CN108780251A - Sealing material for liquid crystal display device, upper and lower conductive material and liquid crystal display element - Google Patents
Sealing material for liquid crystal display device, upper and lower conductive material and liquid crystal display element Download PDFInfo
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- CN108780251A CN108780251A CN201780016932.7A CN201780016932A CN108780251A CN 108780251 A CN108780251 A CN 108780251A CN 201780016932 A CN201780016932 A CN 201780016932A CN 108780251 A CN108780251 A CN 108780251A
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- liquid crystal
- methyl
- crystal display
- mentioned
- acrylate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
-
- 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
Abstract
The object of the present invention is to provide liquid crystal can be inhibited to be inserted into sealant, the sealing material for liquid crystal display device of liquid crystal pollution caused by sealant.In addition, the purpose of the present invention is to provide use the sealing material for liquid crystal display device and manufactured conductive material and liquid crystal display element up and down.The present invention is a kind of sealing material for liquid crystal display device, containing curable resin, also contains polymerization initiator and/or thermal curing agents, the curable resin contains the compound with structure shown in polymerizable functional group and following formula (1).
Description
Technical field
The present invention relates to liquid crystal can be inhibited to be inserted into sealant, the liquid crystal of liquid crystal pollution caused by sealant
Show element sealant.Moreover, it relates to the manufactured conductive material up and down using the sealing material for liquid crystal display device
And liquid crystal display element.
Background technology
In recent years, the manufacturing method as liquid crystal display elements such as liquid crystal displays, from shortening productive temp time, liquid
From the perspective of the optimization of brilliant usage amount, used as patent document 1, it is disclosed Patent Document 2, used and contained
There are the photo-thermal of curable resin, Photoepolymerizationinitiater initiater and thermal curing agents and the liquid of the technique that is referred to as dripping with curing type sealant
Crystalline substance drips mode.
In technique of dripping, first, formed on one by distribution in two electroded transparent substrates rectangular
The seal pattern of shape.Next, the fine droplet of liquid crystal to be dripped to the frame of transparent substrate in the state that sealant is uncured
Interior entire surface is overlapped another transparent substrate immediately, irradiates the light such as ultraviolet light to sealing to carry out precuring.Thereafter, in liquid
It is heated when crystalline substance annealing to carry out main solidification, makes liquid crystal display element.It, can be with pole if carrying out the fitting of substrate under reduced pressure
High efficiency manufactures liquid crystal display element, and the present technique of dripping has become the mainstream of the manufacturing method of liquid crystal display element.
In addition, in the present age that the various mobile devices with liquid crystal display panel such as mobile phone, portable game machine are popularized, dress
The miniaturization set is the project needed most.As the method for miniaturization, the narrow architrave of liquid crystal display part can be enumerated, such as will be close
The position in envelope portion is configured under black matrix" (hereinafter also referred to " narrow architrave design ").
If however, the liquid crystal display element of narrow architrave design is manufactured to drip technique, due to existing because of black matrix"
And light is caused not shine the position of sealing, so there are following situations：The part for not carrying out photocuring fully is generated, it is uncured
Sealant contacted with liquid crystal.In this case, it has the following problems：Sometimes liquid crystal is inserted into sealant, and broken seal occurs, and
Liquid crystal is set to leak out；Uncured sealant is dissolved out into liquid crystal, and liquid crystal is contaminated.
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2001-133794 bulletins
Patent document 2：International Publication No. 02/092718
Invention content
Problem to be solved by the invention
The present invention relates to liquid crystal can be inhibited to be inserted into sealant, the liquid crystal of liquid crystal pollution caused by sealant
Show element sealant.In addition, the purpose of the present invention is to provide use the sealing material for liquid crystal display device and it is manufactured on
Lower conductive material and liquid crystal display element.
The means used to solve the problem
The present invention is a kind of sealing material for liquid crystal display device, containing curable resin, also contain polymerization initiator and/
Or thermal curing agents, above-mentioned curable resin contain the compound with structure shown in polymerizable functional group and following formula (1).
Hereinafter, being described in detail to the present invention.
The inventors discovered that：It is available to press down by using the compound with specific structure as curable resin
Liquid crystal processed is inserted into sealant, the sealing material for liquid crystal display device of liquid crystal pollution caused by sealant, so that complete
The present invention.
The sealing material for liquid crystal display device of the present invention contains curable resin.
Above-mentioned curable resin contain with structure shown in polymerizable functional group and above-mentioned formula (1) compound (hereinafter,
Referred to as " polymerizable compound of the present invention ").By containing polymerizable compound of the present invention, liquid crystal of the invention
Display element can inhibit liquid crystal to be inserted into sealant with sealant, the liquid crystal pollution caused by sealant.
Wherein, polymerizable compound preferably of the present invention is with knot shown in polymerizable functional group and following formula (2)
The compound of structure.
In formula (2), R1And R2Each independently represent hydrogen or methyl.
Polymerizable functional group possessed by polymerizable compound of the present invention is preferably (methyl) acryloyl group or ring
Oxygroup, more preferably (methyl) acryloyl group.
It should be noted that in this specification, above-mentioned " (methyl) acryloyl group " means acryloyl group or methacryl
Base.
The preferred lower limit of the molecular weight of polymerizable compound of the present invention is 300, preferred upper limit 4000.By making
The molecular weight of polymerizable compound of the present invention is the range, thus in the case where the deteriorations such as coating will not be made, institute
Sealing material for liquid crystal display device inhibit liquid crystal to be inserted into sealant, the effect of liquid crystal pollution caused by sealant
It is better.It should be noted that in the present specification, about above-mentioned " molecular weight ", for the specific compound of molecular structure
Speech, is the molecular weight found out by structural formula, the wide compound of the distribution for the degree of polymerization and the modified not specific compound in position
For, it is indicated sometimes using weight average molecular weight.In the present specification, above-mentioned " weight average molecular weight " is to utilize gel permeation chromatography
The value that method (GPC) is measured and is found out based on polystyrene conversion.It is converted based on polystyrene as by GPC to measure
Weight average molecular weight when pillar used, can enumerate such as Shodex LF-804 (Showa electrician corporation).
From viewpoints such as cementability, anti-penetrability, preferably above-mentioned curable resin is in addition to polymerism of the present invention
Except compound, also contain other polymerizable compounds.
It is of the present invention in 100 parts by weight of curable resin in the case of containing above-mentioned other polymerizable compounds
Polymerizable compound content preferred lower limit be 1 parts by weight, preferred upper limit is 50 parts by weight.It is of the present invention by making
The content of polymerizable compound is the range, thus in the case where not making the deteriorations such as cementability, anti-penetrability, the liquid crystal of gained
Display element inhibits liquid crystal to be inserted into sealant with sealant, the effect of liquid crystal pollution caused by sealant is better.
The more preferable lower limit of the content of polymerizable compound of the present invention is 2 parts by weight, the more preferable upper limit is 45 parts by weight, into one
Step preferred lower limit is 20 parts by weight.
As above-mentioned other polymerizable compounds, the chemical combination included by polymerizable compound of the present invention can be enumerated
Other than object, other epoxides, others (methyl) acrylic compounds etc..Wherein, it is inserted into from inhibition liquid crystal
The superior aspect of effect of liquid crystal pollution in sealant, caused by sealant is set out, preferably by other epoxy compounds
Object is applied in combination with imidazoles system thermal curing agents.
As above-mentioned other epoxides, such as bisphenol A type epoxy resin, bisphenol f type epoxy resin, double can be enumerated
Phenol E types epoxy resin, bisphenol-s epoxy resin, 2,2 '-diallyl bisphenol type epoxy resin, A Hydrogenated Bisphenol A type asphalt mixtures modified by epoxy resin
Fat, propylene oxide addition bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, thioether-type asphalt mixtures modified by epoxy resin
Fat, diphenyl ether type epoxy resin, dicyclopentadiene-type epoxy resin, naphthalene type epoxy resin, phenol novolak type epoxy resin,
O-cresol phenolic epoxy varnish, dicyclopentadiene novolac type epoxy resin, biphenyl phenolic resin varnish type epoxy resin,
Naphthol novolac type epoxy resin, glycidyl amine type epoxy resin, alkyl polyols type epoxy resin, modified rubber type ring
Oxygen resin, epihydric alcohol ester compound etc..
As the commercially available product of above-mentioned bisphenol A type epoxy resin, it (is Mitsubishi that can enumerate such as jER828EL, jER1004
Learn corporation), Epiclon 850CRP (DIC corporations) etc..
As the commercially available product of above-mentioned bisphenol f type epoxy resin, it (is Mitsubishi Chemical that can enumerate such as jER806, jER4004
Corporation) etc..
As the commercially available product of above-mentioned bisphenol E-type epoxy resin, such as R710 (Printec Co., LTD. system) etc. can be enumerated.
As the commercially available product of above-mentioned bisphenol-s epoxy resin, such as Epiclon EXA1514 (DIC corporations) can be enumerated
Deng.
As the commercially available product of above-mentioned 2,2 '-diallyl bisphenol type epoxy resin, such as RE-810NM (Japan can be enumerated
Chemical drug corporation) etc..
As the commercially available product of above-mentioned A Hydrogenated Bisphenol A type epoxy resin, such as Epiclon EXA7015 (DIC companies can be enumerated
System) etc..
As the commercially available product of above-mentioned propylene oxide addition bisphenol A type epoxy resin, such as EP-4000S (ADEKA can be enumerated
Corporation) etc..
As the commercially available product of above-mentioned resorcinol type epoxy resin, such as EX-201 (Nagase ChemteX can be enumerated
Corporation systems) etc..
As the commercially available product of above-mentioned biphenyl type epoxy resin, such as jER YX-4000H (Mitsubishi Chemical Ind's system) can be enumerated
Deng.
As the commercially available product of above-mentioned thioether-type epoxy resin, such as YSLV-50TE (Zhu Jin chemical companies of Nippon Steel can be enumerated
System) etc..
As the commercially available product of above-mentioned diphenyl ether type epoxy resin, can enumerating such as YSLV-80DE, (aurification public affairs are lived by Nippon Steel
Department's system) etc..
As the commercially available product of above-mentioned dicyclopentadiene-type epoxy resin, such as EP-4088S (ADEKA corporations) can be enumerated
Deng.
As the commercially available product of above-mentioned naphthalene type epoxy resin, such as Epiclon HP4032, Epiclon EXA- can be enumerated
4700 (being DIC corporations) etc..
As the commercially available product of above-mentioned phenol novolak type epoxy resin, can enumerating such as Epiclon N-770, (DIC is public
Department's system) etc..
As the commercially available product of above-mentioned o-cresol phenolic epoxy varnish, such as Epiclon N-670-EXP- can be enumerated
S (DIC corporations) etc..
As the commercially available product of above-mentioned dicyclopentadiene novolac type epoxy resin, such as Epiclon HP7200 can be enumerated
(DIC corporations) etc..
As the commercially available product of above-mentioned biphenyl phenolic resin varnish type epoxy resin, can enumerating such as NC-3000P, (Japanese chemical drug is public
Department's system) etc..
As the commercially available product of above-mentioned naphthol novolac type epoxy resin, can enumerating such as ESN-165S, (gold is lived by Nippon Steel
Chemical company's system) etc..
As the commercially available product of above-mentioned glycidyl amine type epoxy resin, such as jER630 (Mitsubishi Chemical Inds can be enumerated
System), Epiclon 430 (DIC corporations), TETRAD-X (gas chemical company of Mitsubishi system) etc..
As the commercially available product of abovementioned alkyl polyol type epoxy resin, can enumerating such as ZX-1542, (aurification is lived by Nippon Steel
Corporation), Epiclon 726 (DIC corporations), Epolight 80MFA (chemical company of common prosperity society system), Denacol EX-
611 (Nagase ChemteX Corporation systems) etc..
The commercially available product of modified version epoxy resin as above-mentioned rubber, it (is Nippon Steel that can enumerate such as YR-450, YR-207
Firmly aurification corporation), Epolead PB (Daicel corporation) etc..
As the commercially available product of above-mentioned epihydric alcohol ester compound, such as Denacol EX-147 (Nagase can be enumerated
ChemteX Corporation systems) etc..
As other commercially available products of above-mentioned epoxide, such as YDC-1312, YSLV-80XY, YSLV-90CR can be enumerated
(being that aurification corporation is lived by Nippon Steel), XAC4151 (Asahi Kasei Corporation's system), jER1031, jER1032 (are Mitsubishi Chemical
Corporation), EXA-7120 (DIC corporations), TEPIC (Nissan Chemical corporation) etc..
In addition, above-mentioned curable resin can also contain the change with epoxy group and (methyl) acryloyl group in 1 molecule
Object is closed as above-mentioned other epoxides.As this kind of compound, can enumerate for example by making that there are 2 or more epoxy groups
Epoxide a part of epoxy group reacted with (methyl) acrylic acid obtained by part (methyl) acrylated epoxy tree
Fat etc..
In above-mentioned part (methyl) acrylic modified epoxy resin, as commercially available product, such as UVACURE1561 can be enumerated
(Daicel-Allnex corporations) etc..
As above-mentioned other (methyl) acrylic compounds, such as epoxy (methyl) acrylate, (first can be enumerated
Base) acrylate compounds, carbamate (methyl) acrylate etc..Wherein, preferred epoxy (methyl) acrylate.Separately
Outside, from reactive height, above-mentioned others (methyl) acrylic compounds preferably have 2 or more in the molecule
(methyl) acryloyl group.
It should be noted that in this specification, above-mentioned " (methyl) acrylate " means acrylate or methacrylic acid
Ester, above-mentioned " epoxy (methyl) acrylate " indicate to make whole epoxy groups in epoxide to be reacted with (methyl) acrylic acid
Obtained by compound.
As above-mentioned epoxy (methyl) acrylate, it can enumerate for example that so that epoxide is passed through with (methyl) acrylic acid normal
Rule method reacted in the presence of basic catalyst and person etc..
As the epoxide as the raw material for synthesizing above-mentioned epoxy (methyl) acrylate, can enumerate with above
The identical epoxide of other epoxides also described containing person as above-mentioned other polymerizable compounds.
As the commercially available product of above-mentioned epoxy (methyl) acrylate, can enumerate such as EBECRYL860, EBECRYL3200,
EBECRYL3201、EBECRYL3412、EBECRYL3600、EBECRYL3700、EBECRYL3701、EBECRYL3702、
EBECRYL3703, EBECRYL3708, EBECRYL3800, EBECRYL6040, EBECRYLRDX63182 (are Daicel-
Allnex corporations), EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (be the villages Xin Zhong chemistry
Industrial group's system), Epoxy Ester M-600A, Epoxy Ester 40EM, Epoxy Ester 70PA, Epoxy Ester
200PA、Epoxy Ester 80MFA、Epoxy Ester 3002M、Epoxy Ester 3002A、Epoxy Ester
1600A、Epoxy Ester 3000M、Epoxy Ester 3000A、Epoxy Ester 200EA、Epoxy Ester 400EA
(being chemical company of common prosperity society system), Denacol Acrylate DA-141, Denacol Acrylate DA-314,
Denacol Acrylate DA-911 (being Nagase ChemteX Corporation systems) etc..
As the monofunctional compound in above-mentioned (methyl) acrylate compounds, such as (methyl) acrylic acid first can be enumerated
Ester, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate,
(methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) n-octyl, (methyl) acrylic acid are different pungent
Ester, the different nonyl ester of (methyl) acrylic acid, (methyl) isodecyl acrylate, (methyl) lauryl acrylate, the different meat of (methyl) acrylic acid
Cardamom ester, (methyl) stearyl acrylate, (methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 2- hydroxy propyl esters, (first
Base) acrylic acid 2- hydroxybutyls, (methyl) acrylic acid 4- hydroxybutyls, (methyl) cyclohexyl acrylate, (methyl) acrylic acid is different
Norbornene ester, (methyl) acrylic acid dicyclopentenyl ester, (methyl) benzyl acrylate, (methyl) acrylic acid 2- methoxy acrylates, (first
Base) acrylic acid 2- ethoxy ethyl esters, (methyl) acrylic acid 2- butoxyethyls, (methyl) acrylic acid 2- phenoxy ethyls, (first
Base) acrylic methoxy glycol ester, (methyl) methoxyethyl macrogol ester, (methyl) acrylic acid phenoxy group diethyl two
Alcohol ester, (methyl) acrylic acid phenoxy group macrogol ester, (methyl) tetrahydrofurfuryl acrylate, ethyl carbitol (methyl) propylene
Acid esters, (methyl) acrylic acid 2,2,2- trifluoro ethyl esters, 2,2,3,3- tetrafluoro propyl ester of (methyl) acrylic acid, (methyl) acrylic acid 1H,
1H, 5H- octafluoro pentyl ester, acid imide (methyl) acrylate, (methyl) dimethylaminoethyl acrylate, (methyl) acrylic acid diethyl
Amino ethyl ester, 2- (methyl) acryloyl-oxyethyls succinic acid, 2- (methyl) acryloyl-oxyethyls hexahydrophthalic acid, 2-
(methyl) acryloyl-oxyethyl 2- hydroxypropyl phthalates, 2- (methyl) acryloyl-oxyethyl phosphate, (first
Base) glycidyl acrylate etc..
In addition, as 2 functional compounds in above-mentioned (methyl) acrylate compounds, such as 1,3-BDO can be enumerated
Two (methyl) acrylate, 1,4-butanediol two (methyl) acrylate, 1,6- hexylene glycols two (methyl) acrylate, 1,9- nonyls
Glycol two (methyl) acrylate, 1,10- decanediols two (methyl) acrylate, ethylene glycol two (methyl) acrylate, diethyl
Glycol two (methyl) acrylate, tetraethylene glycol two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, the positive fourths of 2-
Base -2- ethyls -1,3-PD two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, two (first of tripropylene glycol
Base) acrylate, polypropylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, ethyleneoxide addition be double
Phenol A bis- (methyl) acrylate, propylene oxide addition bisphenol-A two (methyl) acrylate, two (first of ethyleneoxide addition Bisphenol F
Base) acrylate, dihydroxymethyl dicyclopentadienyl two (methyl) acrylate, ethylene-oxide-modified isocyanuric acid two (methyl)
Acrylate, 2- hydroxyls -3- (methyl) acryloxypropyl (methyl) acrylate, carbonate diol two (methyl) acrylic acid
Ester, polyetherdiol two (methyl) acrylate, polyester-diol two (methyl) acrylate, polycaprolactone glycol two (methyl) propylene
Acid esters, polybutadiene diol two (methyl) acrylate etc..
In addition, as compounds more than 3 functions in above-mentioned (methyl) acrylate compounds, such as three hydroxyls can be enumerated
Methylpropane three (methyl) acrylate, ethyleneoxide addition trimethylolpropane tris (methyl) acrylate, propylene oxide add
At trimethylolpropane tris (methyl) acrylate, caprolactone modification trimethylolpropane tris (methyl) acrylate, epoxy second
Alkane addition isocyanuric acid three (methyl) acrylate, glycerine three (methyl) acrylate, propylene oxide addition glycerine three (methyl)
Acrylate, pentaerythrite three (methyl) acrylate, three (methyl) acryloyl-oxyethyl phosphates, double trimethylolpropane
Four (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, two seasons penta 4
Alcohol six (methyl) acrylate etc..
Above-mentioned carbamate (methyl) acrylate for example can be by having 2 isocyanate group relative to 1 equivalent
Isocyanate compound makes (methyl) acrylic acid derivative that 2 equivalents have hydroxyl exist in the tin based compound of catalytic amount
Under reacted and obtained.
As above-mentioned isocyanate compound, such as isophorone diisocyanate, 2,4- toluene diisocynates can be enumerated
Ester, 2,6- toluene di-isocyanate(TDI)s, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, diphenyl methane-
4,4 '-diisocyanate (MDI), hydrogenation MDI, polymeric MDI, 1,5- naphthalene diisocyanates, norbornene alkyl diisocyanate, connection first
Aniline diisocyanate, benzene dimethylene diisocyanate (XDI), hydrogenation XDI, lysine diisocyanate, triphenyl methane
Triisocyanate, three (isocyanate phenyl) thiophosphates, tetramethylxylylene diisocyanate, 1,6,11- ten one
Alkane triisocyanate etc..
In addition, as above-mentioned isocyanate compound, such as can also use through polyalcohol and excessive isocyanates
The isocyanate compound of chain elongation obtained by the reaction of compound.
As above-mentioned polyalcohol, such as ethylene glycol, propylene glycol, glycerine, D-sorbite, trimethylolpropane, carbon can be enumerated
Acid esters glycol, polyetherdiol, polyester-diol, polycaprolactone glycol etc..
As above-mentioned (methyl) acrylic acid derivative with hydroxyl, for example single (methyl) acrylic acid hydroxy alkyl can be enumerated
Ester, list (methyl) acrylate of dihydric alcohol, list (methyl) acrylate of trihydroxylic alcohol or two (methyl) acrylate, epoxy
(methyl) acrylate etc..
As above-mentioned list (methyl) acrylic acid hydroxy alkyl ester, such as (methyl) acrylic acid 2- hydroxyl ethyl esters, (methyl) can be enumerated
Acrylic acid 2- hydroxypropyl acrylates, (methyl) acrylic acid 2- hydroxy butyl esters, (methyl) acrylic acid 4- hydroxy butyl esters etc..
As above-mentioned dihydric alcohol, such as ethylene glycol, propylene glycol, 1,3-PD, 1,3-BDO, Isosorbide-5-Nitrae-fourth two can be enumerated
Alcohol, polyethylene glycol etc..
As above-mentioned trihydroxylic alcohol, can enumerate such as trimethylolethane, trimethylolpropane, glycerine.
As above-mentioned epoxy (methyl) acrylate, can enumerate such as bisphenol-a epoxy acrylate.
As the commercially available product of above-mentioned carbamate (methyl) acrylate, such as M-1100, M-1200, M- can be enumerated
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 (are
Daicel-Allnex corporations), Art Resin UN-330, Art Resin SH-500B, Art Resin UN-1200TPK,
Art Resin UN-1255、Art Resin UN-3320HB、Art Resin UN-7100、Art Resin UN-9000A、
Art Resin UN-9000H (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 the villages Xin Zhong system), AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H,
UA-306I, UA-306T (being chemical company of common prosperity society system) etc..
For the present invention sealing material for liquid crystal display device, preferably by curable resin (methyl) acryloyl group with
The content ratio of epoxy group is set as 50: 50~95: 5 with molar ratio computing.
The sealing material for liquid crystal display device of the present invention contains polymerization initiator and/or thermal curing agents.
As above-mentioned polymerization initiator, can enumerate such as radical polymerization initiator, cationic polymerization initiators.
As above-mentioned radical polymerization initiator, the optical free radical polymerization generated free radicals by irradiation by light can be enumerated and drawn
The hot radical polymerization initiator etc. sent out agent, generated free radicals by heating.
As above-mentioned optical free radical polymerization initiator, can enumerate for example benzophenone based compound, acetophenone based compound,
Acylphosphine oxide compound, titanocenes based compound, oxime ester based compound, benzoin ether based compound, thioxanthones system chemical combination
Object etc..
As the commercially available product of above-mentioned optical free radical polymerization initiator, such as IRGACURE 184, IRGACURE can be enumerated
369、IRGACURE 379、IRGACURE 651、IRGACURE 819、IRGACURE 907、IRGACURE 2959、
IRGACURE OXE01, IRGACURE OXE02, Lucirin TPO (being BASF AG's system), NCI-930 (ADEKA companies
System), SPEEDCURE EMK (Japanese Siberhegner corporations), benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl
Base ether (being Tokyo chemical conversion industry corporation) etc..
As above-mentioned hot radical polymerization initiator, can enumerate such as the formation by azo-compound, organic peroxide
Initiator.Wherein, the initiator preferably formed by polymeric azo compound is (hereinafter also referred to as " polymeric azo causes
Agent ").
It should be noted that in this specification, polymeric azo compound refers to being generated with azo group and by heat
Compound that can make the cured free radical of (methyl) acryloyl group, that number-average molecular weight is 300 or more.
The preferred lower limit of the number-average molecular weight of above-mentioned polymeric azo compound is 1000, preferred upper limit is 300,000.Pass through
It is the range to make the number-average molecular weight of above-mentioned polymeric azo compound, so as to inhibit liquid crystal pollution, and and curability
Resin is easy to be mixed.The more preferable lower limit of the number-average molecular weight of above-mentioned polymeric azo compound be 5000, more preferably on
100,000 are limited to, further preferred lower limit is 10,000, the further preferred upper limit is 90,000.
It should be noted that in the present specification, above-mentioned number-average molecular weight is carried out using gel permeation chromatography (GPC)
The value for measuring and being found out based on polystyrene conversion.The number-average molecular weight to convert based on polystyrene is measured as by GPC
When pillar, can enumerate such as Shodex LF-804 (Showa electrician corporation).
As above-mentioned polymeric azo compound, can enumerate for example with via azo group and by multiple polyalkylene oxides, poly-
The compound of structure obtained by the bonding of the units such as dimethyl siloxane.
The macromolecule idol of structure obtained by being bonded the units such as multiple polyalkylene oxides as above-mentioned have via azo group
Nitrogen compound, it is however preferred to have the compound of polyethylene oxide structure.As this kind of polymeric azo compound, can enumerate for example
4,4 '-azos bis- (4- cyanopentanoic acids) are with condensation polymer, 4, the 4 '-azos bis- (4- cyanopentanoic acids) of polyalkylene glycol and with end
The condensation polymer etc. of the dimethyl silicone polymer of Amino End Group.
As the commercially available product of above-mentioned polymeric azo compound, such as VPE-0201, VPE-0401, VPE- can be enumerated
0601, VPS-0501, VPS-1001 (being and Wako Pure Chemical Industries corporation) etc..
In addition, as not being high molecular azo-compound, can enumerate such as V-65, V-501 (is and Wako Pure Chemical Industries
Corporation) etc..
As above-mentioned organic peroxide, such as ketone peroxide, peroxy ketal, hydrogen peroxide, dialkyl group peroxide can be enumerated
Compound, peroxyester, diacyl peroxide, peroxy dicarbonate etc.
As above-mentioned cationic polymerization initiators, can be suitble to use light cationic polymerization initiator.Above-mentioned light cation is poly-
As long as closing initiator to irradiate by light by generate Bronsted acid or lewis acid, there is no particular limitation, can be that ionic light produces
Acid type, or nonionic light produces acid type.
As above-mentioned light cationic polymerization initiator, such as aromatic diazonium salt, aromatic halonium salts, aromatic series can be enumerated
The metal-organic complexs such as the salts such as sulfonium salt, iron-allene complex object, titanocenes complex compound, aryl-silane alcohol-aluminium complex
Class etc..
As the commercially available product of above-mentioned light cationic polymerization initiator, can enumerate such as Adeka Optomer SP-150,
Adeka Optomer SP-170 (being ADEKA corporations) etc..
The content of above-mentioned polymerization initiator relative to 100 parts by weight of curable resin, preferred lower limit be 0.01 parts by weight,
The preferred upper limit is 10 parts by weight.By making the content of above-mentioned polymerization initiator be the range, to the liquid crystal display member of gained
Part can inhibit liquid crystal pollution with sealant, and storage stability, curability are better.The content of above-mentioned polymerization initiator is more
Preferred lower limit is 0.1 parts by weight, the more preferable upper limit is 5 parts by weight.
As described above, above-mentioned other epoxides are preferably applied in combination in the sealing material for liquid crystal display device of the present invention
With imidazoles system thermal curing agents.
The fusing point of more preferable above-mentioned imidazoles system thermal curing agents is 80 DEG C or less.
As above-mentioned imidazoles system thermal curing agents, such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 1- cyano can be enumerated
Ethyl -2- phenylimidazoles, 1- cyano ethyl -2- phenylimidazole trimellitic acids salt, 2,4- diamino -6- (2 '-methylimidazoles
Base-(1 '))-ethyl-s-triazine, 2,4- diamino -6- (2 '-methylimidazolyls-(1 '))-ethyl-s-triazine isocyanuric acid add
At object etc..
In addition, as above-mentioned imidazoles system thermal curing agents, adduction type curing agent can be used.It is solid by using above-mentioned adduction type
Agent can inhibit the excessive thickening of sealant.
As above-mentioned adduction type curing agent, can enumerate such as by imidazolium compounds and being obtained by reaction epoxide
Adduct.
As the commercially available product of above-mentioned adduction type curing agent, can enumerate such as Amicure PN-23, Amicure PN-23J,
Amicure PN-H、Amicure PN-31、Amicure PN-31J、Amicure PN-40、Amicure PN-40J、
Amicure PN-50, Amicure PN-F, Amicure MY-24, Amicure MY-H (are the fine scientific & technical corporation of aginomoto
System), P-0505 (four countries' chemical conversion industry corporation), P-200 (Mitsubishi Chemical Ind's system) etc..
As other thermal curing agents, such as organic acid hydrazides, amine compounds, polynary phenol system compound, acid anhydrides can be enumerated
Deng.Wherein, it is suitble to the organic acid hydrazides using solid.
As above-mentioned organic acid hydrazides, such as sebacic dihydrazide, isophthalic dihydrazide, two acyl of adipic acid can be enumerated
Hydrazine, acid dihydrazide etc..
As the commercially available product of above-mentioned organic acid hydrazides, can enumerate such as SDH, ADH (being great mound chemical company system),
Amicure VDH, Amicure VDH-J, Amicure UDH, Amicure UDH-J (being the fine scientific & technical corporation's system of aginomoto)
Deng.
The content of above-mentioned thermal curing agents relative to 100 parts by weight of above-mentioned curable resin, preferred lower limit be 1 parts by weight,
The preferred upper limit is 50 parts by weight.By making the content of above-mentioned thermal curing agents be the range, so as in the liquid for not making gained
Keep Thermocurable better in the case of the deteriorations such as the coating of crystal display element sealant.The content of above-mentioned thermal curing agents
The more preferable upper limit is 30 parts by weight.
For the sealing material for liquid crystal display device of the present invention, from flexibility, the cementability etc. for improving solidfied material, or suppression
Liquid crystal processed is inserted into sealant, sealant dissolve out the effect into liquid crystal it is better from the perspective of, preferably comprise soft grain
Son.
As above-mentioned soft particle, such as silicon-type particle, ethylene base system particle, polyurethane series particle, fluorine can be enumerated
It is particle, nitrile system particle etc..Wherein, preferably silicon-type particle, ethylene base system particle.
As above-mentioned silicon-type particle, dispersibility from the viewpoint of in resin, preferred organic silicon rubber particle.
As above-mentioned ethylene base system particle, it is suitble to use (methyl) acrylic particles.
Above-mentioned (methyl) acrylic particles can be by making the monomer for being used as raw material be polymerize using well known method
And it obtains.Specifically, can enumerate for example make in the presence of radical polymerization initiator monomer carry out suspension polymerisation method,
So that noncrosslinking seed particles is absorbed monomer in the presence of radical polymerization initiator and makes seed particles swelling to be planted
The method etc. of son polymerization.
As the monomer as the raw material for being used to form above-mentioned (methyl) acrylic particles, such as (methyl) third can be enumerated
Olefin(e) acid alkyl esters, (methyl) esters of acrylic acid containing oxygen atom, the monomer containing nitrile, fluorine-containing (methyl) esters of acrylic acid etc. are single
Functional monomer.
As above-mentioned (methyl) alkyl-acrylates, such as (methyl) methyl acrylate, (methyl) acrylic acid can be enumerated
Ethyl ester, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) 2-ethyl hexyl acrylate, (first
Base) 2-EHA, (methyl) lauryl acrylate, (methyl) acrylic acid cetyl, (methyl) stearyl acrylate,
(methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate etc..
As above-mentioned (methyl) esters of acrylic acid containing oxygen atom, can enumerate such as (methyl) acrylic acid 2- hydroxy methacrylates,
(methyl) glycerol acrylate, polyoxyethylene (methyl) acrylate, (methyl) glycidyl acrylate etc..
As the above-mentioned monomer containing nitrile, such as (methyl) acrylonitrile etc. can be enumerated.
As above-mentioned fluorine-containing (methyl) esters of acrylic acid, such as (methyl) acrylic acid trifluoromethyl ester, (methyl) can be enumerated
Five fluorine ethyl ester of acrylic acid etc..
Wherein, preferably (methyl) alkyl-acrylates can increase this is because the Tg of homopolymer is low and apply 1g loadings
When deflection.
In addition, in order to cross-linked structure, tetramethylol methane four (methyl) acrylate, tetra methylol can also be used
Methane three (methyl) acrylate, tetramethylol methane two (methyl) acrylate, trimethylolpropane tris (methyl) acrylic acid
Ester, dipentaerythritol six (methyl) acrylate, dipentaerythritol five (methyl) acrylate, glycerine three (methyl) acrylic acid
Ester, glycerine two (methyl) acrylate, (poly-) ethylene glycol two (methyl) acrylate, (poly-) propylene glycol two (methyl) acrylic acid
Ester, (poly-) tetramethylene two (methyl) acrylate, 1,4-butanediol two (methyl) acrylate, 1,6- hexylene glycols two (methyl)
The polyfunctional monomers such as acrylate, isocyanuric acid skeleton three (methyl) acrylate.Wherein, due between crosslinking points molecular weight it is big,
Deflection when applying 1g loadings can be increased, so it is preferred that (poly-) ethylene glycol two (methyl) acrylate, (poly-) propylene glycol two
(methyl) acrylate, (poly-) tetramethylene two (methyl) acrylate, 1,4-butanediol two (methyl) acrylate, 1,6- oneself
Glycol two (methyl) acrylate.
For the usage amount of above-mentioned cross-linkable monomer, as being used to form the raw material of above-mentioned (methyl) acrylic particles
Whole monomers in, preferred lower limit is 1 weight %, the preferred upper limit is 90 weight %.By making above-mentioned cross-linkable monomer
Usage amount is 1 weight % or more, to which solvent resistance improves, swelling etc. will not be caused to ask when being kneaded with various sealant raw materials
Topic, is easy to be uniformly dispersed.By making the usage amount of above-mentioned cross-linkable monomer for 90 weight % hereinafter, restoring so as to reduce
Rate.The more preferable lower limit of the usage amount of above-mentioned cross-linkable monomer is 3 weight %, the more preferable upper limit is 80 weight %.
In turn, other than the monomer of these acrylic acid series, styrenic monomers, vinyl ethers, carboxylic can also be used
Sour vinyl ester, unsaturated hydrocarbons, halogen-containing monomer, triallylcyanurate, Triallyl isocyanurate, three allyls
Base trimellitate, divinylbenzene, diallyl phthalate, diallyl acrylamide, diallyl ether, γ-(first
Base) monomers such as acryloyloxypropyltrimethoxysilane, vinyltrimethoxysilane.
As above-mentioned styrenic monomers, such as styrene, α-methylstyrene, trimethoxysilyl benzene can be enumerated
Ethylene etc..
As above-mentioned vinyl ethers, such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether can be enumerated
Deng.
As above-mentioned vinyl esters of carboxylic acids class, can enumerate for example vinyl acetate, vinyl butyrate, vinyl laurate,
Stearic acid vinyl ester etc..
As above-mentioned unsaturated hydrocarbons, can enumerate such as ethylene, propylene, isoprene, butadiene.
As above-mentioned halogen-containing monomer, can enumerate such as vinyl chloride, vinyl fluoride, chlorostyrene.
As above-mentioned (methyl) acrylic particles, it is suitable for use of nucleocapsid (methyl) acrylate copolymer particle.
As the commercially available product of above-mentioned nucleocapsid (methyl) acrylate copolymer particle, can enumerating such as F351, (ZEON is melted into
Corporation) etc..
In addition, as above-mentioned ethylene base system particle, such as polydivinylbenezene particle, polychlorobutadiene grain can also be used
Son, butadiene rubber particle etc..
The preferred lower limit of the average grain diameter of above-mentioned softness particle is 0.01 μm, preferred upper limit is 10 μm.It is above-mentioned soft by making
The average grain diameter of soft particle be the range, to can be improved gained sealing material for liquid crystal display device solidfied material softness
Property, cementability, or inhibit liquid crystal is inserted into sealant, sealant is dissolved out into liquid crystal effect better.Above-mentioned softness
The more preferable lower limit of the average grain diameter of particle is 0.1 μm, the more preferable upper limit is 8 μm.
It should be noted that in this specification, the average grain diameter of above-mentioned softness particle refers to：For match be mixed in sealant it
Preceding particle is worth obtained from being measured by using laser diffraction formula particle size distribution device.Spread out as above-mentioned laser
Formula particle size distribution device is penetrated, MASTERSIZER 2000 (Malvern Instruments Ltd. systems) etc. can be used.
It is above-mentioned softness particle hardness preferred lower limit be 10, preferred upper limit 50.By making the hard of above-mentioned soft particle
Degree is the range, to which the flexibility of solidfied material of sealing material for liquid crystal display device, the cementability of gained, or suppression can be improved
It is better that liquid crystal processed is inserted into sealant, sealant dissolves out the effect into liquid crystal.It is above-mentioned softness particle hardness it is more excellent
Select that lower limit is 20, the more preferable upper limit is 40.
It should be noted that in this specification, the hardness of above-mentioned softness particle refers to utilizing the side according to JIS K 6253
The Durometer A hardness that method is measured.
In 100 parts by weight of sealing material for liquid crystal display device of the present invention, the preferred lower limit of the content of above-mentioned softness particle
It is 50 parts by weight for 5 parts by weight, preferred upper limit.Content by making above-mentioned soft particle is the range, to make painting
Flexibility, the cementability of the solidfied material of the sealing material for liquid crystal display device of gained are improved in the case of the deteriorations such as cloth, or
Inhibit liquid crystal to be inserted into sealant, the effect of liquid crystal pollution caused by sealant it is better.Above-mentioned softness particle contains
The more preferable lower limit of amount is 10 parts by weight, the more preferable upper limit is 45 parts by weight.
For the raising of viscosity, the improvement of the cementability based on stress dispersion effect, the improvement of linear expansivity the purpose of, this
The sealing material for liquid crystal display device of invention preferably comprises filler.
As above-mentioned filler, such as inorganic filler, organic in addition to above-mentioned soft particle contained substance can be enumerated
Filler.
As above-mentioned inorganic filler, such as silica, talcum, bead, asbestos, gypsum, diatomite, green can be enumerated
Soil, bentonite, montmorillonite, sericite, atlapulgite, aluminium oxide, zinc oxide, iron oxide, magnesia, tin oxide, titanium oxide, carbon
Sour calcium, magnesium carbonate, magnesium hydroxide, aluminium hydroxide, aluminium nitride, silicon nitride, barium sulfate, calcium silicates etc..
In 100 parts by weight of sealing material for liquid crystal display device of the present invention, the preferred lower limit of the content of above-mentioned filler is
10 parts by weight, preferred upper limit are 70 parts by weight.By making the content of above-mentioned filler be the range, to which coating will not be made
Improvement of cementability and other effects is better in the case of Deng deteriorating.The more preferable lower limit of the content of above-mentioned filler is 20 weight
Part, the more preferable upper limit are 60 parts by weight.
The sealing material for liquid crystal display device of the present invention preferably comprises silane coupling agent.Above-mentioned silane coupling agent mainly has
As for by the effect of the bonding additives be bonded well such as sealant and substrate.
As above-mentioned silane coupling agent, can be suitble to use such as 3- TSL 8330s, 3- mercaptopropyis three
Methoxy silane, 3- glycidoxypropyltrime,hoxysilanes, 3- isocyanate propyl trimethoxysilanes etc..These substances
So that improving the excellent effect with the cementability of substrate etc., can inhibit to cure by being chemically bonded with curable resin
Property resin flows out in liquid crystal.
The present invention 100 parts by weight of sealing material for liquid crystal display device in, the content of above-mentioned silane coupling agent it is preferred under
It is limited to 0.1 parts by weight, preferred upper limit is 10 parts by weight.Content by making above-mentioned silane coupling agent is the range, can inhibit liquid
The generation of crystalline substance pollution, and the effect for improving cementability is better.The more preferable lower limit of the content of above-mentioned silane coupling agent is 0.3
Parts by weight, the more preferable upper limit are 5 parts by weight.
The sealing material for liquid crystal display device of the present invention can also contain opacifier.By containing above-mentioned opacifier, to
The sealing material for liquid crystal display device of the present invention can be suitable as shading sealant.
As above-mentioned opacifier, black such as iron oxide, titanium, nigrosine, Cyanine Black, fullerene, carbon black, resin packet can be enumerated
Cover type carbon black etc..Wherein, preferably titanium is black.
Above-mentioned titanium is black be compared to the average transmittance of the light for 300~800nm of wavelength, it is attached for ultraviolet range
The substance that the transmissivity of close, particularly 370~450nm of wavelength light is got higher.That is, it is the shading for having following properties that above-mentioned titanium is black
Agent：By will be seen that the light of the wavelength in light region fully covers, to be assigned to the sealing material for liquid crystal display device of the present invention
Light-proofness is given, on the other hand, makes the light transmission of the wavelength near ultraviolet range.As the used for liquid crystal display element close of the present invention
The opacifier contained by agent, the preferably high substance of insulating properties are sealed, the opacifier high as insulating properties, titanium is black also to be adapted for.
Above-mentioned titanium is black to play sufficient effect non-surface treated, but surface can also be used through coupling agent etc.
The processed titanium of organic principle is black or by inorganic constituents such as silica, titanium oxide, germanium oxide, aluminium oxide, zirconium oxide, magnesia
The surface treated titaniums such as the titanium of cladding is black are black.Wherein, black exhausted from that can further increase using the processed titanium of organic principle
Edge this point set out and it is preferred that.
In addition, using containing above-mentioned titanium it is black as opacifier the present invention sealing material for liquid crystal display device and manufacture
Liquid crystal display element have sufficient light-proofness, therefore can realize no light leakage and with high contrast and with excellent figure
As the liquid crystal display element of display quality.
The commercially available product black as above-mentioned titanium, it (is Mitsubishi's synthesis that can enumerate such as 12S, 13M, 13M-C, 13R-N, 14M-C
Materials Co., Ltd's system), Tilack D (red fringe chemical conversion corporation) etc..
The preferred lower limit of the black specific surface area of above-mentioned titanium is 13m2/ g, preferred upper limit 30m2/ g, more preferable lower limit are
15m2/ g, the more preferable upper limit are 25m2/g。
In addition, the preferred lower limit of the black volume resistance of above-mentioned titanium is 0.5 Ω cm, preferred upper limit is 3 Ω cm, more preferably
Lower limit is 1 Ω cm, the more preferable upper limit is 2.5 Ω cm.
The primary particle size of above-mentioned opacifier as long as liquid crystal display element substrate between distance hereinafter, as long as do not limit especially
Fixed, preferred lower limit is 1nm, the preferred upper limit is 5000nm.By making the primary particle size of above-mentioned opacifier be the range, to
Keep light-proofness better in the case where the deteriorations such as the coating of sealing material for liquid crystal display device of gained will not be made.Above-mentioned screening
The more preferable lower limit of the primary particle size of photo etching is 5nm, the more preferable upper limit is 200nm, and further preferred lower limit is 10nm, further
Preferred upper limit is 100nm.
It should be noted that the primary particle size of above-mentioned opacifier can use NICOMP 380ZLS (PARTICLE
SIZING SYSTEMS corporations), above-mentioned opacifier is scattered in and is measured in solvent (water, organic solvent etc.).
In 100 parts by weight of sealing material for liquid crystal display device of the present invention, the preferred lower limit of the content of above-mentioned opacifier is 5
Parts by weight, preferred upper limit are 80 parts by weight.By making the content of above-mentioned opacifier be the range, to which gained will not be being reduced
Sealing material for liquid crystal display device for after the cementability of substrate, solidification intensity, can play in the case of illustrative it is more excellent
Different light-proofness.The more preferable lower limit of the content of above-mentioned opacifier is 10 parts by weight, the more preferable upper limit is 70 parts by weight, further
Preferred lower limit is 30 parts by weight, the further preferred upper limit is 60 parts by weight.
The sealing material for liquid crystal display device of the present invention can also further contain reactive diluent, interval as needed
The additives such as object, curing accelerator, antifoaming agent, levelling agent, polymerization inhibitor.
As manufacture the present invention sealing material for liquid crystal display device method, can enumerate for example using homogenous disperse machine,
The mixing machines such as homogeneous mixer, universal mixer, planetary mixer, kneader, 3 roller machines, by curable resin, polymerization initiator
And/or the method etc. of the mixing such as thermal curing agents and the silane coupling agent that is added as needed on.
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 this sealing material for liquid crystal display device containing the present invention and electrically conductive microparticle is also this hair
It is one of bright.
As above-mentioned electrically conductive microparticle, metal ball can be used, be formed with conductive metal layer on the surface of resin particle
Particle etc..Wherein, the particle of conductive metal layer is formed on the surface of resin particle because the excellent resilience of resin particle can
It is conductively connected in the case where not damaging transparent substrate etc., therefore is suitable.
The manufactured liquid crystal using the sealing material for liquid crystal display device of the present invention or the conductive material up and down of the present invention
Show that element is also one of present invention.
The method of liquid crystal display element as the manufacture present invention can be suitble to use liquid crystal dripping process, specifically, can
It enumerates such as the method with following each process.
First, following process is carried out：Glass substrate, polyethylene terephthalate in electrodes such as subsidiary ito thin films
On one in 2 substrates such as substrate, the used for liquid crystal display element of the present invention is coated with by silk-screen printing, distributor coating etc.
Sealant, to formed frame-shaped seal pattern process.Next, carrying out following process：In the liquid crystal display member of the present invention
Part the fine droplet of liquid crystal is dripped in the state of uncured with sealant the seal pattern for being applied to substrate frame in, in vacuum
The process of another substrate of lower overlapping.Then, the seal pattern part of the sealing material for liquid crystal display device to the present invention is carried out
It irradiates the light such as ultraviolet light and makes the process of sealant precuring and the sealant through precuring is heated to keep its master solid
The process of change.By the above method, liquid crystal display element can be obtained.
Invention effect
According to the present invention, it is possible to provide liquid crystal can be inhibited to be inserted into sealant, the liquid crystal pollution caused by sealant
Sealing material for liquid crystal display device.In addition, according to the present invention, it is possible to provide be made using the sealing material for liquid crystal display device
Conductive material up and down and liquid crystal display element.
Specific implementation mode
Embodiment is exemplified below the present invention is described in more detail, but the present invention is not limited in these embodiments.
(making of polymerizable compound A of the present invention)
Bisphenol-A 228g (1.0mol) and epichlorohydrin 92g (1.0mol) inputs had into agitating device, thermometer and dropping liquid leakage
In the reactor of bucket, 100 DEG C are heated to, is added dropwise in ethyl alcohol 30g and dissolves solution obtained by sodium ethoxide 5g (0.1mol), knot is added dropwise
Shu Hou, stir within 5 hours.Then, by the hydrochloric acid and ion exchange water washing of reactant 0.1mol/L, remove generate salt and
Impurity.Then, evaporating and being dried under reduced pressure for epichlorohydrin is carried out, the PART EPOXY resin of the bisphenol-A as intermediate is obtained.
By the intermediate 142g of gained, acrylic acid 36g (0.5mol), diethylene glycol monoethyl ether acetic acid esters 500g, triphenyl
Phosphine 1g and hydroquinone methyl ether 100mg inputs have the reactor of agitating device and thermometer, are carried out 5 hours at 120 DEG C
Heating stirring.The reaction solution of gained is subjected to reprecipitation with methanol, is dried under reduced pressure, obtains the present invention as reaction product
The polymerizable compound A (weight average molecular weight 380).
It should be noted that the polymerizable compound A of the present invention of gained passes through1H-NMR、13C-NMR and FT-IR
It analyzes and is confirmed as with acryloyl group as polymerizable functional group and with structure (R shown in above-mentioned formula (2)1And R2For first
Base) compound.
(making of polymerizable compound B of the present invention)
Bisphenol F 200g (1.0mol) and epichlorohydrin 92g (1.0mol) inputs had into agitating device, thermometer and dropping liquid
The reactor of funnel is heated to 100 DEG C, is added dropwise in ethyl alcohol 30g and dissolves solution obtained by sodium ethoxide 5g (0.1mol), and knot is added dropwise
Shu Hou, stir within 5 hours.Then, by the hydrochloric acid and ion exchange water washing of reactant 0.1mol/L, remove generate salt and
Impurity.Then, evaporating and being dried under reduced pressure for epichlorohydrin is carried out, the PART EPOXY resin of the Bisphenol F as intermediate is obtained.
By the intermediate 128g of gained, acrylic acid 36g (0.5mol), diethylene glycol monoethyl ether acetic acid esters 500g, triphenyl
Phosphine 1g and hydroquinone methyl ether 100mg inputs have in the reactor of agitating device and thermometer, and it is small that 5 are carried out at 120 DEG C
When heating stirring.The reaction solution of gained is subjected to reprecipitation with methanol, is dried under reduced pressure, obtains this hair as reaction product
The bright polymerizable compound B (weight average molecular weight 350).
It should be noted that the polymerizable compound B of the present invention of gained passes through1H-NMR、13C-NMR and FT-IR
Analysis is confirmed as with acryloyl group as polymerizable functional group and with structure (R shown in above-mentioned formula (2)1And R2For hydrogen)
Compound.
(making of polymerizable compound C of the present invention)
By novolac resin (weight average molecular weight 3300) 150g, acrylic acid 36g (0.5mol), diethylene glycol monoethyl ether second
Acid esters 500g, triphenylphosphine 1g and hydroquinone methyl ether 100mg inputs have in the reactor of agitating device and thermometer,
5 hours heating stirrings are carried out at 120 DEG C.As above-mentioned novolac resin, use EP6050G (the organic material corporation of the rising sun).It will
The reaction solution of gained carries out reprecipitation with methanol, is dried under reduced pressure, and polymerizable compound C of the present invention is thus obtained
(weight average molecular weight 3800).
It should be noted that the polymerizable compound C of the present invention of gained passes through1H-NMR、13C-NMR and FT-IR
Analysis is confirmed as having acryloyl group as polymerizable functional group and with the compound of structure shown in above-mentioned formula (1).
(making of polymerizable compound D of the present invention)
By novolac resin (weight molecular weight 4800) 150g, acrylic acid 36g (0.5mol), diethylene glycol monoethyl ether second
Acid esters 500g, triphenylphosphine 1g and hydroquinone methyl ether 100mg inputs have in the reactor of agitating device and thermometer,
5 hours heating stirrings are carried out at 120 DEG C.As above-mentioned novolac resin, use EPR5030G (the organic material corporation of the rising sun).It will
The reaction solution of gained carries out reprecipitation with methanol, is dried under reduced pressure, and polymerizable compound D of the present invention is thus obtained
(weight average molecular weight 5300).
It should be noted that the polymerizable compound D of the present invention of gained passes through1H-NMR, 13C-NMR and FT-
IR is analyzed, and is confirmed as having acryloyl group as polymerizable functional group and with the compound of structure shown in above-mentioned formula (1).
(Examples 1 to 8 and comparative example 1)
According to the mix ratio recorded in table 1, by each material planetary stirring machine (Thinky corporations, " あ わ と り Practice
Taro ") mixed after, and then mixed with 3 roller machines, thus prepare the liquid crystal display of Examples 1 to 8 and comparative example 1
Element sealant.
<Evaluation>
For the sealing material for liquid crystal display device obtained in Examples and Comparative Examples, conduct the following evaluation.As a result
It is shown in table 1.
(illustrative)
Relative to 100 parts by weight of each sealing material for liquid crystal display device obtained in Examples and Comparative Examples, pass through row
Planetary agitating device makes the spacer particle (ponding chemical industrial company system, " Micropearl SP-2050 ") 1 of 5 μm of average grain diameter
Parts by weight are uniformly dispersed.Then, the sealant for being dispersed with the spacer particle is filled in distribution syringe (Musashi
Engineering, Inc. system, " PSY-10E ") in, deaeration processing is carried out, distributor (Musashi is then utilized
Engineering, Inc. system, " SHOTMASTER300 ") it is rectangular to describe on the transparent electrode substrate with ito thin film
The mode of frame is coated with sealant.Next, making another transparent substrate be pasted under the decompression of 5Pa using vacuum forming apparatus
It closes.30 seconds 100mW/cm are irradiated to the unit after fitting using metal halide lamp2Ultraviolet light after, heated at 120 DEG C 1 small
When and make sealant heat cure, produce unit.Sealant in observation gained unit, sealant, which is not broken, bad not to be had yet
The case where having the fluctuating of end and can depicting clearly lines, is denoted as "○", by without break it is bad but the end of sealant produce
The situation of raw fluctuating etc. is denoted as " △ ", will generate the bad situation that breaks and is denoted as "×", to have rated illustrative.
(cementability)
Relative to 100 parts by weight of each sealing material for liquid crystal display device obtained in Examples and Comparative Examples, pass through row
Planetary agitating device makes the spacer particle (ponding chemical industrial company system, " Micropearl SP-2050 ") 1 of 5 μm of average grain diameter
Parts by weight are uniformly dispersed.Then, take denier this be dispersed with the sealant of spacer particle in corning glass 1737 (20mm ×
50mm × thickness 0.7mm) central portion, on it be overlapped homotype glass and make sealing material for liquid crystal display device squeeze diffusion.
Then, using metal halide light irradiation 100mW/cm2Ultraviolet light after 30 seconds, and being heated 1 hour at 120 DEG C makes sealant consolidate
Change, obtains test film.
To the test film of gained, adhesive strength is measured using tensometer.It is 150N/cm by adhesive strength2Above situation
It is denoted as "○", is 50N/cm by adhesive strength2Less than 150N/cm2The case where be denoted as " △ ", adhesive strength is less than
50N/cm2The case where be denoted as "×", evaluate cementability.
(anti-penetrability)
Relative to 100 parts by weight of each sealing material for liquid crystal display device obtained in Examples and Comparative Examples, pass through row
Planetary agitating device makes the spacer particle (ponding chemical industrial company system, " Micropearl SP-2050 ") 1 of 5 μm of average grain diameter
Parts by weight are uniformly dispersed.Then, the sealant that this is dispersed with to spacer particle is filled in distribution syringe (Musashi
Engineering, Inc. system, " PSY-10E "), deaeration processing is carried out, distributor (Musashi is then utilized
Engineering, Inc. system, " SHOTMASTER300 ") it is rectangular to describe on the transparent electrode substrate with ito thin film
The mode of frame is coated with sealant.Then, the fine droplet of TN liquid crystal (Chisso corporations, " JC-5001LA ") is utilized into liquid crystal
Dripping device carries out coating of dripping, and so that another transparent substrate is bonded under the vacuum of 5Pa using vacuum forming apparatus.?
After being just bonded, 30 seconds 100mW/cm of metal halide light irradiation are used immediately2Ultraviolet light, and then heating is 1 small at 120 DEG C
When and make sealant heat cure, obtain liquid crystal display element (5 μm of cell gap).The liquid crystal display element of gained is exposed to
PCT conditions (121 DEG C, 100%RH, 2atm) 12 hours.It is aobvious using optics to being exposed to the liquid crystal display element after PCT conditions
Micro mirror is observed, the result is that：The case where moisture is not mixed into liquid crystal portion completely is denoted as "○", will only a small amount of mixed feelings of moisture
Condition is denoted as " △ ", and the case where large quantity of moisture that can confirm that is mixed into range estimation is denoted as "×", evaluates anti-penetrability.
(anti-insertion)
Relative to 100 parts by weight of each sealing material for liquid crystal display device obtained in Examples and Comparative Examples, pass through row
Planetary agitating device makes the spacer particle (ponding chemical industrial company system, " Micropearl SP-2050 ") 1 of 5 μm of average grain diameter
Parts by weight are uniformly dispersed.Then, the sealant that this is dispersed with to spacer particle is filled in distribution syringe (Musashi
Engineering, Inc. system, " PSY-10E ") in, deaeration processing is carried out, distributor (Musashi is then utilized
Engineering, Inc. system, " SHOTMASTER300 ") it is rectangular to describe on the transparent electrode substrate with ito thin film
The mode of frame is coated with sealant.Then, the fine droplet of TN liquid crystal (Chisso corporations, " JC-5001LA ") is utilized into liquid crystal
Dripping device carries out coating of dripping, and so that another transparent substrate is bonded under the vacuum of 5Pa using vacuum forming apparatus.Patch
It is being placed at room temperature for after ten minutes after conjunction, is using 30 seconds 100mW/cm of metal halide light irradiation2Ultraviolet light, then at 120 DEG C
Lower heating makes sealant heat cure in 1 hour, obtains liquid crystal display element (5 μm of cell gap).To the liquid crystal display element of gained
It is sealed the shape observation of pattern.As a result, the case where shape of seal pattern is not confused by internal liquid crystal is denoted as
"○", the shape of seal pattern is disturbed but the case where liquid crystal does not puncture seal pattern is denoted as " △ ", liquid crystal is punctured close
It seals pattern and leaks to external situation and be denoted as "×", evaluate anti-insertion.
[table 1]
Industrial availability
According to the present invention, it is possible to provide liquid crystal can be inhibited to be inserted into sealant, the liquid crystal pollution caused by sealant
Sealing material for liquid crystal display device.In addition, according to the present invention, it is possible to provide be made using the sealing material for liquid crystal display device
Conductive material up and down and liquid crystal display element.
Claims (7)
1. a kind of sealing material for liquid crystal display device, which is characterized in that containing curable resin, also contain polymerization initiator and/
Or thermal curing agents,
The curable resin contains the compound with structure shown in polymerizable functional group and following formula (1),
2. sealing material for liquid crystal display device according to claim 1, which is characterized in that have polymerizable functional group and formula
(1) compound of structure shown in is the compound for having structure shown in polymerizable functional group and following formula (2),
In formula (2), R1And R2Each independently represent hydrogen or methyl.
3. sealing material for liquid crystal display device according to claim 1 or 2, which is characterized in that polymerizable functional group is (first
Base) acryloyl group or epoxy group.
4. sealing material for liquid crystal display device according to claim 1,2 or 3, which is characterized in that have polymerism function
The molecular weight of the compound of structure shown in group and formula (1) is 300~4000.
5. sealing material for liquid crystal display device according to claim 1,2,3 or 4, which is characterized in that curable resin 100
In parts by weight, the content of the compound with structure shown in polymerizable functional group and formula (1) is the parts by weight of 1 parts by weight~50.
6. a kind of conductive material up and down, which is characterized 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 element, which is characterized in that be using the liquid crystal display element described in claim 1,2,3,4 or 5
It is manufactured with the conductive material up and down described in sealant or claim 6.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016191493 | 2016-09-29 | ||
| JP2016-191493 | 2016-09-29 | ||
| PCT/JP2017/034718 WO2018062168A1 (en) | 2016-09-29 | 2017-09-26 | Sealing agent for liquid crystal display elements, vertically conducting material and liquid crystal display element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108780251A true CN108780251A (en) | 2018-11-09 |
Family
ID=61760628
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201780016932.7A Pending CN108780251A (en) | 2016-09-29 | 2017-09-26 | Sealing material for liquid crystal display device, upper and lower conductive material and liquid crystal display element |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP7000159B2 (en) |
| KR (1) | KR20190053134A (en) |
| CN (1) | CN108780251A (en) |
| TW (1) | TWI746654B (en) |
| WO (1) | WO2018062168A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113826043A (en) * | 2019-07-01 | 2021-12-21 | 积水化学工业株式会社 | Sealing agent for display element, vertical conduction material and display element |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006009308A1 (en) * | 2004-07-22 | 2006-01-26 | Three Bond Co., Ltd. | Curable composition |
| CN101176033A (en) * | 2005-05-09 | 2008-05-07 | 积水化学工业株式会社 | Sealing material for liquid crystal dropping method, vertically conducting material, and liquid crystal display element |
| JP2014006325A (en) * | 2012-06-22 | 2014-01-16 | Nippon Kayaku Co Ltd | Liquid crystal sealing agent and liquid crystal display cell using the same |
| JP2014115639A (en) * | 2012-11-13 | 2014-06-26 | Sekisui Chem Co Ltd | Sealing compound for liquid crystal display elements, vertical conduction material, liquid crystal display element, and hydrazide based thermosetting agent |
| JP2015206997A (en) * | 2014-04-09 | 2015-11-19 | 協立化学産業株式会社 | Liquid crystal sealant adaptable to flexible liquid crystal panel |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US7253131B2 (en) | 2001-05-16 | 2007-08-07 | Sekisui Chemical Co., Ltd. | Curing resin composition and sealants and end-sealing materials for displays |
| KR101974708B1 (en) * | 2014-07-24 | 2019-05-02 | 미쓰이 가가쿠 가부시키가이샤 | Liquid crystal sealing agent and production method for liquid crystal display panel |
-
2017
- 2017-09-26 CN CN201780016932.7A patent/CN108780251A/en active Pending
- 2017-09-26 WO PCT/JP2017/034718 patent/WO2018062168A1/en active Application Filing
- 2017-09-26 KR KR1020187025222A patent/KR20190053134A/en not_active IP Right Cessation
- 2017-09-26 JP JP2017553445A patent/JP7000159B2/en active Active
- 2017-09-28 TW TW106133275A patent/TWI746654B/en active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006009308A1 (en) * | 2004-07-22 | 2006-01-26 | Three Bond Co., Ltd. | Curable composition |
| CN101176033A (en) * | 2005-05-09 | 2008-05-07 | 积水化学工业株式会社 | Sealing material for liquid crystal dropping method, vertically conducting material, and liquid crystal display element |
| JP2014006325A (en) * | 2012-06-22 | 2014-01-16 | Nippon Kayaku Co Ltd | Liquid crystal sealing agent and liquid crystal display cell using the same |
| JP2014115639A (en) * | 2012-11-13 | 2014-06-26 | Sekisui Chem Co Ltd | Sealing compound for liquid crystal display elements, vertical conduction material, liquid crystal display element, and hydrazide based thermosetting agent |
| JP2015206997A (en) * | 2014-04-09 | 2015-11-19 | 協立化学産業株式会社 | Liquid crystal sealant adaptable to flexible liquid crystal panel |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113826043A (en) * | 2019-07-01 | 2021-12-21 | 积水化学工业株式会社 | Sealing agent for display element, vertical conduction material and display element |
| CN113924351A (en) * | 2019-07-01 | 2022-01-11 | 积水化学工业株式会社 | Sealing agent for display element, vertical conduction material and display element |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20190053134A (en) | 2019-05-17 |
| JP7000159B2 (en) | 2022-01-19 |
| TW201819524A (en) | 2018-06-01 |
| TWI746654B (en) | 2021-11-21 |
| JPWO2018062168A1 (en) | 2019-07-11 |
| WO2018062168A1 (en) | 2018-04-05 |
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