taken as 100 parts by mass.

Description

Liquid crystal sealing agent and use the liquid crystal display of this liquid crystal sealing agent
Technical field
The present invention is used in method liquid crystal sealing agent (liquidcrystalsealant) under the liquid crystal drop of method (liquidcrystaldroppingmethod) under liquid crystal drop about one and uses the liquid crystal display (liquidcrystaldisplaycell) of this liquid crystal sealing agent.More specifically, about method liquid crystal sealing agent under a kind of liquid crystal drop and the liquid crystal display using this liquid crystal sealing agent, this liquid crystal sealing agent is liquid crystal mixing in patience (insertionresistance) as excellent for liquid crystal sealing agent, and moisture permeability is extremely low, and be also excellent person in the general characteristic of the such as liquid crystal sealing agent of tack strength etc. and so on.
Background technology
In recent years, along with the maximization of liquid crystal display, as the manufacture method of liquid crystal display, propose a kind of production higher so-called " under liquid crystal drop method " (See patent document 1,2).Specifically, under this liquid crystal drop method be on a substrate form the cofferdam (weir) be made up of liquid crystal sealing agent inner side drip after liquid crystal, laminating (bonding) another substrate, then, the manufacture method that liquid crystal sealing agent is hardened.
But, if method under liquid crystal drop, because liquid crystal can contact with liquid crystal sealing agent before liquid crystal sealing agent hardens, liquid crystal sealing agent is made to mix phenomenon (insertionphenomenon) due to the pressure of liquid crystal, even also likely cause subsiding the situation of (collapse), and this is the place of problem.And use up and heat liquid crystal drop under method, if the situation of the part of sufficient Ultraviolet radiation cannot be obtained at the shade also existed owing to being positioned at distribution etc., also can there is this problem.In addition, do not implementing Ultraviolet radiation, and only with the situation that heat makes liquid crystal sealing agent harden, be also problem great especially.In order to head it off, then must improve the degree of accuracy measured under liquid crystal drop, however, during heating due to the cure step at liquid crystal sealing agent, liquid crystal still can expand, and then has any problem to suppress above-mentioned phenomenon of mixing completely.
In addition, for method liquid crystal sealing agent under liquid crystal drop, the various problems needing to solve as being called the workability such as general characteristic or storage stability such as low liquid crystal pollution, high tack strength, high moisture-proof, high-fire resistance are also had.
For solving this problem, then various technology is proposed.
At document 3, then organobentonite (bentonite) one's purpose in coming figure is used to solve above-mentioned problem.Although the method has certain effect for mix (insertion) of liquid crystal, be difficult to deserve to be called enough.
At document 4, then the liquid crystal sealing agent of a kind of use fumed silica (White Carbon black) (fumedsilica) of open use, polymercaptan (polythiol) carries out the method for the staged process of B-(B-stageprocess) of liquid crystal sealing agent.But the method but has and causes processing procedure (process) elongated, and causes the shortcoming of the device needed needed for its processing procedure.
At document 5, then open a kind of by using hot radical polymerization initiator to improve setting rate, with method liquid crystal sealing agent under the liquid crystal drop mixed preventing liquid crystal.
At document 6,7, then openly a kind of poly-silicone rubber (siliconerubber) particulate is used to prevent method liquid crystal sealing agent under the liquid crystal drop mixed of liquid crystal for physically, but because water vapor (watervapor) penetrability of poly-silicone rubber is high, moisture-proof poor reliability.
As mentioned above, although very energetically in the exploitation carrying out liquid crystal sealing agent, as having excellent mixing patience and at low liquid crystal pollution, high tack strength etc. as being also excellent person in the general characteristic of liquid crystal sealing agent, not yet complete at present.
Prior art document
Patent documentation
Patent documentation 1: Japanese Patent Laid-Open No. Sho 63-179323 publication
Patent documentation 2: Japanese Patent Laid-Open 10-239694 publication
Patent documentation 3: Japanese Patent Laid-Open 2010-14771 publication
Patent documentation 4: Japanese Patent Laid-Open 2011-150181 publication
Patent documentation 5: No. 2011/061910th, Jap.P. International Publication
Patent documentation 6: Japanese Patent Laid-Open 2009-139922 publication
Patent documentation 7: Japanese Patent Laid-Open 2010-256777 publication
Summary of the invention
The desired problem solved of invention
The present invention is used in method liquid crystal sealing agent under the liquid crystal drop of method under liquid crystal drop about a kind of, more specifically, the invention provides method liquid crystal sealing agent under a kind of liquid crystal drop and use the liquid crystal display of this liquid crystal sealing agent, this liquid crystal sealing agent is liquid crystal mixing in patience as excellent for liquid crystal sealing agent, and moisture permeability is extremely low, and at such as tack strength etc. as being also excellent person in the general characteristic of liquid crystal sealing agent.
The technological means of dealing with problems
Inventor through studying intensively, Jie fruit Fa Xian ﹕ comprise 10% deformation force (displacementforce) for below 2.0MPa and vapor transmission rate (watervaporpermeability) for being less than 100cc/m 2organic filler (organicfiller) and the hardening compound of 24hatm, and the content of organic filler is occupy a certain amount of above liquid crystal sealing agent for the total amount of hardening compound, can have very excellent mix patience and reliability (reliability) for excellent, find based on this and complete the present invention.
In addition; in this manual; so-called " (methyl) acrylic acid series [(meth) acrylic] " means " acrylic acid series (acrylic) and/or metha crylic (methacrylic) ", and so-called " (methyl) acryloyl group [(meth) acryloylgroup] " means " acryloyl group (acryloylgroup) and/or methacryl (methacryloylgroup) ".
That is, the present invention is about following 1) ~ 11) person.
1) a method liquid crystal sealing agent under liquid crystal drop, wherein, comprises organic filler (I) and has the hardening compound (II) of (methyl) acryloyl group, and
Above-mentioned organic filler (I) be 10% deformation force be below 2.0MPa and vapor transmission rate for being less than 100cc/m 224hatm,
When the total amount of above-mentioned hardening compound (II) is set to 100 mass parts, the content of above-mentioned organic filler (I) is more than 20 mass parts.
2) as above-mentioned 1) as described in liquid crystal drop under method liquid crystal sealing agent, wherein, above-mentioned hardening compound (II) comprises the compound with resorcinol skeleton (resorcinskeleton).
3) as above-mentioned 1) or 2) as described in liquid crystal drop under method liquid crystal sealing agent, wherein, comprise further hot radical polymerization initiator (thermalradicalpolymerizationinitiator) (III).
4) as above-mentioned 1) to 3) according to any one of liquid crystal drop under method liquid crystal sealing agent, wherein, comprise further epoxy resin (epoxyresin) (IV).
5) as above-mentioned 1) to 4) according to any one of liquid crystal drop under method liquid crystal sealing agent, wherein, comprise further thermoinitiators (thermalcuringagent) (V).
6) as above-mentioned 1) to 5) according to any one of liquid crystal drop under method liquid crystal sealing agent, wherein, above-mentioned organic filler (I) is polyurethane particulate (polyurethanemicroparticle).
7) as above-mentioned 3) as described in liquid crystal drop under method liquid crystal sealing agent, wherein, above-mentioned hot radical polymerization initiator (III) is 1,2-two (trimethylsiloxy group)-1,1,2,2-tetraphenyl ethane.
8) as above-mentioned 5) as described in liquid crystal drop under method liquid crystal sealing agent, wherein, above-mentioned thermoinitiators (V) is organic acid hydrazide compound (organicacidhydrazidecompound).
9) as above-mentioned 1) to 8) according to any one of liquid crystal drop under method liquid crystal sealing agent, wherein, comprise further silane coupling agent (silanecouplingagent) (VI).
10) a kind of manufacture method of liquid crystal display, wherein, in the liquid crystal display be made up of two plate bases, be formed on a substrate by as above-mentioned 1) to 9) and according to any one of liquid crystal drop under method liquid crystal sealing agent the inner side in cofferdam that forms drip after liquid crystal, to fit another substrate, then by heat, method liquid crystal sealing agent under above-mentioned liquid crystal drop is hardened.
11) liquid crystal display, wherein, is sealed to form with hardening thing, and this hardening thing is by as above-mentioned 1) to 9) according to any one of liquid crystal drop under method liquid crystal sealing agent hardened obtain.
Effect of invention
Method liquid crystal sealing agent under liquid crystal drop of the present invention, due to liquid crystal to mix patience very excellent, easily can carry out manufacture liquid crystal display.In addition, because particularly low-moisture permeability (moisturepermeability) is excellent, the liquid crystal display completed is then for long-term reliability is high person.Further, tack strength etc. are also excellent as the general characteristic of liquid crystal sealing agent.That is, under liquid crystal drop of the present invention, method liquid crystal sealing agent can realize easily carrying out manufacturing excellent liquid crystal display person.
Embodiment
Liquid crystal sealing agent of the present invention is (hereinafter referred to as " liquid crystal sealing agent ".) be the manufacture method being used in following liquid crystal display, namely, under liquid crystal drop, method ﹕ is at the liquid crystal display be made up of two plate bases, be formed on a substrate by as above-mentioned 1) to 9) and according to any one of liquid crystal drop under method liquid crystal sealing agent the inner side in cofferdam that forms drip after liquid crystal, to fit another substrate, then by heat, above-mentioned liquid crystal sealing agent is hardened.
Illustrated by the project of prior art, if method under liquid crystal drop, because liquid crystal can contact with liquid crystal sealing agent before liquid crystal sealing agent hardens, make liquid crystal sealing agent mix phenomenon due to the pressure of liquid crystal, even also likely cause the situation of subsiding.
Method under this liquid crystal drop; if use the hardening compound (II) comprising organic filler (I) that 10% deformation force is below 2.0MPa and there is (methyl) acryloyl group; and when the total amount of hardening compound (II) is set to 100 mass parts; when the total amount of organic filler (I) is the liquid crystal sealing agent of more than 20 mass parts, then liquid crystal will become few for mixing of liquid crystal sealing agent.Can thinking that its 10% deformation force is the extremely soft organic filler of below 2.0MPa, being formed cofferdam due to the pressure of upper and lower base plate by compressing, to resist the cause of liquid crystal expansion (expansion) pressure.
If 10% deformation force of organic filler (I) is for during more than 2.0MPa, is formed cofferdam owing to cannot compress with the pressure of upper and lower base plate, therefore cannot resist mixing of liquid crystal fully.In addition, relative to total amount 100 mass parts of hardening compound (II), if when the content of organic filler (I) is for being less than 20 mass parts, then formed cofferdam can not become the person of being integrated, namely, due to many gaps can be produced, still mixing of liquid crystal cannot be resisted fully.
In addition, so-called " 10% deformation force of organic filler (I) ", mean and organic filler (I) is compressed and makes its diameter can power required for 10% displacement (distortion) (displace), micro-compression tester (microscopiccompressiontester) (MCT-510) that such as company of Shimadzu Seisakusho Ltd. (ShimadzuCorp.) can be used to make in addition mensuration person.
Liquid crystal panel needs high moisture-proof reliability.Liquid crystal sealing agent of the present invention, due to total amount 100 mass parts relative to hardening compound, comprise more than organic filler (I) 20 mass parts, if during the organic filler using vapor transmission rate large, then the moisture permeability of sealant (sealant) hardening thing can be made to become large terrifically.Therefore, organic filler (I) is that vapor transmission rate is necessary for and is less than 100cc/m 224hatm.Usual 10% deformation force is little organic filler, then have that cross-linking density is low, vapor transmission rate can become large tendency.In addition, the tendency that vapor transmission rate is large is that the organic filler that polarity is high is not so good as nonpolar organic filler.
In addition, vapor transmission rate, can be used in the differential pressure method disclosed in Japanese JISK7126, is measured with GTRTec (stock) company (GTRTecCorporation) GTR-30X processed.
Be used in the organic filler (I) of liquid crystal sealing agent of the present invention, as long as when 10% deformation force and vapor transmission rate can meet above-mentioned condition, then there is no special restriction, can Lie Ju ﹕ polyamide micro-particle, fluorine system particulate, ethylene series particulate, Polyester particulate, rubber particle etc., and above-mentioned condition person can be met.
Above-mentioned organic filler (I), is preferably the situation at rubber particle.As rubber particle, can Lie Ju ﹕ such as natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene butadiene ribber (SBR), butyl rubber (IIR), nitrile rubber (nitrilerubber) (NBR), ethylene propylene rubber (EPM, EP), chloroprene rubber (CR), ACM (ACM, ANM), chlorosulfonic acid esterification polyethylene rubber (chlorosulfonatedpolyethylenerubber, CSM), amido formate rubber (PUR), fluororubber (FKM, FPM), polysulfide rubber (polysulfiderubber) (thiokol (thiokol)) etc.Two or more may be used in combination for these organic fillers (I).In these, be preferably amido formate rubber, styrene rubber, styrene-olefin rubber, ACM (acrylicrubber).
As above-mentioned amido formate rubber, known polyurethane particulate can be used.The shape of particle can be unsetting, also can be spherical or proper sphere shape.As for the formation of atomic polyurethane, such as Polyester, polyethers system, polycarbonate-based etc. polyurethane and these potpourri can be used.In addition, also can at other thermoplastic elastomer etc. of polyurethane fusion polyester elastomer, polyamide elastomer, styrene series elastomer, Fuoroelastomer, polybutadiene based elastomers, amido formate/vinyl chloride elastic body, vinyl copolymer etc.Although there is no particular determination, when forming the superficial layer of polyurethane, be preferably the cross-linking type polyurethane used through using the multifunctional composition of more than trifunctional in the some of diisocyanate (diisocyanate) composition of the reaction raw materials of polyurethane or segment growing agent (chainextender), be unlikely to make it and be dissolved in organic solvent etc. or swelling.Commercial goods, is preferably UCD-5050D, UCD-5070D (being industrial group (DainichiseikaColor & ChemicalsMfg.Co., Ltd.) system of refining large day above); JB-800T (Gen Shang industrial group (NegamiChemicalIndustrialCo., Ltd.) system).
The commercial goods of styrene rubber, is preferably RABALON rTMt320C, T331C, SJ4400, SJ5400, SJ6400, SJ4300C, SJ5300C, SJ6300C (being Mitsubishi Chemical Ind (MitsubishiChemicalCorporation) system above).
The commercial goods of styrene-olefin rubber, is preferably SEPTON rTMsEPS2004, SEPS2063 (being Kuraray company (KurarayCo., Ltd.) system above).
Using the situation of ACM, also can for the ACM of core shell structure (core-shellstructure) be made up of two kinds of ACMs.
In addition, in this manual, upper target " rTM" mean registered trademark.
Be used as the mean grain size of the organic filler of organic filler (I), if time too large, when manufacturing liquid crystal cells (liquidcrystalcell) of close clearance (narrowgap), the bad essential factor in the gap (gap) when cannot form lower glass substrate in laminating smoothly etc. can be become, therefore be suitably with less than 20 μm, be preferably less than 10 μm.Particle diameter is measured by electron microscope method.
In addition, as above-mentioned, be the pressure with upper and lower base plate in the present invention, organic filler (I) compressed and forms cofferdam, to resist mixing of liquid crystal.Therefore, when the thickness (seal clearance (the sealgap)) 90%D of organic filler (I) being set to the liquid crystal sealing agent after A (μm), upper and lower base plate laminating is set to B (μm), is then preferably and can meets following formula (1) ﹕
0μm≦A－B≦15.0μm(1)
At this, the size-grade distribution of organic filler can laser diffraction scattering sedimentograph (laserdiffraction/scatteringparticlesizedistributionmeasu ringapparatus) (dry type) (Seishin enterprise (stock) company (SeishinEnterpriseCo., Ltd.) makes; Etc. LMS-30) measured.This size-grade distribution can obtain the volume reference data of filling agent, and can use as being called " 90%D " to represent.So-called " 90%D " be represent measure size-grade distribution and mark and draw particle diameter at transverse axis, the accumulation of volume distributed median when the longitudinal axis marks and draws accumulation (%) of volume distributed median is particle diameter when being equivalent to 90%, can be used as the index of size-grade distribution.
Comprise in use and can meet above formula (1) and the situation with the liquid crystal sealing agent of the organic filler (I) of 90%D, then to count in the volume reference of the organic filler (I) after laminating upper and lower base plate the amount being equivalent to 10%, the size of seal clearance can be compressed into, to resist mixing of liquid crystal.The value of A-B is more preferred from more than 1.0 μm and less than 13.0 μm, is more preferred from more than 2.0 μm further and less than 10.0 μm.
For obtaining the organic filler of desired mean grain size, also progressive operation can be applied to organic filler (I).If when implementing this operation, then also contribute to removing oversize grain, and the organic filler (I) with distinct size-grade distribution can be prepared.Because oversize grain can cause being easy to cause the cell gap of liquid crystal display (cellgap) bad, be preferably and implement this progressive operation.
Progressive operation, can, such as after injecting type grinding machine (jetmillcrusher) JM-0202 (Seishin enterprise (stock) Inc.) is pulverized, airflow classification machine (pneuamaticclassifier) N05 (Seishin enterprise (stock) Inc.) be used to implement.For more effectively implementing this operation, also spreading agent etc. can be used.
Liquid crystal sealing agent of the present invention comprises the hardening compound (II) with (methyl) acryloyl group.This hardening compound (II), as long as be when carrying out polyreaction person by light or heat, then there is no special restriction.
As the compound with (methyl) acryloyl group, can Lie Ju ﹕ such as (methyl) acrylic ester ((meth) acrylicester), (methyl) acrylic acid epoxy ester etc.As (methyl) acrylic ester, can Lie Ju ﹕ benzyl methacrylate, cyclohexyl methacrylate, dimethacrylate glycerine ester, three acrylic acid glycerine esters, EO upgrading three acrylic acid glycerine ester, the new Doutrate of acrylic acid, three acrylic acid trihydroxy methyl propyl ester, three (propenyloxy group ethyl) chlorinated isocyanurates, six acrylic acid two newly Doutrate, the sweet amine alcohol ester of three acrylic acid fluorine etc.(methyl) acrylic acid epoxy ester obtains in a known manner by epoxy resin and (methyl) acrylic acid reaction.As the epoxy resin of raw material, there is no special restriction, be preferably the epoxy resin of more than two senses, can Lie Ju ﹕ such as 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, polyglycidyl type epoxy resin, glycidyl amine type epoxy resin, hydantoins (glycolylurea) type epoxy resin (hydantointypeepoxyresin), isocyanurate type epoxy resin, there is the phenol novolak type epoxy resin of tris-phenol skeleton, other, it is then the bisglycidyl ethers compound of two sense phenols of catechol (catechol) (catechol), resorcinol (resorcinol) etc., the bisglycidyl ethers compound of two sense alcohols, and these halogenide, hydride etc.In these, from the viewpoint of liquid crystal pollution, be then preferably the epoxy resin with resorcinol skeleton, can Lie Ju ﹕ such as resorcinol bisglycidyl ethers etc.In addition, epoxy radicals there is no special restriction with the ratio of (methyl) acryloyl group, suitably can select from the viewpoint of processing procedure adaptability and liquid crystal pollution.
Therefore; preferably hardening compound (II); then such as, for there is (methyl) acryloyl group and there is hardening compound, the acrylate of resorcinol bisglycidyl ethers or the methacrylate of resorcinol bisglycidyl ethers of resorcinol skeleton.
In addition, in liquid crystal sealing agent of the present invention, auto polymerization (self-polymerizable) compound not needing to add initiating agent (initiator) etc. can also be comprised.Can Lie Ju ﹕ such as maleimide (maleimide) (maleimide) compound, the compound etc. be disclosed in Japanese Patent Laid-Open 2005-239746 publication.
In addition, the containing ratio that hardening compound (II) occupies in liquid crystal sealing agent, when the total amount of liquid crystal sealing agent is set to 100 mass parts, is preferably in the scope of 30 ~ 90 mass parts, is more preferred from about 50 ~ 90 mass parts.
In above-mentioned hardening compound (II), be preferably in the situation being included in a part the compound with more than 3 (methyl) acryloyl groups.In a part, have the compound of more than 3 (methyl) acryloyl groups, because crosslinking rate (reaction velocity) is quick, what can realize excellence mixes patience.In addition, using the situation of the method, then improving reactive method from the quantity increasing hot radical polymerization initiator etc. different, operation usability (handlingproperty) is also excellent.
As the compound in a part with more than 3 (methyl) acryloyl groups, can Lie Ju ﹕ KAYARAD rTMpET-30, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DPEA-12, GPO-303, TMPTA, THE-330, TPA-320, TPA-330, D-310, D-330, RP-1040, UX-5000, DPHA-40H (being Japanese chemical drug (stock) company (NipponKayakuCo., Ltd.) system above); NKEster rTMa-9300, A-9300-1CL, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3LM-N, A-TMPT, AD-TMP, ATM-35E, A-TMMT, A-9550, A-DPH (above Shi Xinzhong village chemical industry (stock) company (Shin-NakamuraChemicalCo., Ltd.) system); SR295, SR350, SR355, SR399, SR494, CD501, SR502, CD9021, SR9035, SR9041 (being SARTOMER (stock) company (SARTOMER) system above) etc.In these, being preferably in molar-averaged formula weight is the situation of more than 800, is preferably such as KAYARAD rTMdPCA-20, DPCA-30, DPEA-12.In addition, be preferably the situation of hardening compound containing C1-C4 alkylene oxide (-O-R-O-) in molecule, then special good be KAYARAD rTMdPEA-12.
Liquid crystal sealing agent of the present invention also can comprise hot radical polymerization initiator (III).Hot radical polymerization initiator, as long as producing free radical (radical) by heating, and when causing the compound of segment polyreaction (chainpolymerizationreaction), then there is no special restriction, can Lie Ju ﹕ organic peroxide, azo-compound, benzoin compound, benzoin ether compound, acetophenone compound, benzo pinacol (benzopinacol) etc., be applicable to using benzo pinacol.Such as organic peroxide, Kayamekku rTMa, M, R, L, LH, SP-30C, PercadoxCH-50L, BC-FF, cadoxB-40ES, Percadox14, 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, Percadox16, Kayacarbon rTMbIC-75, AIC-75 (being KayakuAkzo (stock) company (KayakuAkzoCo., Ltd.) system above); Permek rTMn, H, S, F, D, G, Perhexa rTMh, HC, TMH, C, V, 22, MC, Percure rTMaH, AL, HB, Perbutyl rTMh, C, ND, L, Percumyl rTMh, D, Peroyl rTMiB, IPP, Perocta rTMnD (being Japanese grease (stock) company (NOFCorporation) system above) etc. can available from commercial goods.In addition, as azo-compound, VA-044, V-070, VPE-0201, VSP-1001 (being pure pharmaceutical worker's industry (stock) company (WakoPureChemicalIndustries, Ltd.) system above with light) etc. can available from commercial goods.
As above-mentioned hot radical polymerization initiator (III), be preferably the hot radical polymerization initiator in molecule without o-o bond knot (-O-O-) or nitrogen-nitrogen bond (-N=N-).There is the hot radical polymerization initiator of o-o bond knot (-O-O-) or nitrogen-nitrogen bond (-N=N-) in molecule, due to a large amount of oxygen or nitrogen can be produced when free radical produces, therefore have with the state remaining bubble (bubble) in liquid crystal sealing agent and harden, causing the misgivings that the characteristics such as tack strength reduce.The hot radical polymerization initiator of benzo pinacol system (comprise through by benzo pinacol in addition chemical modification person) is particularly suitable for using.Specifically, can Lie Ju ﹕ benzo pinacol, 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, two (trimethylsiloxy group)-1 of 2-, 1, 2, 2-tetraphenyl ethane, 1, two (the triethyl siloxy)-1 of 2-, 1, 2, 2-tetraphenyl ethane, 1, two (the three grades of Butyldimethylsilanyloxy)-1 of 2-, 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-three grades of Butyldimethylsilanyloxy-1, 1, 2, 2-tetraphenyl ethane etc., be 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-three grades of Butyldimethylsilanyloxy-1,1,2,2-tetraphenyl ethane, 1, two (trimethylsiloxy group)-1 of 2-, 1,2,2-tetraphenyl ethane, be more preferred from 1-hydroxyl-2-trimethylsiloxy group-1,1,2,2-tetraphenyl ethane, 1,2-two (trimethylsiloxy group)-1,1,2,2-tetraphenyl ethane, Te Jia is 1,2-two (trimethylsiloxy group)-1,1,2,2-tetraphenyl ethane.
Above-mentioned benzo pinacol has changed into industry (stock) company (TokyoChemicalIndustryCo., Ltd.) and light pure pharmaceutical worker's industry (stock) company etc. in market sale by Tokyo.In addition, the compound of the hydroxyl of benzo pinacol etherificate in addition can well known method easily be synthesized.In addition, by the compound of the hydroxyl of benzo pinacol silylation etherificate in addition, then by by corresponding benzo pinacol and various silanizing agent (silylatingagent), the method for carrying out heating under the alkaline catalysts (basiccatalyst) such as pyridine (pyridine) exist is to synthesize acquisition.As silanizing agent, trimethyl chlorosilane (TMCS), hexamethyldisilazane (HMDS), two (TMS) trifluoroacetamide (BSTFA) of N, O-or the chlorotriethyl silane (TECS) of triethyl silicane agent or three grades of butyl methyl silane (TBMS) etc. of three grades of butyldimethylsilane agents of lifting the known trimethyl silane agent of ﹕ can be arranged.These reagent can easily available from the market of silicon derivative manufacturer etc.About the reacting dose of silanizing agent, relative to the hydroxyl 1 mole of subject compound (targetcompound), be preferably 1.0 ~ 5.0 times moles, be more preferred from 1.5 ~ 3.0 times moles.If when being less than 1.0 times moles, then because reaction efficiency is not good, the reaction time is elongated and can promote thermal decomposition.If during more than 5.0 times moles, then when recycling, malsegregation or refining difficulty will be caused.
This hot radical polymerization initiator is preferably and makes its particle diameter become fine and disperse equably.Its mean grain size, if time too large, when manufacturing the liquid crystal display of close clearance, the bad essential factor in gap when cannot form lower glass substrate in laminating (bonded) smoothly etc. can be become, therefore be preferably less than 5 μm, be more preferred from less than 3 μm.In addition, although also can be become fine without end, lower limit is about 0.1 μm usually.Particle diameter is with laser diffraction scattering sedimentograph (dry type) (Seishin enterprise (stock) Inc.; LMS-30) measure.
The content of this hot radical polymerization initiator, when being 100 mass parts by the total amount of liquid crystal sealing agent of the present invention, being then preferably 0.0001 ~ 10 mass parts, being more preferred from 0.0005 ~ 5 mass parts, and special good is 0.001 ~ 3 mass parts.
Liquid crystal sealing agent of the present invention, adds epoxy resin (IV) and can expect and improve tack strength further.Spendable epoxy resin there is no special restriction, be preferably the epoxy resin of more than two senses, can Lie Ju ﹕ such as 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, polyglycidyl type epoxy resin, glycidyl amine type epoxy resin, hydantoins (glycolylurea) type epoxy resin, isocyanurate type epoxy resin, there is the phenol novolak type epoxy resin of tris-phenol skeleton, other is then the bisglycidyl ethers compound of the bisglycidyl ethers compound of two sense phenols, two sense alcohols, and these halogenide, hydride etc.In these, from the viewpoint of liquid crystal pollution, be then preferably bisphenol-type epoxy resin, phenolic resin varnish type epoxy resin.The content that epoxy resin (IV) occupies in liquid crystal sealing agent when the total amount of liquid crystal sealing agent is set to 100 mass parts, is then about 1 ~ 30 mass parts.
Liquid crystal sealing agent of the present invention also can comprise thermoinitiators (V).Thermoinitiators (V) there is no special restriction, can arrange and lift the many first amines (polyvalentamines) of ﹕, polyatomic phenol (polyvalentphenols), organic acid hydrazide compound etc., but be particularly suitable for using solid-state organic acid hydrazides (organicacidhydrazide).Salicylic acid hydrazides, benzoic acid hydrazide, 1-naphthoic acid hydrazides, terephthaldehyde's acid dihydrazide, the isophthalic dihydrazide, 2 of lifting ﹕ such as aromatic hydrazide can be arranged, 6-naphthoic acid two hydrazides, 2,6-pyridine two hydrazides, 1,2,4-benzene three hydrazides, 1,4,5,8-naphthoic acid four hydrazides, burnt melitic acid, four hydrazides etc.In addition, if aliphatics hydrazide compound, can Lie Ju ﹕ such as formylhydrazine (formhydrazide), acetylhydrazide, propionic acid hydrazides, grass acid dihydrazide, acid dihydrazide, succinic acid hydrazide ii, glutaric, adipic dihydrazide, heptandioic acid two hydrazides, sebacic dihydrazide, Isosorbide-5-Nitrae-cyclohexane two hydrazides, winestone acid dihydrazide, apple acid dihydrazide, iminodiacetic acid two hydrazides, N, N ' the two half card hydrazine of-hexa-methylene (N, N '-hexamethylenebissemicarbazide), citric acid three hydrazides, nitrogen base acetic acid three hydrazides (nitriloaceticacidtrihydrazide), cyclohexane tricarboxylic acid three hydrazides, two (diamine base the carbonyl ethyl)-5-isopropyl hydantoins of 1,3-, is preferably the dihydrazide compound of figured silk fabrics amino acid hydantoins skeleton (carbon atom of hydantoins ring is the skeleton replaced with isopropyl), three (1-diamine base carbonvlmethyl) chlorinated isocyanurates, three (2-diamine base carbonylethyl) chlorinated isocyanurates, three (3-joins amino-carbonyl propyl group) chlorinated isocyanurates, two (2-diamine base carbonylethyl) chlorinated isocyanurates etc.This thermoinitiators can separately, also can be two or more used in combination.From the viewpoint that sclerous reaction and potentiality (potential) balance, be then preferably isophthalic dihydrazide, acid dihydrazide, adipic dihydrazide, sebacic dihydrazide, three (1-diamine base carbonvlmethyl) chlorinated isocyanurates, three (2-diamine base carbonylethyl) chlorinated isocyanurates, three (3-joins amino-carbonyl propyl group) chlorinated isocyanurates; Te Jia is acid dihydrazide, sebacic dihydrazide.Using content time thermoinitiators so (V), when the total amount of liquid crystal sealing agent is set to 100 mass parts, is then about 1 ~ 30 mass parts.
Liquid crystal sealing agent of the present invention, further adds silane coupling agent (VI), can expect and improve tack strength or moisture-proof.As this silane coupling agent (VI), can Lie Ju ﹕ 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxypropyl dimethoxysilane, 3-glycidoxypropyl diethoxy silane, 2-(3, 4-epoxycyclohexyl) ethyl trimethoxy silane, N-phenyl-γ-aminocarbonyl propyl trimethoxy silane, N-(2-amido ethyl)-3-aminocarbonyl propyl methyl dimethoxysilane, N-(2-amido ethyl)-3-aminocarbonyl propyl trimethoxy silane, 3-aminocarbonyl propyl triethoxysilane, 3-sulfhydryl propyl trimethoxy silicane, vinyltrimethoxy silane, N-(2-(vinyl benzylamino) ethyl)-3-aminocarbonyl propyl trimethoxy silane hydrochloride, 3-methacryloxypropyl trimethoxy silane, 3-chloropropylmethyldimethoxysilane, 3-r-chloropropyl trimethoxyl silane etc.These silane coupling agents, due in KBM series, KBE is serial etc. and by sale such as SHIN-ETSU HANTOTAI's chemical industry (stock) company (Shin-EtsuChemicalCo., Ltd.), can easily obtain from market.The content that silane coupling agent (VI) occupies in liquid crystal sealing agent when the entirety of liquid crystal sealing agent of the present invention is set to 100 mass parts, is then applicable with 0.05 ~ 3 mass parts.
Liquid crystal sealing agent of the present invention, except mentioned component and composition comprised if desired, also can be persons such as comprising such as Photoepolymerizationinitiater initiater (photo-polymerizationinitiator), radical polymerization inhibitor (radicalpolymerizationinhibitor), inorganic filler, hardening accelerator (curingaccelerator), pigment, leveling agent (levelingagent), defoamer (defoamer), solvent.
As above-mentioned Photoepolymerizationinitiater initiater, as long as free radical or acid can be produced in the irradiation of ultraviolet or visible ray, and when causing the compound of segment polyreaction, then there is no special restriction, can Lie Ju ﹕ such as benzyl dimethyl ketal, 1-hydroxycyclohexylphenylketone, diethyl oxygen sulphur mouth mountain pass star (thioxanthone), diphenylketone, 2-EAQ, 2-hydroxy-2-methyl propionyl benzene, 2-methyl-(4-(methyl mercapto) phenyl)-2-morpholinyl-1-propane, 2, 4, 6-trimethyl benzoyl diphenyl base phosphine oxide, camphorquinone, 9-Fluorene ketone, Diphenyl disulfide ether etc.Specifically, IRGACURE rTM651,184,2959,127,907,396,379EG, 819,784,754,500, OXE01, OXE02, DAROCURE rTM1173, LUCIRIN rTMtPO (being BASF AG (BASFCorporation) system above); SEIKUOL rTMz, BZ, BEE, BIP, BBI (being Seiko chemistry (stock) company (SeikoChemicalCo., Ltd.) system above) etc.
In addition, from the viewpoint of liquid crystal pollution, then be preferably to be used in molecule and have (methyl) acrylic acid series base [(meth) acrylicgroup] person, the reaction product of such as isocyanic acid 2-methacryloyloxyethyl and 1-[4-(2-hydroxyl-oxethyl)-phenyl]-2-hydroxy-2-methyl-1-propane-1-ketone is applicable to using.This compound can obtain according to the method manufacture disclosed in No. 2006/027982nd, International Publication.
When using Photoepolymerizationinitiater initiater, its containing ratio in liquid crystal sealing agent total amount, is generally 0.001 ~ 3 quality %, is preferably 0.002 ~ 2 quality %.
As above-mentioned radical polymerization inhibitor, as long as during for carrying out with the free radical produced by Photoepolymerizationinitiater initiater or hot radical polymerization initiator etc. reacting and preventing the compound be polymerized, then there is no special restriction, quinone system, piperidines system, steric hindrance type phenol system, nitrous base system (nitroso-based) etc. can be used.Specifically, can Lie Ju ﹕ naphthoquinones, 2 hydroxy naphthalene quinone, 2 methyl naphthoquinone, 2-methoxynaphthoquinone, 2,2,6,6-tetramethyl piperidine-1-oxygen base, 2,2,6,6-tetramethyl-4-hydroxy piperidine-1-oxygen base, 2,2,6,6-tetramethyl-4-methoxy piperide-1-oxygen base, 2,2,6,6-tetramethyl-4-Phenoxypiperidines-1-oxygen base, quinhydrones (hydroquinone), 2-methylnaphthohydroquinone, 2-methoxyhydroquinon, 1,4-benzoquinone, Butylated hydroxy anethole, 2,6-, bis--three grades of butyl-4-ethyl-phenols, 2,6-, bis--three grades of butyl cresols, β-(3,5-, bis--three grades of butyl-4-hydroxy phenyls) propionic acid stearyl ester [stearyl β-(3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2 '-di-2-ethylhexylphosphine oxide (4-ethyl-6-three grades of butylphenols), 4,4 '-sulfenyl two (3-methyl-6-three grades of butylphenols), 4,4 '-butylidene two (3-methyl-6-three grades of butylphenols), two [1,1-dimethyl-2-[β-(3-tri-grades of butyl-4-hydroxy-5-methyl base phenyl) propionyloxy] ethyl]-2,4,8,10-tetra-oxaspiro [5, the 5] undecanes of 3,9-, four-[methylene-3-(propionic acid 3 ', 5 '-two-three grade of butyl-4 '-hydroxylphenyl ester) methane, 1,3,5-tri-(3 ', 5 '-two-three grade of butyl-4 '-hydroxyphenylmethyl)-secondary three nitrogen-2,4,6-(1H, 3H, 5H) triketone, p methoxy phenol, 4-methoxyl-1-naphthols, sulfenyl diphenylamine, the aluminium salt of N-nitroso-phenylhydroxylamine, trade name ADEKASTABLA-81, trade name ADEKASTABLA-82 (being rising sun electrochemical industry (stock) company (ADEKACorporation) system above) etc., but be not limited to these persons.In these, be preferably the radical polymerization inhibitor of naphthoquinones system, quinhydrones system, nitrous base system, piperazine system (piperazine-based); Be more preferred from naphthoquinones, 2 hydroxy naphthalene quinone, quinhydrones, 2,6-bis--three grades of butyl paracresol, POLYSTOP7300P (Bai Dong (stock) company (HakutoCo., Ltd.) system); The best is POLYSTOP7300P (Bai Dong (stock) Inc.).
Radical polymerization inhibitor, although there is the method for adding when synthesizing hardening compound (II), or make it be dissolved in the method for hardening compound (II) and/or hot radical polymerization initiator (III), but in order to obtain more effective effect, be preferably and hardening compound (II) and/or hot radical polymerization initiator (III) are added, and the method making it dissolve.
The content of radical polymerization inhibitor, in liquid crystal sealing agent total amount of the present invention, is preferably 0.0001 ~ 1 quality %, is more preferred from 0.001 ~ 0.5 quality %, and special good is 0.01 ~ 0.2 quality %.
Use above-mentioned inorganic filler, can expect that tack strength improves or moisture-proof reliability improves.As inorganic filler, can Lie Ju ﹕ fused silica (fusedsilica), crystalline silica (crystallinesilica), 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 preferred from fused silica, crystalline silica, aluminium oxide, talcum.Two or more may be used in combination for these inorganic fillers.Its mean grain size, if too large time, when manufacturing the liquid crystal cells of close clearance, the bad essential factor in gap when cannot form the upper lower glass substrate of laminating smoothly etc. can be become, being therefore suitable with 3 μm below, being preferably less than 2 μm.Particle diameter is with laser diffraction scattering sedimentograph (dry type) (Seishin enterprise (stock) Inc.; LMS-30) measure.The content of inorganic filler in liquid crystal sealing agent, when the entirety of liquid crystal sealing agent of the present invention is set to 100 mass parts, is then generally 1 ~ 60 mass parts, is preferably 1 ~ 40 mass parts.If the content of inorganic filler be very little time, then the tack strength of glass substrate is reduced, and moisture-proof reliability is also poor, therefore also likely causes the situation that the reduction of the tack strength after moisture absorption increases.On the other hand, if when the content of inorganic filler is too many, then likely cause the situation that not easily cannot be formed the gap of liquid crystal cells by conquassation (collapse).
As above-mentioned hardening accelerator, can Lie Ju ﹕ organic acid or imidazoles (imidazole) etc.
As organic acid, can Lie Ju ﹕ organic carboxyl acid or organic phosphoric acid etc., be preferably the situation at organic carboxyl acid.Specifically, can Lie Ju ﹕ phthalic acid, m-phthalic acid, terephthalic acid (TPA), trimellitic acid (1,2,4-benzenetricarboxylic acid), diphenylketone tetracarboxylic acid, furandicarboxylic acid etc. aromatic carboxylic acid; Succinic acid (succinic acid), hexane diacid, dodecanedioic acid, resinosis acid (decanedioic acid), thiodipropionic acid, cyclohexane cyclohexanedimethanodibasic, three (2-carboxymethyl group) chlorinated isocyanurates, three (2-carboxy ethyl) chlorinated isocyanurates, three (2-carboxypropyl) chlorinated isocyanurates, two (2-carboxy ethyl) chlorinated isocyanurates etc.
In addition, as imidazolium compounds, can Lie Ju ﹕ glyoxal ethyline, 2-phenylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-glyoxal ethyline, 1-1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecyl imidazole, 2,4-bis-amido-6 (2 '-methylimidazole (1 ')) ethyl-s-three nitrogen, 2,4-bis-amido-6 (2 '-undecyl imidazole (1 ')) ethyl-s-three nitrogen, 2,4-bis-amido-6 (2 '-ethyl-4-methylimidazole (1 ')) ethyl-s-three nitrogen, 2,4-bis-amido-6 (2 '-methylimidazole (1 ')) ethyl-s-three nitrogen isocyanuric acid addition product, the 2:3 addition product of glyoxal ethyline isocyanuric acid, 2-phenylimidazole isocyanuric acid addition product, 2-phenyl-3,5-bishydroxymethyl imidazoles, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyan ethoxyl methyl imidazoles etc.
The content of hardening accelerator in liquid crystal sealing agent, when the total amount of liquid crystal sealing agent is set to 100 mass parts, is then generally 0.1 ~ 10 mass parts, is preferably 1 ~ 5 mass parts.
Liquid crystal display of the present invention is that the specific interval of one-tenth arranged opposite, is sealed surrounding with liquid crystal sealing agent of the present invention by a pair substrate through forming special electrodes on substrate, and gap encloses liquid crystal person betwixt.The kind of the liquid crystal be enclosed there is no special restriction.At this, so-called " substrate " is that the substrate combined at least having a transmitance (light-transmitting) in one be made up of glass, quartz, plastics, silicon (silicon) etc. formed.Its method for making is after Xia ﹕ adds the sept (spacers) (clearance control material (gapcontrolmaterial)) of glass fibre etc. in liquid crystal sealing agent, use divider (dispenser) in the one of this pair substrate, after screen printing apparatus (screenprintingapparatus) etc. is coated with this liquid crystal sealing agent, because of in requisition at 80 ~ 120 DEG C temporarily harden (temporarycuring).Then, drip in the inner side in the cofferdam be made up of this liquid crystal sealing agent liquid crystal, and coincide (overlay) another glass substrate in a vacuum, and form gap.After gap is formed, because of in requisition for 1000mJ/cm 2~ 6000mJ/cm 2ultraviolet irradiated, then carry out sclerosis 1 ~ 2 hour at 90 ~ 130 DEG C, by this, liquid crystal display of the present invention can be obtained.Obtain liquid crystal display of the present invention as above-mentioned, then have no way of in the display caused by liquid crystal pollution bad (displaydefects), and tackness, moisture-proof person excellent in reliability.As sept, can arrange and lift ﹕ such as glass fibre, silicon dioxide bead, macromolecule bead etc.Its diameter is different in response to object, is generally 2 ~ 8 μm, is preferably 4 ~ 7 μm.Its use amount, relative to liquid crystal sealing agent 100 mass parts of the present invention, is then generally 0.1 ~ 4 mass parts, is preferably 0.5 ~ 2 mass parts, be more preferred from about 0.9 ~ 1.5 mass parts.
Be used in the liquid crystal sealing agent of liquid crystal display manufacture method of the present invention, such as, can following method obtain.First, in the hardening compound (II) because of in requisition for dissolving fusion epoxy resin (IV).Secondly, at this potpourri because of in requisition for dissolves silicon alkane coupling agent (VI).Secondly, cause is in requisition for being added with machine filling agent (I), hot radical polymerization initiator (III), thermoinitiators (V), inorganic filler, defoamer (defoamer), leveling agent (levelingagent), solvent etc., mixed equably with known mixing arrangement, such as three roll shape roller mills, sand mill, bowl mill etc., and filtered with metallic sieve (metalmesh).
Liquid crystal sealing agent of the present invention, the patience (insertionresistance) of mixing for liquid crystal, for very good, causes mixing or phenomenon that sealant subsides of liquid crystal even if be also unlikely in the baseplate-laminating step of method, heating steps under liquid crystal drop.Therefore, stably liquid crystal display can be manufactured.In addition, the speed be crosslinked due to hardening resin is fast, constituent is also few for the dissolved (elution) of liquid crystal, and the display that can reduce liquid crystal display is bad.In addition, because storage stability is also excellent, the manufacture of liquid crystal display is suitable for.Further, its hardening thing is also excellent in the various hardening thing characteristics such as tack strength, thermotolerance, moisture-proof, and particularly moisture permeability is very low.Therefore, the liquid crystal sealing agent of the application of the invention, can manufacture liquid crystal display excellent in reliability.In addition, use the liquid crystal display manufactured by liquid crystal sealing agent of the present invention, also can meet that voltage retention (voltageholdingratio) is high fully, ion concentration (iondensity) is low as the necessary characteristic of liquid crystal display.
The manufacture method of liquid crystal display of the present invention, because liquid crystal mixes as seldom for liquid crystal sealing agent, is also applicable to method under the liquid crystal drop by means of only heat.By means of only method under the liquid crystal drop of heat, from the viewpoint of producing interval time (takttime) etc., be then better.
Embodiment
Hereinafter, illustrate in greater detail the present invention with synthesis example, embodiment, but the present invention is not limited to embodiment.In addition, beyond special record, " part " and " % " in this article take quality as benchmark.
In addition, 10% deformation force of organic filler is the numerical value measured with the micro-compression tester of Inc. of Shimadzu Seisakusho Ltd. (MCT-510), and water vapor permeability is the numerical value measured with GTRTec (stock) company (GTRTecCorporation) GTR-30X processed.
[synthesis example 1]
[synthesis of full acrylic acid series (acrylic) compound of resorcinol bisglycidyl ethers]
Resorcinol bisglycidyl ethers 181.2 parts (long rapids industry (stock) company (NagaseChemteXCorporation) that changes into of EX-201 ﹕ makes) is dissolved in toluene 266.8 parts, this is added to the dibutyl hydroxy toluene 0.8 part as polymerization inhibitor (polymerizationinhibitor), and be warming up to 60 DEG C.Then, add 117.5 parts, the acrylic acid of 100% equivalent of epoxy radicals, and be warming up to 80 DEG C, the chlorination trimethyl ammonium 0.6 part as reaction catalyst is added to this, and 98 DEG C of stir abouts 30 hours, acquisition reactant liquor.This reactant liquor is washed, and is heated up in a steamer except toluene, by this, obtained the acrylic acid epoxy ester 293 parts of object resorcinol bisglycidyl ethers.Obtain the reactivity equivalent of acrylic acid epoxy ester, in theoretical value then for 183.
[synthesis example 2]
[synthesis of 1,2-two (trimethylsiloxy group)-1,1,2,2-tetraphenyl ethane]
Commercially available benzo pinacol (Tokyo changes into (stock) company (TokyoChemicalCo., Ltd.) makes) 100 parts is dissolved in dimethylformaldehyde 350 parts.This is added to the pyridine 32 parts as alkali catalyst (basecatalyst), BSTFA (chemical industrial company of SHIN-ETSU HANTOTAI (Shin-EtsuChemicalCo. as silanizing agent, Ltd.) make) 150 parts, and be warming up to 70 DEG C, stir 2 hours.Obtained reactant liquor is cooled, is stirred, while add 200 parts, water, product is precipitated and unreacted silanizing agent is deactivated (deactivation) simultaneously.After precipitated product in addition isolated by filtration, fully washed.Secondly, obtained product is dissolved in acetone, adds water and carry out recrystallization and refined.Obtain two 105.6 parts, (trimethylsiloxy group)-1,1,2, the 2-tetraphenyl ethane (productive rate (yield) 88.3%) of object 1,2-.
With HPLC (High Performance Liquid chromatography method ﹕ HighPerformanceLiquidChromatography)) carry out analysis result, purity is 99.0% (area percentage).
[embodiment 1 ~ 2, comparative example 1 ~ 4]
Be used in each composition of following the amount of Table 1, carry out the manufacture of liquid crystal sealing agent.Manufacture method is as follows.
First, by the fusion of epoxy resin (IV) heating for dissolving in hardening compound (II), after being cooled to room temperature, sequentially add silane coupling agent (VI), organic filler (I), hot radical polymerization initiator (III), thermoinitiators (V), inorganic filler, by using three roll shape roller mills (three-rollmill) to be mixed equably, and filter with metallic sieve (635 meshes (mesh)).
[table 1]
(I)-1 ﹕ UCN-5050D (industrial group's system of refining large day)
(10% Bian Xing Li ﹕ 0.1MPa, vapor transmission degree (watervaporpermeability) ﹕ 90cc/m 224hatm, 90%D ﹕ 7.1 μm, Ping equal Li Jing ﹕ 4.9 μm).
(I)-2 ﹕ JB-800T (Gen Shang industrial group system)
(10% Bian Xing Li ﹕ 1.4MPa, vapor transmission Du ﹕ 80cc/m 224hatm, 90%D ﹕ 9.6 μm, Ping equal Li Jing ﹕ 6.0 μm).
(I)-3 ﹕ KMP-594 (SHIN-ETSU HANTOTAI's chemical industry (stock) Inc.)
(10% Bian Xing Li ﹕ 0.6MPa, vapor transmission Du ﹕ 210cc/m 224hatm, 90%D ﹕ 7.0 μm, Ping equal Li Jing ﹕ 5.0 μm).
(I)-4 ﹕ SE-3107A (refine in Sumitomo (stock) company (SumitomoSeikaChemicalsCo., Ltd.) makes)
(10% Bian Xing Li ﹕ 3.1MPa, vapor transmission Du ﹕ 10cc/m 224hatm, 90%D ﹕ about 20.0 μm, Ping equal Li Jing ﹕ 12.0 μm).
(II)-1 ﹕ has the acrylic acid epoxy ester (synthesized with synthesis example 1) of resorcinol skeleton.
(III)-1 ﹕ 1,2-two (trimethylsiloxy group)-1,1,2,2-tetraphenyl ethane (synthesized with synthesis example 2).
(IV)-1 ﹕ ethyleneoxide addition bisphenol-s epoxy resin (synthesized by the method disclosed in No. 4211942nd, Jap.P.).
(V)-1 ﹕ tri-(2-diamine base carbonylethyl) chlorinated isocyanurates Crushing of Ultrafine product
(Japanese precision chemical (stock) company (JapanFinechemCompany, Inc.) ﹕ HCIC processed, with injector-type mill (jetmill) in addition micro mist be broken into mean grain size 1.5 μm of persons).
(VI)-1 ﹕ 3-glycidoxypropyltrime,hoxysilane (Chisso (stock) company (ChissoCorporation) ﹕ SilaAceS-510).
(VI)-2 ﹕ N-(2-amido ethyl) 3-aminocarbonyl propyl trimethoxy silane (SHIN-ETSU HANTOTAI's chemical industry (stock) Gong Si ﹕ K8M-603).
O-1 ﹕ spherical silicon dioxide (SHIN-ETSU HANTOTAI's chemical industry (stock) Gong Si ﹕ X-24-9163A; A mean grain size 110nm).
O-2 ﹕ tri-(3-carboxy ethyl) chlorinated isocyanurates
(four countries change into industry (stock) company (ShikokuChemicalsCorporation) ﹕ CIC processed acid, with injector-type mill in addition micro mist be broken into mean grain size 1.5 μm of persons).
O-3 ﹕ POLYSTOP7300P (Bai Dong (stock) Inc.).
The patience of mixing of liquid crystal is assessed
Use with the liquid crystal sealing agent manufactured by embodiment, comparative example, make the liquid crystal display of seal clearance 5 μm, cell gap 5 μm, and carry out mixing property of observation.Test method is as follows.
Add as the glass fibre 1 part of the diameter 5 μm of sept each 100 parts of liquid crystal sealing agent, in addition mix and blend deaeration (degassing), and be filled in syringe (syringe).On the glass substrate having ITO (tin indium oxide) transparency electrode, by the liquid crystal sealing agent be previously filled in syringe, use divider (SHOTMASTER300 ﹕ Musashi engineering (stock) company (MusashiEngineering, Inc.) make), carry out the coating of seal pattern (sealpattern) and illusory seal pattern (dummysealpattern), secondly, by liquid crystal (MLC-3007; Merck (stock) company (MerckLtd.) make) tiny droplets, drip in the frame of seal pattern (sealpattern).Further, at another sheet on the glass substrate of friction treatment (rubbingprocess), by (NATOCO sept (NATOCOspacer) KSEB-525F of sept in face; Natoco (stock) company (NatocoCo., Ltd.) makes; Gap width after laminating 5 μm) scattered, heat fixation, and use laminating apparatus in a vacuum together with the previous baseplate-laminating through the liquid crystal that drips.Open at air and after forming gap, place 10 minutes, carry out the heat hardening of 1 hour in 120 DEG C of baking ovens after, with the interface of polarized light microscope observing sealant and liquid crystal, and assessing according to following benchmark.The results are shown in table 2.
○ ﹕ sealant do not observe the mixing of liquid crystal,
× ﹕ observes mixing of liquid crystal at sealant.
[moisture permeability assessment]
By with the liquid crystal sealing agent manufactured by embodiment, comparative example, with mould release film (releasefilm) (PET-38AL-5; Lintec (stock) company (LintecCorporation) makes) clamp, and after being molded into 100 μm of thickness by stacking-up machine (laminater), carry out heat hardening 60 minutes at 120 DEG C.Then, use Lyssy vapor transmission degree meter (permeationanalyzer) L80 type (SystechInstruments company (SystechInstrumentsLtd.) system), under 60 DEG C of environment, carry out moisture permeability mensuration according to the method for Japanese JISK7129A.The results are shown in table 2.
○ ﹕ measurement result is for being less than 100g/m 224h,
× ﹕ measurement result is 100g/m 2more than 24h.
[table 2]
By the result of table 2, if embodiment 1 and 2, then liquid crystal can be caused to mix lower making liquid crystal display being unlikely, in addition, moisture-penetrability is also low.If comparative example 1, although there is the patience of mixing for liquid crystal, but show high moisture-penetrability.If comparative example 2 to 4, then liquid crystal display cannot be made due to mixing of liquid crystal.Therefore, superiority of the present invention can be confirmed.
Industry utilizes possibility
Liquid crystal sealing agent of the present invention, because the patience of mixing for liquid crystal is very excellent, makes it easily can carry out manufacture liquid crystal display.In addition, particularly low-moisture permeability is excellent, and the liquid crystal display completed is long-term reliability is high person.Further, tack strength etc. are also excellent as the general characteristic of liquid crystal sealing agent.That is, liquid crystal sealing agent of the present invention is can realize easily manufacturing excellent liquid crystal display person.

Claims (11)

1. a method liquid crystal sealing agent under liquid crystal drop, wherein, comprises organic filler (I) and has the hardening compound (II) of (methyl) acryloyl group, and
Described organic filler (I) be 10% deformation force be below 2.0MPa and vapor transmission rate for being less than 100cc/m 224hatm,
When the total amount of described hardening resin (II) is set to 100 mass parts, the content of described organic filler (I) is more than 20 mass parts.
2. method liquid crystal sealing agent under liquid crystal drop according to claim 1, wherein, described hardening compound (II) comprises the compound with resorcinol skeleton.
3. method liquid crystal sealing agent under liquid crystal drop according to claim 1 and 2, wherein, comprises hot radical polymerization initiator (III) further.
4. method liquid crystal sealing agent under the liquid crystal drop according to any one in claims 1 to 3, wherein, comprises epoxy resin (IV) further.
5. method liquid crystal sealing agent under the liquid crystal drop according to any one in Claims 1-4, wherein, comprises thermoinitiators (V) further.
6. method liquid crystal sealing agent under the liquid crystal drop according to any one in claim 1 to 5, wherein, described organic filler (I) is polyurethane particulate.
7. method liquid crystal sealing agent under liquid crystal drop according to claim 3, wherein, described hot radical polymerization initiator (III) is 1,2-two (trimethylsiloxy group)-1,1,2,2-tetraphenyl ethane.
8. method liquid crystal sealing agent under liquid crystal drop according to claim 5, wherein, described thermoinitiators (V) is organic acid hydrazide compound.
9. method liquid crystal sealing agent under the liquid crystal drop according to any one in claim 1 to 8, wherein, comprises silane coupling agent (VI) further.
10. the manufacture method of a liquid crystal display, wherein, in the liquid crystal display be made up of two plate bases, be formed on a substrate by the liquid crystal drop according to any one in claim 1 to 9 under the inner side in cofferdam that forms of method liquid crystal sealing agent drip after liquid crystal, to fit another substrate, then by heat, method liquid crystal sealing agent under described liquid crystal drop is hardened.
11. 1 kinds of liquid crystal displays, wherein, are sealed to form with hardening thing, and method liquid crystal sealing agent under liquid crystal drop according to any one of claim 1 to 9 is hardened obtained by this hardening thing.
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