CN109564371A - Polymerizable compound, sealing material for liquid crystal display device, upper and lower conductive material and liquid crystal display element - Google Patents
Polymerizable compound, sealing material for liquid crystal display device, upper and lower conductive material and liquid crystal display element Download PDFInfo
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- CN109564371A CN109564371A CN201780050484.2A CN201780050484A CN109564371A CN 109564371 A CN109564371 A CN 109564371A CN 201780050484 A CN201780050484 A CN 201780050484A CN 109564371 A CN109564371 A CN 109564371A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1339—Gaskets; Spacers; Sealing of cells
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- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
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- Liquid Crystal (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention is a kind of sealing material for liquid crystal display device containing polymerizable compound shown in formula (1).In formula (1), A indicates methylene, methylmethylene, dimethylmethylene, oxygen atom, sulphur atom or sulfonyl, X indicates ethyleneoxy group ethyl, two (ethyleneoxy group) ethyls, three (ethyleneoxy group) ethyls, four (ethyleneoxy group) ethyls, propylidene oxygroup propyl, two (propylidene oxygroup) propyl, three (propylidene oxygroup) propyl, four (propylidene oxygroup) propyl, butylidene oxygroup butyl, two (butylidene oxygroup) butyl, three (butylidene oxygroup) butyl, four (butylidene oxygroup) butyl, or carbon atom number is 2 or more and 15 alkylidenes below, Y1 and Y2 each independently represents group shown in following formula (2-1) or (2-2), and, Y1 and Y2 at least one of for group shown in following formula (2-1), n be 1 or more and 5 or less ( Average value).In formula (2-1) and formula (2-2), * indicates bonding position；In formula (2-1), R indicates hydrogen atom or methyl.
Description
Technical field
The present invention relates to can in cementability, anti-penetrability and the excellent sealing material for liquid crystal display device of low liquid crystal pollution
The polymerizable compound used.In addition, the present invention relates to the sealing material for liquid crystal display device containing the polymerizable compound, with
And manufactured conductive material and liquid crystal display element up and down using the sealing material for liquid crystal display device.
Background technique
In recent years, the manufacturing method as liquid crystal display elements such as liquid crystal displays, from shortening productive temp time, liquid
From the perspective of brilliant dosage optimizes, photo-thermal is used as having used disclosed in patent document 1, patent document 2 and with admittedly
Change type sealant be referred to as liquid crystal dripping process mode, the photo-thermal and with curing type sealant contain curable resin,
Photoepolymerizationinitiater initiater and thermal curing agents.
In liquid crystal dripping process, firstly, by distribute on one in two electroded substrates formed it is rectangular
The seal pattern of shape.Then, the tiny droplets of liquid crystal are dripped in the sealing frame of substrate in the state that sealant is uncured,
It is overlapped another substrate under vacuum, precuring is carried out to light such as sealing irradiation ultraviolet lights.Thereafter, it heats main solid to carry out
Change, to make liquid crystal display element.Now, which becomes the mainstream of the manufacturing method of liquid crystal display element.
However, in the modern times that the various mobile devices for being attached to liquid crystal display panels such as mobile phone, portable game become increasingly popular,
The miniaturization of device is to need most the project of solution.As the method for miniaturization, the narrow architrave of liquid crystal display part can be enumerated,
Such as configure the position of sealing the operation (below also referred to as " narrow architrave design ") under black matrix.
In such narrow architrave design, sealant itself is also drawn thinner, and therefore, previous sealant exists such as
Lower problem: cementability, anti-penetrability are insufficient, and the display that liquid crystal display element is easy to happen because of liquid crystal pollution etc. is bad.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2001-133794 bulletin
Patent document 2: International Publication No. 02/092718
Summary of the invention
Problem to be solved by the invention
The object of the present invention is to provide cementability, anti-penetrability and the excellent liquid crystal display elements of low liquid crystal pollution
With polymerizable compound workable in sealant.It is further an object that providing containing the polymerizable compound
Sealing material for liquid crystal display device and manufactured conductive material and liquid crystal up and down using the sealing material for liquid crystal display device
Display element.
The method for solving problem
The present invention 1 is a kind of polymerizable compound, is indicated by following formula (1).
[changing 1]
In formula (1), A indicates methylene, methylmethylene, dimethylmethylene, oxygen atom, sulphur atom or sulfonyl, X table
Show ethyleneoxy group ethyl, two (ethyleneoxy group) ethyls, three (ethyleneoxy group) ethyls, four (ethyleneoxy group) ethyls, Asia
Propyl oxygroup propyl, two (propylidene oxygroup) propyl, three (propylidene oxygroup) propyl, four (propylidene oxygroup) propyl, butylidene
Oxygroup butyl, two (butylidene oxygroup) butyl, three (butylidene oxygroup) butyl, four (butylidene oxygroup) butyl or carbon atom
Number is 2 or more and 15 alkylidenes below, Y1And Y2Group shown in following formula (2-1) or (2-2) is each independently represented, and
And Y1And Y2At least one of for group shown in following formula (2-1), n is 1 or more and 5 or less (average values).
[changing 2]
In formula (2-1) and formula (2-2), * indicates bonding position；In formula (2-1), R indicates hydrogen atom or methyl.
In addition, the present invention 2 is a kind of sealing material for liquid crystal display device, and containing curable resin, above-mentioned curability tree
Rouge contains polymerizable compound shown in following formula (1).
[changing 3]
In formula (1), A indicates methylene, methylmethylene, dimethylmethylene, oxygen atom, sulphur atom or sulfonyl, X table
Show ethyleneoxy group ethyl, two (ethyleneoxy group) ethyls, three (ethyleneoxy group) ethyls, four (ethyleneoxy group) ethyls, Asia
Propyl oxygroup propyl, two (propylidene oxygroup) propyl, three (propylidene oxygroup) propyl, four (propylidene oxygroup) propyl, butylidene
Oxygroup butyl, two (butylidene oxygroup) butyl, three (butylidene oxygroup) butyl, four (butylidene oxygroup) butyl or carbon atom
Number is 2 or more and 15 alkylidenes below, Y1And Y2Group shown in following formula (2-1) or (2-2) is each independently represented, and
And Y1And Y2At least one of for group shown in following formula (2-1), n is 1 or more and 5 or less (average values).
[changing 4]
In formula (2-1) and formula (2-2), * indicates bonding position；In formula (2-1), R indicates hydrogen atom or methyl.
The present invention described below.
Inventors have surprisingly found that: polymerizable compound pollution caused by liquid crystal with specific structure is low, and
Cementability and anti-excellent moisture permeability.Thus, present inventor have discovered that by cooperating the polymerizable compound as curability tree
Rouge, so as to obtain cementability, anti-penetrability and the excellent sealing material for liquid crystal display device of low liquid crystal pollution, thus complete
At the present invention.
The polymerizable compound (hereinafter also referred to as " polymerizable compound of the invention ") of the present invention 1 is by above-mentioned formula (1)
It indicates.
The polymerizable compound of the invention pollution caused by liquid crystal is low and cementability and anti-excellent moisture permeability, therefore
It can be suitable as the curable resin of sealing material for liquid crystal display device.
Sealing material for liquid crystal display device (hereinafter also referred to as " the sealing used for liquid crystal display element of the invention of the present invention 2
Agent ") contain curable resin.
Above-mentioned curable resin contains polymerizable compound shown in above-mentioned formula (1) (that is, polymerism chemical combination of the invention
Object).By containing polymerizable compound of the invention as above-mentioned curable resin, so that of the invention is used for liquid crystal display element
The cementability of sealant, anti-penetrability and low liquid crystal pollution become excellent.
In above-mentioned formula (1), A indicates methylene, methylmethylene, dimethylmethylene, oxygen atom, sulphur atom or sulphonyl
Base.Wherein, from the viewpoints such as the acquisition easiness of raw material, preferably methylene, methylmethylene, dimethylmethylene.
In above-mentioned formula (1), X indicates ethyleneoxy group ethyl, two (ethyleneoxy group) ethyls, three (ethyleneoxy group) second
Base, four (ethyleneoxy group) ethyls, propylidene oxygroup propyl, two (propylidene oxygroup) propyl, three (propylidene oxygroup) propyl, four
(propylidene oxygroup) propyl, butylidene oxygroup butyl, two (butylidene oxygroup) butyl, three (butylidene oxygroup) butyl, four (Aden
Base oxygroup) butyl or carbon atom number be 2 or more and 15 alkylidenes below.Wherein, from viewpoints such as treatability, preferably
It is 2 or more and 8 or less for ethyleneoxy group ethyl, two (ethyleneoxy group) ethyls, three (ethyleneoxy group) ethyls, carbon atom number
Alkylidene.
In above-mentioned formula (1), Y1And Y2Each independently represent group shown in above-mentioned formula (2-1) or (2-2), also, Y1With
Y2At least one of for group shown in above-mentioned formula (2-1).That is, polymerizable compound of the invention can have in two ends
There is (methyl) acryloyl group, there can also be (methyl) acryloyl group an end, and there is epoxy group in another end.
It should be noted that above-mentioned " (methyl) acryloyl group " refers to acryloyl group or methacryl in this specification
Base.
In above-mentioned formula (1), n is 1 or more and 5 or less (average values).
The preferred upper limit of above-mentioned n is 3.By making above-mentioned n 3 hereinafter, to resulting sealing material for liquid crystal display device
Viscosity it is not too high, coating, treatability become more excellent.
As the method for manufacturing polymerizable compound of the invention, can enumerate for example makes to be equivalent in above-mentioned formula (1)
Y1And Y2Part be group shown in above-mentioned formula (2-2) di-epoxy compounds part or all of epoxy group and (first
Base) method etc. reacted of acrylic acid.
As the method for manufacturing above-mentioned di-epoxy compounds, the bisphenols such as making bisphenol-A and triethylene glycol can be enumerated
Divinyl ether etc. has to be reacted with the divinyl ether compounds of the comparable structure of X of above-mentioned formula (1), and makes thus to obtain
To two ends there is the method etc. further reacted with epichlorohydrin of compound of phenolic hydroxyl group.
In addition, such as EPICLON EXA4850 series can be enumerated as the commercially available product among above-mentioned di-epoxy compounds
(DIC corporation) etc..
The preferred lower limit of the content of polymerizable compound of the invention in above-mentioned 100 parts by weight of curable resin is 5 weights
Measure part, preferred upper limit is 80 parts by weight.It is more than 5 parts by weight of content by making polymerizable compound of the invention, thus this
The cementability of the sealing material for liquid crystal display device of invention becomes more excellent.By the content for making polymerizable compound of the invention
For 80 parts by weight hereinafter, to which the viscosity of sealing material for liquid crystal display device of the invention will not become excessively high, coating, processing
Property becomes more excellent.The more preferable lower limit of the content of polymerizable compound of the invention is 10 parts by weight, the more preferable upper limit is 50
Parts by weight.
Above-mentioned curable resin preferably comprises other polymerism chemical combination other than polymerizable compound of the invention
Object.
As above-mentioned other polymerizable compounds, can enumerate in addition to chemical combination contained by polymerizable compound of the invention
Except object, other (methyl) acrylic compounds, other epoxides etc..
It should be noted that above-mentioned " (methyl) acrylic compounds " refer to acrylic compounds or methacrylic acid in this specification
Class, above-mentioned " (methyl) acrylic compounds " refer to the compound with (methyl) acryloyl group.
As above-mentioned other (methyl) acrylic compounds, such as epoxy (methyl) acrylate, (first can be enumerated
Base) acrylate compounds, carbamate (methyl) acrylate etc..Wherein, preferably epoxy (methyl) acrylate.This
Outside, from reactive height, above-mentioned others (methyl) acrylic compounds are preferably in the molecule with 2 or more
(methyl) acryloyl group.
It should be noted that above-mentioned " (methyl) acrylate " refers to acrylate or methacrylic acid in this specification
Ester, above-mentioned " epoxy (methyl) acrylate " are that whole epoxy groups in epoxide is instigated to carry out instead with (methyl) acrylic acid
Compound obtained from answering.
As above-mentioned epoxy (methyl) acrylate, can enumerate for example make epoxide and (methyl) acrylic acid according to
Epoxy obtained from conventional method is reacted in the presence of basic catalyst (methyl) acrylate etc..
As the epoxide become for synthesizing the raw material of above-mentioned epoxy (methyl) acrylate, can enumerate for example
Bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol E-type epoxy resin, bisphenol-s epoxy resin, 2,2 '-diallyls
Bisphenol A type epoxy resin, A Hydrogenated Bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, thioether type ring
Oxygen resin, diphenyl ether type epoxy resin, dicyclopentadiene-type epoxy resin, naphthalene type epoxy resin, phenol novolak type epoxy,
O-cresol phenol aldehyde type epoxy resin, dicyclopentadiene phenolic type epoxy resin, biphenyl phenol aldehyde type epoxy resin, naphthol novolac type ring
Oxygen resin, glycidyl amine type epoxy resin, modified rubber type epoxy resin, epihydric alcohol ester compound etc..
As the commercially available product among above-mentioned bisphenol A type epoxy resin, can enumerate such as jER828EL, jER1004 (is
Mitsubishi Chemical Ind's system), EPICLON EXA-850CRP (DIC corporation) etc..
As the commercially available product among above-mentioned bisphenol f type epoxy resin, can enumerate such as jER806, jER4004 (is three
Water chestnut chemical company system) etc..
As the commercially available product among above-mentioned bisphenol E-type epoxy resin, such as R710 (PRINTEC corporation) can be enumerated
Deng.
As the commercially available product among above-mentioned bisphenol-s epoxy resin, such as EPICLON EXA-1514 (DIC can be enumerated
Corporation) etc..
As the commercially available product among above-mentioned 2,2 '-diallyl bisphenol type epoxy resin, such as RE-810NM can be enumerated
(Japanese chemical drug corporation) etc..
As the commercially available product among above-mentioned A Hydrogenated Bisphenol A type epoxy resin, such as EPICLON EXA-7015 can be enumerated
(DIC corporation) etc..
As the commercially available product among above-mentioned resorcinol type epoxy resin, such as EX-201 (Nagase can be enumerated
ChemteX corporation) etc..
As the commercially available product among above-mentioned biphenyl type epoxy resin, such as jER YX-4000H (Mitsubishi Chemical can be enumerated
Corporation) etc..
As the commercially available product among above-mentioned thioether-type epoxy resin, can enumerating such as YSLV-50TE, (aurification is lived by Nippon Steel
Learn corporation) etc..
As the commercially available product among above-mentioned diphenyl ether type epoxy resin, can enumerating such as YSLV-80DE, (gold is lived by Nippon Steel
Chemical company's system) etc..
As the commercially available product among above-mentioned dicyclopentadiene-type epoxy resin, can enumerating such as EP-4088S, (ADEKA is public
Department's system) etc..
As the commercially available product among above-mentioned naphthalene type epoxy resin, such as EPICLON HP4032, EPICLON can be enumerated
EXA-4700 (being DIC corporation) etc..
As the commercially available product among above-mentioned phenol novolak type epoxy, such as EPICLON N-770 (DIC can be enumerated
Corporation) etc..
As the commercially available product among above-mentioned o-cresol phenol aldehyde type epoxy resin, such as EPICLON N-670- can be enumerated
EXP-S (DIC corporation) etc..
As the commercially available product among above-mentioned dicyclopentadiene phenolic type epoxy resin, such as EPICLON can be enumerated
HP7200 (DIC corporation) etc..
As the commercially available product among above-mentioned biphenyl phenol aldehyde type epoxy resin, such as NC-3000P (Japanese chemical drug can be enumerated
Corporation) etc..
As the commercially available product among above-mentioned naphthol novolac type epoxy resin, can enumerating such as ESN-165S, (Nippon Steel is lived
Aurification corporation) etc..
As the commercially available product among above-mentioned glycidyl amine type epoxy resin, such as jER630 (Mitsubishi Chemical can be enumerated
Corporation), EPICLON430 (DIC corporation), TETRAD-X (gas chemical company, Mitsubishi system) etc..
Commercially available product among modified version epoxy resin as above-mentioned rubber, can enumerate such as YR-450, YR-207 (is
Aurification corporation is lived by Nippon Steel), Epolead PB (Daicel corporation) etc..
As the commercially available product among above-mentioned epihydric alcohol ester compound, such as Denacol EX-147 can be enumerated
(Nagase ChemteX corporation) etc..
As the monofunctional compound among above-mentioned (methyl) acrylate compounds, such as (methyl) propylene can be enumerated
Sour methyl esters, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) n-butyl acrylate, (methyl) i-butyl
Ester, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) n-octyl, (methyl) acrylic acid
Different monooctyl ester, the different nonyl ester of (methyl) acrylic acid, (methyl) isodecyl acrylate, (methyl) lauryl acrylate, (methyl) acrylic acid
Different myristin, (methyl) stearyl acrylate, (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxy propyl ester,
(methyl) acrylic acid 2- hydroxybutyl, (methyl) acrylic acid 4- hydroxybutyl, (methyl) cyclohexyl acrylate, (methyl) acrylic acid
Isobornyl thiocyanoacetate, (methyl) acrylic acid dicyclopentenyloxyethyl methacrylate, (methyl) benzyl acrylate, (methyl) acrylic acid 2- methoxy acrylate, (first
Base) acrylic acid 2- ethoxy ethyl ester, (methyl) acrylic acid 2- butoxyethyl, (methyl) acrylic acid 2- phenoxy ethyl, methoxy
Ethyl glycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate, phenoxy group diethylene glycol (methyl) propylene
Acid esters, phenoxy group polyethylene glycol (methyl) acrylate, (methyl) tetrahydrofurfuryl acrylate, ethyl carbitol (methyl) acrylic acid
Ester, (methyl) acrylic acid 2,2,2- trifluoro ethyl ester, 2,2,3,3- tetrafluoro propyl ester of (methyl) acrylic acid, (methyl) acrylic acid 1H, 1H,
5H- octafluoro pentyl ester, acid imide (methyl) acrylate, (methyl) dimethylaminoethyl acrylate, (methyl) acrylic acid diethylamino
Base ethyl ester, 2- (methyl) acryloyl-oxyethyl succinic acid, 2- (methyl) acryloyl-oxyethyl hexahydrophthalic acid, 2-
(methyl) acryloyl-oxyethyl -2- hydroxypropyl phthalate, 2- (methyl) acryloyl-oxyethyl phosphate, (first
Base) glycidyl acrylate etc..
In addition, closing object as the difunctional among above-mentioned (methyl) acrylate compounds, such as 1,3- can be enumerated
Butanediol two (methyl) acrylate, 1,4-butanediol two (methyl) acrylate, 1,6- hexylene glycol two (methyl) acrylate,
1,9- nonanediol two (methyl) acrylate, 1,10- decanediol two (methyl) acrylate, ethylene glycol two (methyl) acrylic acid
Ester, diethylene glycol two (methyl) acrylate, tetraethylene glycol two (methyl) acrylate, polyethylene glycol two (methyl) acrylic acid
Ester, 2- normal-butyl -2- ethyl -1,3-PD two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, 3 the third two
Alcohol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, ethylene oxide
Addition bisphenol-A two (methyl) acrylate, propylene oxide addition bisphenol-A two (methyl) acrylate, ethyleneoxide addition Bisphenol F
Two (methyl) acrylate, dihydroxymethyl dicyclopentadienyl two (methyl) acrylate, ethylene-oxide-modified isocyanuric acid two
(methyl) acrylate, 2- hydroxyl -3- (methyl) acryloxypropyl (methyl) acrylate, carbonate diol two (methyl)
Acrylate, polyetherdiol two (methyl) acrylate, polyester-diol two (methyl) acrylate, two (first of polycaprolactone glycol
Base) acrylate, polybutadiene diol two (methyl) acrylate etc..
In addition, example can be enumerated as the compound more than trifunctional among above-mentioned (methyl) acrylate compounds
Such as trimethylolpropane tris (methyl) acrylate, ethyleneoxide addition trimethylolpropane tris (methyl) acrylate, epoxy
Propane addition trimethylolpropane tris (methyl) acrylate, caprolactone modification trimethylolpropane tris (methyl) acrylate,
Ethyleneoxide addition isocyanuric acid three (methyl) acrylate, glycerol three (methyl) acrylate, propylene oxide addition glycerol three
(methyl) acrylate, pentaerythrite three (methyl) acrylate, three (methyl) acryloyl-oxyethyl phosphates, bis- (three hydroxyls
Methylpropane) four (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylic acid
Ester, dipentaerythritol six (methyl) acrylate etc..
Above-mentioned carbamate (methyl) acrylate can be for example, by (methyl) acrylic acid derivative 2 for making to have hydroxyl
Equivalent in the presence of the tin based compound of catalytic amount with 2 isocyanate group 1 equivalent of isocyanate compound into
Row reaction is to obtain.
As above-mentioned isocyanate compound, such as isophorone diisocyanate, 2,4- toluene diisocyanate can be enumerated
Acid esters, 2,6- toluene di-isocyanate(TDI), hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, diphenylmethyl
4,4 '-diisocyanate (MDI) of alkane-, hydrogenation MDI, polymeric MDI, 1,5- naphthalene diisocyanate, norbornene alkyl diisocyanate,
Tolidine diisocyanate, benzene dimethylene diisocyanate (XDI), hydrogenation XDI, lysine diisocyanate, triphenyl
Methane triisocyanate, three (isocyanate phenyl) thiophosphates, tetramethylxylylene diisocyanate, 1,6,11-
Hendecane triisocyanate etc..
In addition, also can be used as above-mentioned isocyanate compound through polyalcohol and excessive isocyanates chemical combination
The isocyanate compound of chain elongation obtained from the reaction of object.
As above-mentioned polyalcohol, can enumerate for example ethylene glycol, propylene glycol, glycerol, D-sorbite, trimethylolpropane,
Carbonate diol, polyetherdiol, polyester-diol, polycaprolactone glycol etc..
As above-mentioned (methyl) acrylic acid derivative with hydroxyl, for example single (methyl) dihydroxypropyl alkane can be enumerated
Base ester, list (methyl) acrylate of dihydric alcohol, trihydroxylic alcohol list (methyl) acrylate or two (methyl) acrylate, epoxy
(methyl) acrylate etc..
As above-mentioned list (methyl) hydroxyalkyl acrylates, can enumerate such as (methyl) acrylic acid 2- hydroxy methacrylate,
(methyl) acrylic acid 2- hydroxy propyl ester, (methyl) acrylic acid 2- hydroxybutyl, (methyl) acrylic acid 4- hydroxybutyl etc..
As above-mentioned dihydric alcohol, such as ethylene glycol, propylene glycol, 1,3-PD, 1,3-BDO, Isosorbide-5-Nitrae-fourth can be enumerated
Glycol, polyethylene glycol etc..
As above-mentioned trihydroxylic alcohol, can enumerate such as trimethylolethane, trimethylolpropane, glycerol.
As above-mentioned epoxy (methyl) acrylate, can enumerate such as bisphenol-a epoxy acrylate.
As the commercially available product among above-mentioned carbamate (methyl) acrylate, such as East Asia Synesis Company can be enumerated
Carbamate (methyl) acrylate, root of carbamate (methyl) acrylate of system, DAICEL-ALLNEX corporation
Carbamate (methyl) acrylate of upper industrial group, chemical industrial company, the village Xin Zhong carbamate (methyl)
Acrylate, carbamate (methyl) acrylate of chemical company, common prosperity society etc..
As carbamate (methyl) acrylate of above-mentioned East Asia Synesis Company, can enumerate such as M-1100,
M-1200, M-1210, M-1600 etc..
As carbamate (methyl) acrylate of above-mentioned DAICEL-ALLNEX corporation, can enumerate for example
EBECRYL210、EBECRYL220、EBECRYL230、EBECRYL270、EBECRYL1290、EBECRYL2220、
EBECRYL4827、EBECRYL4842、EBECRYL4858、EBECRYL5129、EBECRYL6700、EBECRYL8402、
EBECRYL8803, EBECRYL8804, EBECRYL8807, EBECRYL9260 etc..
As carbamate (methyl) acrylate of above-mentioned Gen Shang industrial group, can enumerate (such as Art
Resin UN-330、Art Resin SH-500B、Art Resin UN-1200TPK、Art Resin UN-1255、Art
Resin UN-3320HB, Art Resin UN-7100, Art Resin UN-9000A, Art Resin UN-9000H etc..
As carbamate (methyl) acrylate of chemical industrial company, the above-mentioned village Xin Zhong, such as U- can be enumerated
2HA、U-2PHA、U-3HA、U-4HA、U-6H、U-6HA、U-6LPA、U-10H、U-15HA、U-108、U-108A、U-122A、U-
122P、U-324A、U-340A、U-340P、U-1084A、U-2061BA、UA-340P、UA-4000、UA-4100、UA-4200、
UA-4400, UA-5201P, UA-7100, UA-7200, UA-W2A etc..
As carbamate (methyl) acrylate of chemical company, above-mentioned common prosperity society, such as AH- can be enumerated
600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA-306T etc..
As above-mentioned other epoxides, can be used becomes with above-mentioned for synthesizing above-mentioned epoxy (methyl) third
The identical epoxide of the epoxide of the raw material of olefin(e) acid ester.
In addition, can contain has epoxy group and (methyl) third in 1 molecule as above-mentioned other polymerizable compounds
The compound of enoyl-.As such compound, can enumerate for example by making that there are 2 or more epoxy groups in 1 molecule
Part (methyl) acrylic acid modified ring obtained from a part of epoxy group of epoxide is reacted with (methyl) acrylic acid
Oxygen resin etc..
As the commercially available product among above-mentioned part (methyl) acrylic modified epoxy resin, can enumerate for example
UVACURE1561 (DAICEL-ALLNEX corporation) etc..
From the viewpoint of inhibiting liquid crystal pollution, it is above-mentioned others polymerizable compounds preferably have-OH base ,-NH- base ,-
NH2The hydrogen bonds unit such as base.
(methyl) acryloyl group and ring for sealing material for liquid crystal display device of the invention, in curable resin
Oxygroup it is total in the ratio of (methyl) acryloyl group be preferably set to 30% or more and 95% or less.By making above-mentioned (methyl)
The ratio of acryloyl group is 30% or more, so that uncured epoxy resin ingredient hardly remains after polymerisation, low liquid crystal is dirty
Metachromia becomes more excellent.By making the ratio 95% of above-mentioned (methyl) acryloyl group hereinafter, to resulting liquid crystal display member
The cementability of part sealant becomes more excellent.
Sealing material for liquid crystal display device of the invention can contain polymerization initiator.
As above-mentioned polymerization initiator, can be suitble to using radical polymerization initiator.
As above-mentioned radical polymerization initiator, the optical free radical polymerization generated free radicals by light irradiation can be enumerated
Initiator, the hot radical polymerization initiator generated free radicals by heating etc..
As above-mentioned optical free radical polymerization initiator, can enumerate for example oxime ester based compound, benzophenone based compound,
Acetophenone based compound, acylphosphine oxide compound, titanocenes based compound, benzoin ether based compound, thioxanthones etc..
As the commercially available product among above-mentioned optical free radical polymerization initiator, the light that can enumerate such as BASF AG is free
Base polymerization initiator, optical free radical polymerization initiator of Tokyo chemical conversion industry corporation etc..
As the optical free radical polymerization initiator of above-mentioned BASF AG, can enumerate such as IRGACURE 184,
IRGACURE 369、IRGACURE 379、IRGACURE 651、IRGACURE 819、IRGACURE 907、IRGACURE
2959, IRGACURE OXE01, Lucirin TPO etc..
As the optical free radical polymerization initiator of above-mentioned Tokyo chemical conversion industry corporation, such as benzoin first can be enumerated
Ether, benzoin ethyl ether, benzoin iso-propylether etc..
Relative to above-mentioned 100 parts by weight of curable resin, the preferred lower limit of the content of above-mentioned optical free radical polymerization initiator
It is 10 parts by weight for 0.1 parts by weight, preferred upper limit.By 0.1 parts by weight of content for making above-mentioned optical free radical polymerization initiator
More than, so that the photo-curable of sealant for liquid crystal dripping process of the invention becomes more excellent.By making above-mentioned optical free radical
The content of polymerization initiator is 10 parts by weight hereinafter, thus the low liquid crystal pollution of sealant for liquid crystal dripping process of the invention
Property, storage stability become more excellent.
As above-mentioned hot radical polymerization initiator, can enumerate such as the shape as azo-compound, organic peroxide
At hot radical polymerization initiator.Wherein, the initiator preferably formed by polymeric azo compound is (following to be also referred to as
" polymeric azo initiator ").
It should be noted that polymeric azo compound refers in this specification: there is azo group and generated by heat
The free radical that (methyl) acryloyl group can be made to be cured, 300 or more number-average molecular weight compound.
The preferred lower limit of the number-average molecular weight of above-mentioned polymeric azo compound is 1000, preferred upper limit is 300,000.Pass through
Make the number-average molecular weight of the above-mentioned polymeric azo compound range, so as to inhibit liquid crystal pollution and easy and curability
Resin mixing.The more preferable lower limit of the number-average molecular weight of above-mentioned polymeric azo compound is 5000, the more preferable upper limit is 100,000,
Further preferred lower limit is 10,000, the further preferred upper limit is 90,000.
It should be noted that above-mentioned number-average molecular weight is measured by gel permeation chromatography (GPC) in this specification
And the value found out using polystyrene conversion.When as measuring the number-average molecular weight based on polystyrene conversion by GPC
Pillar, can enumerate such as Shodex LF-804 (Showa electrician corporation).
As above-mentioned polymeric azo compound, can enumerate for example with being bonded with multiple polycyclic oxygen by azo group
The compound of the structure of the units such as alkane, dimethyl silicone polymer.
Polymeric azo as the above-mentioned structure for having and being bonded with the units such as multiple polyalkylene oxides by azo group
Object is closed, preferably there is polyethylene oxide structure.
As above-mentioned polymeric azo compound, specifically, such as 4 can be enumerated, 4 '-azos are bis- (4- cyanopentanoic acid)
With condensation polymer, 4, the 4 '-azos bis- (4- cyanopentanoic acids) of polyalkylene glycol and with the dimethyl silicone polymer of terminal amino group
Condensation polymer etc..
As the commercially available product among above-mentioned polymeric azo compound, can enumerate such as VPE-0201, VPE-0401,
VPE-0601, VPS-0501, VPS-1001 (being and Wako Pure Chemical Industries corporation) etc..
In addition, the commercially available product of the azo-compound as on-macromolecular, can enumerate such as V-65, V-501 (is and light
Chun Yao industrial group system) etc..
As above-mentioned organic peroxide, such as ketone peroxide, ketal peroxide, hydrogen peroxide, dialkyl group can be enumerated
Peroxide, peroxyester, diacyl peroxide, peroxy dicarbonate etc..
Relative to above-mentioned 100 parts by weight of curable resin, the preferred lower limit of the content of above-mentioned hot radical polymerization initiator
It is 10 parts by weight for 0.05 parts by weight, preferred upper limit.By 0.05 weight of content for making above-mentioned hot radical polymerization initiator
Part or more, so that the Thermocurable of sealing material for liquid crystal display device of the invention becomes more excellent.By making above-mentioned heat freely
The content of base polymerization initiator is 10 parts by weight hereinafter, thus the low liquid crystal pollution of sealing material for liquid crystal display device of the invention
Property, storage stability become more excellent.The more preferable lower limit of the content of above-mentioned hot radical polymerization initiator be 0.1 parts by weight,
The more preferable upper limit is 5 parts by weight.
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, amine compounds, polynary phenol system compound, acid anhydrides can be enumerated
Deng.Wherein, can be suitble to using organic acid hydrazides.
As above-mentioned organic acid hydrazides, such as sebacic dihydrazide, isophthalic dihydrazide, adipic acid two can be enumerated
Bis- (Hydrazinocarbonyl ethyl) -5- isopropyl hydantoins of hydrazides, acid dihydrazide, 1,3- etc..
As the commercially available product among above-mentioned organic acid hydrazides, the organic acid acyl of such as great Zhong chemical company can be enumerated
The organic acid hydrazides etc. of the fine scientific & technical corporation of hydrazine, aginomoto.
As the organic acid hydrazides of above-mentioned great Zhong chemical company, can enumerate such as SDH, ADH.
As the organic acid hydrazides of the fine scientific & technical corporation of above-mentioned aginomoto, can enumerate such as AMICURE VDH,
AMICURE VDH-J, AMICURE UDH, AMICURE UDH-J etc..
Relative to above-mentioned 100 parts by weight of curable resin, the preferred lower limit of the content of above-mentioned thermal curing agents be 1 parts by weight,
Preferred upper limit is 50 parts by weight.More than 1 parts by weight of content by making above-mentioned thermal curing agents, thus liquid crystal display of the invention
The Thermocurable of element sealant becomes more excellent.By make above-mentioned thermal curing agents 50 parts by weight of content hereinafter, to
The viscosity of sealing material for liquid crystal display device of the invention will not become excessively high, and coating, treatability become more excellent.Above-mentioned heat
The more preferable upper limit of the content of curing agent is 30 parts by weight.
Cementability is further increased for adjustment viscosity, based on stress dispersion effect, is improved linear expansivity, is further mentioned
The purpose of anti-penetrability of high solidification object, sealing material for liquid crystal display device of the invention preferably comprise filler.
As above-mentioned filler, inorganic filler, organic filler can be used.
As above-mentioned inorganic filler, can enumerate for example silica, talcum, bead, asbestos, gypsum, diatomite,
Terre verte, bentonite, montmorillonite, sericite, atlapulgite, aluminium oxide, zinc oxide, iron oxide, magnesia, tin oxide, titanium oxide,
Calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminium hydroxide, aluminium nitride, silicon nitride, barium sulfate, calcium silicates etc..
As above-mentioned organic filler, can enumerate for example polyester micropartical, polyurethane particulate, polyvinyl particle,
Acrylic polymer particle etc..
The preferred lower limit of the content of above-mentioned filler in 100 parts by weight of sealing material for liquid crystal display device of the invention is
5 parts by weight, preferred upper limit are 70 parts by weight.More than 5 parts by weight of content by making above-mentioned filler, to further increase
Cementability and other effects becomes more excellent.By making 70 parts by weight of content of above-mentioned filler hereinafter, to liquid crystal of the invention
The viscosity of display element sealant will not become excessively high, and coating, treatability become more excellent.The content of above-mentioned filler
More preferable lower limit is 10 parts by weight, the more preferable upper limit is 60 parts by weight.
Sealing material for liquid crystal display device of the invention preferably comprises silane coupling agent.Above-mentioned silane coupling agent mainly has
As for by the effect of the be bonded bonding additives better such as sealant and substrate.
As above-mentioned silane coupling agent, can be suitble to using such as 3- TSL 8330,3- mercaptopropyi three
Methoxy silane, 3- glycidoxypropyltrime,hoxysilane, 3- isocyanate propyl trimethoxysilane etc..For these
For silane coupling agent, make the excellent effect improved with the cementability of substrate etc., and by carrying out chemistry with curable resin
It is bonded and is able to suppress curable resin and flows out in liquid crystal.
The content of above-mentioned silane coupling agent in 100 parts by weight of sealing material for liquid crystal display device of the invention it is preferred under
It is limited to 0.1 parts by weight, preferred upper limit is 10 parts by weight.It is more than 0.1 parts by weight of content by making above-mentioned silane coupling agent, from
And the effect for further increasing cementability etc. becomes more excellent.By make 10 parts by weight of content of above-mentioned silane coupling agent with
Under, so that the low liquid crystal pollution of sealing material for liquid crystal display device of the invention becomes more excellent.Above-mentioned silane coupling agent
The more preferable lower limit of content is 0.3 parts by weight, the more preferable upper limit is 5 parts by weight.
Sealing material for liquid crystal display device of the invention can contain opacifier.By containing above-mentioned opacifier, thus this
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 can be enumerated
Cover type carbon black etc..Wherein, preferably titanium is black.
Above-mentioned titanium is black be near ultraviolet range, the transmission of especially wavelength 370nm or more and 450nm light below
Rate is higher than the substance of the average transmittance for wavelength 300nm or more and 800nm light below.That is, it is under having that above-mentioned titanium is black
State the opacifier of property: to sealing used for liquid crystal display element of the invention and sufficiently covering the light of wavelength of visible light region
On the other hand agent, which assigns light-proofness, makes the light transmission of the wavelength near ultraviolet range.As liquid crystal display element of the invention
With the opacifier contained in sealant, the preferably high substance of insulating properties, the opacifier high as insulating properties is also suitably for titanium
It is black.
Above-mentioned titanium is black to play sufficient effect non-surface treated, but surface also can be used and be coupled agent
Treated that titanium is black for equal organic principles；It is oxidized the inorganic constituents such as silicon, titanium oxide, germanium oxide, aluminium oxide, zirconium oxide, magnesia
The surface treated titaniums such as the titanium covered is black are black.Wherein, from the viewpoint of it can further increase insulating properties, preferably had
Treated that titanium is black for machine ingredient.
In addition, using containing the black sealing material for liquid crystal display device of the invention as opacifier of above-mentioned titanium and manufacturing
Liquid crystal display element has sufficient light-proofness, therefore can be realized with high contrast without light leakage and with excellent image
The liquid crystal display element of display quality.
As above-mentioned titanium it is black among commercially available product, the titanium that can enumerate such as Mitsubishi General Materials corporation is black, red fringe
It is black etc. at the titanium of corporation.
Titanium as above-mentioned Mitsubishi General Materials corporation is black, can enumerate such as 12S, 13M, 13M-C, 13R-N, 14M-
C etc..
Titanium as above-mentioned red fringe chemical conversion corporation is black, can enumerate such as Tilack D.
The preferred lower limit of the black specific surface area of above-mentioned titanium is 13m2/ g, preferred upper limit 30m2/ g, more preferable lower limit are
15m2/ g, the more preferable upper limit are 25m2/g。
In addition, the preferred lower limit of the black volume resistance of above-mentioned titanium is 0.5 Ω cm, preferred upper limit is 3 Ω cm, more preferably
Lower limit is 1 Ω cm, the more preferable upper limit is 2.5 Ω cm.
The primary particle size of above-mentioned opacifier as long as liquid crystal display element substrate between distance hereinafter, as long as do not limit especially
It is fixed, preferred lower limit 1nm, preferred upper limit 5000nm.By making the primary particle size of the above-mentioned opacifier range, so as to
Keep light-proofness more excellent, the drawing property etc. without making resulting sealing material for liquid crystal display device deteriorates.Above-mentioned opacifier
The more preferable lower limit of primary particle size is 5nm, the more preferable upper limit is 200nm, further preferred lower limit be 10nm, further preferably on
It is limited to 100nm.
It should be noted that NICOMP 380ZLS (PARTICLE can be used in the primary particle size of above-mentioned opacifier
SIZING SYSTEMS corporation), it is scattered in above-mentioned opacifier in solvent (water, organic solvent etc.) and measures.
The preferred lower limit of the content of above-mentioned opacifier in 100 parts by weight of sealing material for liquid crystal display device of the invention is
5 parts by weight, preferred upper limit are 80 parts by weight.More than 5 parts by weight of content by making above-mentioned opacifier, thus liquid of the invention
Crystal display element sealant can play superior light-proofness.By make 80 parts by weight of content of above-mentioned opacifier with
Under, so that the intensity and coating after the cementability of sealing material for liquid crystal display device of the invention, solidification become more excellent.On
The more preferable lower limit for stating the content of opacifier is 10 parts by weight, the more preferable upper limit is 70 parts by weight.
Sealing material for liquid crystal display device of the invention further can contain reactive diluent, interval as needed
The additives such as object, curing accelerator, defoaming agent, levelling agent, polymerization inhibitor.
As the method for manufacturing sealing material for liquid crystal display device of the invention, can enumerate for example using homogenous disperse
The mixing machines such as device, mixer for well-distribution, omnipotent mixer, planetary-type mixer, kneader, triple-roller mill, by curable resin, basis
Need and the mixed methods etc. such as the polymerization initiator, thermal curing agents, filler, the silane coupling agent that add.
By cooperating electrically conductive microparticle into sealing material for liquid crystal display device of the invention, led up and down so as to manufacture
Logical material.Such conductive material up and down containing sealing material for liquid crystal display device and electrically conductive microparticle of the invention is also this
One of invention.
As above-mentioned electrically conductive microparticle, metal ball can be used, be formed with conductive metal layer on the surface of resin particle
Electrically conductive microparticle etc..Wherein, the electrically conductive microparticle that conductive metal layer is formed on the surface of resin particle passes through resin particle
Excellent resilience and the ground such as transparent substrate can not be damaged and be conductively connected, so be suitble to.
The manufactured liquid crystal using sealing material for liquid crystal display device of the invention or conductive material up and down of the invention
Show that element is also one of present invention.
As the method for manufacturing liquid crystal display element of the invention, can be suitble to using liquid crystal dripping process, specifically, can
It enumerates such as following methods.
Liquid crystal display element can be obtained and with the method for following processes, firstly, carrying out following process: passing through silk
Wire mark brush, distributor coating etc. are in glass substrate, PET substrate of the electrodes such as subsidiary ito thin film etc. two
It opens on one in substrate, sealing material for liquid crystal display device of the invention is coated with, to form the work of the seal pattern of frame-shaped
Sequence；Next, carrying out following process: in the state that sealing material for liquid crystal display device of the invention is uncured, by liquid crystal
Tiny droplets, which are dripped, to be applied in the frame of the seal pattern of substrate, is overlapped the process of another substrate under vacuum；Thereafter, it carries out such as
Lower process: to light such as the seal pattern partial illumination ultraviolet lights of sealing material for liquid crystal display device of the invention, to make to seal
The process of agent progress precuring；And the sealant through precuring is heated and it is made to carry out leading cured process.
The effect of invention
In accordance with the invention it is possible to provide cementability, anti-penetrability and excellent used for liquid crystal display element of low liquid crystal pollution
Workable polymerizable compound in sealant.In addition, in accordance with the invention it is possible to providing the liquid crystal containing the polymerizable compound
Display element sealant and manufactured conductive material and liquid crystal display up and down using the sealing material for liquid crystal display device
Element.
Specific embodiment
Embodiment described below is described in more detail the present invention, but the present invention is not limited to these embodiments.
(synthesis of intermediate epoxide (A-1))
456 parts by weight of bisphenol-A and 202 parts by weight of triethyleneglycol divinylether are put into flask, stir 6 at 120 DEG C
Hour and make its reaction, obtain intermediate phenolic compounds.
Liquid temperature is restored to room temperature, adds 925 parts by weight of epichlorohydrin and 150 parts by weight of n-butanol and is made uniform molten
Liquid is warming up to 60 DEG C.Then, 5 hours 40% sodium hydrate aqueous solution, 220 parts by weight of dripping are expended, and then small in 60 DEG C of reactions 1
When.After reaction, remaining epichlorohydrin is evaporated by vacuum distillation, obtains crude epoxidation and closes object.To resulting thick epoxy
600 parts by weight of methyl iso-butyl ketone (MIBK) and 100 parts by weight of n-butanol are added in compound and solution is made, and are added into the solution
10% sodium hydrate aqueous solution, 30 parts by weight after reacting it 2 hours, are repeated 3 times and carry out water using 200 parts by weight of water
It washes, measures the pH of cleaning solution, confirmation reaches neutral.Then, implement azeotropic dehydration, and then evaporate solvent, obtain intermediate epoxy
Compound (A-1).
(synthesis of polymerizable compound (B-1) of the invention)
Intermediate epoxide (A-1) 404 parts by weight, 36 parts by weight of acrylic acid, triphenylphosphine 0.5 are put into flask
0.05 parts by weight of parts by weight and dibutyl hydroxy toluene stir 6 hours at 100 DEG C, thus make its reaction.By gained reactant benefit
After cleaning 3 times with 1000 parts by weight of pure water, by being evaporated under reduced pressure water removal of making a return journey, polymerizable compound of the invention (B-1) is obtained.
It should be noted that passing through1H-NMR、13C-NMR and FT-IR is analyzed and is confirmed: resulting polymerization of the invention
Property compound (B-1) in, the A in formula (1) is dimethylmethylene, and X is two (ethyleneoxy group) ethyls, Y1And Y2Among one
Person is group shown in formula (2-1) (R is hydrogen atom), and another one is group shown in formula (2-2).Furthermore confirm: the present invention
Polymerizable compound (B-1) be compound that n (average value) in formula (1) is 1.3.
(synthesis of polymerizable compound (C-1) of the invention)
Intermediate epoxide (A-1) 404 parts by weight, 72 parts by weight of acrylic acid, triphenylphosphine 0.5 are put into flask
0.05 parts by weight of parts by weight and dibutyl hydroxy toluene stir 6 hours at 100 DEG C, thus make its reaction.By gained reactant benefit
After cleaning 3 times with 1000 parts by weight of pure water, by being evaporated under reduced pressure water removal of making a return journey, polymerizable compound of the invention (C-1) is obtained.
It should be noted that passing through1H-NMR、13C-NMR and FT-IR is analyzed and is confirmed: resulting polymerization of the invention
Property compound (C-1) in, the A in formula (1) is dimethylmethylene, and X is two (ethyleneoxy group) ethyls, Y1And Y2It is formula (2-
1) group shown in (R is hydrogen atom).Furthermore confirm: polymerizable compound (C-1) of the invention is that the n in formula (1) is (average
Value) be 1.3 compound.
(synthesis of polymerizable compound (C-1M) of the invention)
It other than replacing 72 parts by weight of acrylic acid, is carried out and the above-mentioned " (present invention in addition to using 86 parts by weight of methacrylic acid
Polymerizable compound (C-1) synthesis) " identical operation, obtain polymerizable compound of the invention (C-1M).
It should be noted that passing through1H-NMR、13C-NMR and FT-IR is analyzed and is confirmed: resulting polymerization of the invention
Property compound (C-1M) in, the A in formula (1) is dimethylmethylene, and X is two (ethyleneoxy group) ethyls, Y1And Y2It is formula
Group shown in (2-1) (R is methyl).Furthermore confirm: polymerizable compound (C-1M) of the invention is that the n in formula (1) is (flat
Mean value) be 1.3 compound.
(synthesis of intermediate epoxide (A-2))
202 weight of triethyleneglycol divinylether is replaced in addition to using bis- 170 parts by weight of (vinyl oxygroup) hexane of 1,6-
It measures except part, progress and above-mentioned " (synthesis of intermediate epoxide (A-1)) " identical operation obtain intermediate epoxidation
It closes object (A-2).
(synthesis of polymerizable compound (C-2) of the invention)
Intermediate epoxide (A-1) 404 is replaced in addition to using 388 parts by weight of intermediate epoxide (A-2)
Except parts by weight, progress and above-mentioned " (synthesis of polymerizable compound (C-1) of the invention) " identical operation obtain the present invention
Polymerizable compound (C-2).
It should be noted that passing through1H-NMR、13C-NMR and FT-IR is analyzed and is confirmed: resulting polymerization of the invention
Property compound (C-2) in, the A in formula (1) is dimethylmethylene, and X is hexa-methylene, Y1And Y2It is base shown in formula (2-1)
Group (R is hydrogen atom).Furthermore confirm: polymerizable compound (C-2) of the invention is that the n (average value) in formula (1) is 1.2
Compound.
(synthesis of epoxy pronane modification bisphenol-a epoxy acrylate)
Intermediate epoxide (A- is replaced in addition to using 260 parts by weight of epoxy pronane modification bisphenol A type epoxy resin
1) except 404 parts by weight, progress and above-mentioned " (synthesis of polymerizable compound (C-1) of the invention) " identical operation are obtained
Epoxy pronane modification bisphenol-a epoxy acrylate.As above-mentioned epoxy pronane modification bisphenol A type epoxy resin, use
ADEKA RESIN EP-4000S (ADEKA corporation).
(embodiment 1~11 and comparative example 1~3)
According to the match ratio recorded in table 1,2, using planetary stirring machine, (THINKY corporation, " あ わ と り practices too
Youth ") each material is mixed after, and then mixed using triple-roller mill, thus prepare embodiment 1~11 and comparative example 1
~3 sealing material for liquid crystal display device.
<evaluation>
For sealing material for liquid crystal display device obtained in embodiment and comparative example, conduct the following evaluation.By result
It is shown in table 1,2.
(cementability)
Using planetary agitating device, make spacer particle (ponding chemical industrial company system, " Micropearl SI-
H050 ") 1 parts by weight are evenly dispersed in each sealing material for liquid crystal display device 100 as obtained from embodiment and comparative example
In parts by weight, denier is coated on to the central portion of corning glass 1737 (long 50mm × wide 20mm × thickness 0.7mm).By same type
The glass of type is overlapped on it and by sealing material for liquid crystal display device drawout, is used metal halide light irradiation 30 seconds
100mW/cm2Ultraviolet light, then 120 DEG C heat 1 hour and make sealant cures, obtain adhesive test piece.
For resulting adhesive test piece, adhesive strength is measured using tensometer.
(low liquid crystal pollution and anti-penetrability)
It is dispersed in spacer particle (ponding chemical industrial company system, " Micropearl SI-H050 ") 1 parts by weight logical
It crosses in each 100 parts by weight of sealing material for liquid crystal display device obtained from embodiment and comparative example, it is subsidiary through brushing at two
On one in the substrate of alignment films and transparent electrode, applied in such a way that the line width of sealant reaches 1mm using distributor
Cloth.Then, the tiny droplets of liquid crystal (CHISSO corporation, " JC-5004LA ") are dripped and is applied to the substrate of subsidiary transparent electrode
Sealant frame in whole face, the substrate of another subsidiary transparent electrode is bonded immediately, using metal halide lamp to sealant
30 seconds 100mW/cm of partial illumination2Ultraviolet light, then 120 DEG C heat 1 hour and make sealant cures, obtain liquid crystal display
Element.For each sealing material for liquid crystal display device obtained in embodiment and comparative example, make respectively low liquid crystal pollution and
Liquid crystal display element involved in the evaluation of anti-penetrability.
The evaluation of low liquid crystal pollution is proceed as follows: being become resulting liquid crystal display element and is applied with 1000 at 60 DEG C
The state of hour voltage, then confirms the degree of the liquid crystal aligning disorder near sealant by visual observation.In addition, anti-penetrability
Evaluation be proceed as follows: become resulting liquid crystal display element and be applied with 1000 hours voltage at 60 DEG C, 95%RH
Then state confirms the degree of the liquid crystal aligning disorder near sealant by visual observation.
Liquid crystal aligning disorder is judged by irregular colour, when according to the degree, absolutely not irregular colour of irregular colour
It is denoted as that "○", " △ ", there are number of colors not there are being denoted as when a little irregular colour when being denoted as " ◎ ", slightly there is irregular colour
It is denoted as "×" when, has rated liquid crystal pollution.
It should be noted that being evaluated as " ◎ ", the liquid crystal display element of "○" is the absolutely not water of problem in practical
It is flat.
[table 1]
[table 2]
Industrial availability
In accordance with the invention it is possible to provide cementability, anti-penetrability and excellent used for liquid crystal display element of low liquid crystal pollution
Workable polymerizable compound in sealant.In addition, in accordance with the invention it is possible to providing the liquid crystal containing the polymerizable compound
Display element sealant and manufactured conductive material and liquid crystal display up and down using the sealing material for liquid crystal display device
Element.
Claims (5)
1. a kind of sealing material for liquid crystal display device, which is characterized in that it contains curable resin,
The curable resin contains polymerizable compound shown in following formula (1),
In formula (1), A indicates that methylene, methylmethylene, dimethylmethylene, oxygen atom, sulphur atom or sulfonyl, X indicate sub-
Ethyl oxygroup ethyl, two (ethyleneoxy group) ethyls, three (ethyleneoxy group) ethyls, four (ethyleneoxy group) ethyls, propylidene
Oxygroup propyl, two (propylidene oxygroup) propyl, three (propylidene oxygroup) propyl, four (propylidene oxygroup) propyl, butylidene oxygroup
Butyl, two (butylidene oxygroup) butyl, three (butylidene oxygroup) butyl, four (butylidene oxygroup) butyl or carbon atom number are 2
Above and 15 alkylidenes below, Y1And Y2Each independently represent group shown in following formula (2-1) or (2-2), also, Y1
And Y2At least one of for group shown in following formula (2-1), n with average value be calculated as 1 or more and 5 hereinafter,
In formula (2-1) and formula (2-2), * indicates bonding position, and in formula (2-1), R indicates hydrogen atom or methyl.
2. sealing material for liquid crystal display device according to claim 1, which is characterized in that 100 parts by weight of curable resin
In formula (1) shown in polymerizable compound content be 5 parts by weight more than and 80 parts by weight below.
3. a kind of conductive material up and down, which is characterized in that it contains sealing used for liquid crystal display element of any of claims 1 or 2
Agent and electrically conductive microparticle.
4. a kind of liquid crystal display element, which is characterized in that it is using used for liquid crystal display element close described in as claimed in claim 1 or 22
Seal agent or it is as claimed in claim 3 up and down conductive material and it is manufactured.
5. a kind of polymerizable compound, which is characterized in that its by following formula (1) indicate,
In formula (1), A indicates that methylene, methylmethylene, dimethylmethylene, oxygen atom, sulphur atom or sulfonyl, X indicate sub-
Ethyl oxygroup ethyl, two (ethyleneoxy group) ethyls, three (ethyleneoxy group) ethyls, four (ethyleneoxy group) ethyls, propylidene
Oxygroup propyl, two (propylidene oxygroup) propyl, three (propylidene oxygroup) propyl, four (propylidene oxygroup) propyl, butylidene oxygroup
Butyl, two (butylidene oxygroup) butyl, three (butylidene oxygroup) butyl, four (butylidene oxygroup) butyl or carbon atom number are 2
Above and 15 alkylidenes below, Y1And Y2Each independently represent group shown in following formula (2-1) or (2-2), also, Y1
And Y2At least one of for group shown in following formula (2-1), n with average value be calculated as 1 or more and 5 hereinafter,
In formula (2-1) and formula (2-2), * indicates bonding position, and in formula (2-1), R indicates hydrogen atom or methyl.
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| JP2016244430 | 2016-12-16 | ||
| JP2016-244430 | 2016-12-16 | ||
| PCT/JP2017/044574 WO2018110552A1 (en) | 2016-12-16 | 2017-12-12 | Polymerizable compound, sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN104981732A (en) * | 2013-03-06 | 2015-10-14 | 积水化学工业株式会社 | Sealing agent for liquid crystal dropping methods, vertically conducting material, and liquid crystal display element |
| CN105283803A (en) * | 2013-06-11 | 2016-01-27 | 积水化学工业株式会社 | Sealing agent for liquid crystal dropping methods, vertically conducting material, and liquid crystal display element |
| CN105579898A (en) * | 2013-11-13 | 2016-05-11 | 积水化学工业株式会社 | Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element |
| CN105683225A (en) * | 2013-12-05 | 2016-06-15 | 积水化学工业株式会社 | Polymerizable monomer, polymer compound, photocurable resin composition, sealing element for liquid crystal display element, vertical conduction material, and liquid crystal display element |
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| JP3583326B2 (en) | 1999-11-01 | 2004-11-04 | 協立化学産業株式会社 | Sealant for dripping method of LCD panel |
| CA2446125A1 (en) | 2001-05-16 | 2002-11-21 | Sekisui Chemical Co., Ltd. | Curing resin composition and sealants and end-sealing materials for displays |
| WO2004108790A1 (en) * | 2003-06-04 | 2004-12-16 | Sekisui Chemical Co., Ltd. | Curing resin composition, sealing material for liquid crystal display device and liquid crystal display device |
| KR100943421B1 (en) | 2007-12-24 | 2010-02-19 | 연세대학교 산학협력단 | Photopolymerizable monomer having an unsaturated double bond with an epoxy group and a photopolymerizable composition containing the same |
| JP6754933B2 (en) * | 2014-04-09 | 2020-09-16 | 協立化学産業株式会社 | Liquid crystal sealant applicable to flexible liquid crystal panels |
| JP2016060744A (en) | 2014-09-12 | 2016-04-25 | 積水化学工業株式会社 | Sealing agent for organic electroluminescence display element |
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- 2017-12-12 JP JP2017566877A patent/JP7000164B2/en active Active
- 2017-12-12 KR KR1020187031833A patent/KR102467952B1/en active Active
- 2017-12-12 CN CN201780050484.2A patent/CN109564371B/en active Active
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|---|---|---|---|---|
| JP2004189942A (en) * | 2002-12-12 | 2004-07-08 | Shin Etsu Chem Co Ltd | Silicone-modified acrylate resin and photocurable resin composition |
| CN104981732A (en) * | 2013-03-06 | 2015-10-14 | 积水化学工业株式会社 | Sealing agent for liquid crystal dropping methods, vertically conducting material, and liquid crystal display element |
| CN105283803A (en) * | 2013-06-11 | 2016-01-27 | 积水化学工业株式会社 | Sealing agent for liquid crystal dropping methods, vertically conducting material, and liquid crystal display element |
| CN105579898A (en) * | 2013-11-13 | 2016-05-11 | 积水化学工业株式会社 | Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element |
| CN105683225A (en) * | 2013-12-05 | 2016-06-15 | 积水化学工业株式会社 | Polymerizable monomer, polymer compound, photocurable resin composition, sealing element for liquid crystal display element, vertical conduction material, and liquid crystal display element |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2018110552A1 (en) | 2018-06-21 |
| JPWO2018110552A1 (en) | 2019-11-07 |
| CN109564371B (en) | 2021-09-14 |
| TW201839086A (en) | 2018-11-01 |
| TWI823843B (en) | 2023-12-01 |
| JP7000164B2 (en) | 2022-01-19 |
| KR20190091191A (en) | 2019-08-05 |
| KR102467952B1 (en) | 2022-11-16 |
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