CN105283803B - Sealant for liquid crystal dripping process, up and down conductive material and liquid crystal display cells - Google Patents
Sealant for liquid crystal dripping process, up and down conductive material and liquid crystal display cells Download PDFInfo
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- CN105283803B CN105283803B CN201480032864.XA CN201480032864A CN105283803B CN 105283803 B CN105283803 B CN 105283803B CN 201480032864 A CN201480032864 A CN 201480032864A CN 105283803 B CN105283803 B CN 105283803B
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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
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1341—Filling or closing of cells
- G02F1/13415—Drop filling process
-
- 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
- G02F2202/00—Materials and properties
- G02F2202/16—Materials and properties conductive
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- Chemical & Material Sciences (AREA)
- Nonlinear Science (AREA)
- Optics & Photonics (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Mathematical Physics (AREA)
- Liquid Crystal (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Sealing Material Composition (AREA)
- Epoxy Resins (AREA)
Abstract
It is an object of the present invention to provide the low sealant for liquid crystal dripping process of a kind of excellent in adhesion and solidfied material penetrability.In addition, a kind of it is an object of the present invention to provide conductive material up and down and liquid crystal display cells using the sealant for liquid crystal dripping process.The present invention is a kind of sealant for liquid crystal dripping process, it contains curable resin and radical polymerization initiator and/or thermal curing agents, wherein, above-mentioned curable resin contains epoxy resin and (methyl) acrylic resin, the content of above-mentioned epoxy resin in the above-mentioned parts by weight of curable resin 100 is 5~70 parts by weight, and above-mentioned epoxy resin contains more than the weight % of dicyclopentadiene phenolic type epoxy resin 20.
Description
Technical field
The present invention relates to the low sealant for liquid crystal dripping process of a kind of excellent in adhesion and solidfied material penetrability.Separately
Outside, the present invention relates to a kind of conductive material up and down being made using the sealant for liquid crystal dripping process and liquid crystal display member
Part.
Background technology
In recent years, as the manufacture method of liquid crystal display cells, from shortening pitch time, the optimized of amount of liquid crystal is used
Viewpoint is set out, and contains curable resin, photopolymerization using having used as disclosed in patent document 1, patent document 2
The photo-thermal of initiator and thermal curing agents is simultaneously referred to as the liquid crystal drop under type of technique of dripping with curing type sealant.
In technique of dripping, first, form rectangular by distributor on one in 2 electroded transparency carriers
The seal pattern of shape.Then, the fine droplet of liquid crystal is added drop-wise to the whole of transparency carrier in the state of sealant is uncured
Inframe, makes another transparency carrier overlapping, precuring is carried out to light such as sealing irradiation ultraviolet radiations immediately.Then, heating and
Main solidification is carried out, liquid crystal display cells are made.By carrying out the laminating of substrate under reduced pressure, so as to high efficiency system
Liquid making crystal display element, now, the technique of dripping have turned into the main flow of the manufacture method of liquid crystal display cells.
Along with the popularization at tablet terminal or portable end end, liquid crystal display cells are needed all the more under hot and humid environment
The moisture-proof reliabilities such as driving, for sealant, need further exist for preventing the performance of the immersion from outside water.In order that
The moisture-proof reliability of liquid crystal display cells is improved, it is necessary to make the cementability of sealant and substrate etc. improve and make sealant
The penetrability reduction of solidfied material.But, for sealant, it is difficult to take into account high adhesiveness and low-moisture permeability.
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
Invent problem to be solved
It is an object of the present invention to provide the low liquid crystal dripping process of a kind of excellent in adhesion and solidfied material penetrability is used
Sealant.In addition, it is an object of the present invention to provide it is a kind of using the sealant for liquid crystal dripping process and be made up and down lead
Logical material and liquid crystal display cells.
Means for solving the problems
The present invention is a kind of sealant for liquid crystal dripping process, and it is drawn containing curable resin and radical polymerization
The sealant for liquid crystal dripping process of agent and/or thermal curing agents is sent out, wherein, above-mentioned curable resin contains epoxy resin and (first
Base) acrylic resin, the content of the epoxy resin in the above-mentioned parts by weight of curable resin 100 is 5~70 parts by weight, and
Above-mentioned epoxy resin contains more than the weight % of dicyclopentadiene phenolic type epoxy resin 20.
Hereinafter, the present invention is described in detail.
The inventors discovered that, by the dicyclopentadiene phenolic type asphalt mixtures modified by epoxy resin for coordinating specified quantitative as curable resin
Fat, so as to can obtain the low sealant for liquid crystal dripping process of excellent in adhesion and solidfied material penetrability, so far, is completed
The present invention.
The sealant for liquid crystal dripping process of the present invention contains curable resin.
Above-mentioned curable resin contains epoxy resin.
Above-mentioned epoxy resin contains dicyclopentadiene phenolic type epoxy resin.By containing above-mentioned dicyclopentadiene phenolic type
Epoxy resin, so as to make the sealant for liquid crystal dripping process of the present invention have high adhesiveness and low-moisture permeability concurrently.
As above-mentioned dicyclopentadiene phenolic type epoxy resin, specifically, it can enumerate what is for example represented by following formula (1)
Compound etc..
[changing 1]
In formula (1), n is 1~5, preferably 1.
As the commercially available product in above-mentioned dicyclopentadiene phenolic type epoxy resin, such as HP-7200, HP-7200L can be enumerated
(being DIC company systems) etc..
Above-mentioned epoxy resin can also contain other asphalt mixtures modified by epoxy resin on the basis of above-mentioned dicyclopentadiene phenolic type epoxy resin
Fat.
In the case of containing other above-mentioned epoxy resin, the above-mentioned dicyclopentadiene phenolic type ring in above-mentioned epoxy resin
The lower limit of the content of oxygen tree fat is 20 weight %.If the content of above-mentioned dicyclopentadiene phenolic type epoxy resin is less than 20 weights
% is measured, then the sealant for liquid crystal dripping process of gained can not be made fully to have given play to the effect for having high adhesiveness and low-moisture permeability concurrently
Really.The preferred lower limit of the content of above-mentioned dicyclopentadiene phenolic type epoxy resin is 25 weight %.Above-mentioned epoxy resin is excellent
Choosing is only made up of above-mentioned dicyclopentadiene phenolic type epoxy resin.
In addition, the content of the above-mentioned dicyclopentadiene phenolic type epoxy resin in the parts by weight of curable resin 100 is preferably low
In 70 parts by weight.If the content of above-mentioned dicyclopentadiene phenolic type epoxy resin is more than 70 parts by weight, the liquid crystal drop of gained
The viscosity of lower technique sealant becomes too high, and coating is deteriorated sometimes.Above-mentioned dicyclopentadiene phenolic type epoxy resin contains
Amount is more preferably below 30 parts by weight, below more preferably 10 parts by weight.
As above-mentioned other epoxy resin, it can enumerate for example：It is bisphenol A type epoxy resin, bisphenol f type epoxy resin, double
Phenol S types epoxy resin, 2,2 '-diallyl bisphenol type epoxy resin, bisphenol-A epoxy resin, expoxy propane addition are double
Phenol A types epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, thioether-type epoxy resin, diphenyl ether type epoxy
Dicyclopentadiene-type epoxy resin, naphthalene type epoxy resin beyond resin, dicyclopentadiene phenolic type, phenol novolak type asphalt mixtures modified by epoxy resin
Fat, orthoresol phenol aldehyde type epoxy resin, biphenyl phenol aldehyde type epoxy resin, naphthol novolac type epoxy resin, glycidic amine type ring
Oxygen tree fat, alkyl polyols type epoxy resin, modified rubber type epoxy resin, epihydric alcohol ester compound, bisphenol A-type epithio
Resin etc..These epoxy resin may be used singly or in combination of two or more.
As the commercially available product in above-mentioned bisphenol A type epoxy resin, it (is Mitsubishi that can enumerate such as jER 828, jER 1004
Chemical company's system), EPICLON 850CRP (DIC company systems) etc..
As the commercially available product in above-mentioned bisphenol f type epoxy resin, such as jER 806, jER 4004, jER can be enumerated
YL983U (being Mitsubishi Chemical Ind's system).
As the commercially available product in above-mentioned bisphenol-s epoxy resin, such as EPICLON EXA1514 (DIC companies can be enumerated
System) etc..
As above-mentioned 2, the commercially available product in 2 '-diallyl bisphenol type epoxy resin can enumerate such as RE-810NM (days
This chemical drug company system) etc..
As the commercially available product in above-mentioned bisphenol-A epoxy resin, can enumerating such as EPICLON EXA7015, (DIC is public
Department's system), jER YX8000 (Mitsubishi Chemical Ind's system) etc..
As the commercially available product in above-mentioned expoxy propane addition bisphenol A type epoxy resin, such as EP-4000S can be enumerated
(ADEKA company systems) etc..
As the commercially available product in above-mentioned resorcinol type epoxy resin, such as EX-201 (Nagase Chemtex can be enumerated
Company system) etc..
As the commercially available product in above-mentioned biphenyl type epoxy resin, such as jER YX-4000H (Mitsubishi Chemical Inds can be enumerated
System) etc..
As the commercially available product in above-mentioned thioether-type epoxy resin, can enumerating such as YSLV-50TE, (it is public that aurification is lived by Nippon Steel
Department's system) etc..
As the commercially available product in above-mentioned diphenyl ether type epoxy, can enumerating such as YSLV-80DE, (aurification is lived by Nippon Steel
Learn company system) etc..
As the commercially available product in the dicyclopentadiene-type epoxy resin beyond above-mentioned dicyclopentadiene phenolic type, example can be enumerated
Such as EP-4088S (ADEKA company systems).
As the commercially available product in above-mentioned naphthalene type epoxy resin, such as EPICLON HP4032, EPICLON EXA- can be enumerated
4700 (being DIC company systems) etc..
As the commercially available product in above-mentioned phenol novolak type epoxy, such as EPICLON N-770 (DIC companies can be enumerated
System) etc..
As the commercially available product in above-mentioned orthoresol phenol aldehyde type epoxy resin, such as EPICLON N-670-EXP-S can be enumerated
(DIC company systems) etc..
As the commercially available product in above-mentioned biphenyl phenol aldehyde type epoxy resin, such as NC-3000P (Japanese chemical drug companies can be enumerated
System) etc..
As the commercially available product in above-mentioned naphthol novolac type epoxy resin, can enumerating such as ESN-165S, (aurification is lived by Nippon Steel
Learn company system) etc..
As the commercially available product in above-mentioned glycidyl amine type epoxy resin, such as (Mitsubishi Chemical Inds of jER 630 can be enumerated
System), EPICLON 430 (DIC company systems), TETRAD-X (Mitsubishi Gas Chemical company system) etc..
As the commercially available product in abovementioned alkyl polyol type epoxy resin, can enumerating such as ZX-1542, (aurification is lived by Nippon Steel
Learn company system), EPICLON 726 (DIC company systems), EPOLIGHT 80MFA (common prosperity company chemistry company system), DENACOL
EX-611 (Nagase Chemtex company systems) etc..
As the commercially available product in above-mentioned modified rubber type epoxy resin, it (is new day that can enumerate such as YR-450, YR-207
Iron lives aurification company system), EPOLEAD PB (Daicel chemical industrial company system) etc..
As the commercially available product in above-mentioned epihydric alcohol ester compound, such as DENACOL EX-147 (Nagase can be enumerated
Chemtex company systems) etc..
As the commercially available product in above-mentioned bisphenol A-type episulfide resin, such as jER YL-7000 (Mitsubishi Chemicals can be enumerated
Company system) etc..
As other commercially available products in above-mentioned epoxy resin, such as YDC-1312, YSLV-80XY, YSLV-90CR can be enumerated
(being that aurification company system is lived by Nippon Steel), XAC4151 (Asahi Kasei Corporation's system), jER 1031, jER 1032 (are Mitsubishi
Learn company system), EXA-7120 (DIC company systems) etc..
In addition, as above-mentioned other epoxy resin, can contain has epoxy radicals and (methyl) acryloyl-oxy in 1 molecule
The resin of base.As such compound, can enumerate for example makes a part of epoxy in the compound with more than 2 epoxy radicals
Base and part (methyl) acrylic modified epoxy resin etc. obtained from (methyl) propylene acid reaction.Above-mentioned part (methyl) propylene
Sour modified epoxy (methyl) acrylic resin not described later, but it is used as epoxy resin.
It should be noted that can use by making a part of epoxy radicals of above-mentioned dicyclopentadiene phenolic type epoxy resin
With part (methyl) acrylic modified epoxy resin obtained from (methyl) propylene acid reaction.
As above-mentioned part (methyl) acrylic modified epoxy resin, specifically, for example, it can be made as described below：Make
Phenol novolak type epoxy (DIC company systems, " N-770 ") 190g is dissolved in toluene 500mL, and triphen is added into the solution
Base phosphine 0.1g and uniform solution is made, in the solution of gained under return stirring with 2 hours be added dropwise acrylic acid 35g, then
Further carry out return stirring 6 hours, then remove toluene, thus obtain 50 moles of % epoxy radicals and propylene acid reaction and obtain
Part acrylic acid modified phenol phenol aldehyde type epoxy resin (now, 50% there occurs part acrylic acid be modified).
As the commercially available product in above-mentioned part (methyl) acrylic modified epoxy resin, such as UVACURE1561 can be enumerated
(DaicelAllnex company systems).
The lower limit of the content of above-mentioned epoxy resin in the above-mentioned parts by weight of curable resin 100 is that 5 parts by weight, the upper limit are 70
Parts by weight.If the content of above-mentioned epoxy resin be less than 5 parts by weight, above-mentioned dicyclopentadiene phenolic type epoxy resin contain quantitative change
Few, therefore, the sealant for liquid crystal dripping process of gained becomes that high adhesiveness and low-moisture permeability can not be had concurrently.If above-mentioned asphalt mixtures modified by epoxy resin
The content of fat then becomes easily occur liquid crystal pollution more than 70 parts by weight.The preferred lower limit of the content of above-mentioned epoxy resin is
10 parts by weight, the upper limit preferably are that 65 parts by weight, preferred lower limit are that 15 parts by weight, the preferred upper limit are 60 parts by weight.
In addition, in the above-mentioned parts by weight of curable resin 100, except above-mentioned part (methyl) acrylic modified epoxy resin with
The preferred lower limit of the content of outer epoxy resin is that 3 parts by weight, the upper limit preferably are 59 parts by weight.If except above-mentioned part (first
Base) content of epoxy resin beyond acrylic modified epoxy resin is less than 3 parts by weight, then above-mentioned dicyclopentadiene phenolic type ring
The content of oxygen tree fat tails off, and the sealant for liquid crystal dripping process of gained becomes that high adhesiveness and low moisture-inhibiting can not be had concurrently sometimes
Property.If the content of the epoxy resin in addition to above-mentioned part (methyl) acrylic modified epoxy resin has more than 59 parts by weight
When produce liquid crystal pollution.The preferred lower limit of the content of above-mentioned epoxy resin is that 5 parts by weight, the preferred upper limit are 30 weight
Part, the preferred upper limit are 20 parts by weight.
Above-mentioned curable resin contains (methyl) acrylic resin.
Above-mentioned (methyl) acrylic resin can be enumerated for example：By making (methyl) acrylic acid and the compound with hydroxyl
Ester compounds obtained by reaction, by make (methyl) acrylic acid and epoxide react obtained by epoxy (methyl) acrylic acid
Ester, by make isocyanates with hydroxyl (methyl) acrylic acid derivative reaction obtained by carbamate (methyl) propylene
Acid esters etc..
It should be noted that in this manual, above-mentioned (methyl) acrylic resin refers to there is (methyl) acryloyl
The resin of base, above-mentioned (methyl) acryloyl group refers to acryloyl group or methylacryloyl.In addition, above-mentioned (methyl) acrylate
Refer to acrylate or methacrylate.Above-mentioned epoxy (methyl) acrylate refer to whole epoxy radicals of epoxide with
Epoxy (methyl) acrylate obtained by (methyl) propylene acid reaction.
Wherein, above-mentioned (methyl) acrylic resin preferably comprises the whole of above-mentioned dicyclopentadiene phenolic type epoxy resin
Dicyclopentadiene phenolic type epoxy (methyl) acrylate of epoxy radicals and (methyl) propylene acid reaction.
As the ester compounds of the simple function in above-mentioned ester compounds, it can enumerate for example：(methyl) acrylic acid -2- hydroxyl second
Ester, (methyl) 2-hydroxypropyl acrylate, (methyl) acrylic acid -4- hydroxy butyl esters, (methyl) acrylic acid -2- hydroxy butyl esters, (methyl) third
Olefin(e) acid isobutyl ester, (methyl) tert-butyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) lauryl acrylate, (methyl) third
Olefin(e) acid stearyl, (methyl) isobornyl acrylate, (methyl) cyclohexyl acrylate, (methyl) acrylic acid -2- methoxyl groups
Ethyl ester, methoxy ethyl glycol (methyl) acrylate, (methyl) acrylic acid -2- ethoxy ethyl esters, (methyl) acrylic acid tetrahydrochysene chaff
Ester, (methyl) benzyl acrylate, ethyl carbitol (methyl) acrylate, (methyl) acrylate, phenoxy group two
Ethylene glycol (methyl) acrylate, phenoxy group polyethylene glycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylic acid
Ester, (methyl) acrylic acid 2,2,2- trifluoro ethyl esters, (methyl) acrylic acid 2,2,3,3- tetrafluoros propyl ester, (methyl) acrylic acid 1H, 1H,
5H- octafluoros pentyl ester, acid imide (methyl) acrylate, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propylene
Propyl propionate, (methyl) n-butyl acrylate, (methyl) cyclohexyl acrylate, (methyl) acrylic acid-2-ethyl caproite, (methyl) third
Olefin(e) acid n-octyl, the different nonyl ester of (methyl) acrylic acid, the different myristin of (methyl) acrylic acid, (methyl) acrylic acid -2- butoxy second
Ester, (methyl) acrylic acid -2- phenoxy ethyls, (methyl) acrylic acid dicyclopentenyloxyethyl methacrylate, (methyl) isodecyl acrylate, (methyl)
Acrylic acid diethylamino ethyl ester, (methyl) acrylate, 2- (methyl) acryloyl-oxyethyls butanedioic acid,
The adjacent benzene two of 2- (methyl) acryloyl-oxyethyl hexahydrophthalic acid ester, 2- (methyl) acryloyl-oxyethyl -2- hydroxypropyls
Formic acid esters, (methyl) glycidyl acrylate, 2- (methyl) acryloyl-oxyethyl phosphate etc..
As the ester compounds of 2 functions in above-mentioned ester compounds, it can enumerate for example：1,4- butanediols two (methyl) propylene
Acid esters, 1,3 butylene glycol two (methyl) acrylate, 1,6-HD two (methyl) acrylate, 1,9- nonanediols two (methyl)
Acrylate, 1,10- decanediols two (methyl) acrylate, (methyl) acrylic acid of 2- normal-butyl -2- ethyl -1,3- propane diols two
Ester, DPG two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, polypropylene glycol (methyl) acrylate,
Ethylene glycol two (methyl) acrylate, diethylene glycol two (methyl) acrylate, tetraethylene glycol two (methyl) acrylate, poly- second
Glycol two (methyl) acrylate, expoxy propane addition bisphenol-A two (methyl) acrylate, (first of ethyleneoxide addition bisphenol-A two
Base) acrylate, ethyleneoxide addition Bisphenol F two (methyl) acrylate, dihydroxymethyl dicyclopentadienyl two (methyl) third
Olefin(e) acid ester, 1,3 butylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, ethylene-oxide-modified isocyanide urea
Sour two (methyl) acrylate, 2- hydroxyls -3- (methyl) acryloxypropyl (methyl) acrylate, carbonate diol two
(methyl) acrylate, PTMEG two (methyl) acrylate, polyester-diol two (methyl) acrylate, polycaprolactone glycol
Two (methyl) acrylate, polybutadiene diol two (methyl) acrylate etc..
As ester compounds more than 3 functions in above-mentioned ester compounds, it can enumerate for example：Pentaerythrite three (methyl) third
Olefin(e) acid ester, trimethylolpropane tris (methyl) acrylate, expoxy propane addition trimethylolpropane tris (methyl) acrylate,
Ethyleneoxide addition trimethylolpropane tris (methyl) acrylate, caprolactone modification trimethylolpropane tris (methyl) acrylic acid
Ester, ethyleneoxide addition isocyanuric acid three (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol
Six (methyl) acrylate, double (trimethylolpropanes) four (methyl) acrylate, pentaerythrite four (methyl) acrylate, third
Triol three (methyl) acrylate, expoxy propane addition glycerine three (methyl) acrylate, three (methyl) acryloxy second
Base phosphate etc..
As above-mentioned epoxy (methyl) acrylate, can enumerate for example makes epoxy resin and (methyl) third according to conventional method
Olefin(e) acid epoxy (methyl) acrylate etc. obtained by reaction in the presence of base catalyst.
For as the epoxide for the raw material that synthesizes above-mentioned epoxy (methyl) acrylate, can be used with it is upper
The epoxy resin identical epoxy resin stated.
As above-mentioned epoxy (methyl) acrylate, specifically, for example, it can be made as described below：At 90 DEG C, one
Side send into air, while to resorcinol type epoxy resin (Nagase Chemtex company systems, " EX-201 ") 360 parts by weight,
It is used as the parts by weight of p methoxy phenol 2 of polymerization inhibitor, the parts by weight of triethylamine 2 as catalysts, the parts by weight of acrylic acid 210
Return stirring is carried out, and them is reacted 5 hours, resorcinol type epoxy acrylate is thus obtained.
As the commercially available product 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
(be common prosperity company chemical company system), DENACOL ACRYLATE DA-141, DENACOL ACRYLATE DA-314,
DENACOL ACRYLATE DA-911 (being Nagase Chemtex company systems) etc..
Above by make isocyanates with hydroxyl (methyl) acrylic acid derivative reaction obtained by carbamate
(methyl) acrylate, for example can be by making the equivalent of compound 1 with 2 NCOs, (methyl) with having hydroxyl
The equivalent of acrylic acid derivative 2 reacts and obtained in the presence of the tin based compound of catalytic amount.
For the isocyanates as the raw material of above-mentioned carbamate (methyl) acrylate, it can enumerate for example：It is different
Isophorone diisocyanate, 2,4 toluene diisocyanate, 2,6- toluene di-isocyanate(TDI)s, hexamethylene diisocyanate, three
Methyl hexamethylene diisocyanate, diphenyl methane -4,4 '-diisocyanate (MDI), hydrogenation MDI, aggretion type MDI, 1,5-
Naphthalene diisocyanate, norbornene alkyl diisocyanate, tolidine diisocyanate, XDI (XDI),
Hydrogenate XDI, lysine diisocyanate, triphenylmethane triisocyanate, three (isocyanate phenyl) thiophosphates, tetramethyl
Base XDI, 1,6,10- hendecane triisocyanates etc..
In addition, just being obtained as above by making isocyanates be reacted with (methyl) acrylic acid derivative with hydroxyl
Carbamate (methyl) acrylate raw material isocyanates for, can also use by ethylene glycol, glycerine, mountain
Pears sugar alcohol, trimethylolpropane, (poly-) propane diols, carbonate diol, PTMEG, polyester-diol, polycaprolactone glycol etc. are more
Isocyanate compound of first alcohol with chain elongation obtained from the reaction of excessive isocyanates
Just derive as raw material, with hydroxyl (methyl) acrylic acid of above-mentioned carbamate (methyl) acrylate
Thing, can be enumerated for example：(methyl) acrylic acid -2- hydroxyl ethyl esters, (methyl) 2-hydroxypropyl acrylate, (methyl) acrylic acid -4- hydroxyl fourths
Commercially available product or ethylene glycol, propane diols, 1,3- propane diols, 1,3 butylene glycol, the 1,4- such as ester, (methyl) acrylic acid -2- hydroxy butyl esters
List (methyl) acrylate, trimethylolethane, trimethylolpropane, glycerine of the dihydric alcohols such as butanediol, polyethylene glycol etc.
The epoxy acrylic such as list (methyl) acrylate of trihydroxylic alcohol or two (methyl) acrylate, bisphenol A modified epoxy acrylate
Ester etc..
As above-mentioned carbamate (methyl) acrylate, specifically, for example, it can be made as described below：Add three
The parts by weight of hydroxymethyl-propane 134, the parts by weight of BHT 0.2 as polymerization inhibitor, the di lauric dibutyl as catalysts
The parts by weight of tin 0.01, the parts by weight of IPDI 666, while carrying out return stirring to it at 60 DEG C, while making
It reacts 2 hours, then, adds the parts by weight of acrylic acid 2- hydroxyl ethyl esters 51, while feeding air, while being carried out at 90 DEG C to it
Return stirring simultaneously makes it react 2 hours, is thus made.
As the commercially available product in above-mentioned carbamate (methyl) acrylate, such as M-1100, M-1200, M- can be enumerated
1210th, M-1600 (being East Asia Synesis Company system), EBECRYL230, EBECRYL270, EBECRYL4858,
EBECRYL8402、EBECRYL8804、EBECRYL8803、EBECRYL8807、EBECRYL9260、EBECRYL1290、
EBECRYL5129、EBECRYL4842、EBECRYL210、EBECRYL4827、EBECRYL6700、EBECRYL220、
EBECRYL2220 (being Daicel UCB. S.A. (BE) Bruxelles Belgium system), Artresin UN-9000H, Artresin UN-9000A,
Artresin UN-7100、Artresin UN-1255、Artresin UN-330、Artresin UN-3320HB、Artresin
UN-1200TP K, Artresin SH-500B (being Gen Shang industrial groups system), U-122P, U-108A, U-340P, U-4HA,
U-6HA、U-324A、U-15HA、UA-5201P、UA-W2A、U-1084A、U-6LPA、U-2HA、U-2PHA、UA-4100、UA-
7100、UA-4200、UA-4400、UA-340P、U-3HA、UA-7200、U-2061BA、U-10H、U-122A、U-340A、U-
108th, U-6H, UA-4000 (being chemical industrial company of Xin Zhong villages system), AH-600, AT-600, UA-306H, AI-600, UA-
101T, UA-101I, UA-306T, UA-306I (being the chemical company system of common prosperity company) etc..
From suppressing the dysgenic aspect to liquid crystal, above-mentioned (methyl) acrylic resin preferably has-OH
Base ,-NH- bases ,-NH2The hydrogen bond unit such as base, from the easiness grade of synthesis, particularly preferably epoxy (methyl) acrylic acid
Ester.
In addition, above-mentioned (methyl) acrylic resin preferably has 2~3 in the molecule from the high aspect of reactivity
(methyl) acryloyl group.
The sealant for liquid crystal dripping process of the present invention contains radical polymerization initiator and/or thermal curing agents.
As above-mentioned radical polymerization initiator, optical free radical polymerization initiator, hot radical polymerization initiator can be enumerated
Deng.
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, thioxanthones system chemical combination
Thing etc..
As the commercially available product in above-mentioned optical free radical polymerization initiator, can enumerate such as IRGACURE184,
IRGACURE369、IRGACURE379、IRGACURE651、IRGACURE819、IRGACURE907、IRGACURE2959、
IRGACUREOXE01, Lucirin TPO (being BASF Japan company systems), NCI-930 (ADEKA company systems),
SPEEDCURE EMK (DKSH JAPAN company systems), benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether (are
Tokyo chemical conversion industry company system) etc..
As above-mentioned hot radical polymerization initiator, it can enumerate such as peroxide, azo-compound.Wherein, preferably
Polymeric azo initiator comprising polymeric azo compound.
It should be noted that in this manual, polymeric azo initiator refers to：With azo group and heated and give birth to
Into compound free radical, that number-average molecular weight is more than 300 that can solidify (methyl) acryloxy.
The preferred lower limit of the number-average molecular weight of above-mentioned polymeric azo initiator is that the 1000, upper limit preferably is 300,000.
If the number-average molecular weight of above-mentioned polymeric azo initiator is less than 1000, polymeric azo initiator is brought not to liquid crystal sometimes
Good influence.If the number-average molecular weight of above-mentioned polymeric azo initiator is more than 300,000, sometimes the mixing into curable resin
Become difficult.The preferred lower limit of the number-average molecular weight of above-mentioned polymeric azo initiator is that 5000, the preferred upper limit is
100000, further preferred lower limit is 10,000, the further preferred upper limit is 90,000.
It should be noted that in this manual, above-mentioned number-average molecular weight is carried out using gel permeation chromatography (GPC)
The value for determining and being converted and being obtained by polystyrene.The equal molecule of number converted as being determined by GPC based on polystyrene
Chromatographic column during amount, can be enumerated such as Shodex LF-804 (Showa electrician company system).
As above-mentioned polymeric azo initiator, it can enumerate for example：With making multiple polyalkylene oxides or poly- by azo group
Structure, the polymeric azo initiator of the units such as dimethyl siloxane bonding.
It is used as the polymeric azo of the above-mentioned structure for having and being bonded the units such as multiple polyalkylene oxides by azo group
Initiator, preferably the polymeric azo initiator with PEO structure., can as such polymeric azo initiator
Condensation polymer, the 4,4'- azos for enumerating such as 4,4'- azos double (4- cyanopentanoic acids) and PAG are double (4- cyanopentanoic acids)
With the condensation polymer of the dimethyl silicone polymer with terminal amino group etc..
As above-mentioned organic peroxide, such as ketone peroxide, ketal peroxide, hydroperoxides, dioxane can be enumerated
Base peroxide, peroxyester, diacyl peroxide, peroxy dicarbonate etc..
As the commercially available product in above-mentioned hot radical polymerization initiator, can enumerate such as PERBUTYL O, PERHEXYL O,
PERBUTYL PV (being day oily company system), V-30, V-501, V-601, VPE-0201, VPE-0401, VPE-0601 (are
With Wako Pure Chemical Industries company system) etc..
The content of above-mentioned radical polymerization initiator lower limit preferred for the above-mentioned parts by weight of curable resin 100
It is 10 parts by weight for 0.01 parts by weight, the upper limit preferably.If the content of above-mentioned radical polymerization initiator is less than 0.01 parts by weight,
Sometimes the sealant for liquid crystal dripping process of gained can not then cured sufficiently.If the content of above-mentioned radical polymerization initiator
More than 10 parts by weight, then storage-stable is reduced sometimes.
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, suitably using the organic acid hydrazides of solid-state.
As the organic acid hydrazides of above-mentioned solid-state, acyl in double (diazanyl carbon the ethyl) -5- isopropyl second of such as 1,3- can be enumerated
Urea (1,3- PVC ス (ヒ De ラ ジ ノ カ Le ボ ノ エ チ Le) -5- イ ソ プ ロ ピ Le ヒ ダ Application ト イ Application), decanedioic acid two
Hydrazides, isophthalic dihydrazide, adipic dihydrazide, acid dihydrazide etc., as commercially available product, for example, can be included
SDH (Japanese FINECHEM company systems), ADH (great mound chemical company system), AMICURE VDH, AMICURE VDH-J, AMICURE
UDH (being AJINOMOTO FINE-TECHNO company systems) etc..
The content of above-mentioned thermal curing agents lower limit preferred for the above-mentioned parts by weight of curable resin 100 is 1 weight
Part, the upper limit preferably are 50 parts by weight.If the content of above-mentioned thermal curing agents is less than 1 parts by weight, it can not make the present invention's sometimes
Sealant for liquid crystal dripping process is cured sufficiently.If the content of above-mentioned thermal curing agents is more than 50 parts by weight, sometimes of the invention
The viscosity of sealant for liquid crystal dripping process uprise, coating is deteriorated.The preferred upper limit of the content of above-mentioned thermal curing agents
For 30 parts by weight.
The sealant for liquid crystal dripping process of the present invention preferably comprises curing accelerator.In order that above-mentioned bicyclopentadiene phenol
Aldehyde type epoxy resin is cured sufficiently, and needs to be heated at a higher temperature, but by using above-mentioned curing accelerator,
Even if so as to not heated at high temperature, can also cure sufficiently it, can fully give play to have concurrently high adhesiveness and
The effect of low-moisture permeability.
As above-mentioned curing accelerator, such as imidazoles system curing accelerator, mercaptan system curing accelerator, tertiary amine system can be enumerated
Curing accelerator etc..Wherein, from the aspect that curing rate is fast and viscosity climbing at room temperature is low, imidazoles system is preferably comprised
Curing accelerator and/or mercaptan system curing accelerator.
As above-mentioned imidazoles system curing accelerator, can enumerate such as 1- cyano ethyls -2- phenylimidazoles, 2,4- diaminourea -
6- [2 '-methylimidazolyl-(1 ')]-ethyl-s-triazine, 2- phenyl -4- methyl -5- hydroxymethylimidazoles etc..
As above-mentioned mercaptan system curing accelerator, such as tri-thiol acetic acid trihydroxy methyl propyl ester, tri-thiol acetic acid can be enumerated
Trihydroxy methyl ethyl ester etc..
The content of above-mentioned curing accelerator lower limit preferred for the above-mentioned parts by weight of curable resin 100 is 1 weight
It is 10 parts by weight to measure part, the upper limit preferably.If liquid crystal of the content of above-mentioned curing accelerator less than 1 parts by weight, sometimes gained
Technique of dripping is not cured sufficiently with sealant, or in order that it solidifies and needs to be heated at high temperature.If above-mentioned solid
Change the content of accelerator more than 10 parts by weight, then the cementability of the sealant for liquid crystal dripping process of gained is deteriorated sometimes.
For the sealant for liquid crystal dripping process of the present invention, for the cementability brought by stress dispersion effect
The purpose such as improvement, the improvement of linear expansivity, filler can also be contained.
As above-mentioned filler, can enumerate for example talcum, asbestos, silica, diatomite, terre verte, bentonite, calcium carbonate,
Magnesium carbonate, aluminum oxide, montmorillonite, zinc oxide, iron oxide, magnesia, tin oxide, titanium oxide, magnesium hydroxide, aluminium hydroxide, glass
The inorganic fillers such as glass 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.
The preferred lower limit of content of above-mentioned filler in the parts by weight of sealant for liquid crystal dripping process 100 of the present invention is
5 parts by weight, the upper limit preferably are 70 parts by weight.If the content of above-mentioned filler is less than 5 parts by weight, can not fully it play sometimes
Go out improvement of cementability and other effects.If the content of above-mentioned filler is used more than 70 parts by weight, the sometimes liquid crystal dripping process of gained
The viscosity of sealant becomes too high, and coating is deteriorated.The preferred lower limit of the content of above-mentioned filler is 10 parts by weight, more preferably
The upper limit be 60 parts by weight.
The sealant for liquid crystal dripping process of the present invention contains silane coupler.
It is suitable to use such as 3- TSL 8330s, 3- mercaptopropyi front threes as above-mentioned silane coupler
TMOS, 3- glycidoxypropyltrime,hoxysilanes, 3- isocyanates propyl trimethoxy silicanes etc..They can be single
Solely use, and two or more can also be used.
The content of above-mentioned silane coupler in the parts by weight of sealant for liquid crystal dripping process 100 of the present invention it is preferred
Lower limit is that 0.1 parts by weight, the upper limit preferably are 20 parts by weight.If the content of above-mentioned silane coupler is less than 0.1 parts by weight, have
Shi Wufa has fully given play to the effect that silane coupler is brought with.If the content of above-mentioned silane coupler is more than 20 weights
Part is measured, then the sealant for liquid crystal dripping process of gained can cause liquid crystal pollution sometimes.The content of above-mentioned silane coupler is more
It is preferred that lower limit be that 0.5 parts by weight, the preferred upper limit are 10 parts by weight.
The sealant for liquid crystal dripping process of the present invention can contain opacifier.By containing above-mentioned opacifier, so that originally
The sealant for liquid crystal dripping process of invention can be suitable for use as shading sealant.
As above-mentioned opacifier, black such as iron oxide, titanium, nigrosine, Cyanine Black, fullerene, carbon black, resin coating can be enumerated
Cap-type carbon black etc..Wherein, preferably titanium is black.
Above-mentioned titanium is black to be, compared with the average transmittance of its light to 300~800nm of wavelength, it is attached to ultraviolet range
Closely, it is particularly the material that the transmissivity of 370~450nm of wavelength light is uprised.That is, black above-mentioned titanium is the shading with following property
Agent：By the light for the wavelength for fully covering visible region, and screening is assigned to the sealant for liquid crystal dripping process of the present invention
Photosensitiveness, on the other hand, makes the light transmission of the wavelength near ultraviolet range.Thus, as above-mentioned optical free radical polymerization initiator,
Above-mentioned light cationic polymerization initiator, by using the light of the wavelength (370~450nm) uprised using the black transmissivity of above-mentioned titanium
And it is capable of the material of initiation reaction, so as to further increase the photo-curable of sealant for liquid crystal dripping process of the present invention
Greatly.In addition, on the other hand, being used as the opacifier contained by the sealant for liquid crystal dripping process of the present invention, preferably insulating properties
High material, as the high opacifier of insulating properties, preferably titanium is black.
For above-mentioned titanium is black, every 1 μm of optical concentration (OD values) is preferably more than 3, and more preferably more than 4.It is above-mentioned
The higher the better for the black light-proofness of titanium, and the preferred upper limit of the black OD values of above-mentioned titanium is not particularly limited, but usually less than 5.
For above-mentioned titanium is black, even not surface treated titanium is black, sufficient effect can be also given play to, can also have been made
With：Titanium of the surface after the processing of the organic principles such as coupling agent is black, surface is oxidized silicon, titanium oxide, germanium oxide, aluminum oxide, oxidation
Titanium after the surface treated such as titanium is black of the inorganic constituents such as zirconium, magnesia covering is black.Wherein, the titanium after being handled by organic principle is black
It is preferred from can further improve insulating properties aspect.
Manufactured in addition, using as the sealant for liquid crystal dripping process of the invention of opacifier containing above-mentioned titanium is black
Liquid crystal display cells have sufficient light-proofness, therefore, it is possible to realize no spilling for light and with high-contrast and with excellent
The liquid crystal display cells of different display quality of image.
As commercially available product of the above-mentioned titanium in black, it (is Mitsubishi Material Company that can enumerate such as 12S, 13M, 13M-C, 13R-N
System), 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 upper limit preferably are 30m2/ g, preferred lower limit
For 15m2/ g, the preferred upper limit are 25m2/g。
In addition, it is 3 Ω cm, more that the preferred lower limit of the black volume resistance of above-mentioned titanium, which is 0.5 Ω cm, the upper limit preferably,
It is preferred that lower limit be that 1 Ω cm, the preferred upper limit are 2.5 Ω cm.
The primary particle size of above-mentioned opacifier if the distance between the substrate of liquid crystal display cells below, then do not limit especially
It is fixed, but preferred lower limit is that 1nm, the upper limit preferably are 5 μm.If the primary particle size of above-mentioned opacifier is less than 1nm, the liquid of gained
The drip viscosity or thixotropy of technique sealant of crystalline substance significantly increases, and workability is deteriorated sometimes.If the once grain of above-mentioned opacifier
Footpath is more than 5 μm, then the sealant for liquid crystal dripping process of gained is deteriorated to the coating of substrate sometimes.Above-mentioned opacifier is once
The preferred lower limit of particle diameter be 5nm, the preferred upper limit be 200nm, further preferred lower limit be 10nm, further preferably
The upper limit be 100nm.
The preferred lower limit of the content of above-mentioned opacifier in the parts by weight of sealant for liquid crystal dripping process 100 of the present invention
It is 80 parts by weight for 5 parts by weight, the upper limit preferably.If the content of above-mentioned opacifier is less than 5 parts by weight, it can not be filled sometimes
The light-proofness divided.If the content of above-mentioned opacifier is more than the sealant for liquid crystal dripping process pair of 80 parts by weight, sometimes gained
Intensity decreases after the adaptation of substrate, solidification, or illustrative decline.The preferred lower limit of the content of above-mentioned opacifier is 10
Parts by weight, the preferred upper limit are that 70 parts by weight, further preferred lower limit are that 30 parts by weight, the further preferred upper limit are 60
Parts by weight.
The sealant for liquid crystal dripping process of the present invention can also contain as needed is used for the reactivity dilution for adjusting viscosity
Agent, for adjusting thixotropic thixotropic agent, for adjust the polymer microbeads of panel gap at equal intervals thing, defoamer, levelling agent,
Other known additives such as polymerization inhibitor.
As the method for the sealant for liquid crystal dripping process of the manufacture present invention, it can enumerate for example by curable resin, certainly
Homogenous disperse machine, homogeneous mixing are utilized by base polymerization initiator and/or thermal curing agents, the silane coupler being added as needed on etc.
Method that the mixers such as machine, universal mixer, planetary-type mixer, kneader, 3 roller machines are mixed etc..
By coordinating electrically conductive microparticle in the sealant for liquid crystal dripping process of the present invention, led up and down so as to manufacture
Logical material.If using this conductive material up and down, reliably inter-electrode conductive can be connected.
The conductive material up and down of sealant for liquid crystal dripping process and electrically conductive microparticle containing the present invention is also the present invention
One of.
As above-mentioned electrically conductive microparticle, it can be used and for example form conductive metal layer on the surface of metal ball, resin particle
Electrically conductive microparticle etc..Wherein, from the excellent resilience by resin particle, and can be in the case where not damaging transparency carrier etc.
Realize that the aspect being conductively connected is set out, the electrically conductive microparticle of conductive metal layer is preferably formd on the surface of resin particle.
The liquid crystal being made using the sealant for liquid crystal dripping process of the present invention or the conductive material up and down of the present invention
It is one of present invention to show element.
As the method for the liquid crystal display cells of the manufacture present invention, it can enumerate such as the method with following process：
Under a upper liquid crystal drop by coating present invention such as silk-screen printing, distributor coatings in 2 substrates with ito thin film etc.
Technique sealant, the process for forming rectangular seal pattern；The fine droplet of liquid crystal is dripped and is coated on seal pattern
Whole inframe, the process for making another substrate overlapping under vacuo；Purple is irradiated to the sealant for liquid crystal dripping process of the present invention
The light such as outside line and make the process of sealant precuring；And the sealant after precuring is heated and makes the work of its main solidification
Sequence.
Invention effect
According to the present invention, it is possible to provide the low liquid crystal dripping process sealing of a kind of excellent in adhesion and solidfied material penetrability
Agent.In addition, according to the present invention, it is possible to provide a kind of conductive material up and down for being made using the sealant for liquid crystal dripping process and
Liquid crystal display cells.
Embodiment
Hereinafter, embodiment is enumerated to illustrate the present invention in further detail, but the present invention is not merely defined in these realities
Apply example.
(embodiment 1)
Using planetary stirring machine (THINKY company systems, " あ わ と り Practice Taros "), two rings of curable resin will be used as
Pentadiene phenol aldehyde type epoxy resin (DIC company systems, " EPICLON HP-7200 ") 5 parts by weight, it is used as (methyl) acrylic compounds tree
The parts by weight of bisphenol type epoxy methacrylate 95 of fat, diphenyl (2,4, the 6- front threes as optical free radical polymerization initiator
Epoxide benzoyl) phosphine oxide (BASF Japan company systems, " Lucirin TPO ") 1.5 parts by weight, third as thermal curing agents
Dihydrazi (Japanese Finechem company systems, " MDH ") 1.1 parts by weight, the 2- undecyl imidazoles as curing accelerator
0.2 parts by weight, talcum (Japanese talcum company system, " NANO ACE D-600F ") 10 parts by weight as filler and it is used as silicon
After 3- glycidoxypropyltrime,hoxysilanes (CHISSO company systems, " S510 ") 1.5 parts by weight mixing of alkane coupling agent, enter
One step is mixed using three-roller, thus prepares the sealant for liquid crystal dripping process of embodiment 1.
(embodiment 2~15, comparative example 1~9)
Using each material of the match ratio described in table 1~3, in addition, operate, prepare similarly to Example 1
The sealant for liquid crystal dripping process of embodiment 2~15, comparative example 1~9.
＜ evaluates ＞
Following evaluation has been carried out to the sealant for liquid crystal dripping process obtained in embodiment and comparative example.Result is shown
In table 1~3.
(1) coating
Each sealant for liquid crystal dripping process obtained in each embodiment and each comparative example is filled into the note of distribution
In emitter (Musashi Engineering company systems, " PSY-10E "), deaeration processing is carried out.Then, using distributor (Musashi
Engineering company systems, " SHOTMASTER300 "), to retouch on one in 2 transparent electrode substrates with ito thin film
The mode for drawing rectangular frame is coated with sealant.Then, dripped with liquid crystal dripping device and be coated with TN liquid crystal (CHISSO companies
System, " JC-5001LA ") fine droplet, another transparency carrier of being fitted with vacuum forming apparatus under 5Pa decompression.With gold
Belong to halide lamp and 3000mJ/cm is irradiated to the unit after laminating2Ultraviolet, then, at 120 DEG C heat 60 minutes, thus
Make sealant heat cure, for each sealant, 100 liquid crystal display cells are made respectively.Liquid crystal display obtained by observation
The liquid crystal display cells broken in sealing are set to " ◎ ", by what is broken in sealing by element for the situation of 0
Liquid crystal display cells are that the situation of 1~3 is set to "○", is 4~10 by the liquid crystal display cells broken in sealing
Situation be set to " △ ", the situation that the liquid crystal display cells broken in sealing are more than 11 be set to "×", from
And coating is evaluated.
(2) cementability
Coordinate 1 weight % silica in each sealant for liquid crystal dripping process obtained in embodiment and comparative example
Sept (ponding chemical industrial company system, " SI-H055 "), drops in 2 alkali glass with ito film with small drop and tests
On one in piece (30 × 40mm), and fitted another glass test piece with crosswise thereon, with metal halide lamp pair
Gained laminating thing irradiation 3000mJ/cm2Ultraviolet, then at 120 DEG C heat 60 minutes, thus obtain adhesive test piece.
Tension test (5mm/sec) is carried out in the fixture configured up and down of the adhesive test piece.By obtained measured value (kgf) divided by
Seal coated sections product (cm2) obtained by value be 60kgf/cm2Situation above is evaluated as " ◎ ", will be 40kgf/cm2More than
And less than 60kgf/cm2Situation be evaluated as "○", will be 10kgf/cm2Above and less than 40kgf/cm2Situation be evaluated as
" △ ", by less than 10kgf/cm2Situation be evaluated as "×", so as to be evaluated cementability.
(3) moisture-proof of solidfied material
In smooth mold release film, using coating machine by each liquid crystal dripping process obtained in embodiment and comparative example with close
Envelope agent is applied to 200~300 μm of thickness.Then, metal halide light irradiation 3000mJ/cm is utilized2Ultraviolet after, 120
Heated 60 minutes at DEG C, thus obtain moisture permeability measure film.Utilize the moisture-inhibiting of the water vapor proof barrier packaging material according to JIS Z 0208
The method of test method (agar diffusion method) is spent, moisture permeability test cup, the moisture permeability measure film obtained by installation is made, and put into temperature
In the baking oven for spending 80 DEG C of humidity 90%RH, so as to determine moisture permeability.The value of the moisture permeability of gained is less than 50g/m224 is small
When situation be set to " ◎ ", will be 50g/m224 hours less than 70g/m2The situation of 24 hours is set to "○", will be
70g/m224 hours less than 100g/m2The situation of 24 hours is set to " △ ", will be 100g/m2More than 24 hours
Situation be set to "×", so as to have rated the moisture-proof of solidfied material.
(4) display performance (liquid crystal display cells after being driven after hot and humid lower keeping of liquid crystal display cells
Color spot evaluation)
The sealant for liquid crystal dripping process obtained in each embodiment and comparative example is filled to (military to the syringe of distribution
Hide Engineering company systems, " PSY-10E ") in, carry out deaeration processing.Then, with distributor (Musashi Engineering
Company system, " SHOTMASTER300 "), to describe rectangle on one in 2 transparent electrode substrates with ito thin film
The mode of frame be coated with sealant.Then, dripped coating TN liquid crystal (CHISSO company systems, " JC- with liquid crystal dripping device
5001LA ") fine droplet, another transparency carrier of being fitted with vacuum forming apparatus under 5Pa decompression.Use metal halide
Thing lamp irradiates 3000mJ/cm to the unit after laminating2Ultraviolet, then at 120 DEG C heat 60 minutes, thus make sealant
Heat cure, for each sealant, makes 5 liquid crystal display cells respectively.By the liquid crystal display cells of gained in temperature 80
DEG C, preserve 36 hours in the environment of humidity 90%RH after, implement AC3.5V voltage driving, visually observe semi-tone (original text：
Zhong Inter Tone) sealant periphery.The situation that can't see color spot completely on sealant periphery is evaluated as " ◎ ", is possible to slightly see
Situation to thin color spot is evaluated as "○", there will be and be clearly evaluated as " △ " compared with the situation of heavy colour spot, will be not powered on
In the case of just see that the situation of color spot is evaluated as "×".
Industrial applicability
According to the present invention, it is possible to provide the low liquid crystal dripping process of a kind of excellent in adhesion and solidfied material penetrability is with close
Seal agent.In addition, according to the present invention, it is possible to provide a kind of conductive material up and down being made using the sealant for liquid crystal dripping process
And liquid crystal display cells.
Claims (8)
1. a kind of sealant for liquid crystal dripping process, it is characterised in that be to manufacture liquid crystal display cells using liquid crystal dripping process
When used sealant for liquid crystal dripping process, the sealant for liquid crystal dripping process contains curable resin, free radical
Polymerization initiator and/or thermal curing agents, wherein,
The curable resin contains epoxy resin and (methyl) acrylic resin, and the epoxy resin contains in 1 molecule
Resin with epoxy radicals He (methyl) acryloxy,
The content of the epoxy resin in the parts by weight of curable resin 100 is 5~70 parts by weight, and the epoxy resin
In the content of dicyclopentadiene phenolic type epoxy resin be more than 20 weight %, two rings in the parts by weight of curable resin 100
The content of pentadiene phenol aldehyde type epoxy resin is below 30 parts by weight.
2. sealant for liquid crystal dripping process according to claim 1, it is characterised in that contain curing accelerator.
3. sealant for liquid crystal dripping process according to claim 2, it is characterised in that curing accelerator contains imidazoles system
Curing accelerator and/or mercaptan system curing accelerator.
4. the sealant for liquid crystal dripping process according to claim 1,2 or 3, it is characterised in that (methyl) acrylic compounds
Resin contains dicyclopentadiene phenolic type epoxy (methyl) acrylate.
5. the sealant for liquid crystal dripping process according to claim 1,2 or 3, it is characterised in that contain opacifier.
6. sealant for liquid crystal dripping process according to claim 4, it is characterised in that contain opacifier.
7. conductive material above and below one kind, it is characterised in that contain the liquid crystal dripping process 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 contain the liquid crystal dripping process described in claim 1,2,3,4,5 or 6
With sealant or contain the conductive material up and down described in claim 7.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013123112 | 2013-06-11 | ||
| JP2013-123112 | 2013-06-11 | ||
| PCT/JP2014/064579 WO2014199853A1 (en) | 2013-06-11 | 2014-06-02 | Sealing agent for liquid crystal dropping methods, vertically conducting material, and liquid crystal display element |
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|---|---|
| CN105283803A CN105283803A (en) | 2016-01-27 |
| CN105283803B true CN105283803B (en) | 2017-08-01 |
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| Country | Link |
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| JP (1) | JP5827752B2 (en) |
| KR (1) | KR102215671B1 (en) |
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| CN106796376A (en) * | 2015-05-08 | 2017-05-31 | 积水化学工业株式会社 | Sealing material for liquid crystal display device, upper and lower conductive material and liquid crystal display cells |
| KR102606399B1 (en) * | 2015-05-20 | 2023-11-24 | 세키스이가가쿠 고교가부시키가이샤 | Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element |
| JP6097454B1 (en) * | 2015-09-02 | 2017-03-15 | 積水化学工業株式会社 | Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element |
| TWI707946B (en) * | 2016-01-07 | 2020-10-21 | 日商積水化學工業股份有限公司 | Sealant for liquid crystal display element, vertical conduction material and liquid crystal display element |
| JP6918693B2 (en) * | 2016-01-26 | 2021-08-11 | 積水化学工業株式会社 | Light-shielding sealant for liquid crystal display elements, vertical conductive materials, and liquid crystal display elements |
| KR102426816B1 (en) * | 2016-05-17 | 2022-07-28 | 세키스이가가쿠 고교가부시키가이샤 | Sealing agent for liquid crystal display elements, vertical conduction material, and liquid crystal display element |
| CN108780248A (en) * | 2016-08-24 | 2018-11-09 | 积水化学工业株式会社 | Sealing material for liquid crystal display device, upper and lower conductive material and liquid crystal display element |
| KR20190053134A (en) * | 2016-09-29 | 2019-05-17 | 세키스이가가쿠 고교가부시키가이샤 | A sealing agent for a liquid crystal display element, an upper and lower conductive material, and a liquid crystal display element |
| WO2018110552A1 (en) * | 2016-12-16 | 2018-06-21 | 積水化学工業株式会社 | Polymerizable compound, sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element |
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| CN102640040A (en) * | 2010-08-10 | 2012-08-15 | 积水化学工业株式会社 | Sealant for liquid crystal dropping method |
| CN103026292A (en) * | 2011-04-05 | 2013-04-03 | 积水化学工业株式会社 | Light-shielding sealing agent for liquid crystal display element, top-to-bottom conductive material, and liquid crystal display element |
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| JPH103084A (en) * | 1996-06-18 | 1998-01-06 | Sumitomo Bakelite Co Ltd | Sealing material composition for liquid crystal display element, and liquid crystal display element formed by using the same |
| JP4292611B2 (en) | 1999-01-29 | 2009-07-08 | 住友ベークライト株式会社 | Sealing material composition for liquid crystal display element and liquid crystal display element using the same |
| JP2001064483A (en) * | 1999-08-27 | 2001-03-13 | Sumitomo Bakelite Co Ltd | Sealing material composition for liquid crystal display device |
| 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 |
| EP1405888A1 (en) | 2001-05-16 | 2004-04-07 | Sekisui Chemical Co., Ltd. | Curing resin composition and sealants and end-sealing materials for displays |
| CN103261957B (en) * | 2010-12-09 | 2015-04-29 | 积水化学工业株式会社 | Sealing material for liquid-crystal dropping process, material for vertical conduction, and liquid-crystal display element |
| JP5119374B1 (en) * | 2011-06-28 | 2013-01-16 | 積水化学工業株式会社 | Sealing agent for liquid crystal dropping method, manufacturing method of sealing agent for liquid crystal dropping method, vertical conduction material, and liquid crystal display element |
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2014
- 2014-06-02 WO PCT/JP2014/064579 patent/WO2014199853A1/en active Application Filing
- 2014-06-02 JP JP2014528727A patent/JP5827752B2/en active Active
- 2014-06-02 KR KR1020157031586A patent/KR102215671B1/en active IP Right Grant
- 2014-06-02 CN CN201480032864.XA patent/CN105283803B/en active Active
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|---|---|---|---|---|
| CN102640040A (en) * | 2010-08-10 | 2012-08-15 | 积水化学工业株式会社 | Sealant for liquid crystal dropping method |
| CN103026292A (en) * | 2011-04-05 | 2013-04-03 | 积水化学工业株式会社 | Light-shielding sealing agent for liquid crystal display element, top-to-bottom conductive material, and liquid crystal display element |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5827752B2 (en) | 2015-12-02 |
| TW201506137A (en) | 2015-02-16 |
| JPWO2014199853A1 (en) | 2017-02-23 |
| CN105283803A (en) | 2016-01-27 |
| KR102215671B1 (en) | 2021-02-15 |
| TWI624534B (en) | 2018-05-21 |
| KR20160018480A (en) | 2016-02-17 |
| WO2014199853A1 (en) | 2014-12-18 |
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