CN106796376A - Sealing material for liquid crystal display device, upper and lower conductive material and liquid crystal display cells - Google Patents

Sealing material for liquid crystal display device, upper and lower conductive material and liquid crystal display cells Download PDF

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Publication number
CN106796376A
CN106796376A CN201680003125.7A CN201680003125A CN106796376A CN 106796376 A CN106796376 A CN 106796376A CN 201680003125 A CN201680003125 A CN 201680003125A CN 106796376 A CN106796376 A CN 106796376A
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liquid crystal
crystal display
display device
mentioned
sealing material
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林秀幸
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Sekisui Chemical Co Ltd
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Sekisui Chemical Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL 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
    • G02F1/00Devices 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
    • G02F1/01Devices 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 
    • G02F1/13Devices 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
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1339Gaskets; Spacers; Sealing of cells
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL 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
    • G02F1/00Devices 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
    • G02F1/01Devices 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 
    • G02F1/13Devices 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
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1339Gaskets; Spacers; Sealing of cells
    • G02F1/13398Spacer materials; Spacer properties

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Nonlinear Science (AREA)
  • Optics & Photonics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Mathematical Physics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Liquid Crystal (AREA)
  • Sealing Material Composition (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

Even if the present invention is provided, light shielding part curability is excellent, under hot and humid environment also have excellent moisture-proof and cementability and can suppress the uneven sealing material for liquid crystal display device for occurring of display of liquid crystal display cells.In addition, it is an object of the invention to provide the conductive material up and down and liquid crystal display cells that are manufactured using the sealing material for liquid crystal display device.The present invention is a kind of sealing material for liquid crystal display device; it is the sealing material for liquid crystal display device containing curable resin and hot radical polymerization initiator; wherein, above-mentioned curable resin contains in a molecule to have in more than 2 compounds and a molecule of acryloyl group has more than 2 compounds of methylacryloyl.

Description

Sealing material for liquid crystal display device, upper and lower conductive material and liquid crystal display cells
Technical field
Even if the present invention relates to light shielding part curability it is excellent, also there is under hot and humid environment excellent moisture-proof and viscous Connecing property and the uneven sealing material for liquid crystal display device for occurring of display of liquid crystal display cells can be suppressed.In addition, the present invention is also The conductive material up and down and liquid crystal display cells for being directed to use with the sealing material for liquid crystal display device and manufacturing.
Background technology
In recent years, for the manufacture method of the liquid crystal display cells such as liquid crystal display, from shorten productive temp time, Optimization is used from the viewpoint of amount of liquid crystal, in conventional vacuum injection mode, such as disclosed in patent document 1, patent document 2 It is such to have used photo-thermal and turned into main flow with the liquid crystal drop under type referred to as technique of dripping of curing type sealant.
In technique of dripping, first, length is formed using distributor on a substrate in 2 electroded transparency carriers The seal pattern of square shape.Then, the tiny droplets of liquid crystal are added drop-wise to the frame of transparency carrier in the state of sealant is uncured On interior whole face, another transparency carrier is overlapped immediately, to light such as sealing irradiation ultraviolet radiations, carry out precuring.Afterwards, in liquid crystal Heated during annealing and carry out main solidification, make liquid crystal display cells.If wanting to carry out the laminating of substrate under reduced pressure, can be with High efficiency system liquid making crystal display element.
But, in mobile phone, portable game etc. in the modern times of the mobile device popularization with various liquid crystal panels, device Small-sized turn to the problem for needing most solution.As the method for miniaturization, the narrow frame of liquid crystal display part can be enumerated, for example, entered Go and the position of sealing is configured under black matrix (below, also referred to as " narrow frame design ").
If however, manufacturing the liquid crystal display cells of narrow frame design with technique of dripping, there is problems with:Because of black matrix And there is the position that light does not arrive at sealing, therefore in the case where photocuring system sealant is used, generation is not entered fully Row light irradiation causes the sealant dissolution in solidification way without the part for being solidified, and can pollute liquid crystal.
Prior art literature
Patent document
Patent document 1:Japanese Unexamined Patent Publication 2001-133794 publications
Patent document 2:International Publication No. 02/092718
The content of the invention
The invention problem to be solved
Even if it is an object of the invention to provide light shielding part curability it is excellent, under hot and humid environment also have it is excellent Moisture-proof and cementability and the uneven sealing material for liquid crystal display device for occurring of display of liquid crystal display cells can be suppressed.Separately Outward, it is an object of the invention to provide the conductive material up and down and liquid crystal manufactured using the sealing material for liquid crystal display device Show element.
Means for solving the problems
The present invention is a kind of sealing material for liquid crystal display device, and it is triggered containing curable resin and hot radical polymerization The sealing material for liquid crystal display device of agent, wherein, above-mentioned curable resin contains has more than 2 acryloyl groups in a molecule There are more than 2 compounds of methylacryloyl in compound and a molecule.
The present invention is described in detail below.
Present inventors studied herein below:Make curability by coordinating hot radical polymerization initiator in the encapsulant Resin solidifies rapidly, so as to suppress the liquid crystal pollution produced to liquid crystal by the sealant dissolution in solidification way.Even if however, In the case of using hot radical polymerization initiator, problems with is there is also:When shading design is strict, the crosslinking of light shielding part is close Spend and insufficient, moisture-proof, cementability under hot and humid environment become insufficient, after being preserved under hot and humid environment Display can occur uneven in liquid crystal display cells.
Therefore, present inventor has performed further investigation, as a result finding:In the sealant containing hot radical polymerization initiator In, there are more than 2 methacryls by using having in a molecule in the compounds and a molecule of more than 2 acryloyl groups The compound of base reaches more than specified temp, makes as curable resin, the glass transition temperature such that it is able to make solidfied material Light shielding part curability is excellent, even if also having excellent moisture-proof and cementability under hot and humid environment, can suppress liquid crystal The display of display element is uneven to be occurred.So that complete the present invention.
Sealing material for liquid crystal display device of the invention contains curable resin.
Above-mentioned curable resin contains in a molecule to have in more than 2 compounds and a molecule of acryloyl group has 2 The compound of individual above methylacryloyl.
Hereinafter, will also have in an above-mentioned molecule in the compounds and an above-mentioned molecule of more than 2 acryloyl groups has 2 The compound of above methylacryloyl is referred to as poly- (methyl) acyclic compound.
It is explained, in this specification, above-mentioned " (methyl) acrylic acid " refers to acrylic acid and/or methacrylic acid.
As above-mentioned poly- (methyl) acyclic compound, the compound and (methyl) third for example, made with hydroxyl can be enumerated (methyl) acrylate compounds obtained by olefine acid reaction, make (methyl) acrylic acid and epoxy obtained by epoxide reaction (methyl) acrylate, make (methyl) acrylic acid derivative with hydroxyl and amino first obtained by isocyanate compound reaction Acid esters (methyl) acrylate etc. and be the compounds in a molecule with more than 2 (methyl) acryloyl groups.
It is explained, above-mentioned " (methyl) acrylate " refers to acrylate or methacrylate, above-mentioned " epoxy (first Base) acrylate " it is to instigate the whole epoxy radicals in epoxide and compound obtained by (methyl) propylene acid reaction, it is above-mentioned " (methyl) acryloyl group " refers to acryloyl group or methylacryloyl.
As (methyl) acrylate compounds of 2 functions in above-mentioned (methyl) acrylate compounds, can enumerate for example 1,3-BDO two (methyl) acrylate, BDO two (methyl) acrylate, 1,6- hexylene glycols two (methyl) propylene Acid esters, 1,9- nonanediols two (methyl) acrylate, 1,10- decanediols two (methyl) acrylate, 2- normal-butyl -2- ethyls - 1,3-PD two (methyl) acrylate, ethylene glycol two (methyl) acrylate, diethylene glycol two (methyl) acrylate, four Ethylene glycol two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, DPG two (methyl) acrylate, 3 third Glycol two (methyl) acrylate, polypropylene glycol (methyl) acrylate, ethyleneoxide addition bisphenol-A two (methyl) acrylic acid Ester, expoxy propane addition bisphenol-A two (methyl) acrylate, ethyleneoxide addition Bisphenol F two (methyl) acrylate, dihydroxy first Base dicyclopentadienyl two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, ethylene-oxide-modified isocyanuric acid Two (methyl) acrylate, 2- hydroxyls -3- (methyl) acryloxypropyl (methyl) acrylate, (first of carbonate diol two Base) acrylate, PTMEG two (methyl) acrylate, polyester-diol two (methyl) acrylate, polycaprolactone glycol two (methyl) acrylate, polybutadiene diol two (methyl) acrylate etc..
In addition, as (methyl) acrylate compounds more than 3 functions in above-mentioned (methyl) acrylate compounds, can Enumerate for example:Trimethylolpropane tris (methyl) acrylate, ethyleneoxide addition trimethylolpropane tris (methyl) acrylic acid Ester, expoxy propane addition trimethylolpropane tris (methyl) acrylate, caprolactone modification trimethylolpropane tris (methyl) third Olefin(e) acid ester, pentaerythrite three (methyl) acrylate, ethyleneoxide addition isocyanuric acid three (methyl) acrylate, glycerine three (methyl) acrylate, expoxy propane addition glycerine three (methyl) acrylate, three (methyl) acryloyl-oxyethyl phosphoric acid Ester, two (trihydroxy methyl) propane four (methyl) acrylate, pentaerythrite four (methyl) acrylate, (first of dipentaerythritol five Base) acrylate, dipentaerythritol six (methyl) acrylate etc..
As above-mentioned epoxy (methyl) acrylate, can enumerate for example:Conventionally in the presence of base catalyst Under make epoxide and epoxy (methyl) acrylate etc. obtained by (methyl) propylene acid reaction.
As the epoxide as the raw material for synthesizing above-mentioned epoxy (methyl) acrylate, can enumerate for example double Phenol A types epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, 2,2 '-diallyl bisphenol type epoxy resin, hydrogen Change bisphenol-type epoxy resin, expoxy propane addition bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy tree Fat, thioether-type epoxy resin, diphenyl ether type epoxy, dicyclopentadiene-type epoxy resin, naphthalene type epoxy resin, phenol line Type phenolic resin varnish type epoxy resin, o-cresol novolak type epoxy resin, bicyclopentadiene novolac-type ring Oxygen tree fat, biphenyl novolac type epoxy resins, naphthols novolac type epoxy resins, glycidyl amine epoxy tree Fat, alkyl polyols type epoxy resin, modified rubber type epoxy resin, epihydric alcohol ester compound, bisphenol A-type episulfide tree Fat etc..
As product commercially available in above-mentioned bisphenol A type epoxy resin, can enumerate such as jER828EL, jER1001, JER1004 (being Mitsubishi Chemical Ind's system), Epiclon 850-S (DIC company systems) etc..
As product commercially available in above-mentioned bisphenol f type epoxy resin, such as jER806, jER4004 can be enumerated and (be three Water chestnut chemical company system) etc..
Used as product commercially available in above-mentioned bisphenol-s epoxy resin, (DIC is public can to enumerate such as Epiclon EXA1514 Department's system) etc..
Used as above-mentioned 2, commercially available product, can enumerate such as RE-810NM in 2 '-diallyl bisphenol type epoxy resin (Japanese chemical drug company system) etc..
As product commercially available in above-mentioned A Hydrogenated Bisphenol A type epoxy resin, such as Epiclon EXA7015 can be enumerated (DIC company systems) etc..
As product commercially available in above-mentioned expoxy propane addition bisphenol A type epoxy resin, such as EP-4000S can be enumerated (ADEKA company systems) etc..
As product commercially available in above-mentioned resorcinol type epoxy resin, such as EX-201 (Nagase can be enumerated ChemteX company systems) etc..
As product commercially available in above-mentioned biphenyl type epoxy resin, such as jER YX-4000H (Mitsubishi Chemicals can be enumerated Company system) etc..
Used as product commercially available in above-mentioned thioether-type epoxy resin, (aurification is lived by Nippon Steel can to enumerate such as YSLV-50TE Learn company system) etc..
Used as product commercially available in above-mentioned diphenyl ether type epoxy, (Nippon Steel lives can to enumerate such as YSLV-80DE Aurification company system) etc..
As product commercially available in above-mentioned dicyclopentadiene-type epoxy resin, such as EP-4088S (ADEKA can be enumerated Company system) etc..
As product commercially available in above-mentioned naphthalene type epoxy resin, such as Epiclon HP4032, Epiclon can be enumerated EXA-4700 (being DIC company systems) etc..
As product commercially available in above-mentioned phenol novolak resin type epoxy resin, such as Epiclon N- can be enumerated 770 (DIC company systems) etc..
As product commercially available in above-mentioned o-cresol novolak type epoxy resin, such as Epiclon can be enumerated N-670-EXP-S (DIC company systems) etc..
As product commercially available in above-mentioned bicyclopentadiene novolac type epoxy resins, can enumerate for example Epiclon HP7200 (DIC company systems) etc..
As product commercially available in above-mentioned biphenyl novolac type epoxy resins, such as NC-3000P can be enumerated (Japanese chemical drug company system) etc..
As product commercially available in above-mentioned naphthols novolac type epoxy resins, such as ESN-165S can be enumerated (aurification company system is lived by Nippon Steel) etc..
Used as product commercially available in above-mentioned glycidyl amine epoxy resin, (Mitsubishi Chemical is public can to enumerate such as jER630 Department's system), Epiclon 430 (DIC company systems), TETRAD-X (gas chemical company of Mitsubishi system) etc..
Used as product commercially available in abovementioned alkyl polyol type epoxy resin, (Nippon Steel lives can to enumerate such as ZX-1542 Aurification company system), Epiclon 726 (DIC company systems), Epolite 80MFA (, chemical company of common prosperity society system), DENACOL EX-611 (Nagase ChemteX company systems) etc..
As product commercially available in above-mentioned modified rubber type epoxy resin, such as YR-450, YR-207 can be enumerated and (be Aurification company system is lived by Nippon Steel), Epolide PB (Daicel company system) etc..
As product commercially available in above-mentioned epihydric alcohol ester compound, such as DENACOL EX-147 can be enumerated (Nagase ChemteX company systems) etc..
As product commercially available in above-mentioned bisphenol A-type episulfide resin, such as jER YL-7000 (Mitsubishis can be enumerated Chemical company's system) etc..
As other commercially available products in above-mentioned epoxide, such as YDC-1312, YSLV-80XY, YSLV- can be enumerated 90CR (being Nippon Steel's firmly aurification company system), XAC4151 (Asahi Kasei Corporation's system), jER1031, jER1032 (are Mitsubishi Chemical company's system), EXA-7120 (DIC company systems), TEPIC (Nissan Chemical company system) etc..
As product commercially available in above-mentioned epoxy (methyl) acrylate, can enumerate such as EBECRYL860, EBECRYL3200、EBECRYL3201、EBECRYL3412、EBECRYL3600、EBECRYL3700、EBECRYL3701、 EBECRYL3702, EBECRYL3703, EBECRYL3800, EBECRYL6040, EBECRYL RDX63182 (are DAICEL- ALLNEX company systems), EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (be Xin Zhong villages chemistry Industrial group's system), EPOXY ESTER M-600A, EPOXY ESTER 40EM, EPOXY ESTER 70PA, EPOXY ESTER 200PA、EPOXY ESTER 80MFA、EPOXY ESTER 3002M、EPOXY ESTER 3002A、EPOXY ESTER 1600A、EPOXY ESTER 3000M、EPOXY ESTER 3000A、EPOXY ESTER 200EA、EPOXY ESTER 400EA (being chemical company of common prosperity society system), DENACOL ACRYLATE DA-141, DENACOL ACRYLATE DA-314, DENACOL ACRYLATE DA-911 (being Nagase ChemteX company systems) etc..
Above-mentioned carbamate (methyl) acrylate for example can be by making have 2 isocyanates of NCO The equivalent of compound 1 is anti-in the presence of the tin based compound of catalytic amount with the equivalent of (methyl) acrylic acid derivative 2 with hydroxyl Should obtain.
As the isocyanate compound of the raw material as above-mentioned carbamate (methyl) acrylate, can enumerate for example IPDI, 2,4- toluene di-isocyanate(TDI)s, 2,6- toluene di-isocyanate(TDI)s, hexamethylene diisocyanate, Trimethyl hexamethylene diisocyanate, diphenyl methane -4,4 '-diisocyanate (MDI), hydrogenation MDI, polymeric MDI, 1,5- Naphthalene diisocyanate, norbornene alkyl diisocyanate, tolidine diisocyanate, XDI (XDI), Hydrogenation XDI, LDI, triphenylmethane triisocyanate, three (isocyanate phenyl) thiophosphates, tetramethyl Base XDI, 1,6,11- hendecane triisocyanates etc..
In addition, as above-mentioned isocyanate compound, such as ethylene glycol, propane diols, glycerine, sorb can also be used The polyalcohols such as alcohol, trimethylolpropane, carbonate diol, PTMEG, polyester-diol, polycaprolactone glycol and excessive isocyanide Isocyanate compound after chain elongation obtained by ester compound reaction.
(methyl) acrylic acid with hydroxyl as the raw material as above-mentioned carbamate (methyl) acrylate spreads out Biology, can enumerate for example:The binary such as ethylene glycol, propane diols, 1,3-PD, 1,3-BDO, BDO, polyethylene glycol List (methyl) acrylate of alcohol;List (methyl) acrylic acid of the trihydroxylic alcohols such as trimethylolethane, trimethylolpropane, glycerine Ester or two (methyl) acrylate;Bisphenol type epoxy (methyl) acrylate etc. epoxy (methyl) acrylate etc..
As product commercially available in above-mentioned carbamate (methyl) acrylate, can enumerate for example:M-1100、M- 1200th, M-1210, M-1600 (being East Asia Synesis Company system);EBECRYL230、EBECRYL270、EBECRYL4858、 EBECRYL8402、EBECRYL8804、EBECRYL8803、EBECRYL8807、EBECRYL9260、EBECRYL1290、 EBECRYL5129、EBECRYL4842、EBECRYL210、EBECRYL4827、EBECRYL6700、EBECRYL220、 EBECRYL2220 (is DAICEL-ALLNEX company systems);Art Resin UN-9000H、Art Resin UN-9000A、 Art Resin UN-7100、Art Resin UN-1255、Art Resin UN-330、Art Resin UN-3320HB、Art Resin UN-1200TPK, Art Resin SH-500B (being Gen Shang industrial groups system);U-2HA、U-2PHA、U-3HA、U- 4HA、U-6H、U-6LPA、U-6HA、U-10H、U-15HA、U-122A、U-122P、U-108、U-108A、U-324A、U-340A、 U-340P、U-1084A、U-2061BA、UA-340P、UA-4100、UA-4000、UA-4200、UA-4400、UA-5201P、UA- 7100th, UA-7200, UA-W2A (being chemical industrial company of Xin Zhong villages system);AI-600、AH-600、AT-600、UA-101I、 UA-101T, UA-306H, UA-306I, UA-306T (being chemical company of common prosperity society system) etc..
Suppressing the dysgenic aspect to liquid crystal, above-mentioned poly- (methyl) acyclic compound is preferably with-OH Base ,-NH- bases ,-NH2Poly- (methyl) acyclic compound of the hydrogen bond unit such as base.
Above-mentioned curable resin is preferably comprised selected from bisphenol type epoxy (methyl) acrylate, bisphenol E-type epoxy (methyl) At least one conduct in acrylate, bisphenol F type epoxy (methyl) acrylate and bisphenol S type epoxy (methyl) acrylate Poly- (methyl) acyclic compound.
Methylacryloyl in above-mentioned curable resin entirety is relative to acryloyl group and the total amount of methylacryloyl Ratio preferred lower limit be 5 moles of %.It is 5 moles of more than % by making the ratio of above-mentioned methylacryloyl, so that Obtain the display of liquid crystal display cells of the suppression of gained sealing material for liquid crystal display device after preservation under hot and humid environment not Equal effect is more excellent.The preferred lower limit of the ratio of above-mentioned methylacryloyl is 10 moles of %.
In addition, from viewpoints such as cementabilities, the preferred upper limit of the ratio of above-mentioned methylacryloyl is 80 moles of %, The preferred upper limit is 70 moles of %.
There are more than 2 chemical combination of acryloyl group in an above-mentioned molecule in overall 100 weight portions of above-mentioned curable resin The preferred lower limit of the content of thing is 5 weight portions, the preferred upper limit is 70 weight portions.By making that there are 2 in an above-mentioned molecule The content of the compound of above acryloyl group is the scope, so that the sealing material for liquid crystal display device of gained remains excellent Cementability, and make the effect for suppressing display inequality to the liquid crystal display cells after preservation under hot and humid environment more excellent. The preferred lower limit in an above-mentioned molecule with the content of the compound of more than 2 acryloyl groups is 20 weight portions, more preferably The upper limit be 60 weight portions.
There is more than 2 methylacryloyls in an above-mentioned molecule in overall 100 weight portions of above-mentioned curable resin The preferred lower limit of the content of compound is 1 weight portion, the preferred upper limit is 75 weight portions.Have in an above-mentioned molecule by making More than 2 contents of the compound of methylacryloyl are the scope, so that gained sealing material for liquid crystal display device is maintained Excellent cementability, and make to suppress the effect for showing inequality more to the liquid crystal display cells after being preserved under hot and humid environment It is excellent.It is 5 weight to have more than the 2 preferred lower limits of the content of the compound of methylacryloyl in an above-mentioned molecule Part, the preferred upper limit be 60 weight portions, further preferred lower limit be 20 weight portions, the further preferred upper limit be 50 weight Part.
Above-mentioned curable resin can not hinder (methyl) propylene containing simple function in the range of the purpose of the present invention Acid compound.
In addition, for purposes such as the cementabilities for improving gained sealing material for liquid crystal display device, above-mentioned curable resin can Not hinder to contain epoxide in the range of the purpose of the present invention.
As above-mentioned epoxide, can enumerate for example:As the original for synthesizing above-mentioned epoxy (methyl) acrylate The epoxide of material;There is more than 1 epoxy radicals and 1 part (methyl) acrylic acid of (methyl) acryloyl group in one molecule Modified epoxy etc..Wherein, above-mentioned curable resin has more than 1 epoxy radicals and 1 (first in preferably comprising a molecule Base) acryloyl group part (methyl) acrylic modified epoxy resin.
In the case of containing above-mentioned epoxide as above-mentioned curable resin, in above-mentioned curable resin entirety Epoxy radicals is 50 moles of % relative to the preferred upper limit of the ratio of the total amount of acryloyl group, methylacryloyl and epoxy radicals. It is 50 moles of below % by making the ratio of above-mentioned epoxy radicals, such that it is able to suppress molten by gained sealing material for liquid crystal display device The liquid crystal pollution that solution is produced in liquid crystal, makes the display performance of gained liquid crystal display cells more excellent.The ratio of above-mentioned epoxy radicals The preferred upper limit be 20 moles of %.
In addition, having more than 1 epoxy radicals and 1 (methyl) acryloyl group in above-mentioned curable resin contains a molecule Part (methyl) acrylic modified epoxy resin in the case of, the above-mentioned portion in overall 100 weight portions of above-mentioned curable resin The preferred lower limit for dividing the content of (methyl) acrylic modified epoxy resin is 3 weight portions, the preferred upper limit is 50 weight portions.It is logical Cross and above-mentioned part (methyl) acrylic modified epoxy resin is used with the scope, so that gained sealing material for liquid crystal display device It is excellent in adhesion, and make the uneven excellent effect for occurring of display of suppression gained liquid crystal display cells.Above-mentioned part (first Base) acrylic modified epoxy resin content preferred lower limit for 5 weight portions, the preferred upper limit be 40 weight portions.
Sealing material for liquid crystal display device of the invention contains hot radical polymerization initiator.
As above-mentioned hot radical polymerization initiator, can enumerate and for example be formed by azo-compound, organic peroxide etc. Hot radical polymerization initiator.Wherein, the initiator for preferably being formed by polymeric azo compound (is also referred to as " high score below Sub- azo initiator ").
It is explained, polymeric azo initiator refers in this manual:With azo group and using be thermally generated can Free radical, the number-average molecular weight for the free-radical polymerised groups such as (methyl) acryloyl group is reacted are more than 300 change Compound.
The preferred lower limit of the number-average molecular weight of above-mentioned polymeric azo initiator is that 1000, the preferred upper limit is 300,000. It is the scope by making the number-average molecular weight of above-mentioned polymeric azo initiator, such that it is able to prevent the harmful effect to liquid crystal, And more easily can be mixed into curable resin.The number-average molecular weight of above-mentioned polymeric azo initiator it is preferred Lower limit is that 5000, the preferred upper limit is 100,000, and further preferred lower limit is that 10,000, the further preferred upper limit is 90,000.
It is explained, in this manual, above-mentioned number-average molecular weight is to be measured simultaneously using gel permeation chromatography (GPC) The value tried to achieve based on polystyrene conversion.Color during as the number-average molecular weight for utilizing GPC measure based on polystyrene conversion Spectrum post, can enumerate such as Shodex LF-804 (Showa electrician company system) etc..
As above-mentioned polymeric azo initiator, can enumerate for example to have being bonded multiple polyalkylene oxides by azo group, gathering The polymeric azo initiator of structure obtained by the units such as dimethyl siloxane.
Draw with being bonded the polymeric azos of structure obtained by unit such as multiple polyalkylene oxides by azo group as above-mentioned Hair agent, preferably the polymeric azo initiator with PEO structure.As this kind of polymeric azo initiator, can enumerate Such as 4, condensation polymer, 4 of 4 '-azo two (4- cyanopentanoic acids) and PAG, 4 '-azo two (4- cyanopentanoic acids) and tool Have condensation polymer of the dimethyl silicone polymer of terminal amino group etc., specifically, can enumerate such as VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 (being and Wako Pure Chemical Industries company system) etc..
In addition, as the example for not being high molecular azo-compound, V-65, V-501 can be enumerated and (be and the pure medicine work of light Industry company system) etc..
As above-mentioned organic peroxide, such as ketone peroxide, ketal peroxide, hydrogen peroxide, dialkyl group mistake can be enumerated Oxide, peroxy esters, diacyl peroxide, peroxy dicarbonate etc..
Relative to the weight portion of curable resin 100, the preferred lower limit of the content of above-mentioned hot radical polymerization initiator is 0.05 weight portion, the preferred upper limit are 10 weight portions.It is the scope by making the content of above-mentioned hot radical polymerization initiator, from And suppress the liquid crystal pollution caused by unreacted hot radical polymerization initiator, and make gained sealing used for liquid crystal display element The Thermocurable of agent is more excellent.The preferred lower limit of the content of above-mentioned hot radical polymerization initiator is 0.1 weight portion, more excellent The upper limit of choosing is 5 weight portions.
Relative to the weight portion of above-mentioned curable resin 100, the above-mentioned heat in sealing material for liquid crystal display device of the invention The preferred lower limit of the content of radical polymerization initiator is 0.1 weight portion, the preferred upper limit is 10 weight portions.It is above-mentioned by making The content of hot radical polymerization initiator is more than 0.1 weight portion, so that the thermosetting of gained sealing material for liquid crystal display device The property changed is more excellent.By making the content of above-mentioned hot radical polymerization initiator be below 10 weight portions, so that gained liquid crystal Showing the viscosity of element sealant will not become too high, make coating etc. more excellent.Above-mentioned hot radical polymerization initiator contains The preferred lower limit of amount is 0.15 weight portion, the preferred upper limit is 8 weight portions.
Sealing material for liquid crystal display device of the invention can also be containing light certainly in addition to above-mentioned hot radical polymerization initiator By base polymerization initiator.
As above-mentioned optical free radical polymerization initiator, can enumerate for example benzophenone based compound, acetophenone based compound, Acylphosphine oxide based compound, titanocenes based compound, oxime ester based compound, benzoin ether based compound, benzil, thioxanthones Deng.
As product commercially available in above-mentioned optical free radical polymerization initiator, can enumerate such as IRGACURE 184, IRGACURE 369、IRGACURE 379、IRGACURE 651、IRGACURE 819、IRGACURE 907、IRGACURE 2959th, IRGACURE OXE01, Lucirin TPO (being BASF AG's system), benzoin methylether, benzoin ethyl ether, benzoin Isopropyl ether (be Tokyo chemical conversion industry company system) etc..
Relative to the weight portion of above-mentioned curable resin 100, the content of above-mentioned optical free radical polymerization initiator it is preferred under 0.1 weight portion, the preferred upper limit are limited to for 10 weight portions.By making the content of above-mentioned optical free radical polymerization initiator be 0.1 weight More than amount part, so that the photo-curable of the sealing material for liquid crystal display device of gained is more excellent.By making above-mentioned optical free radical The content of polymerization initiator is below 10 weight portions, thus will not a large amount of remained unreacted optical free radical polymerization initiator, make The weatherability of gained sealing material for liquid crystal display device is more excellent.The content of above-mentioned optical free radical polymerization initiator it is preferred Lower limit is 0.2 weight portion, the preferred upper limit is 8 weight portions.
Sealing material for liquid crystal display device of the invention can contain thermal curing agents.
As above-mentioned thermal curing agents, such as organic acid hydrazides, imdazole derivatives, amines, polyhydric phenols system can be enumerated Compound, acid anhydrides etc..Wherein, solid organic acid hydrazides is preferably used.
As the organic acid hydrazides of above-mentioned solid, the double (acyls in diazanyl carbonyl ethyl -5- isopropyl second of such as 1,3- can be enumerated Urea), sebacic dihydrazide, isophthalic dihydrazide, adipic dihydrazide, acid dihydrazide etc., as commercially available product Product, can enumerate for example:AMICURE VDH, AMICURE UDH (being Ajinomoto Fine-Techno company systems);SDH、 IDH, ADH (are great mound chemical company system);MDH (Japanese FINECHEM company systems) etc..
Relative to the weight portion of above-mentioned curable resin 100, the preferred lower limit of the content of above-mentioned thermal curing agents is 1 weight Part, the preferred upper limit are 50 weight portions.By making the content of above-mentioned thermal curing agents be more than 1 weight portion, so that the liquid of gained The Thermocurable of crystal display element sealant is more excellent.By making the content of above-mentioned thermal curing agents for below 50 weight portions, from And the viscosity of gained sealant will not become too high, make coating more excellent.The content of above-mentioned thermal curing agents it is preferred on It is limited to 30 weight portions.
Sealing material for liquid crystal display device of the invention can be based on the viscous of stress dispersion effect for improving viscosity, improving Connecing property, improve linear expansivity, further improve the purpose such as moisture-proof of solidfied material and contain filler.
As filler, can enumerate for example:Talcum, asbestos, silica, diatomite, terre verte, bentonite, calcium carbonate, carbon Sour magnesium, aluminum oxide, montmorillonite, zinc oxide, iron oxide, magnesia, tin oxide, titanium oxide, magnesium hydroxide, aluminium hydroxide, glass The inorganic fillers such as pearl, silicon nitride, barium sulfate, gypsum, calcium silicates, sericite, atlapulgite, aluminium nitride;Polyester micropartical, poly- ammonia The organic fillers such as ester particulate, polyvinyl particulate, acrylic polymer particulate, core-shell acrylic-resin copolymer particle Deng.These fillers may be used alone, can also be used in combination two or more.
The preferred lower limit of the content of the above-mentioned filler in the weight portion of sealing material for liquid crystal display device of the invention 100 For 10 weight portions, the preferred upper limit are 70 weight portions.It is the scope by making the content of above-mentioned filler, so as to suppress coating Deng variation, and make raising cementability and other effects more excellent.The preferred lower limit of the content of above-mentioned filler be 20 weight portions, The preferred upper limit is 60 weight portions.
Sealing material for liquid crystal display device of the invention preferably comprises silane coupler.Above-mentioned silane coupler mainly has As the effect of the bonding additives for making the good bondings such as sealant and substrate.
As above-mentioned silane coupler, from the excellent effect for making raising and the cementability of substrate etc., can by with solidification Property resin be chemically bonded suppress curable resin in liquid crystal flow out in terms of set out, preferably use for example N- phenyl- 3- TSL 8330s, 3- TSL 8330s, 3-mercaptopropyi trimethoxy silane, 3- epoxies third Epoxide propyl trimethoxy silicane, 3- isocyanates propyl trimethoxy silicanes etc..These silane couplers both can individually make With, it is also possible to it is applied in combination two or more.
The content of the above-mentioned silane coupler in the weight portion of sealing material for liquid crystal display device of the invention 100 it is preferred Lower limit is 0.1 weight portion, the preferred upper limit is 20 weight portions.It is the scope by making the content of above-mentioned silane coupler, so that Suppress the generation of liquid crystal pollution, and make the effect of raising cementability more excellent.The content of above-mentioned silane coupler is more preferably Lower limit for 0.5 weight portion, the preferred upper limit be 10 weight portions.
Sealing material for liquid crystal display device of the invention can contain opacifier.By containing above-mentioned opacifier, so that originally The sealing material for liquid crystal display device of invention can be suitable as shading sealant.
As above-mentioned opacifier, black such as iron oxide, titanium, nigrosine, Cyanine Black, fullerene, carbon black, resin quilt can be enumerated Cover type carbon black etc..Wherein, preferably titanium is black.
It is attached for ultraviolet range compared with the average transmittance of the light for 300~800nm of wavelength that above-mentioned titanium is black Closely, it is particularly the material that the transmissivity of the light of 370~450nm of wavelength is uprised.That is, it is by fully masking visible ray that above-mentioned titanium is black The light of the wavelength in region and to sealing material for liquid crystal display device of the invention assign light-proofness, and on the other hand have make it is ultraviolet The opacifier of the property that the light of the wavelength of line areas adjacent is passed through.Therefore, for above-mentioned optical free radical polymerization initiator, pass through It is capable of the material of initiation reaction using the light of the wavelength (370~450nm) uprised using the black transmissivity of above-mentioned titanium, so as to The photo-curable of sealing material for liquid crystal display device of the invention is enough set further to increase.On the other hand, as liquid of the invention Contained opacifier in crystal display element sealant, preferably insulating properties material high, it is also excellent as insulating properties opacifier high Select titanium black.
The black optical concentration (OD values) of every 1 μm of above-mentioned titanium is preferably more than 3, more preferably more than 4.The black screening of above-mentioned titanium The higher the better for photosensitiveness, and the black OD values of above-mentioned titanium have no special preferred upper limit, but usually less than 5.
Even if the above-mentioned black non-surface treated of titanium can also play sufficient effect, it is also possible to be had through coupling agent etc. using surface The treated titanium of machine composition is black;The inorganic constituents such as silicon, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide, magnesia are oxidized to be coated to The titanium surface-treated titanium such as black it is black.Wherein, the aspect of insulating properties can be further being improved, is preferably being processed with organic principle The titanium crossed is black.
In addition, using having coordinated, above-mentioned titanium is black to be manufactured as the sealing material for liquid crystal display device of the invention of opacifier Liquid crystal display cells there is sufficient light-proofness, therefore can realize unglazed spilling and there is high-contrast and with excellent The liquid crystal display cells of different display quality of image.
As black middle the commercially available product of above-mentioned titanium, such as 12S, 13M, 13M-C, 13R-N can be enumerated and (be Mitsubishi Materials company systems), Tilack D (red fringe chemical conversion company system) etc..
The preferred lower limit of the black specific surface area of above-mentioned titanium is 13m2/ g, the preferred upper limit are 30m2/ g, preferred lower limit It is 15m2/ g, the preferred upper limit are 25m2/g。
In addition, the preferred lower limit of the black volume resistance of above-mentioned titanium be 0.5 Ω cm, the preferred upper limit be 3 Ω cm, more Preferred lower limit is 1 Ω cm, the preferred upper limit is 2.5 Ω cm.
As long as the primary particle size of above-mentioned opacifier for liquid crystal display cells substrate between distance below, then have no especially limit It is fixed, but preferred lower limit is that 1nm, the preferred upper limit are 5 μm.It is the scope by making the primary particle size of above-mentioned opacifier, so that Coating of gained sealing material for liquid crystal display device etc. will not be made to be deteriorated, light-proofness can be made more excellent.Above-mentioned opacifier The preferred lower limit of primary particle size is that 5nm, the preferred upper limit are 200nm, and further preferred lower limit is 10nm, further The preferred upper limit is 100nm.
It is explained, the primary particle size of above-mentioned opacifier can use NICOMP 380ZLS (PARTICLE SIZING SYSTEMS company systems) and above-mentioned opacifier is measured after being scattered in solvent (water, organic solvent etc.).
The preferred lower limit of the content of the above-mentioned opacifier in the weight portion of sealing material for liquid crystal display device of the invention 100 For 5 weight portions, the preferred upper limit are 80 weight portions.By making the content of above-mentioned opacifier be more than 5 weight portions, so that gained The light-proofness of sealing material for liquid crystal display device is more excellent.By making the content of above-mentioned opacifier for below 80 weight portions, so that Make gained sealing material for liquid crystal display device more excellent to the intensity and drawing property after adaptation, the solidification of substrate.Above-mentioned shading The preferred lower limit of the content of agent is 10 weight portions, the preferred upper limit is 70 weight portions, and further preferred lower limit is 30 Weight portion, the further preferred upper limit are 60 weight portions.
Sealing material for liquid crystal display device of the invention can further contain the reaction for adjusting viscosity as needed Spacer, 3- rubigan -1,1- dimethyl ureas, isocyanide urea such as property diluent, polymer beads for adjusting panel gap The additives such as the curing accelerators such as carboxylic acid, defoamer, levelling agent, polymerization inhibitor, other coupling agents.
Method as sealing material for liquid crystal display device of the invention is manufactured, can enumerate for example:Using homogenous disperse machine, The mixers such as homogeneous mixer, universal mixer, planetary-type mixer, kneader, three-roller are by curable resin, hot radical Method that the additive such as polymerization initiator and the silane coupler that is added as needed on is mixed etc..
The preferred lower limit of the glass transition temperature of the solidfied material of sealing material for liquid crystal display device of the invention is 100 ℃.It it is more than 100 DEG C by making the glass transition temperature of above-mentioned solidfied material, so that suppressing to be preserved under hot and humid environment The effect that the display of liquid crystal display cells afterwards is uneven is more excellent.The glass transition temperature of above-mentioned solidfied material it is preferred under It is limited to 110 DEG C.
In addition, from from the viewpoint of cementability, the preferred upper limit of the glass transition temperature of above-mentioned solidfied material is 130 DEG C, the preferred upper limit is 120 DEG C.
It is explained, in this manual, above-mentioned " glass transition temperature " refers to be obtained using Measurement of Dynamic Viscoelasticity To loss angle tangent (tan δ) maximum in there is the maximum caused by micro-Brownian movement when temperature, it is possible to use It is measured using the existing known method of determination of viscoelasticity device.In addition, just determining consolidating for above-mentioned glass transition temperature For compound, in the case where sealing material for liquid crystal display device is solidified by heating, can be by small in 120 DEG C of heating 1 When obtain, in the case where solidifying it by light irradiation, can be by irradiating the 100mW/cm of 30 seconds2Ultraviolet come Obtain.
Coordinate electrically conductive microparticle by sealing material for liquid crystal display device of the invention, led up and down such that it is able to manufacture Logical material.This kind of conductive material up and down containing sealing material for liquid crystal display device of the invention and electrically conductive microparticle is also this hair It is one of bright.
As above-mentioned electrically conductive microparticle, it is possible to use such as metal ball, be formed with conducting metal on the surface of resin particle Electrically conductive microparticle of layer etc..Wherein, the electrically conductive microparticle of conductive metal layer is formed with because of resin particle on the surface of resin particle Excellent resilience and the ground such as transparency carrier can not be damaged and be conductively connected, therefore be preferred.
Use the liquid crystal display of sealing material for liquid crystal display device of the invention or upper and lower conductive material of the invention Element is also one of present invention.
Method as liquid crystal display cells of the invention are manufactured, is adapted to use liquid crystal dripping process, specifically, can arrange The citing such as method with following operation:On a transparency carrier in 2 transparency carriers with electrodes such as ito thin films The sealing figure of frame-shaped is formed so that the modes such as silk-screen printing, distributor coating are coated with sealing material for liquid crystal display device of the invention The operation of case;The tiny droplets of coating of liquid crystalline are added dropwise in the whole face of the inframe of seal pattern, the work of another substrate is overlapped under vacuo Sequence;And heated and made the operation of sealant cures.
Invention effect
Even if according to the present invention it is possible to provide light shielding part curability it is excellent, under hot and humid environment also have it is excellent Moisture-proof and cementability and the uneven sealing material for liquid crystal display device for occurring of display of liquid crystal display cells can be suppressed.Separately Outward, according to the present invention it is possible to provide the conductive material up and down and liquid crystal manufactured using the sealing material for liquid crystal display device Show element.
Specific embodiment
Embodiment is exemplified below further to be described in detail the present invention, but the present invention is not limited to these implementations Example.
(embodiment 1~12, comparative example 1~4)
According to the match ratio that table 1,2 is recorded, by the planetary agitating device of each material use (THINKY company systems, " deaeration white silk Taro (Japanese original text:あ わ と り Practice Taros) ") stirring after, uniformly mixed with ceramic three-roller, obtain embodiment 1~12, ratio Compared with the sealing material for liquid crystal display device of example 1~4.
<Evaluate>
Sealing material for liquid crystal display device to gained in embodiment and comparative example carries out following evaluation.Result such as table 1, Shown in 2.
(1) glass transition temperature
Each sealing material for liquid crystal display device of gained in embodiment 1~12 and comparative example 1~3 is small in 120 DEG C of heating 1 When, sealant is fully cured, the film of 300 μm of thickness is made, it is made test film.To the liquid crystal display unit of gained in comparative example 4 Part sealant, 30 seconds 100mW/cm of metal halide light irradiation are used instead of being heated 1 hour at 120 DEG C2Ultraviolet, by This obtains test film.To the test film of gained, using Measurement of Dynamic Viscoelasticity device, (IT measures Heat & Control Pty Ltd.'s system, " DVA- 200 " dynamic viscoelastic) is determined under -80~200 DEG C, 10Hz, the temperature conduct of the maximum of loss angle tangent (tan δ) is tried to achieve Glass transition temperature.
(2) cementability (cementability after initial cementability and high temperature and humidity test)
Coordinate the silica of 1 weight % in the embodiment and comparative example in each sealing material for liquid crystal display device of gained Spacer (ponding chemical industrial company system, " SI-H055 "), in 2 alkali glass test films (30 × 40mm) with ito film It is added dropwise tiny droplets on one alkali glass test film, and is fitted another glass test piece with crosswise thereon.Then, to implementing Each sealing material for liquid crystal display device of gained is heated 1 hour with 120 DEG C in example 1~12 and comparative example 1~3, is thus glued Connect test film.To the sealing material for liquid crystal display device of gained in comparative example 4, metal is used instead of being heated 1 hour at 120 DEG C Halide lamp irradiates 30 seconds 100mW/cm2Ultraviolet, thus obtain adhesive test piece.In matching somebody with somebody up and down for gained adhesive test piece If chuck and carry out tension test (5mm/sec).
In addition, for the adhesive test piece being similarly fabricated to, being placed in the environment of 121 DEG C, 100%RH, 2 air pressure After 48 hours, tension test (5mm/sec) is carried out.
According to by gained measured value (kgf) (cm is accumulated divided by sealing coated sections2) obtained by value be 290kgf/cm2More than Situation is set to " ◎ ", is 270kgf/cm by the value2Above and less than 290kgf/cm2Situation be set to "○", be by the value 250kgf/cm2Above and less than 270kgf/cm2Situation be set to " △ ", by the value less than 250kgf/cm2Situation be set to "×", have rated cementability after initial cementability and high temperature and humidity test.
(3) light shielding part curability
Prepare to be deposited with the demifacet of the corning glass of thickness 0.7mm the substrate (A) of chromium respectively and preceding surface has been deposited with The substrate of chromium (B).Then, spacer particulate (ponding chemical industrial company system, " Micro-Pearl SI-H050 ", 5 μm) is made 1 weight portion is distributed in the weight portion of each sealing material for liquid crystal display device 100 of gained in embodiment and comparative example, and this is sealed Agent is coated on the central portion border of non-steam plating part (chromium steam plating part with) of substrate A, and then adhesive substrates B fully crushes sealant. Then, each sealing material for liquid crystal display device to gained in embodiment 1~12 and comparative example 1~3 is heated 1 hour with 120 DEG C, Make sealant cures.To the sealing material for liquid crystal display device of gained in comparative example 4, instead of heat 1 hour at 120 DEG C and from base Plate A sides use 30 seconds 100mW/cm of metal halide light irradiation2Ultraviolet, make sealant cures.
Afterwards, substrate A and B are peeled off using cutter, is pointed to from the border of the chromium steam plating part of substrate A and non-steam plating part to chromium Steam plating part lateral deviation determines spectrum, and try to achieve as follows close from the sealant of 50 μm of position using micro- IR methods The conversion ratio of (methyl) acryloyl group in envelope agent.That is, by 815~800cm-1Peak area be set to the peak of (methyl) acryloyl group Area, by 845~820cm-1Peak area be set to compare peak area, according to following formula calculate (methyl) acryloyl group conversion Rate, according to the situation that the conversion ratio of (methyl) acryloyl group is more than 95% is set into "○", the conversion ratio for more than 90% and Situation less than 95% is set to the situation of " △ ", the conversion ratio less than 90% and is set to "×", have rated light shielding part curability.
The conversion ratio (%) of (methyl) acryloyl group=(1- (peak area of (methyl) acryloyl group after sealant cures/ Control peak area after sealant cures)/(before the peak area/sealant cures of (methyl) acryloyl group before sealant cures Control peak area)) × 100
(4) display performance (liquid driven after being preserved after just making and under hot and humid environment of liquid crystal display cells The irregular colour evaluation of crystal display element)
Each sealing material for liquid crystal display device of gained in embodiment and comparative example is filled into distributor syringe In (Musashi Engineering company systems, " PSY-10E "), deaeration treatment is carried out.Then, distributor (Musashi is used Engineering company systems, " SHOTMASTER300 "), a transparent electricity in 2 transparent electrode substrates with ito thin film On electrode substrate to describe rectangular frame in the way of be coated with sealant.Then, coating TN liquid crystal is added dropwise with liquid crystal Dropping feeder The tiny droplets of (Chisso company systems, " JC-5001LA "), being fitted under the decompression of 5Pa using vacuum forming apparatus, another is saturating Bright substrate, forms element.For each sealing material for liquid crystal display device of gained in embodiment 1~12 and comparative example 1~3, lead to Cross and gained element is heated 1 hour with 120 DEG C, so that sealant cures, are fabricated to liquid crystal display cells.To in comparative example 4 The sealing material for liquid crystal display device of gained, is shone so that 120 DEG C are heated 1 hour instead of by gained element using metal halide lamp Penetrate 30 seconds 100mW/cm2Ultraviolet, thus make sealant cures, be fabricated to liquid crystal display cells.Liquid crystal display to gained Element, after being preserved 36 hours after just making and in the environment of 80 DEG C of humidity 90%RH of temperature, makes it with the voltage of AC3.5V Drive, and visually to be observed.Uneven (color is shown according to will not observed completely in the edge part of liquid crystal display cells It is uneven) situation be set to " ◎ ", will edge part observe the uneven situation of a little shallower display be set to "○", will be at edge Portion has a case that clearly deeper display inequality is set to " △ ", not only will have clearly deeper display not in edge part The situation that the equal and display inequality extends to central portion is set to "×", have rated the display performance of liquid crystal display cells.
[table 1]
[table 2]
Industrial applicability
Even if according to the present invention it is possible to provide light shielding part curability it is excellent, under hot and humid environment also have it is excellent Moisture-proof and cementability and the uneven sealing material for liquid crystal display device for occurring of display of liquid crystal display cells can be suppressed.Separately Outward, according to the present invention it is possible to provide the conductive material up and down and liquid crystal display manufactured using the sealing material for liquid crystal display device Element.

Claims (8)

1. a kind of sealing material for liquid crystal display device, it is characterised in that it is drawn containing curable resin and hot radical polymerization The sealing material for liquid crystal display device of agent is sent out, wherein,
The curable resin contain in a molecule have in more than 2 compounds and a molecule of acryloyl group have 2 with The compound of upper methylacryloyl.
2. sealing material for liquid crystal display device according to claim 1, it is characterised in that the first in curable resin entirety Base acryloyl group is 5 moles of more than % relative to the ratio of acryloyl group and the total amount of methylacryloyl.
3. sealing material for liquid crystal display device according to claim 1 and 2, it is characterised in that in curable resin entirety It is 1~75 weight portion to have more than 2 contents of the compound of methylacryloyl in 100 weight portions, in a molecule.
4. the sealing material for liquid crystal display device according to claim 1,2 or 3, it is characterised in that curable resin contains With the epoxy radicals of more than 1 and 1 part (methyl) acrylic modified epoxy resin of (methyl) acryloyl group in one molecule.
5. the sealing material for liquid crystal display device according to claim 1,2,3 or 4, it is characterised in that the glass of solidfied material It is more than 100 DEG C to change transition temperature.
6. the sealing material for liquid crystal display device according to claim 1,2,3,4 or 5, it is characterised in that contain opacifier.
7. a kind of upper and lower conductive material, it is characterised in that contain the liquid crystal display cells described in claim 1,2,3,4,5 or 6 With sealant and electrically conductive microparticle.
8. a kind of liquid crystal display cells, it is characterised in that with the liquid crystal display cells described in claim 1,2,3,4,5 or 6 With the conductive material up and down described in sealant or claim 7.
CN201680003125.7A 2015-05-08 2016-04-27 Sealing material for liquid crystal display device, upper and lower conductive material and liquid crystal display cells Pending CN106796376A (en)

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TW201702321A (en) 2017-01-16
KR20180003527A (en) 2018-01-09

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