CN107615151A - Sealing material for liquid crystal display device, upper and lower conductive material and liquid crystal display cells - Google Patents
Sealing material for liquid crystal display device, upper and lower conductive material and liquid crystal display cells Download PDFInfo
- Publication number
- CN107615151A CN107615151A CN201680030279.5A CN201680030279A CN107615151A CN 107615151 A CN107615151 A CN 107615151A CN 201680030279 A CN201680030279 A CN 201680030279A CN 107615151 A CN107615151 A CN 107615151A
- Authority
- CN
- China
- Prior art keywords
- liquid crystal
- crystal display
- methyl
- mentioned
- display device
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5046—Amines heterocyclic
- C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
- C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Nonlinear Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Mathematical Physics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Sealing Material Composition (AREA)
- Liquid Crystal (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
It is an object of the invention to provide the sealing material for liquid crystal display device that can take into account curability at low temperatures and storage stability.In addition, the present invention also aims to provide the conductive material up and down for using the sealing material for liquid crystal display device to form and liquid crystal display cells.The present invention is a kind of sealing material for liquid crystal display device, it is the sealing material for liquid crystal display device containing curable resin and thermal curing agents, above-mentioned curable resin contains the curable resin with epoxy radicals, above-mentioned thermal curing agents contain the amine addition compound with the structure from epoxy resin and the structure from amines, and the amines for turning into the source of above-mentioned amine addition compound is that the carbon number of alkyl is 1~20 alkyl imidazole.
Description
Technical field
The present invention relates to the sealing material for liquid crystal display device that can take into account curability at low temperatures and storage stability.In addition,
The invention further relates to the conductive material up and down formed using the sealing material for liquid crystal display device and liquid crystal display cells.
Background technology
In recent years, for the manufacture method of the liquid crystal display cells such as liquid crystal display, from the contracting of productive temp time
It is short, using the optimization of amount of liquid crystal from the viewpoint of, contain using such use disclosed in patent document 1, patent document 2
There is the photo-thermal of curable resin, Photoepolymerizationinitiater initiater and thermal curing agents and be referred to as technique of dripping with the sealant of curing type
Mode.
In technique of dripping, first, formed on a substrate in 2 electroded substrates using distribution rectangular
Seal pattern.Then, the tiny droplets of liquid crystal are added drop-wise in the sealing frame of substrate in the state of sealant is uncured, and true
Overlapping another substrate under sky, the light such as ultraviolet are irradiated to sealing, carry out precuring.Afterwards, heat and carry out main solidification, make
Liquid crystal display cells.The main flow of the technique as the manufacture method of liquid crystal display cells of dripping now.
From energy-saving, liquid crystal stability from the viewpoint of, it is expected to make above-mentioned sealing using the heating of low temperature and short time
Agent heat cure.As the method for making sealant cures using the heating of low temperature and short time, used fusing point low in the past
Thermal curing agents, curing accelerator.It is if attached even in room temperature however, using low-melting thermal curing agents or curing accelerator
Closely also easily cause reaction, therefore the problem of storage stability reduction of sealant be present.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2001-133794 publications
Patent document 2：International Publication No. 02/092718
The content of the invention
The invention problem to be solved
It is an object of the invention to provide can take into account the used for liquid crystal display element close of curability at low temperatures and storage stability
Seal agent.In addition, the present invention also aims to provide the conductive material up and down for using the sealing material for liquid crystal display device to form
And liquid crystal display cells.
Means for solving the problems
The present invention is a kind of sealing material for liquid crystal display device, and it is the liquid crystal containing curable resin and thermal curing agents
Show element sealant, above-mentioned curable resin contains the curable resin with epoxy radicals, and above-mentioned thermal curing agents, which contain, to be had
The amine addition compound of structure from epoxy resin and the structure from amines, turn into coming for above-mentioned amine addition compound
The amines in source is that the carbon number of alkyl is 1~20 alkyl imidazole.
The present invention is described in detail below.
The inventors discovered that：By using the alkyl imidazole of the alkyl chain with length-specific and the adduct of epoxy resin
As thermal curing agents, so as to obtain that the sealing material for liquid crystal display device of curability at low temperatures and storage stability can be taken into account, with
It is of the invention to completing.
The sealing material for liquid crystal display device of the present invention contains thermal curing agents.
Above-mentioned thermal curing agents contain with the structure from epoxy resin and from the structure of amines and the amine compounds
Thing is the amine addition compound of alkyl imidazole described later.By using such a amine addition compound as above-mentioned thermal curing agents, from
And excellent storage stability can be both maintained to improve the curability under low temperature.
As the epoxy resin in the source as above-mentioned amine addition compound, for example, can use with as with epoxy radicals
Curable resin and the same epoxy resin of epoxy resin described later.Wherein, it is however preferred to have the epoxy resin of aromatic rings.It is logical
The epoxy resin for crossing the source for becoming above-mentioned amine addition compound has aromatic rings, so as to further improve the liquid of gained
The storage stability of crystal display element sealant.Epoxy resin as the source of above-mentioned amine addition compound more preferably selects
From at least one kind of in bisphenol A type epoxy resin, bisphenol f type epoxy resin and bisphenol E-type epoxy resin.
Amines as the source of above-mentioned amine addition compound is that the carbon number of alkyl is 1~20 alkyl imidazole.
The alkyl imidazole that carbon number as abovementioned alkyl is 1~20, the preferably carbon number of alkyl are 1~2 alkyl imidazole, more
It is preferred that 2-methylimidazole.
As above-mentioned amine addition compound, it is more suitable for using the compound and/or following formula shown in following formula (1-1)
Compound shown in (1-2).
Containing curable resin and thermal curing agents, above-mentioned curable resin contain the curable resin with epoxy radicals and
Above-mentioned thermal curing agents contain the liquid crystal of the compound shown in compound and/or following formula (1-2) shown in following formula (1-1)
Show that element with sealant is also one of present invention.
[changing 1]
In formula (1-1) and formula (1-2), R1It is the alkyl that carbon number is 1~20, in formula (1-1), R2And R3For hydrogen or methyl
And can be identical or different respectively.
In addition, above-mentioned thermal curing agents are preferably comprised selected from the compound shown in following formula (2-1), following formula (2-2) institute
The conduct of at least one of the compound shown in compound and following formula (2-4) shown in the compound shown, following formula (2-3)
The compound shown in compound and/or above-mentioned formula (1-2) shown in above-mentioned formula (1-1).
[changing 2]
The preferable upper limit of the average grain diameter of above-mentioned amine addition compound is 3 μm.By making above-mentioned amine addition compound
Average grain diameter is less than 3 μm, so as to suppress the de-or gap of the liquid crystal display cells of gained.Above-mentioned amine addition compound
There is no particular restriction for the preferable lower limit of average grain diameter, and substantial lower limit is 0.1 μm.
It is explained, in the case of using amine addition compound of the commercially available average grain diameter more than 3 μm, by carrying out powder
The processing of broken or classification etc., so as to so that average grain diameter is less than 3 μm.
It is explained, in this manual, the average grain diameter and maximum particle diameter described later of above-mentioned amine addition compound refer to：
Amine addition compound before being coupled to sealant is measured using laser diffraction formula particle size distribution device and obtained
Value.As above-mentioned laser diffraction formula particle size distribution device, (the Malvern companies of Mastersizer 2000 can be used
System) etc..
The preferable upper limit of the maximum particle diameter of above-mentioned amine addition compound is 5.0 μm.By making above-mentioned amine addition compound
Maximum particle diameter be less than 5.0 μm so that the gap retentivity of the liquid crystal display cells of gained is more excellent.Above-mentioned amine adduction
The preferred upper limit of the maximum particle diameter of compound is 4.5 μm.The preferable lower limit of the maximum particle diameter of above-mentioned amine addition compound is simultaneously
It is not particularly limited, substantial lower limit is 0.1 μm.
For above-mentioned amine addition compound, add in the amine determined using above-mentioned laser diffraction formula particle size distribution device
In the size distribution of polymerisable compounds, the content ratio of the particle of less than 3.0 μm of particle diameter be preferably in terms of volume frequency 99% with
On.More than 99% is calculated as with volume frequency by the content ratio of the particle for the particle diameter for making less than 3.0 μm, so as to the liquid crystal of gained
The gap retentivity of display element is more excellent.The content ratio of the particle of less than 3.0 μm of particle diameter is most preferably 100%.
Relative to the above-mentioned parts by weight of curable resin 100, the preferable lower limit of the content of above-mentioned amine addition compound is 0.3
Parts by weight, the preferable upper limit are 15 parts by weight.By making the content of above-mentioned amine addition compound be the scope, so as to the liquid of gained
The curability at low temperatures of crystal display element sealant is more excellent, and the effect for suppressing liquid crystal pollution is more excellent.Above-mentioned amine adduction
The preferred lower limit of the content of compound is 0.4 parts by weight, the preferred upper limit is 12 parts by weight, further preferred lower limit
It is 10 parts by weight for 0.5 parts by weight, the further preferred upper limit.
Above-mentioned thermal curing agents can contain other thermal curing agents in addition to above-mentioned amine addition compound.
As other above-mentioned thermal curing agents, such as hydrazides system curing agent, imidazoles system curing agent, polyhydric phenols system can be enumerated and consolidated
Agent, acid anhydrides system curing agent etc..Wherein, it is adapted to use hydrazides system curing agent.
As above-mentioned hydrazides system curing agent, the double (acyls in Hydrazinocarbonyl ethyl -5- isopropyl second of such as 1,3- can be enumerated
Urea) (original text：1,3- PVC ス (ヒ De ラ ジ ノ カ Le ボ エ チ Le -5- イ ソ プ ロ ピ Le ヒ ダ Application ト イ Application)), the last of the ten Heavenly stems two
Acid dihydrazide, isophthalic dihydrazide, adipic dihydrazide, acid dihydrazide etc., as commercially available product, it can enumerate
Such as：AMICURE VDH, AMICURE UDH (being Ajinomoto Fine-Techno company systems), SDH, IDH, ADH are (
Wei great mound chemical company system), MDH (Japanese FINECHEM company systems) etc..
In the case of containing other above-mentioned thermal curing agents, relative to the above-mentioned parts by weight of curable resin 100, above-mentioned heat
The preferable lower limit of the overall content of curing agent is 1 parts by weight, the preferable upper limit is 50 parts by weight.By making above-mentioned thermal curing agents
Overall content is the scope, becomes more excellent so as to the Thermocurable and coating of the sealing material for liquid crystal display device of gained
It is different.The preferred upper limit of the overall content of above-mentioned thermal curing agents is 30 parts by weight.
The sealing material for liquid crystal display device of the present invention contains curable resin.
Above-mentioned curable resin contains the curable resin with epoxy radicals.
As the above-mentioned curable resin with epoxy radicals, 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 '-diallyl bisphenol type epoxy resin, A Hydrogenated Bisphenol A type
Epoxy resin, expoxy propane addition bisphenol A type 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, phenol novolak type epoxy
Resin, orthoresol phenol aldehyde type epoxy resin, dicyclopentadiene phenolic type epoxy resin, biphenyl phenol aldehyde type epoxy resin, naphthols phenol
Aldehyde type epoxy resin, glycidyl amine type epoxy resin, alkyl polyols type epoxy resin, modified rubber type epoxy resin, contracting
Water glyceride compounds etc..
As product commercially available in above-mentioned bisphenol A type epoxy resin, can enumerate such as jER828, jER828EL,
JER1004 (being Mitsubishi Chemical Ind's system), Epiclon850 (DIC company systems) etc..
As commercially available product in above-mentioned bisphenol f type epoxy resin, can enumerate such as jER806, jER4004 (is
Mitsubishi Chemical Ind's system) etc..
As product commercially available in above-mentioned bisphenol E-type epoxy resin, such as EPOX-MK R710, EPOX- can be enumerated
MK R1710 (being PRINTEQ company systems) etc..
As commercially available product in above-mentioned bisphenol-s epoxy resin, such as Epiclon EXA1514 (DIC can be enumerated
Company system) etc..
As commercially available product in above-mentioned 2,2 '-diallyl bisphenol type epoxy resin, such as RE- can be enumerated
810NM (Japanese chemical drug company system) etc..
As commercially available product in above-mentioned A Hydrogenated Bisphenol A type epoxy resin, such as Epiclon EXA7015 can be enumerated
(DIC company systems) etc..
As commercially available product in above-mentioned expoxy propane addition bisphenol A type epoxy resin, such as EP- can be enumerated
4000S (ADEKA company systems) etc..
As commercially available product in above-mentioned resorcinol type epoxy resin, such as EX-201 (Nagase can be enumerated
ChemteX company systems) etc..
As commercially available product in above-mentioned biphenyl type epoxy resin, such as jER YX-4000H (Mitsubishis can be enumerated
Learn company system) etc..
As commercially available product in above-mentioned thioether-type epoxy resin, can enumerating such as YSLV-50TE, (Nippon Steel lives
Aurification company system) etc..
As commercially available product in above-mentioned diphenyl ether type epoxy, such as YSLV-80DE (new days can be enumerated
Iron lives aurification company system) etc..
As commercially available product in above-mentioned dicyclopentadiene-type epoxy resin, such as EP-4088S can be enumerated
(ADEKA company systems) etc..
As commercially available product in above-mentioned naphthalene type epoxy resin, such as Epiclon HP4032, Epiclon can be enumerated
EXA-4700 (being DIC company systems) etc..
As commercially available product in above-mentioned phenol novolak type epoxy, such as Epiclon N-770 can be enumerated
(DIC company systems) etc..
As commercially available product in above-mentioned orthoresol phenol aldehyde type epoxy resin, such as Epiclon N- can be enumerated
670-EXP-S (DIC company systems) etc..
As commercially available product in above-mentioned dicyclopentadiene phenolic type epoxy resin, such as Epiclon can be enumerated
HP7200 (DIC company systems) etc..
As commercially available product in above-mentioned biphenyl phenol aldehyde type epoxy resin, such as NC-3000P (Japanizations can be enumerated
Medicine company system) etc..
As commercially available product in above-mentioned naphthol novolac type epoxy resin, such as ESN-165S (Nippon Steel can be enumerated
Firmly aurification company system) etc..
As commercially available product in above-mentioned glycidyl amine type epoxy resin, such as jER630 (Mitsubishis can be enumerated
Learn company system), Epiclon 430 (DIC company systems), TETRAD-X (gas chemical company of Mitsubishi system) etc..
As commercially available product in abovementioned alkyl polyol type epoxy resin, such as ZX-1542 (new days can be enumerated
Iron lives aurification company system), Epiclon 726 (DIC company systems), Epolite 80MFA (chemical company of common prosperity society system),
Denacol EX-611 (Nagase ChemteX company systems) etc..
As commercially available product in above-mentioned modified rubber type epoxy resin, such as YR-450, YR-207 can be enumerated
(being that aurification company system is lived by Nippon Steel), Epolide PB (Daicel company system) etc..
As commercially available product in above-mentioned epihydric alcohol ester compound, such as Denacol EX-147 can be enumerated
(Nagase ChemteX company systems) etc..
As other commercially available products in above-mentioned epoxide, can enumerate for example：YH-300, YDC-1312,
YSLV-80XY, YSLV-90CR (being that aurification company system is lived by Nippon Steel), XAC4151 (Asahi Kasei Corporation's system),
JER1031, jER1032 (being Mitsubishi Chemical Ind's system), EXA-7120 (DIC company systems), TEPIC (Nissan Chemical companies
System) etc..
The above-mentioned curable resin with epoxy radicals can be part (methyl) acrylic modified epoxy resin.Above-mentioned part
(methyl) acrylic modified epoxy resin refers in 1 molecule respectively with the epoxy radicals of more than 1 and (methyl) of more than 1
The compound of acryloyl group, such as a part for the epoxide for making to have in 1 molecule more than 2 epoxy radicals can be passed through
Epoxy radicals obtains with (methyl) propylene acid reaction.
It is explained, in this manual, above-mentioned " (methyl) acrylic acid " refers to acrylic or methacrylic acid, above-mentioned
" (methyl) acryloyl group " refers to acryloyl group or methylacryloyl.
As commercially available product in above-mentioned part (methyl) acrylic modified epoxy resin, can enumerate for example
UVACURE1561 (DAICEL-ALLNEX company systems) etc..
The content of the above-mentioned curable resin with epoxy radicals in the above-mentioned parts by weight of curable resin 100 it is preferable under
It is limited to 1 parts by weight, the preferable upper limit is 100 parts by weight.It is somebody's turn to do by making the content of the above-mentioned curable resin with epoxy radicals
Scope, so as to which the cementability of the sealing material for liquid crystal display device of gained is more excellent.The above-mentioned curable resin with epoxy radicals
The preferred lower limit of content be 2 parts by weight.
Above-mentioned curable resin can contain except it is above-mentioned with the curable resin of epoxy radicals in addition to other curability
Resin.As above-mentioned other curable resins, preferably (methyl) acyclic compound.
As above-mentioned (methyl) acyclic compound, can enumerate for example：Pass through the compound for making there is hydroxyl and (methyl)
(methyl) acrylate compounds obtained by propylene acid reaction, by making (methyl) acrylic acid and obtained by epoxide reacts
Epoxy (methyl) acrylate, by (methyl) acrylic acid derivative and isocyanate compound that make there is hydroxyl react and
Carbamate (methyl) acrylate etc..Wherein, more preferably epoxy (methyl) acrylate.It is in addition, high from reactivity
Aspect is set out, and above-mentioned (methyl) acyclic compound preferably has the chemical combination of more than 2 (methyl) acryloyl groups in the molecule
Thing.
As (methyl) acrylate compounds of simple function in above-mentioned (methyl) acrylate compounds, example can be enumerated
Such as：(methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) n-butyl acrylate, (first
Base) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) acrylic acid is just pungent
Ester, (methyl) Isooctyl acrylate monomer, the different nonyl ester of (methyl) acrylic acid, (methyl) isodecyl acrylate, (methyl) lauryl
Ester, the different myristin of (methyl) acrylic acid, (methyl) stearyl acrylate ester, (methyl) acrylic acid 2- hydroxy methacrylates, (methyl) third
Olefin(e) acid 2- hydroxy propyl esters, (methyl) acrylic acid 2- hydroxybutyls, (methyl) acrylic acid 4- hydroxybutyls, (methyl) acrylic acid
Cyclohexyl, (methyl) isobornyl acrylate, (methyl) acrylic acid dicyclopentenyloxyethyl methacrylate, (methyl) benzyl acrylate, (methyl) third
Olefin(e) acid 2- methoxy acrylates, (methyl) acrylic acid 2- ethoxy ethyl esters, (methyl) acrylic acid 2- butoxyethyls, (methyl)
Acrylic acid 2- phenoxy ethyls, methoxy ethyl glycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate,
Phenoxy group diethylene glycol (methyl) acrylate, phenoxy group polyethylene glycol (methyl) acrylate, (methyl) acrylic acid tetrahydrochysene chaff
Ester, ethyl carbitol (methyl) acrylate, (methyl) acrylic acid 2,2,2- trifluoro ethyl esters, (methyl) acrylic acid 2,2,3,3-
Tetrafluoro propyl ester, (methyl) acrylic acid 1H, 1H, 5H- octafluoro pentyl ester, acid imide (methyl) acrylate, (methyl) acrylic acid diformazan
Base amino ethyl ester, (methyl) acrylic acid diethylamino ethyl ester, 2- (methyl) acryloyloxyethyl succinate, 2- (first
Base) acryloyl-oxyethyl hexahydrophthalic acid ester, 2- (methyl) acryloyl-oxyethyl 2- hydroxypropyl O-phthalics
Acid esters, 2- (methyl) acryloyl-oxyethyl phosphate, (methyl) glycidyl acrylate etc..
In addition, (methyl) acrylate compounds as 2 functions in above-mentioned (methyl) acrylate compounds, can be enumerated
Such as：1,3 butylene glycol two (methyl) acrylate, 1,4- butanediols two (methyl) acrylate, (first of 1,6-HD two
Base) acrylate, 1,9- nonanediols two (methyl) acrylate, 1,10- decanediols two (methyl) acrylate, ethylene glycol two
(methyl) acrylate, diethylene glycol two (methyl) acrylate, tetraethylene glycol two (methyl) acrylate, polyethylene glycol two
(methyl) acrylate, (methyl) acrylate of 2- normal-butyl -2- ethyl -1,3- the propane diols two, (first of DPG two
Base) acrylate, tripropylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, (the first of neopentyl glycol two
Base) acrylate, ethyleneoxide addition bisphenol-A two (methyl) acrylate, expoxy propane addition bisphenol-A two (methyl) acrylic acid
Ester, ethyleneoxide addition Bisphenol F two (methyl) acrylate, dihydroxymethyl bicyclopentadiene two (methyl) acrylate, epoxy
Oxide-modified isocyanuric acid two (methyl) acrylate, 2- hydroxyls -3- (methyl) acryloxypropyl (methyl) acrylic acid
Ester, carbonate diol two (methyl) acrylate, PTMEG two (methyl) acrylate, polyester-diol two (methyl) acrylic acid
Ester, polycaprolactone glycol two (methyl) acrylate, polybutadiene diol two (methyl) acrylate etc..
In addition, as (methyl) acrylate compounds more than 3 functions in above-mentioned (methyl) acrylate compounds, can
Enumerate for example：Trimethylolpropane tris (methyl) acrylate, ethyleneoxide addition trimethylolpropane tris (methyl) acrylic acid
Ester, expoxy propane addition trimethylolpropane tris (methyl) acrylate, caprolactone modification trimethylolpropane tris (methyl) third
Olefin(e) acid ester, ethyleneoxide addition isocyanuric acid three (methyl) acrylate, glycerine three (methyl) acrylate, expoxy propane addition
Glycerine three (methyl) acrylate, pentaerythrite three (methyl) acrylate, three (methyl) acryloyl-oxyethyl phosphates, two
(trihydroxy methyl) propane four (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) third
Olefin(e) acid ester, dipentaerythritol six (methyl) acrylate etc..
As above-mentioned epoxy (methyl) acrylate, can enumerate for example：Conventionally in the presence of base catalyst
Under make epoxy (methyl) acrylate etc. obtained by epoxide and (methyl) propylene acid reaction.
As the epoxide as the raw material for synthesizing above-mentioned epoxy (methyl) acrylate, can use and work
For the same epoxide of the epoxide cited by the above-mentioned curable resin with epoxy radicals.
As product commercially available in above-mentioned epoxy (methyl) acrylate, can enumerate for example：EBECRYL860、
EBECRYL3200、EBECRYL3201、EBECRYL3412、EBECRYL3600、EBECRYL3700、EBECRYL3701、
EBECRYL3702, EBECRYL3703, EBECRYL3800, EBECRYL6040, EBECRYLRDX63182 (are DAICEL-
ALLNEX company systems)；EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 are (in being new
Chemical industrial company of village system)；EPOXY ESTER M-600A, EPOXY ESTER 40EM, EPOXY ESTER 70PA, EPOXY
ESTER 200PA、EPOXY ESTER80MFA、EPOXY ESTER 3002M、EPOXY ESTER 3002A、EPOXY ESTER
1600A、EPOXY ESTER 3000M、EPOXY ESTER3000A、EPOXY ESTER 200EA、EPOXY ESTER 400EA
(being chemical company of common prosperity society system)；Denacol ACRYLATE DA-141, Denacol ACRYLATE DA-314,
Denacol ACRYLATE DA-911 (being Nagase ChemteX company systems) etc..
Make to have (methyl) acrylic acid derivative of hydroxyl and carbamic acid obtained by the reaction of above-mentioned isocyanate compound
Ester (methyl) acrylate, for example, can by make the equivalent of isocyanate compound 1 with 2 NCOs with hydroxyl
The equivalent of (methyl) acrylic acid derivative 2 of base reacts and obtained in the presence of the tin based compound of catalytic amount.
As the isocyanate compound of the raw material as above-mentioned carbamate (methyl) acrylate, example can be enumerated
Such as：IPDI, 2,4 toluene diisocyanate, 2,6- toluene di-isocyanate(TDI)s, the isocyanide of hexa-methylene two
Acid esters, trimethyl hexamethylene diisocyanate, diphenyl methane -4,4 '-diisocyanate (MDI), hydrogenation MDI, polymerization
MDI, 1,5- naphthalene diisocyanate, norbornene alkyl diisocyanate, tolidine diisocyanate, the isocyanide of phenylenedimethylidyne two
Acid esters (XDI), hydrogenation XDI, lysine diisocyanate, triphenylmethane triisocyanate, three (isocyanate phenyls) are thio
Phosphate, tetramethylxylylene diisocyanate, 1,6,11- hendecane triisocyanates etc..
In addition, the isocyanate compound as the raw material as above-mentioned carbamate (methyl) acrylate, such as
Ethylene glycol, propane diols, glycerine, sorbierite, trimethylolpropane, carbonate diol, PTMEG, polyester two can also be used
The polyalcohols such as alcohol, polycaprolactone glycol and the isocyanates chemical combination after chain elongation obtained by excessive isocyanate compound reaction
Thing.
(methyl) acrylic acid with hydroxyl as the raw material as above-mentioned carbamate (methyl) acrylate spreads out
Biology, it can enumerate for example：(methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 2- hydroxy propyl esters, (methyl) acrylic acid
Single (methyl) hydroxyalkyl acrylates such as 2- hydroxybutyls, (methyl) acrylic acid 4- hydroxybutyls；Ethylene glycol, propane diols,
List (methyl) acrylate of the dihydric alcohols such as 1,3- propane diols, 1,3 butylene glycol, 1,4- butanediols, polyethylene glycol；Three hydroxyl first
List (methyl) acrylate of the trihydroxylic alcohols such as base ethane, trimethylolpropane, glycerine or two (methyl) acrylate；Bisphenol A-type
The epoxies such as epoxy acrylate (methyl) acrylate etc..
As product commercially available in above-mentioned carbamate (methyl) acrylate, can enumerate for example：M-1100, M-
1200th, M-1210, M-1600 (being East Asia Synesis Company system)；EBECRYL210、EBECRYL220、EBECRYL230、
EBECRYL270、EBECRYL1290、EBECRYL2220、EBECRYL4827、EBECRYL4842、EBECRYL4858、
EBECRYL5129、EBECRYL6700、EBECRYL8402、EBECRYL8803、EBECRYL8804、EBECRYL8807、
EBECRYL9260 (being DAICEL ALLNEX company systems)；Art Resin UN-330, Art ResinSH-500B, Art
ResinUN-1200TPK, Art ResinUN-1255, Art ResinUN-3320HB, Art ResinUN-7100, Art
ResinUN-9000A, Art ResinUN-9000H (being Gen Shang industrial groups system)；U-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 (being chemical industrial company of Xin Zhong villages system)；AH-
600th, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA-306T (are common prosperity society
Learn company system) etc..
Contain above-mentioned part (methyl) acrylic modified epoxy resin, above-mentioned (methyl) acrylic acid in above-mentioned curable resin
In the case of compound, the ratio between epoxy radicals and (methyl) acryloyl group in above-mentioned curable resin are preferably 30：70~95：5.
By making the ratio between epoxy radicals and (methyl) acryloyl group be the scope, so as to further improve the liquid crystal display cells of gained
The display performance of the liquid crystal display cells of sealing material for liquid crystal display device obtained by the cementability of sealant and use.
From suppress liquid crystal pollution from the viewpoint of, above-mentioned curable resin preferably with-OH bases ,-NH- bases ,-
NH2The curable resin of the hydrogen bond unit such as base.
The sealing material for liquid crystal display device of the present invention can contain radical polymerization initiator.
As above-mentioned radical polymerization initiator, hot radical polymerization initiator, optical free radical polymerization can be used to trigger
Agent.
As above-mentioned hot radical polymerization initiator, can enumerate such as comprising azo-compound, organic peroxide
Hot radical polymerization initiator.Wherein, from the viewpoint of liquid crystal pollution is suppressed, the initiator of azo-compound is preferably comprised
(below also referred to as " azo initiator "), the initiator more preferably comprising polymeric azo compound (are also referred to as " macromolecule below
Azo initiator ").
It is explained, in this manual, above-mentioned " polymeric azo compound " refers to：With azo group and utilization heat
Generation can make compound free radical, that number-average molecular weight is more than 300 that (methyl) acryloxy solidifies.
The preferable lower limit of the number-average molecular weight of above-mentioned polymeric azo initiator is 1000, the preferable upper limit is 300,000.
It is more than 1000 by making the number-average molecular weight of above-mentioned polymeric azo initiator, so as to suppress liquid crystal pollution.By making
The number-average molecular weight of above-mentioned polymeric azo initiator is the scope, so as to prevent the harmful effect to liquid crystal, and can
To be more easily mixed into curable resin.The preferred lower limit of the number-average molecular weight of above-mentioned polymeric azo initiator is
5000th, the preferred upper limit is 100,000, and further preferred lower limit is 10,000, the further preferred upper limit is 90,000.
It is explained, in this manual, above-mentioned number-average molecular weight is to be measured using gel permeation chromatography (GPC)
And the value for converting to try to achieve by polystyrene.During as the number-average molecular weight to be converted using GPC measure based on polystyrene
Chromatographic column, it can enumerate such as Shodex LF-804 (Showa electrician company system).
As above-mentioned polymeric azo initiator, can enumerate for example：Be bonded by azo group multiple polyalkylene oxides,
The polymeric azo initiator of the structure of the units such as dimethyl silicone polymer.
As the above-mentioned structure for having and the units such as multiple polyalkylene oxides, dimethyl silicone polymer being bonded by azo group
Polymeric azo initiator, preferably the polymeric azo initiator with PEO structure.As such a polymeric azo
Initiator, can enumerate such as 4, and the condensation polymer of 4 '-azo double (4- cyanopentanoic acids) and PAG, 4,4 '-azo is double
(4- cyanopentanoic acids) specifically, can be enumerated for example with having condensation polymer of dimethyl silicone polymer of terminal amino group etc.
VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 (being and Wako Pure Chemical Industries company system) etc..
In addition, the example as the azo initiator in addition to polymeric azo initiator, can enumerate such as V-65, V-
501 (being and Wako Pure Chemical Industries company system) etc..
As above-mentioned organic peroxide, such as ketone peroxide, ketal peroxide, hydrogen peroxide, dialkyl group mistake can be enumerated
Oxide, peroxy esters, diacyl peroxide, peroxy dicarbonate etc..
Relative to the above-mentioned parts by weight of curable resin 100, the content of above-mentioned hot radical polymerization initiator it is preferable under
It is limited to 0.05 parts by weight, the preferable upper limit is 10 parts by weight.By making the content of above-mentioned hot radical polymerization initiator be 0.05
It is more than parts by weight, more excellent so as to the Thermocurable of gained sealing material for liquid crystal display device.By gathering above-mentioned hot radical
The content for closing initiator is below 10 parts by weight, so as to the effect of the suppression liquid crystal pollution of gained sealing material for liquid crystal display device
It is more excellent.The preferred lower limit of the content of above-mentioned hot radical polymerization initiator is 0.1 parts by weight, the preferred upper limit is 5
Parts by weight.
As above-mentioned optical free radical polymerization initiator, can enumerate for example：Benzophenone based compound, acetophenone system chemical combination
Thing, acylphosphine oxide based compound, titanocenes based compound, oxime ester based compound, benzoin ether based compound, benzil, thiophene
Ton ketone etc..
As institute commercially available prod in above-mentioned optical free radical polymerization initiator, can enumerate for example：IRGACURE184、
IRGACURE369、IRGACURE379、IRGACURE651、IRGACURE819、IRGACURE907、IRGACURE2959、
IRGACURE OXE01, IRGACURE OXE02, Lucirin TPO (being BASF AG's system)；Benzoin methylether, benzoin second
Ether, benzoin iso-propylether (being Tokyo chemical conversion industry company system) etc..
Relative to the above-mentioned parts by weight of curable resin 100, the content of above-mentioned optical free radical polymerization initiator it is preferable under
It is limited to 0.1 parts by weight, the preferable upper limit is 10 parts by weight.By making the content of above-mentioned optical free radical polymerization initiator be 0.1 weight
Measure more than part, so as to which the photo-curable of the sealing material for liquid crystal display device of gained is more excellent.By gathering above-mentioned optical free radical
The content for closing initiator is more than 10 parts by weight, so as to which the weatherability of the sealing material for liquid crystal display device of gained is more excellent.On
The preferred lower limit for stating the content of optical free radical polymerization initiator is 0.2 parts by weight, the preferred upper limit is 8 parts by weight.
The sealing material for liquid crystal display device of the present invention can be viscous based on stress dispersion effect for viscosity, improvement is improved
Connecing property, improve linear expansivity, further improve the purpose of moisture-proof of solidfied material and contain filler.
As above-mentioned filler, can enumerate for example：Talcum, asbestos, silica, diatomite, terre verte, bentonite, carbonic acid
Calcium, magnesium carbonate, aluminum oxide, montmorillonite, zinc oxide, iron oxide, magnesia, tin oxide, titanium oxide, magnesium hydroxide, aluminium hydroxide,
The inorganic fillers such as bead, silicon nitride, barium sulfate, gypsum, calcium silicates, sericite, atlapulgite, aluminium nitride；Polyester micropartical,
Polyurethane particulate, polyvinyl particulate, acrylic polymer particulate, core-shell acrylic-resin copolymer particle etc. are organic to be filled out
Fill agent etc..These fillers may be used alone, can also be used in combination two or more.
The preferable lower limit of the content of above-mentioned filler in the parts by weight of sealing material for liquid crystal display device 100 of the present invention
It is 70 parts by weight for 10 parts by weight, the preferable upper limit.By making the content of above-mentioned filler to be more than 10 parts by weight, so as to
Further improving improves cementability and other effects.By making the content of above-mentioned filler be below 70 parts by weight, so as to the liquid of gained
The coating of crystal display element sealant is more excellent.The preferred lower limit of the content of above-mentioned filler is 20 parts by weight, more
The preferable upper limit is 60 parts by weight.
The sealing material for liquid crystal display device of the present invention can contain silane coupler.Above-mentioned silane coupler mainly has
As for by the effect of the bonding additives of the good bonding such as sealant and substrate.
As above-mentioned silane coupler, excellent effect from the cementability for making raising and substrate etc., can by with solidification
Property resin be chemically bonded to suppress that curable resin flows out into liquid crystal in terms of set out, be adapted to use such as N- benzene
Base -3- TSL 8330s, 3- TSL 8330s, 3-mercaptopropyi trimethoxy silane,
3- glycidoxypropyltrime,hoxysilanes, 3- isocyanates propyl trimethoxy silicanes etc..These silane couplers were both
It may be used alone, can also be used in combination two or more.
The present invention the parts by weight of sealing material for liquid crystal display device 100 in above-mentioned silane coupler content it is preferable
Lower limit is 0.1 parts by weight, the preferable upper limit is 20 parts by weight.By make the content of above-mentioned silane coupler for 0.1 parts by weight with
On, so as to further improve the cementability with substrate etc..By make the content of above-mentioned silane coupler for 20 parts by weight with
Under, the effect for suppressing liquid crystal pollution so as to gained sealing material for liquid crystal display device is more excellent.The content of above-mentioned silane coupler
Preferred lower limit be 0.5 parts by weight, the preferred upper limit be 10 parts by weight.
The sealing material for liquid crystal display device of the present invention can further contain the reaction for being used for adjusting viscosity as needed
Property diluent, for adjusting the polymer beads of panel gap part, 3- rubigan -1,1- dimethyl ureas, isocyanide at equal intervals
Urea acid (original text：イ ソ シ ア ヌ Le カ Le ボ Application acid) etc. curing accelerator, defoamer, levelling agent, polymerization inhibitor, other coupling agents
Deng additive.
As the method for the sealing material for liquid crystal display device of the manufacture present invention, can enumerate for example：Using homogenous disperse machine,
The mixers such as homogeneous mixer, universal mixer, planetary-type mixer, kneader, three-roller are by curable resin, thermal curing agents
Method mixed with filler, the additive such as silane coupler being added as needed on etc..
By coordinating electrically conductive microparticle in the sealing material for liquid crystal display device of the present invention, led up and down so as to manufacture
Logical material.The conductive material up and down of such a sealing material for liquid crystal display device containing the present invention and electrically conductive microparticle is also this hair
It is one of bright.
Above-mentioned electrically conductive microparticle is not particularly limited, can use metal ball, on the surface of resin particle formed with conduction
Electrically conductive microparticle of metal level etc..Wherein, in electrically conductive microparticle of the surface of resin particle formed with conductive metal layer because of resin
The excellent elasticity of particulate and the ground such as transparency carrier can not be damaged and be conductively connected, therefore be suitable.
The liquid crystal display formed using the sealing material for liquid crystal display device of the present invention or the conductive material up and down of the present invention
Element is also one of present invention.
As the method for the liquid crystal display cells of the manufacture present invention, it is adapted to use liquid crystal dripping process.Specifically, can arrange
The method that citing such as has following process：Pass through silk screen on one of 2 transparency carriers with electrodes such as ito thin films
The process that printing, distributor coating etc. make the seal pattern of the sealing material for liquid crystal display device formation frame-shaped of the present invention；Close
The process for sealing the tiny droplets, under vacuo another overlapping substrate of the whole face dropwise addition coating of liquid crystalline of inframe of pattern；To seal pattern
The light such as partial illumination ultraviolet and make the process of sealant precuring；And the sealant after precuring is heated and makes it
The process of main solidification.
Invention effect
According to the present invention it is possible to provide the sealing used for liquid crystal display element that can take into account curability at low temperatures and storage stability
Agent.In addition, according to the present invention it is possible to provide the conductive material up and down formed using the sealing material for liquid crystal display device and liquid crystal
Display element.
Embodiment
Being exemplified below embodiment, the present invention will be described in more detail, but the present invention is not limited to these implementations
Example.
(amine addition compound A manufacture)
It is 1 by mixing ratio：1 n-butanol/toluene mixed solution 300mL puts into three-necked flask, then puts into bisphenol A-type
Epoxy resin (Mitsubishi Chemical Ind's system, " jER828 ") 38.0 parts by weight and 2-methylimidazole (Tokyo chemical conversion industry company system)
4.1 parts by weight.After carrying out 4 hours heating stirrings at 65 DEG C, solvent removing and vacuum drying are carried out, obtains having and comes from bis-phenol
The amine addition compound A of the structure of A type epoxy resin and the structure from 2-methylimidazole.
The amine addition compound A of gained is carried out1H-NMR,13C-NMR and IR measure, is thereby confirmed that as above-mentioned formula (2-
1) compound shown in.
(amine addition compound B manufacture)
It is 1 by mixing ratio：1 n-butanol/toluene mixed solution 300mL puts into three-necked flask, then puts into aliphatic
Epoxy resin (aurification company system, " YH-300 " live in Nippon Steel) 30.0 parts by weight and 2-methylimidazole (Tokyo chemical conversion industry
Company system) 4.1 parts by weight.After carrying out 4 hours heating stirrings at 65 DEG C, solvent removing and vacuum drying are carried out, is had
The amine addition compound B of structure from aliphatic epoxy resin and the structure from 2-methylimidazole.
The amine addition compound B of gained is carried out1H-NMR,13C-NMR and IR measure, is thereby confirmed that as above-mentioned formula (2-
2) compound shown in.
(amine addition compound C manufacture)
It is 1 by mixing ratio：1 n-butanol/toluene mixed solution 300mL puts into three-necked flask, then puts into bisphenol A-type
Epoxy resin (Mitsubishi Chemical Ind's system, " jER828 ") 38.0 parts by weight and 2- heptadecyl imidazoles (chemical conversion industry company of four countries
System, " C17Z ") 20.3 parts by weight.After carrying out 4 hours heating stirrings at 65 DEG C, solvent removing and vacuum drying are carried out, is obtained
Amine addition compound C with the structure from bisphenol A type epoxy resin and the structure from 2- heptadecyl imidazoles.
The amine addition compound C of gained is carried out1H-NMR,13C-NMR and IR measure, is thereby confirmed that as above-mentioned formula (2-
3) compound shown in.
(amine addition compound D manufacture)
It is 1 by mixing ratio：1 n-butanol/toluene mixed solution 300mL puts into three-necked flask, then puts into aliphatic
(four countries are melted into for epoxy resin (aurification company system, " YH-300 " live in Nippon Steel) 30.0 parts by weight and 2- heptadecyl imidazoles
Industrial group's system, " C17Z ") 20.3 parts by weight.After carrying out 4 hours heating stirrings at 65 DEG C, carry out solvent removing and vacuum is done
It is dry, obtain the amine addition compound with the structure from aliphatic epoxy resin and the structure from 2- heptadecyl imidazoles
D。
The amine addition compound D of gained is carried out1H-NMR,13C-NMR and IR measure, is thereby confirmed that as above-mentioned formula (2-
4) compound shown in.
(amine addition compound E manufacture)
It is 1 by mixing ratio：In 1 n-butanol/toluene mixed solution 300mL input three-necked flasks, then put into bisphenol-A type ring
Oxygen tree fat (Mitsubishi Chemical Ind's system, " jER828 ") 38.0 parts by weight and 2- phenylimidazoles (and Wako Pure Chemical Industries company system) 7.2
Parts by weight.After carrying out 4 hours heating stirrings at 65 DEG C, solvent removing and vacuum drying are carried out, obtains having and comes from bisphenol A-type
The amine addition compound E of the structure of epoxy resin and structure from 2- phenylimidazoles.
The amine addition compound E of gained is carried out1H-NMR,13C-NMR and IR measure, is thereby confirmed that as following formula (3)
Shown compound.
[changing 3]
(embodiment 1~7, comparative example 1~4)
According to the match ratio described in table 1, by each materials'use planetary stirring machine, (THINKY company systems " practice too by deaeration
Youth ") mixed after, reuse three-roller and mixed, thus prepare each liquid crystal display of embodiment 1~7, comparative example 1~4
Element sealant.
＜ evaluates ＞
Following evaluation is carried out to each sealing material for liquid crystal display device of gained in embodiment and comparative example.As a result such as table
Shown in 1.
(storage stability)
To each sealing material for liquid crystal display device of gained in embodiment and comparative example, the initial viscosity after just manufacture is determined
With the viscosity when preserving 3 days for 25 DEG C, (viscosity after being preserved 3 days at 25 DEG C)/(initial viscosity) is set to rate of change in viscosity, will
Situation of the rate of change in viscosity less than 1.3 is set to " ◎ ", and by rate of change in viscosity be more than 1.3 and the situation less than 1.5 is set to "○",
By rate of change in viscosity be more than 1.5 and the situation less than 2.0 is set to " △ ", and the situation that rate of change in viscosity is more than 2.0 is set to
"×", it have rated storage stability.
It is explained, the viscosity of sealant uses E types viscosimeter (BROOK FIELD company systems, " DV-III ") at 25 DEG C
Lower and rotary speed is determined under conditions of being 1.0rpm.
(curability at low temperatures)
Each sealing material for liquid crystal display device of gained in embodiment and comparative example is filled into distribution syringe
In (Musashi Engineering company systems, " PSY-10E "), deaeration processing is carried out.Then, using distributor (Musashi
Engineering company systems, " SHOTMASTER300 "), to retouch on one of 2 transparent electrode substrates with ito thin film
The mode for painting rectangle frame is coated with sealant.Then, coating is added dropwise to the inframe of the sealant formed with liquid crystal Dropping feeder
The tiny droplets of TN liquid crystal (Chisso company systems, " JC-5001LA "), it is bonded separately under 5Pa decompression using vacuum forming apparatus
One transparency carrier.Metal halide light irradiation 3000mJ/cm is used to the unit after fitting2Ultraviolet after, with 100 DEG C heating
60 minutes, so that sealant heat cure, makes liquid crystal display cells.Ultraviolet irradiation using wave filter interception 340nm with
Under the light of wavelength carry out.After the liquid crystal display cells of gained are preserved 100 hours at 80 DEG C of temperature, with AC3.5V electricity
Pressure is allowed to drive, and is observed by visual observation.It will not observe that display is uneven completely in the edge part of liquid crystal display cells
The situation of (irregular colour) is set to " ◎ ", it will be observed that the uneven situation of a little shallower display is set to "○", and it is clear to have
The uneven situation of deeper display be set to " △ ", have that clearly deeper display is uneven but also this shows in edge part by not only
Show that the uneven situation for extending to central portion is set to "×", the display performance of liquid crystal display cells is evaluated.
(visible-light curing)
Each sealing material for liquid crystal display device of gained in embodiment 5 is coated with about 5 μm on the glass substrate, in the substrate
The glass substrate of upper overlapping same size, then, uses the metal halide light irradiation 100mW/cm of 10 seconds2Light.Light irradiation
Carried out using the light of wave filter interception below 380nm wavelength.Using infrared spectroscopy device (BIORAD company systems,
" FTS3000 ") peak from acryloyl group before and after measure light irradiation, export the peak from acryloyl group after light irradiation and subtract
Few rate.The situation that the slip at the peak from acryloyl group after light irradiation is more than 93% is set to " ◎ ", by the slip
"○" is set to for more than 85% and the situation less than 93%, by the slip be more than 75% and the situation less than 85% is set to
" △ ", situation of the slip less than 75% is set to "×", have rated visible-light curing.
[table 1]
Industrial applicability
According to the present invention it is possible to provide the sealing used for liquid crystal display element that can take into account curability at low temperatures and storage stability
Agent.Furthermore it is possible to provide the conductive material up and down formed using the sealing material for liquid crystal display device and liquid crystal display cells.
Claims (7)
1. a kind of sealing material for liquid crystal display device, it is characterised in that it is the liquid crystal containing curable resin and thermal curing agents
Display element sealant,
The curable resin contains the curable resin with epoxy radicals,
The thermal curing agents contain the amine addition compound with the structure from epoxy resin and the structure from amines,
Amines as the source of the amine addition compound is that the carbon number of alkyl is 1~20 alkyl imidazole.
2. sealing material for liquid crystal display device according to claim 1, it is characterised in that the carbon number of alkyl is 1~20
Alkyl imidazole is 2-methylimidazole.
3. sealing material for liquid crystal display device according to claim 1 or 2, it is characterised in that as amine addition compound
The epoxy resin in source there is aromatic rings.
4. according to the sealing material for liquid crystal display device described in claim 1,2 or 3, it is characterised in that as amine adduction chemical combination
The epoxy resin in the source of thing is in bisphenol A type epoxy resin, bisphenol f type epoxy resin and bisphenol E-type epoxy resin
It is at least one kind of.
5. a kind of sealing material for liquid crystal display device, it is characterised in that it is the liquid crystal containing curable resin and thermal curing agents
Display element sealant,
The curable resin contains the curable resin with epoxy radicals, and the thermal curing agents contain shown in following formula (1-1)
Compound and/or following formula (1-2) shown in compound,
In formula (1-1) and formula (1-2), R1It is the alkyl that carbon number is 1~20, in formula (1-1), R2And R3For hydrogen or methyl and can
With identical or different respectively.
6. a kind of conductive material up and down, it is characterised in that containing used for liquid crystal display element described in claim 1,2,3,4 or 5
Sealant and electrically conductive microparticle.
7. a kind of liquid crystal display cells, it is characterised in that have used for liquid crystal display element described in claim 1,2,3,4 or 5
Conductive material up and down described in sealant or claim 6.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015210051 | 2015-10-26 | ||
| JP2015-210051 | 2015-10-26 | ||
| PCT/JP2016/081549 WO2017073548A1 (en) | 2015-10-26 | 2016-10-25 | Sealing agent for liquid crystal display elements, vertically conducting material and liquid crystal display element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107615151A true CN107615151A (en) | 2018-01-19 |
Family
ID=58631992
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201680030279.5A Pending CN107615151A (en) | 2015-10-26 | 2016-10-25 | Sealing material for liquid crystal display device, upper and lower conductive material and liquid crystal display cells |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP6114893B1 (en) |
| KR (1) | KR20180075431A (en) |
| CN (1) | CN107615151A (en) |
| TW (1) | TWI723060B (en) |
| WO (1) | WO2017073548A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111164178A (en) * | 2018-03-28 | 2020-05-15 | 积水化学工业株式会社 | Composition for electronic material, sealing agent for liquid crystal display element, vertical conduction material, and liquid crystal display element |
| CN111902511A (en) * | 2018-03-23 | 2020-11-06 | 味之素株式会社 | Sealing adhesive |
| CN116790214A (en) * | 2023-05-18 | 2023-09-22 | 浙江羲和新材料科技有限公司 | Sealant composition and application thereof in liquid crystal display element |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7146409B2 (en) | 2018-02-20 | 2022-10-04 | ヘンケルジャパン株式会社 | UV thermosetting adhesive composition |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04168120A (en) * | 1990-10-31 | 1992-06-16 | Toshiba Corp | Liquid epoxy sealing resin composition and resin sealed type semiconductor device using the same composition |
| US5189082A (en) * | 1991-09-26 | 1993-02-23 | Cheil Industries, Inc. | Imide epoxy resins for sealing semiconductor elements |
| CN1957012A (en) * | 2004-03-31 | 2007-05-02 | 旭化成化学株式会社 | Hardener for epoxy resin and epoxy resin composition |
| CN103827741A (en) * | 2011-09-27 | 2014-05-28 | 日本化药株式会社 | Liquid crystal sealing agent, and liquid crystal display cell using same |
| CN104231545A (en) * | 2013-06-17 | 2014-12-24 | 三星电机株式会社 | Insulating resin composition for printed circuit board, insulating film, prepreg, and printed circuit board |
| CN104910844A (en) * | 2014-03-10 | 2015-09-16 | 日立化成株式会社 | Electrically conductive adhesive composition, connection structure, solar battery module, and method for producing same |
| CN104932155A (en) * | 2011-04-08 | 2015-09-23 | 积水化学工业株式会社 | Sealant For One-Drop Fill Process, Vertical-Conduction Material, And Liquid Crystal Display Element |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3024440B2 (en) * | 1993-06-22 | 2000-03-21 | 株式会社スリーボンド | Liquid crystal sealant |
| JP4981414B2 (en) * | 2006-11-07 | 2012-07-18 | 積水化学工業株式会社 | Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element |
| JP5417715B2 (en) * | 2008-02-20 | 2014-02-19 | デクセリアルズ株式会社 | Microencapsulated silane coupling agent |
| KR101194202B1 (en) * | 2008-04-18 | 2012-10-25 | 세키스이가가쿠 고교가부시키가이샤 | Sealing agent for use in liquid crystal dropping process, sealing agent for liquid crystal panel, vertical-conduction material, and liquid crystal display element |
| WO2012002028A1 (en) * | 2010-06-28 | 2012-01-05 | 株式会社Adeka | Curable resin composition |
-
2016
- 2016-10-25 JP JP2016566830A patent/JP6114893B1/en active Active
- 2016-10-25 KR KR1020177024404A patent/KR20180075431A/en not_active IP Right Cessation
- 2016-10-25 CN CN201680030279.5A patent/CN107615151A/en active Pending
- 2016-10-25 WO PCT/JP2016/081549 patent/WO2017073548A1/en active Application Filing
- 2016-10-26 TW TW105134476A patent/TWI723060B/en active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04168120A (en) * | 1990-10-31 | 1992-06-16 | Toshiba Corp | Liquid epoxy sealing resin composition and resin sealed type semiconductor device using the same composition |
| US5189082A (en) * | 1991-09-26 | 1993-02-23 | Cheil Industries, Inc. | Imide epoxy resins for sealing semiconductor elements |
| CN1957012A (en) * | 2004-03-31 | 2007-05-02 | 旭化成化学株式会社 | Hardener for epoxy resin and epoxy resin composition |
| CN104932155A (en) * | 2011-04-08 | 2015-09-23 | 积水化学工业株式会社 | Sealant For One-Drop Fill Process, Vertical-Conduction Material, And Liquid Crystal Display Element |
| CN103827741A (en) * | 2011-09-27 | 2014-05-28 | 日本化药株式会社 | Liquid crystal sealing agent, and liquid crystal display cell using same |
| CN104231545A (en) * | 2013-06-17 | 2014-12-24 | 三星电机株式会社 | Insulating resin composition for printed circuit board, insulating film, prepreg, and printed circuit board |
| CN104910844A (en) * | 2014-03-10 | 2015-09-16 | 日立化成株式会社 | Electrically conductive adhesive composition, connection structure, solar battery module, and method for producing same |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111902511A (en) * | 2018-03-23 | 2020-11-06 | 味之素株式会社 | Sealing adhesive |
| CN111164178A (en) * | 2018-03-28 | 2020-05-15 | 积水化学工业株式会社 | Composition for electronic material, sealing agent for liquid crystal display element, vertical conduction material, and liquid crystal display element |
| CN111164178B (en) * | 2018-03-28 | 2021-03-16 | 积水化学工业株式会社 | Composition for electronic material, sealing agent for liquid crystal display element, vertical conduction material, and liquid crystal display element |
| CN116790214A (en) * | 2023-05-18 | 2023-09-22 | 浙江羲和新材料科技有限公司 | Sealant composition and application thereof in liquid crystal display element |
| CN116790214B (en) * | 2023-05-18 | 2024-04-12 | 浙江羲和新材料科技有限公司 | Sealant composition and application thereof in liquid crystal display element |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2017073548A1 (en) | 2017-11-02 |
| KR20180075431A (en) | 2018-07-04 |
| JP6114893B1 (en) | 2017-04-12 |
| TWI723060B (en) | 2021-04-01 |
| WO2017073548A1 (en) | 2017-05-04 |
| TW201728662A (en) | 2017-08-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103026292B (en) | Light-shielding sealing agent for liquid crystal display element, top-to-bottom conductive material, and liquid crystal display element | |
| CN103430086B (en) | Sealing agent for liquid crystal display element and liquid crystal display element | |
| CN101176033A (en) | Sealing material for liquid crystal dropping method, vertically conducting material, and liquid crystal display element | |
| CN105283803B (en) | Sealant for liquid crystal dripping process, up and down conductive material and liquid crystal display cells | |
| CN104813224B (en) | Sealing material for liquid crystal display device, upper and lower conductive material, the manufacturing method of liquid crystal display element and sealing material for liquid crystal display device | |
| CN103238106B (en) | Sealing material for liquid crystal display device and liquid crystal display cells | |
| CN105579898B (en) | Sealing material for liquid crystal display device, up and down conductive material and liquid crystal display cells | |
| CN103261957A (en) | Sealing material for liquid-crystal dropping process, material for vertical conduction, and liquid-crystal display element | |
| CN107615151A (en) | Sealing material for liquid crystal display device, upper and lower conductive material and liquid crystal display cells | |
| CN104756004A (en) | Sealing agent for one drop fill process, vertically conducting material, and liquid crystal display element | |
| CN106462014A (en) | Sealing agent for liquid crystal dropping methods, vertically conducting material and liquid crystal display element | |
| CN107636524A (en) | Sealing material for liquid crystal display device, upper and lower conductive material and liquid crystal display cells | |
| CN103443698B (en) | Sealant for liquid crystal dripping process, upper and lower conductive material and liquid crystal display cells | |
| CN108351561A (en) | Sealing material for liquid crystal display device, upper and lower conductive material and liquid crystal display element | |
| CN107250903A (en) | Sealing material for liquid crystal display device, up and down conductive material and liquid crystal display cells | |
| CN106796376A (en) | Sealing material for liquid crystal display device, upper and lower conductive material and liquid crystal display cells | |
| CN105849632A (en) | Sealing agent for liquid crystal dropping methods, vertically conducting material and liquid crystal display element | |
| CN105900003A (en) | Sealant for one-drop filling process, vertically conductive material, and liquid crystal display element | |
| CN107111193A (en) | Sealing material for liquid crystal display device, up and down conductive material and liquid crystal display cells | |
| CN108780249A (en) | Sealing material for liquid crystal display device, upper and lower conductive material and liquid crystal display element | |
| CN105229525A (en) | Sealant for liquid crystal dripping process, up and down conductive material and liquid crystal display cells | |
| CN102216841B (en) | Sealing agent for one drop fill, and liquid crystal display element | |
| TWI716440B (en) | Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element | |
| CN105339839A (en) | Liquid-crystal-display-element sealant, vertical conductive material, and liquid-crystal display element | |
| CN107250904A (en) | Sealing material for liquid crystal display device, up and down conductive material and liquid crystal display cells |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20180119 |
|
| WD01 | Invention patent application deemed withdrawn after publication |