CN110168440A - 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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- CN110168440A CN110168440A CN201880006074.2A CN201880006074A CN110168440A CN 110168440 A CN110168440 A CN 110168440A CN 201880006074 A CN201880006074 A CN 201880006074A CN 110168440 A CN110168440 A CN 110168440A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1339—Gaskets; Spacers; Sealing of cells
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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- Engineering & Computer Science (AREA)
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- Sealing Material Composition (AREA)
Abstract
The object of the present invention is to provide a kind of cementability, anti-penetrability and low liquid crystal pollution are excellent, and the sealing material for liquid crystal display device of the liquid crystal display element of excellent impact resistance can be obtained.Further it is an object to manufactured conductive material and liquid crystal display element up and down using the sealing material for liquid crystal display device.The present invention is a kind of sealing material for liquid crystal display device, it contains curable resin and non-reactive polymer, also contain polymerization initiator and/or thermal curing agents, the non-reactive polymer is high with the compatibility of the curable resin and does not have the functional group that can be reacted with the curable resin.
Description
Technical field
The present invention relates to a kind of cementability, anti-penetrability and low liquid crystal pollution are excellent and can obtain excellent impact resistance
Liquid crystal display element sealing material for liquid crystal display device.Moreover, it relates to use the sealing used for liquid crystal display element
Agent and manufactured conductive material and liquid crystal display element up and down.
Background technique
In recent years, the manufacturing method as liquid crystal display elements such as liquid crystal displays, from the shortening of productive temp time,
The viewpoints such as the optimization of liquid crystal usage amount are set out, and the use as disclosed in patent document 1, patent document 2 is used
Photo-thermal and the mode for being referred to as liquid crystal dripping process with curing type sealant.
In liquid crystal dripping process, firstly, the on piece in 2 electroded substrates forms frame-shaped by distribution
Seal pattern.Next, the fine droplet of liquid crystal is added dropwise in the sealing frame of substrate in the state that sealant is uncured,
It is overlapped another plate base under vacuum, precuring is carried out to light such as sealing irradiation ultraviolet lights.Thereafter, it is heated to be led
Solidification, to make liquid crystal display element.Currently, this drips, technique has become the mainstream of the manufacturing method of liquid crystal display element.
However, in the present age that the various mobile devices with liquid crystal display panel such as mobile phone, pocket game machine have been popularized, dress
The miniaturization set is the project most pursued.As the method for miniaturization, the narrow edge of liquid crystal display part can be enumerated, such as will
The position of sealing is configured under black matrix" (hereinafter also referred to as " narrow edge design ").It is designed with this narrow edge, from picture
The distance of plain region to sealant becomes close, and sealant itself also more carefully is described, and accordingly, there exist previous sealants to be bonded
Property aspect be not enough, be easy led to the problem of because of moisture-inhibiting or liquid crystal pollution etc. liquid crystal display element display it is bad.
In addition, more requiring impact resistance with the universal of mobile terminal for liquid crystal display element, sealant being wanted
Seek higher cementability so that even if due tos because of whereabouts of liquid crystal display element etc. by from the case where external impact when
Panel peeling etc. is not caused yet.However, previous sealant is difficult to take into account this high cementability and anti-penetrability or low liquid crystal
Pollution.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2001-133794 bulletin
Patent document 2: International Publication No. 02/092718
Summary of the invention
Problem to be solved by the invention
The purpose of the present invention is to provide a kind of cementability, anti-penetrability and low liquid crystal pollution are excellent and can obtain resistance to
The sealing material for liquid crystal display device of the excellent liquid crystal display element of impact.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 means used to solve the problem
The present invention is a kind of sealing material for liquid crystal display device, is contained: curable resin and non-reactive polymer,
Also contain polymerization initiator and/or thermal curing agents, the compatibility of the non-reactive polymer and the curable resin it is high and
Without the functional group that can be reacted with the curable resin.
Hereinafter, the present invention is described in detail.
Present inventors studied: by being compounded plasticizer in sealing material for liquid crystal display device, to improve sealant
Cementability and solidfied material flexibility, improve the impact resistance of liquid crystal display element.Prevent however, sealant obtained exists
The problem of penetrability difference.Therefore, the present inventor passes through further investigation, as a result, it has been found that: it is specific non-by being compounded in the encapsulant
Reactive polymer, to can get cementability, anti-penetrability and low liquid crystal pollution is excellent and can to obtain impact resistance excellent
The sealing material for liquid crystal display device of different liquid crystal display element, so as to complete the present invention.
Sealing material for liquid crystal display device of the invention contains curable resin.
Above-mentioned curable resin preferably comprises (methyl) acrylic compounds and/or epoxide.
It should be noted that in the present specification, above-mentioned " (methyl) acrylic compounds " mean acrylic compounds or metering system
Acids, above-mentioned " (methyl) acrylic compounds " mean the compound with (methyl) acryloyl group, above-mentioned " (methyl) propylene
Acyl group " means acryloyl group or methylacryloyl.
It as above-mentioned (methyl) acrylic compounds, such as can enumerate: (methyl) acrylate compounds, epoxy (first
Base) acrylate, carbamate (methyl) acrylate etc..Wherein, preferably epoxy (methyl) acrylate.In addition, just
For reactive viewpoint, above-mentioned (methyl) acrylic compounds preferably have 2 or more (methyl) propylene in 1 molecule
Acyl group person.
It should be noted that in the present specification, above-mentioned " (methyl) acrylate " means acrylate or metering system
Acid esters, above-mentioned " epoxy (methyl) acrylate " indicate to carry out epoxy group and (methyl) acrylic acid all in epoxide
Compound obtained by reaction.
It as the monofunctional compound in above-mentioned (methyl) acrylate compounds, such as can enumerate: (methyl) acrylic acid
Methyl esters, (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 methacrylate, (methyl) acrylic acid 2- hydroxy propyl ester, (first
Base) acrylic acid 2- hydroxybutyl, (methyl) acrylic acid 4- hydroxybutyl, (methyl) cyclohexyl acrylate, (methyl) acrylic acid is different
Norbornene ester, (methyl) acrylic acid dicyclopentenyl ester, (methyl) benzyl acrylate, (methyl) acrylic acid 2- methoxy acrylate, (first
Base) acrylic acid 2- ethoxy ethyl ester, (methyl) acrylic acid 2- butoxyethyl, (methyl) acrylic acid 2- phenoxy ethyl, methoxy
Ethyl glycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate, phenoxy group diethylene glycol (methyl) propylene
Acid esters, phenoxy group polyethylene glycol (methyl) acrylate, (methyl) tetrahydrofurfuryl acrylate, ethyl carbitol (methyl) acrylic acid
Ester, (methyl) acrylic acid 2,2,2- trifluoro ethyl ester, 2,2,3,3- tetrafluoro propyl ester of (methyl) acrylic acid, (methyl) acrylic acid 1H, 1H,
5H- octafluoro pentyl ester, acid imide (methyl) acrylate, (methyl) dimethylaminoethyl acrylate, (methyl) acrylic acid diethylamino
Base ethyl ester, succinic acid 2- (methyl) acryloyloxyethyl ester, hexahydrophthalic acid 2- (methyl) acryloyloxyethyl ester, 2- hydroxyl
Base propyl phthalic acid 2- (methyl) acryloyloxyethyl ester, phosphoric acid 2- (methyl) acryloyloxyethyl ester, (methyl) propylene
Acid glycidyl ester etc..
In addition, as 2 functional compounds in above-mentioned (methyl) acrylate compounds, such as can enumerate: 1,3- fourth two
Alcohol two (methyl) acrylate, 1,4-butanediol two (methyl) acrylate, 1,6- hexylene glycol two (methyl) acrylate, 1,9-
Nonanediol two (methyl) acrylate, 1,10- decanediol two (methyl) acrylate, ethylene glycol two (methyl) acrylate, two
Ethylene glycol two (methyl) acrylate, tetraethylene glycol two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, 2- are just
Butyl -2- ethyl -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 pair
Phenol A bis- (methyl) acrylate, propylene oxide addition bisphenol-A two (methyl) acrylate, two (first of ethyleneoxide addition Bisphenol F
Base) acrylate, dihydroxymethyl bicyclopentadiene two (methyl) acrylate, ethylene-oxide-modified isocyanuric acid two (methyl) third
Olefin(e) acid ester, (methyl) acrylic acid 2- hydroxyl -3- (methyl) acryloxy propyl ester, carbonate diol two (methyl) acrylate,
Polyetherdiol two (methyl) acrylate, polyester-diol two (methyl) acrylate, polycaprolactone glycol two (methyl) acrylic acid
Ester, polybutadiene diol two (methyl) acrylate etc..
In addition, as compounds more than 3 functions in above-mentioned (methyl) acrylate compounds, such as can enumerate: three
Hydroxymethyl-propane three (methyl) acrylate, ethyleneoxide addition trimethylolpropane tris (methyl) acrylate, propylene oxide
Addition trimethylolpropane tris (methyl) acrylate, caprolactone modification trimethylolpropane tris (methyl) acrylate, epoxy
Ethane addition isocyanuric acid three (methyl) acrylate, glycerol three (methyl) acrylate, three (first of propylene oxide addition glycerol
Base) acrylate, pentaerythrite three (methyl) acrylate, tricresyl phosphate (methyl) acryloyloxyethyl ester, double trihydroxy methyls third
Alkane four (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, two seasons penta
Tetrol six (methyl) acrylate etc..
As above-mentioned epoxy (methyl) acrylate, for example, can enumerate by make according to conventional methods epoxide with
(methyl) acrylic acid is reacted institute winner etc. in the presence of basic catalyst.
As the epoxide become for synthesizing the raw material of above-mentioned epoxy (methyl) acrylate, such as can enumerate:
Bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, 2,2 '-diallyl bisphenol type epoxy resin,
A Hydrogenated Bisphenol A type epoxy resin, propylene oxide addition bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy
Resin, thioether-type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene-type epoxy resin, naphthalene type epoxy resin, phenol phenol
Aldehyde type epoxy resin, o-cresol phenol aldehyde type epoxy resin, dicyclopentadiene phenolic type epoxy resin, biphenyl phenolic epoxy tree
Rouge, 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 in above-mentioned bisphenol A type epoxy resin, such as can enumerate jER828EL, jER1004 (is Mitsubishi
Chemical company's manufacture), EPICLON 850CRP (manufacture of DIC company) etc..
As the commercially available product in above-mentioned bisphenol f type epoxy resin, such as can enumerate: jER806, jER4004 (are Mitsubishi
Chemical company's manufacture) etc..
As the commercially available product in above-mentioned bisphenol-s epoxy resin, such as EPICLON EXA1514 (DIC corporation can be enumerated
Make) etc..
As the commercially available product in above-mentioned 2,2 '-diallyl bisphenol type epoxy resin, such as RE-810NM (day can be enumerated
The manufacture of this chemical drug company) etc..
As the commercially available product in above-mentioned A Hydrogenated Bisphenol A type epoxy resin, such as EPICLON EXA7015 (DIC public affairs can be enumerated
Department's manufacture) etc..
As the commercially available product in above-mentioned propylene oxide addition bisphenol A type epoxy resin, such as EP-4000S can be enumerated
(manufacture of ADEKA company) etc..
As the commercially available product in above-mentioned resorcinol type epoxy resin, such as EX-201 (Nagase ChemteX can be enumerated
Company's manufacture) etc..
As the commercially available product in above-mentioned biphenyl type epoxy resin, such as jER YX-4000H (Mitsubishi Chemical Ind can be enumerated
Manufacture) etc..
As the commercially available product in above-mentioned thioether-type epoxy resin, for example, can enumerate YSLV-50TE (Nippon Steel live aurification public affairs
Department's manufacture) etc..
As the commercially available product in above-mentioned diphenyl ether type epoxy resin, such as YSLV-80DE can be enumerated (aurification is lived by Nippon Steel
Company's manufacture) etc..
As the commercially available product in above-mentioned dicyclopentadiene-type epoxy resin, such as EP-4088S (ADEKA corporation can be enumerated
Make) etc..
As the commercially available product in above-mentioned naphthalene type epoxy resin, such as EPICLON HP4032, EPICLON EXA- can be enumerated
4700 (being the manufacture of DIC company) etc..
As the commercially available product in above-mentioned phenol novolak type epoxy, such as EPICLON N-770 (DIC company can be enumerated
Manufacture) etc..
As the commercially available product in above-mentioned o-cresol phenol aldehyde type epoxy resin, such as EPICLON N-670-EXP-S can be enumerated
(manufacture of DIC company) etc..
As the commercially available product in above-mentioned dicyclopentadiene phenolic type epoxy resin, such as EPICLON HP7200 can be enumerated
(manufacture of DIC company) etc..
As the commercially available product in above-mentioned biphenyl phenol aldehyde type epoxy resin, such as NC-3000P (Japanese chemical drug company can be enumerated
Manufacture) etc..
As the commercially available product in above-mentioned naphthol novolac type epoxy resin, such as ESN-165S can be enumerated (aurification is lived by Nippon Steel
Company manufacture) etc..
It as the commercially available product in above-mentioned glycidyl amine type epoxy resin, such as can enumerate: jER630 (Mitsubishi Chemical Ind
Manufacture), EPICLON 430 (manufacture of DIC company), TETRAD-X (manufacture of gas chemical company, Mitsubishi) etc..
As the commercially available product in abovementioned alkyl polyol type epoxy resin, such as can enumerate: (gold is lived to ZX-1542 by Nippon Steel
Chemical company manufacture), EPICLON 726 (manufacture of DIC company), Epolight80MFA (manufacture of chemical company, common prosperity society),
DENACOL EX-611 (manufacture of Nagase ChemteX company) etc..
Commercially available product in modified version epoxy resin as above-mentioned rubber, such as can enumerate: YR-450, YR-207 (are new
Day iron is lived aurification company and is manufactured), Epolead PB (manufacture of Daicel company) etc..
As the commercially available product in above-mentioned epihydric alcohol ester compound, such as DENACOL EX-147 (Nagase can be enumerated
The manufacture of ChemteX company) etc..
It as other commercially available products in above-mentioned epoxide, such as can enumerate: YDC-1312, YSLV-80XY, YSLV-
90CR (being that the manufacture of aurification company is lived by Nippon Steel), XAC4151 (Asahi Kasei Corporation's manufacture), jER1031, jER1032 (are
Mitsubishi Chemical Ind's manufacture), EXA-7120 (manufacture of DIC company), TEPIC (manufacture of Nissan Chemical company) etc..
It as the commercially available product in above-mentioned epoxy (methyl) acrylate, such as can enumerate: the manufacture of DAICEL-ALLNEX company
Epoxy (methyl) acrylate, epoxy (methyl) acrylate, the common prosperity society chemistry of the manufacture of chemical industrial company, the village Xin Zhong it is public
Take charge of epoxy (methyl) acrylate, epoxy (methyl) acrylate of Nagase ChemteX company manufacture etc. of manufacture.
As epoxy (methyl) acrylate of above-mentioned DAICEL-ALLNEX company manufacture, such as can enumerate:
EBECRYL860、EBECRYL3200、EBECRYL3201、EBECRYL3412、EBECRYL3600、EBECRYL3700、
EBECRYL3701、EBECRYL3702、EBECRYL3703、EBECRYL3708、EBECRYL3800、EBECRYL6040、
EBECRYL RDX63182 etc..
It as epoxy (methyl) acrylate of chemical industrial company, the above-mentioned village Xin Zhong manufacture, such as can enumerate: EA-
1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 etc..
It as epoxy (methyl) acrylate of chemical company, above-mentioned common prosperity society manufacture, such as can enumerate: 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 etc..
It as epoxy (methyl) acrylate of above-mentioned Nagase ChemteX company manufacture, such as can enumerate: DENACOL
ACRYLATE DA-141, DENACOL ACRYLATE DA-314, DENACOL ACRYLATE DA-911 etc..
Above-mentioned carbamate (methyl) acrylate for example can be by (methyl) acrylic acid derivative for making to have hydroxyl
Isocyanate compound is reacted in the presence of the tin based compound of catalytic amount and is obtained.
It as above-mentioned isocyanate compound, such as can enumerate: isophorone diisocyanate, 2,4- toluene diisocynate
Ester, 2,6- toluene di-isocyanate(TDI), hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, diphenyl methane-
4,4 '-diisocyanate (MDI), hydrogenation MDI, polymeric MDI, 1,5- naphthalene diisocyanate, 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, it is possible to use pass through polyalcohol and excessive isocyanate compound
Reaction chain elongation obtained isocyanate compound.
It as above-mentioned polyalcohol, such as can enumerate: ethylene glycol, propylene glycol, glycerol, D-sorbite, trimethylolpropane, carbon
Acid esters glycol, polyetherdiol, polyester-diol, polycaprolactone glycol etc..
It as above-mentioned (methyl) acrylic acid derivative with hydroxyl, such as can enumerate: hydroxy alkyl list (methyl) propylene
Acid esters, list (methyl) acrylate of dihydric alcohol, trihydroxylic alcohol list (methyl) acrylate or two (methyl) acrylate, epoxy
(methyl) acrylate etc..
As above-mentioned hydroxy alkyl list (methyl) acrylate, such as can enumerate: (methyl) acrylic acid 2- hydroxy methacrylate,
(methyl) acrylic acid 2- hydroxy propyl ester, (methyl) acrylic acid 2- hydroxybutyl, (methyl) acrylic acid 4- hydroxybutyl etc..
It as above-mentioned dihydric alcohol, such as can enumerate: ethylene glycol, propylene glycol, 1,3-PD, 1,3-BDO, Isosorbide-5-Nitrae-fourth
Glycol, polyethylene glycol etc..
It as above-mentioned trihydroxylic alcohol, such as can enumerate: trimethylolethane, trimethylolpropane, glycerol etc..
As above-mentioned epoxy (methyl) acrylate, such as bisphenol-a epoxy acrylate can be enumerated etc..
It as the commercially available product in above-mentioned carbamate (methyl) acrylate, such as can enumerate: East Asia Synesis Company system
Carbamate (methyl) acrylate of carbamate (methyl) acrylate, the manufacture of DATCEL-ALLNEX company for making,
The carbamate that carbamate (methyl) acrylate of Gen Shang industrial group manufacture, chemical industrial company, the village Xin Zhong manufacture
(methyl) acrylate, carbamate (methyl) acrylate of chemical company, common prosperity society manufacture etc..
As carbamate (methyl) acrylate of above-mentioned East Asia Synesis Company manufacture, such as can enumerate: M-1100,
M-1200, M-1210, M-1600 etc..
As carbamate (methyl) acrylate of above-mentioned DAICEL-ALLNEX company manufacture, such as can enumerate:
EBECRYL210、EBECRYL220、EBECRYL230、EBECRYL270、EBECRYL1290、EBECRYL2220、
EBECRYL4827、EBECRYL4842、EBECRYL4858、EBECRYL5129、EBECRYL6700、EBECRYL8402、
EBECRYL8803, EBECRYL8804, EBECRYL8807, EBECRYL9260 etc..
It as carbamate (methyl) acrylate of above-mentioned Gen Shang industrial group manufacture, such as can enumerate: Art
Resin UN-330、Art Resin SH-500B、Art Resin UN-1200TPK、Art Resin UN-1255、Art
Resin UN-3320HB, Art Resin UN-7100, Art Resin UN-9000A, Art Resin UN-9000H etc..
As carbamate (methyl) acrylate of chemical industrial company, the above-mentioned village Xin Zhong manufacture, such as can enumerate:
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 etc..
It as carbamate (methyl) acrylate of chemical company, above-mentioned common prosperity society manufacture, such as can enumerate: AH-
600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA-306T etc..
It as above-mentioned epoxide, such as can enumerate: as the original for synthesizing above-mentioned epoxy (methyl) acrylate
Epoxide, part (methyl) acrylic modified epoxy resin of material etc..
It should be noted that in the present specification, above-mentioned part (methyl) acrylic modified epoxy resin means in 1 molecule
In the compound with epoxy group and each 1 of (methyl) acryloyl group or more, such as can by make in 1 molecule with 2 with
The epoxy group of a part of the epoxide of upper epoxy group is reacted with (methyl) acrylic acid and is obtained.
As the commercially available product in above-mentioned part (methyl) acrylic modified epoxy resin, such as UVACURE1561 can be enumerated
(manufacture of DAICEL-ALLNEX company) etc..
Contain above-mentioned (methyl) acrylic compounds and above-mentioned epoxy in sealing material for liquid crystal display device of the invention
When the case where compound, preferably by above-mentioned curable resin (methyl) acryloyl group and epoxy group it is total in (first
Base) ratio of acryloyl group is set as 30 moles of % or more and 95 mole of % or less.By the ratio for making above-mentioned (methyl) acryloyl group
Rate is the range, to inhibit the generation of liquid crystal pollution, and the cementability of sealing material for liquid crystal display device obtained is more
It is excellent.
From the viewpoint of further suppressing liquid crystal pollution, above-mentioned curable resin preferably have-OH base ,-NH- base ,-
NH2The hydrogen bonds unit such as base.
Sealing material for liquid crystal display device of the invention contains high with the compatibility of above-mentioned curable resin and does not have energy
The non-reactive polymer of enough functional groups reacted with above-mentioned curable resin is (hereinafter also referred to as " non-reaction of the invention
Property polymer ").By containing non-reactive polymer of the invention, sealing material for liquid crystal display device of the invention can be taken into account
Excellent cementability and excellent anti-penetrability.
It should be noted that in the present specification, above-mentioned " the compatibility height with curable resin " means following state.
That is, firstly, mix 30 parts by weight of non-reactive polymer relative to 100 parts by weight of curable resin at 25 DEG C,
Then using blender, (Thinky company is manufactured, " あ わ と りTaro ARE-310 ") under conditions of 1000rpm stir 10
Minute.Thereafter, stand after ten minutes, equably divide into 5 containers, using LC-MS to ingredient contained in each container into
When row analysis, the difference all 2% of the composition of the composition of ingredient contained in each container and ingredient when mixing with
It is interior.
Non-reactive polymer of the invention does not have the functional group that can be reacted with above-mentioned curable resin.
The functional group that can be reacted with above-mentioned curable resin depends on the type of used curable resin, tool
It for body, such as can enumerate: (methyl) acryloyl group, epoxy group, hydroxyl, amino, carboxyl etc..
Become the more excellent person's aspect of low liquid crystal pollution, this hair from sealing material for liquid crystal display device obtained
Bright non-reactive polymer is preferably without function (methyl) acrylic polymer.
The preferred lower limit of the weight average molecular weight of non-reactive polymer of the invention is 1000, and the preferred upper limit is 10,000.
By making 1000 or more the weight average molecular weight of non-reactive polymer of the invention, so that liquid crystal display obtained is first
The cementability of part sealant is more excellent, and the impact resistance of liquid crystal display element obtained is more excellent.It is of the invention by making
The weight average molecular weight of non-reactive polymer is 10,000 hereinafter, so that sealing material for liquid crystal display device obtained is retouched
Drawing property is more excellent.The preferred lower limit of the weight average molecular weight of non-reactive polymer of the invention is 1500, it is preferred on
It is limited to 8000.
It should be noted that in the present specification, above-mentioned weight average molecular weight is by gel permeation chromatography (GPC) and to make
Tetrahydrofuran is used as solvent to be measured, passes through the calculated value of polystyrene conversion.It measures as by GPC by polyphenyl
Ethylene convert resulting weight average molecular weight when pillar, such as Shodex LF-804 (manufacture of Showa electrician company) can be enumerated etc..
The preferred upper limit of the glass transition temperature of non-reactive polymer of the invention is -30 DEG C.It is above-mentioned by making
Glass transition temperature is -30 DEG C hereinafter, to which the cementability of sealing material for liquid crystal display device of the invention is more excellent.It is above-mentioned
The preferred upper limit of glass transition temperature is -50 DEG C.
In addition, from viewpoints such as anti-penetrability, the preferred lower limit of the glass transition temperature of above-mentioned solidfied material is-
100 DEG C, preferred lower limit is -80 DEG C.
It should be noted that in the present specification, above-mentioned " glass transition temperature " means to pass through Measurement of Dynamic Viscoelasticity
The temperature occurred in the maximum of loss angle tangent (tan δ) obtained due to the maximum of micro Brownian motion.Above-mentioned glass
Changing transition temperature can be measured by using the known method of determination of viscoelasticity device etc..
Relative to above-mentioned 100 parts by weight of curable resin, the content of non-reactive polymer of the invention it is preferred under
5 parts by weight are limited to, the preferred upper limit is 150 parts by weight.By 5 parts by weight of content for making non-reactive polymer of the invention
More than, so that the cementability of sealing material for liquid crystal display device obtained is more excellent.By making non-reaction of the invention
Property polymer content be 150 parts by weight hereinafter, so that the cementability of sealing material for liquid crystal display device obtained and
Anti- penetrability is more excellent, and is able to suppress solidfied material and becomes fragile.The content of non-reactive polymer of the invention it is preferred under
20 parts by weight are limited to, the preferred upper limit is 80 parts by weight.
In 100 parts by weight of sealing material for liquid crystal display device of the invention, the content of non-reactive polymer of the invention
Preferred lower limit be 5 parts by weight, the preferred upper limit be 60 parts by weight.By the content for making non-reactive polymer of the invention
More than 5 parts by weight, so that the cementability of sealing material for liquid crystal display device obtained is more excellent.By making the present invention
Non-reactive polymer content be 60 parts by weight hereinafter, so that sealing material for liquid crystal display device obtained it is viscous
Connecing property and anti-penetrability are more excellent, and are able to suppress solidfied material and become fragile.The content of non-reactive polymer of the invention it is more excellent
The lower limit of choosing is 15 parts by weight, and the preferred upper limit is 45 parts by weight.
Sealing material for liquid crystal display device of the invention contains polymerization initiator and/or thermal curing agents.
It as above-mentioned polymerization initiator, such as can enumerate: radical polymerization initiator, cationic polymerization initiators etc..
As above-mentioned radical polymerization initiator, can enumerate: the hot radical polymerization generated free radicals by heating is drawn
Hair agent, the optical free radical polymerization initiator generated free radicals by light irradiation etc..
It as above-mentioned optical free radical polymerization initiator, such as can enumerate: benzophenone cpd, acetophenone compound, acyl
Base phosphine oxide compound, titanocenes compound, oxime ester compound, benzoin ether compound, thioxanthone compounds etc..
It as the commercially available product in above-mentioned optical free radical polymerization initiator, such as can enumerate: 1- hydroxycyclohexylphenylketone, 2-
Benzyl -2- dimethylamino -1- (4- morpholino phenyl) butanone, 1,2- (dimethylamino) -2- ((4- aminomethyl phenyl) methyl) -1-
(4- (4- morpholinyl) phenyl) -1- butanone, 2,2- dimethoxy -1,2- diphenylethane -1- ketone, bis- (2,4,6- trimethylbenzenes
Formoxyl) phenyl phosphine oxide, 2- methyl-1-(4- methyl thio phenyl)-2- morpholinopropane-1- ketone, 1- (4- (2- '-hydroxyethoxy
Base)-phenyl) -2- hydroxy-2-methyl -1- propane -1- ketone, 1- (4- (thiophenyl) phenyl) -1,2- acetyl caproyl 2- (O- benzoyl
Base oxime), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether etc..
Above-mentioned optical free radical polymerization initiator can be used alone, and can also combine two or more use.
As above-mentioned hot radical polymerization initiator, such as can enumerate comprising persons such as azo-compound, organic peroxides.
It wherein, preferably include the polymeric azo initiator of polymeric azo compound.
Above-mentioned hot radical polymerization initiator can be used alone, and can also combine two or more and use.
It should be noted that in the present specification, so-called polymeric azo compound means with azo group and passes through heat
And the cured free radical of (methyl) acryloxy, 300 or more number-average molecular weight compound can be made by generating.
The preferred lower limit of the number-average molecular weight of above-mentioned polymeric azo compound is 1000, and the preferred upper limit is 300,000.
By making the number-average molecular weight of the above-mentioned polymeric azo compound range, the adverse effect to liquid crystal is thus prevented, and
And it can easily mix into curable resin.The preferred lower limit of the number-average molecular weight of above-mentioned polymeric azo compound is
5000, the preferred upper limit is 100,000, and further preferred lower limit is 10,000, and the upper limit even more preferably is 90,000.
It should be noted that in the present specification, above-mentioned number-average molecular weight is by gel permeation chromatography (GPC) and to make
Tetrahydrofuran is used as solvent to be measured, and the value calculated by polystyrene conversion.It measures as by GPC by gathering
Styrene convert number-average molecular weight obtained when pillar, such as Shodex LF-804 (Showa electrician's corporation can be enumerated
Make) etc..
As above-mentioned polymeric azo compound, such as it can enumerate to have and be bonded with multiple polycyclic oxygen by azo group
The polymeric azo compound of structure obtained by the units such as alkane, dimethyl silicone polymer.
Have the macromolecule for being bonded with structure obtained by the units such as multiple polyalkylene oxides by azo group even as above-mentioned
Nitrogen compound, it is however preferred to have polyethylene oxide structure person.
As above-mentioned polymeric azo compound, specifically, can for example enumerate 4,4 '-azos bis- (4- cyanopentanoic acids) with
The condensation polymer of polyalkylene glycol, 4,4 '-azos bis- (4- cyanopentanoic acids) and the dimethyl silicone polymer with terminal amino group
Condensation polymer etc..
It as the commercially available product in above-mentioned polymeric azo initiator, such as can enumerate: VPE-0201, VPE-0401, VPE-
0601, VPS-0501, VPS-1001 (being Fujiphoto and the manufacture of Guang Chun medicine company) etc..In addition, the idol as on-macromolecular
Nitrogen initiator, such as can enumerate: V-65, V-501 (being Fujiphoto and the manufacture of Guang Chun medicine company) etc..
It as above-mentioned organic peroxide, such as can enumerate: ketone peroxide, ketal peroxide, hydrogen peroxide, dialkyl group mistake
Oxide, peroxy esters, diacyl peroxide, peroxy dicarbonate etc..
As above-mentioned cationic polymerization initiators, can be suitble to using light cationic polymerization initiator.Above-mentioned light cation is poly-
As long as closing initiator is to generate Bronsted acid or lewis acid person by light irradiation, it is not particularly limited, can is ionic light
Acid type is produced, acid type can also be produced for nonionic light.
It as above-mentioned light cationic polymerization initiator, such as can enumerate: aromatic diazonium salt, aromatic halonium salts, virtue
The organic metal networks such as the salts such as fragrant race's sulfonium salt, iron-allene complex object, titanocenes complex compound, aryl-silane alcohol-aluminium complex
Close species etc..
As the commercially available product in above-mentioned light cationic polymerization initiator, such as can enumerate: ADEKA OPTOMER SP-150,
ADEKA OPTOMER SP-170 (being the manufacture of ADEKA company) etc..
Relative to above-mentioned 100 parts by weight of curable resin, the preferred lower limit of the content of above-mentioned polymerization initiator is 0.1 weight
Part is measured, the preferred upper limit is 30 parts by weight.It is more than 0.1 parts by weight of content by making above-mentioned polymerization initiator, so that
The curability of sealing material for liquid crystal display device obtained is more excellent.By 30 weight of content for making above-mentioned polymerization initiator
Part is hereinafter, so that the storage stability of sealing material for liquid crystal display device obtained is more excellent.Above-mentioned polymerization initiator
Content preferred lower limit be 1 parts by weight, the preferred upper limit be 10 parts by weight, the further preferred upper limit be 5 weight
Part.
It as above-mentioned thermal curing agents, such as can enumerate: organic acid hydrazides, imdazole derivatives, amine compounds, polynary phenol system
Close object, acid anhydrides etc..Wherein, organic acid hydrazides is preferably used.
Above-mentioned thermal curing agents can be used alone, and can also combine two or more use.
It as above-mentioned organic acid hydrazides, such as can enumerate: sebacic dihydrazide, isophthalic dihydrazide, adipic acid two
Hydrazides, acid dihydrazide etc..
As the commercially available product in above-mentioned organic acid hydrazides, such as can enumerate: the organic acid hydrazides of great Zhong chemical company manufacture,
The organic acid hydrazides etc. of the fine scientific & technical corporation's manufacture of aginomoto.
As the organic acid hydrazides of above-mentioned great Zhong chemical company manufacture, such as SDH, ADH can be enumerated etc..
As the organic acid hydrazides of the fine scientific & technical corporation's manufacture of above-mentioned aginomoto, such as can enumerate: Amicure VDH,
Amicure VDH-J, Amicure UDH, Amicure UDH-J etc..
Relative to above-mentioned 100 parts by weight of curable resin, the preferred lower limit of the content of above-mentioned thermal curing agents is 1 weight
Part, the preferred upper limit is 50 parts by weight.It is obtained so as to not make by making the content of the above-mentioned thermal curing agents range
Coating of sealing material for liquid crystal display device etc. is deteriorated and the more excellent person of Thermocurable is made.The content of above-mentioned thermal curing agents
The preferred upper limit is 30 parts by weight.
In order to adjust viscosity, cementability be further increased based on stress dispersion effect, improves linear expansivity, further mentions
Anti- penetrability of high solidification object etc., sealing material for liquid crystal display device of the invention preferably comprise filler.
As above-mentioned filler, inorganic filler or organic filler can be used.
As above-mentioned inorganic filler, such as can enumerate: silica, talcum, bead, asbestos, gypsum, diatomite,
Terre verte, bentonite, montmorillonite, sericite, atlapulgite, aluminium oxide, zinc oxide, iron oxide, magnesia, tin oxide, titanium oxide,
Calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminium hydroxide, aluminium nitride, silicon nitride, barium sulfate, calcium silicates etc..
It as above-mentioned organic filler, such as can enumerate: polyester micropartical, polyurethane particulate, polyvinyl particle, third
Olefin(e) acid quasi polymer particle etc..
Above-mentioned filler can be used alone, and can also combine two or more and use.
In 100 parts by weight of sealing material for liquid crystal display device of the invention, the preferred lower limit of the content of above-mentioned filler
For 10 parts by weight, the preferred upper limit is 70 parts by weight.By making the content of the above-mentioned filler range, to not make illustrative
Become cementability Deng being deteriorated and further increase and other effects more excellent person.The preferred lower limit of the content of above-mentioned filler is 20
Parts by weight, the preferred upper limit are 60 parts by weight.
Sealing material for liquid crystal display device of the invention preferably comprises silane coupling agent.Above-mentioned silane coupling agent mainly has
As for by the effect of the be bonded bonding additives better such as sealant and substrate.
As above-mentioned silane coupling agent, such as it can be suitble to use: 3- TSL 8330,3- mercaptopropyi three
Methoxy silane, 3- glycidoxypropyltrime,hoxysilane, 3- isocyanate propyl trimethoxysilane etc..These silane
The excellent effect of the cementability of the raising and substrate etc. of coupling agent, is able to suppress and being chemically bonded with curable resin
Curable resin is flowed out into liquid crystal.
Above-mentioned silane coupling agent can be used alone, and can also combine two or more and use.
In 100 parts by weight of sealing material for liquid crystal display device of the invention, the content of above-mentioned silane coupling agent it is preferred
Lower limit is 0.1 parts by weight, and the preferred upper limit is 10 parts by weight.By making the content of the above-mentioned silane coupling agent range, thus
Inhibit the generation of liquid crystal pollution, and becomes cementability and further increase and other effects more excellent person.Above-mentioned silane coupling agent contains
The preferred lower limit of amount is 0.3 parts by weight, and the preferred upper limit is 5 parts by weight.
Sealing material for liquid crystal display device of the invention can contain opacifier.By containing above-mentioned opacifier, so that
Sealing material for liquid crystal display device of the invention can be suitable as shading sealant.
As above-mentioned opacifier, such as can enumerate: iron oxide, titanium be black, nigrosine, Cyanine Black, fullerene, carbon black, resin
Incrusting type carbon black etc..Wherein, preferably titanium is black.
Above-mentioned titanium is black be near ultraviolet range, the transmission of especially wavelength 370nm or more and 450nm light below
Rate is higher than the substance of the average transmittance for wavelength 300nm or more and 800nm light below.That is, it is under having that above-mentioned titanium is black
State the opacifier of property: to sealing used for liquid crystal display element of the invention and sufficiently covering the light of wavelength of visible light region
On the other hand agent, which assigns light-proofness, transmits the light of the wavelength near ultraviolet range.As liquid crystal display of the invention
The high substance of the opacifier contained in element sealant, preferably insulating properties, the opacifier high as insulating properties, is also suitably for
Titanium is black.
Above-mentioned titanium is black to play sufficient effect non-surface treated, but surface also can be used and be coupled agent
Treated that titanium is black for equal organic principles；It is oxidized the inorganic constituents such as silicon, titanium oxide, germanium oxide, aluminium oxide, zirconium oxide, magnesia
The surface treated titaniums such as the titanium of covering is black are black.Wherein, from the viewpoint of it can further increase insulating properties, preferably through organic
Treated that titanium is black for ingredient.
In addition, using containing the black sealing material for liquid crystal display device of the invention as opacifier of above-mentioned titanium and manufacturing
Liquid crystal display element has sufficient light-proofness, therefore can be realized with high contrast without light leakage and with excellent image
The liquid crystal display element of display quality.
As above-mentioned titanium it is black in commercially available product, such as can enumerate: the titanium of Mitsubishi Materials company manufacture is black,
The titanium of red fringe chemical conversion company manufacture is black etc..
Titanium as the manufacture of above-mentioned Mitsubishi Materials company is black, such as can enumerate: 12S, 13M, 13M-C,
13R-N, 14M-C etc..
Titanium as the manufacture of above-mentioned red fringe chemical conversion company is black, such as Tilack D can be enumerated etc..
The preferred lower limit of the black specific surface area of above-mentioned titanium is 13m2/ g, the preferred upper limit are 30m2/ g, preferred lower limit
For 15m2/ g, the preferred upper limit are 25m2/g。
In addition, the preferred lower limit of the black volume resistance of above-mentioned titanium is 0.5 Ω em, the preferred upper limit is 3 Ω cm, more
Preferred lower limit is 1 Ω em, and the preferred upper limit is 2.5 Ω em.
The primary particle size of above-mentioned opacifier as long as liquid crystal display element substrate between distance hereinafter, as long as have no special limit
Fixed, preferred lower limit is 1nm, and the preferred upper limit is 5000nm.It, can not by making the primary particle size of the above-mentioned opacifier range
Illustrative of sealing material for liquid crystal display device obtained etc. is set to be deteriorated and the more excellent person of light-proofness is made.Above-mentioned opacifier
The preferred lower limit of primary particle size is 5nm, and the preferred upper limit is 200nm, and further preferred lower limit is 10nm, further
The preferred upper limit is 100nm.
It should be noted that NICOMP 380ZLS (PARTICLE SIZING can be used in the primary particle size of above-mentioned opacifier
The manufacture of SYSTEMS company) and be scattered in above-mentioned opacifier in solvent (water, organic solvent etc.) to measure.
In 100 parts by weight of sealing material for liquid crystal display device of the invention, the preferred lower limit of the content of above-mentioned opacifier
For 5 parts by weight, the preferred upper limit is 80 parts by weight.By making the content of the above-mentioned opacifier range, so as to not make to be obtained
The cementability of sealing material for liquid crystal display device, the intensity after solidification and illustrative be greatly reduced and play more excellent
Light-proofness.The preferred lower limit of the content of above-mentioned opacifier is 10 parts by weight, and the preferred upper limit is 70 parts by weight, into one
Walking preferred lower limit is 30 parts by weight, and the further preferred upper limit is 60 parts by weight.
Sealing material for liquid crystal display device of the invention can and then contain reactive diluent as needed, spacer, consolidate
Change the additives such as promotor, defoaming agent, levelling agent, polymerization inhibitor.
It as the method for manufacturing sealing material for liquid crystal display device of the invention, such as can enumerate using mixing machine, will consolidate
The property changed resin, polymerization initiator and/or thermal curing agents, non-reactive polymer of the invention and added silicon as needed
The mixed method etc. such as alkane coupling agent.
It as above-mentioned mixing machine, such as can enumerate: homogenous disperse device, mixer for well-distribution, omnipotent mixer, planetary mixing
Device, kneader, three-roller etc..
By being compounded electrically conductive microparticle in sealing material for liquid crystal display device of the invention, so as to manufacture conducting up and down
Material.This conductive material up and down containing sealing material for liquid crystal display device and electrically conductive microparticle of the invention is also the present invention
One of.
As above-mentioned electrically conductive microparticle, metal ball can be used, in the surface of the resin particle person etc. that is formed with conductive metal layer.
Wherein, the electrically conductive microparticle that conductive metal layer is formed on the surface of resin particle can by the excellent resilience of resin particle
The ground such as transparent substrate are not damaged to be conductively connected, so it is preferred that.
The manufactured liquid crystal using sealing material for liquid crystal display device of the invention or conductive material up and down of the invention
Show that element is also one of present invention.
As the method for manufacturing liquid crystal display element of the invention, can be suitble to using liquid crystal dripping process, specifically, example
The method with following each process can such as be enumerated.
Firstly, carrying out following processes: in the glass substrate with electrodes such as ito thin films or polyethylene terephthalate base
An on piece in 2 plate base such as plate passes through the coating sealings used for liquid crystal display element of the invention such as silk-screen printing, distributor coating
Agent and the seal pattern for forming frame-shaped.Next, carrying out following processes: not solid in sealing material for liquid crystal display device of the invention
The fine droplet of liquid crystal is added dropwise in the frame for the seal pattern for being coated on substrate in the state of change, is overlapped another base under vacuum
Plate.Thereafter, it carries out making close the light such as the seal pattern partial illumination ultraviolet light of sealing material for liquid crystal display device of the invention
It seals the process of agent precuring and the sealant of precuring is heated and is allowed to lead cured process, by this method,
It can get liquid crystal display element.
The effect of invention
According to the present invention, it is possible to provide a kind of cementability, anti-penetrability and low liquid crystal pollution are excellent, and can obtain resistance to punching
The sealing material for liquid crystal display device of the excellent liquid crystal display element of hitting property.In addition, according to the present invention, it is possible to provide use the liquid crystal
Display element sealant and manufactured conductive material and liquid crystal display element up and down.
Specific embodiment
Hereinafter, enumerating embodiment the present invention is described in more detail, but the present invention is not limited to these embodiments.
(embodiment 1~11 and comparative example 1~3)
According to documented mix ratio in table 1,2, using planetary stirring machine, (Thinky company is manufactured, " あ ね と り
Taro ") each material is mixed after, and then mixed using three-roller, thus prepare embodiment 1~11 and comparative example 1~3
Sealing material for liquid crystal display device.
" ARUFON UP-1021 " in table is Examples 1 to 5, do not have used in 11 can be with curable resin
The functional group reacted without functional acrylic quasi polymer (weight average molecular weight 1600, -71 DEG C of glass transition temperature).Separately
Outside, " ARUFON UP-1021 " 30 parts by weight (total 260g) are mixed relative to 100 parts by weight of curable resin at 25 DEG C
Afterwards, using blender, (Thinky company is manufactured, " あ ね と りTaro ARE-310 ") 10 are stirred under conditions of 1000rpm
Minute.Thereafter, stand after ten minutes, equably divide into 5 containers, using LC-MS to ingredient contained in each container into
When row analysis, the difference for confirming the composition of the composition for ingredient contained in each container and ingredient when mixing is whole
It is the state within 2%.
" ARUFON UP-1170 " in table be used in embodiment 6~10 do not have can with curable resin into
Row reaction functional group without functional acrylic quasi polymer (weight average molecular weight 8000, -57 DEG C of glass transition temperature).Separately
Outside, " ARUFON UP-1170 " 30 parts by weight (total 260g) are mixed relative to 100 parts by weight of curable resin at 25 DEG C
Afterwards, using blender, (Thinky company is manufactured, " あ ね と りTaro ARE-310 ") 10 are stirred under conditions of 1000rpm
Minute.Thereafter, stand after ten minutes, equably divide into 5 containers, using LC-MS to ingredient contained in each container into
When row analysis, the difference for confirming the composition of the composition for ingredient contained in each container and ingredient when mixing is whole
It is the state within 2%.
" ARUFON UH-2041 " in table is that have hydroxyl as can be with curability tree used in comparative example 2
The acrylic polymer (weight average molecular weight 2500, -50 DEG C of glass transition temperature) for the functional group that rouge is reacted.In addition,
After 25 DEG C mix " ARUFON UH-2041 " 30 parts by weight (total 260g) relative to 100 parts by weight of curable resin,
Using blender, (Thinky company is manufactured, " あ ね と りTaro ARE-310 ") 10 points are stirred under conditions of 1000rpm
Clock.Thereafter, it stands after ten minutes, equably divides into 5 containers, ingredient contained in each container is being carried out using LC-MS
When analysis, the difference for confirming the composition of the composition for ingredient contained in each container and ingredient when mixing is all
State within 2%.
" ARUFON UG-4010 " in table is that have epoxy group as can be with curability used in comparative example 3
The acrylic polymer (weight average molecular weight 2900, -57 DEG C of glass transition temperature) for the functional group that resin is reacted.Separately
Outside, " ARUFON UG-4010 " 30 parts by weight (total 260g) are mixed relative to 100 parts by weight of curable resin at 25 DEG C
Afterwards, using blender, (Thinky company is manufactured, " あ ね と りTaro ARE-310 ") 10 points are stirred under conditions of 1000rpm
Clock.Thereafter, it stands after ten minutes, equably divides into 5 containers, ingredient contained in each container is being carried out using LC-MS
When analysis, the difference for confirming the composition of the composition for ingredient contained in each container and ingredient when mixing is all
State within 2%.
<evaluation>
Following evaluation is carried out to sealing material for liquid crystal display device obtained in Examples and Comparative Examples.It shows the result in
Table 1,2.
(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 make 1 parts by weight 5 μm of average grain diameter of spacer particle (ponding chemical industrial company manufacture,
" Micropearl SP-2050 ") it is uniformly dispersed.Next, the sealant for being dispersed with the spacer particle is filled in distribution
With in syringe (Musashi Engineering, Inc. manufacture, " PSY-10E "), after carrying out deaeration processing, distributor is used
(Musashi Engineering, Inc. manufacture, " SHOTMASTER300 ") in 2 transparent substrates with ito thin film one
On piece is coated with sealant in a manner of describing rectangular frame.Next, being bonded under the decompression of 5Pa using vacuum forming apparatus
Another transparent substrate, thus obtaining unit.100mW/cm is irradiated to unit obtained using metal halide lamp2Ultraviolet light
After (wavelength 365nm) 30 seconds, is heated 1 hour at 120 DEG C and make sealant cures, to obtain test film.It observes obtained
Sealant had both been set as without bad or the case where depicting perfect lines without fluctuating of breaking by the sealant in test film
" ◎ ", though by "○" will be set as the case where producing a little fluctuating without the bad sealant that breaks, though it will be without bad sealing of breaking
Agent, which is produced, is set as " Δ " compared with the case where macrorelief, will generate the bad situation that breaks and is set as "×", to evaluate illustrative.
(cementability)
Disperse spacer in 100 parts by weight of each sealing material for liquid crystal display device obtained in Examples and Comparative Examples
Particle (manufacture of ponding chemical industrial company, " Micropearl SI-H050 ") 1 parts by weight.For being dispersed with the spacer particle
Sealant, in 2 substrates (length 75mm, width 75mm, thickness 0.7mm) with rubbed alignment films and transparent electrode
An on piece by display unit become 45mm × 55mm in a manner of, with the line width of the sealant of 1mm be allocated device coating.It connects down
Come, the fine droplet dropwise addition of liquid crystal (Chisso company manufactures, " JC-5004LA ") is coated on the close of the substrate with transparent electrode
Whole face in the frame of agent is sealed, is immediately bonded another substrate.Next, using metal halide lamp to sealant partial illumination
100mW/cm2Ultraviolet light (wavelength 365nm) 30 seconds after, in 120 DEG C heat 1 hour, thus about in Examples and Comparative Examples
Each liquid crystal display element is made 10 units by each sealing material for liquid crystal display device obtained respectively.
Carry out the drop test for making each liquid crystal display element fall from the eminence of 2m.After drop test, by all units
In not the liquid crystal leakage as caused by peeling or rupture the case where be set as " ◎ ", will be more than 1 unit and less than 4 units
There are the case where liquid crystal leakage to be set as "○" for liquid crystal display element, will be more than 4 units and less than the liquid crystal display of 7 units member
There are the case where liquid crystal leakage to be set as " Δ " for part, and by liquid crystal display elements more than 7 units, there are the case where liquid crystal leakage to set
For "×", to evaluate cementability.
(anti-penetrability)
Using coating machine by each sealing material for liquid crystal display device obtained in Examples and Comparative Examples with thickness 200~
300 μm to be coated into smooth demoulding membranaceous.Next, irradiating 100mW/ to the sealant being coated with using metal halide lamp
cm2Ultraviolet light (wavelength 365nm) 30 seconds after, in 120 DEG C heat 1 hour and make sealant cures, thus obtain moisture permeability survey
Surely cured film is used.It is made by the method for the moisture permeability test method (agar diffusion method) of the water vapor proof barrier packaging material according to JIS Z 0208
Moisture permeability test cup installs moisture permeability measurement cured film obtained, puts into the constant temperature of temperature 60 C humidity 90%RH
Moisture permeability is measured in constant humidity baking oven.By moisture permeability less than 200g/m2" ◎ " is set as the case where r for 24 hours, by 200g/m2·24hr
Above and less than 250g/m2"○" is set as the case where r for 24 hours, by 250g/m2R or more and less than 300g/m for 24 hours2R for 24 hours
Situation is set as " Δ ", by 300g/m2The situation of r or more is set as "×" for 24 hours, to evaluate anti-penetrability.
(low liquid crystal pollution)
It is same with above-mentioned " (cementability) " about each sealing material for liquid crystal display device obtained in Examples and Comparative Examples
Operates and make liquid crystal display element to sample.
After carrying out 100 hours field investigations to liquid crystal display element obtained, confirmation is set as applying at 80 DEG C by visual observation
Liquid crystal aligning disorder after adding the state of 1000 hours voltage.
Liquid crystal aligning disorder is judged according to the irregular colour of peripheral portion and display unit, by absolutely not irregular colour
Situation is set as "○", and " Δ " will be set as the case where peripheral portion confirms a little irregular colour, by irregular colour to display unit
The case where extension, is set as "×", to think poorly of liquid crystal pollution.
[table 1]
[table 2]
Industrial availability
According to the present invention, it is possible to provide a kind of cementability, anti-penetrability and low liquid crystal pollution are excellent, and can obtain resistance to punching
The sealing material for liquid crystal display device of the excellent liquid crystal display element of hitting property.In addition, according to the present invention, it is possible to provide use the liquid crystal
Display element sealant and manufactured conductive material and liquid crystal display element up and down.
Claims (7)
1. a kind of sealing material for liquid crystal display device, which is characterized in that containing curable resin and non-reactive polymer, also
Containing polymerization initiator and/or thermal curing agents, the compatibility of the non-reactive polymer and the curable resin is high and not
With the functional group that can be reacted with the curable resin.
2. sealing material for liquid crystal display device according to claim 1, wherein the non-reactive polymer is no function
(methyl) acrylic polymer.
3. sealing material for liquid crystal display device according to claim 1 or 2, wherein the weight of the non-reactive polymer
Average molecular weight is 1000 or more and 10,000 or less.
4. sealing material for liquid crystal display device according to claim 1,2 or 3, wherein the non-reactive polymer
Glass transition temperature is -30 DEG C or less.
5. sealing material for liquid crystal display device according to claim 1,2,3 or 4, wherein relative to the curability tree
100 parts by weight of rouge, the content of the non-reactive polymer are 5 parts by weight or more and 150 parts by weight or less.
6. a kind of conductive material up and down, containing sealing material for liquid crystal display device described in claim 1,2,3,4 or 5 and leads
Electrical particle.
7. a kind of liquid crystal display element, be using sealing material for liquid crystal display device described in claim 1,2,3,4 or 5 or
It is as claimed in claim 6 up and down conductive material and it is manufactured.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017-118626 | 2017-06-16 | ||
| JP2017118626 | 2017-06-16 | ||
| PCT/JP2018/022763 WO2018230655A1 (en) | 2017-06-16 | 2018-06-14 | Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110168440A true CN110168440A (en) | 2019-08-23 |
| CN110168440B CN110168440B (en) | 2022-10-18 |
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| CN201880006074.2A Active CN110168440B (en) | 2017-06-16 | 2018-06-14 | Sealing agent for liquid crystal display element, vertical conduction material, and liquid crystal display element |
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| Country | Link |
|---|---|
| JP (1) | JP7088833B2 (en) |
| KR (1) | KR102613597B1 (en) |
| CN (1) | CN110168440B (en) |
| WO (1) | WO2018230655A1 (en) |
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| US20030147034A1 (en) * | 1999-11-01 | 2003-08-07 | Kyoritsu Chemical & Co., Ltd | Sealing agent for LC dropping method for LCD panels |
| JP2005281493A (en) * | 2004-03-30 | 2005-10-13 | Yokohama Rubber Co Ltd:The | Resin composition |
| JP2010144092A (en) * | 2008-12-19 | 2010-07-01 | Nitto Denko Corp | Resin composition |
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| JP2014034169A (en) * | 2012-08-09 | 2014-02-24 | Tombow Pencil Co Ltd | Eraser |
| JP2014054812A (en) * | 2012-09-14 | 2014-03-27 | Tombow Pencil Co Ltd | Eraser |
| CN104024356A (en) * | 2011-12-21 | 2014-09-03 | 汉高股份有限及两合公司 | Dry bonding acrylate adhesive layers |
| JP2016044187A (en) * | 2014-08-19 | 2016-04-04 | 積水化学工業株式会社 | Curable resin composition, sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element |
| CN106462014A (en) * | 2014-10-08 | 2017-02-22 | 积水化学工业株式会社 | Sealing agent for liquid crystal dropping methods, vertically conducting material and liquid crystal display element |
| CN106661410A (en) * | 2014-08-20 | 2017-05-10 | 株式会社可乐丽 | Acrylic adhesive composition and adhesive product |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1405888A1 (en) | 2001-05-16 | 2004-04-07 | Sekisui Chemical Co., Ltd. | Curing resin composition and sealants and end-sealing materials for displays |
-
2018
- 2018-06-14 CN CN201880006074.2A patent/CN110168440B/en active Active
- 2018-06-14 WO PCT/JP2018/022763 patent/WO2018230655A1/en active Application Filing
- 2018-06-14 JP JP2018534760A patent/JP7088833B2/en active Active
- 2018-06-14 KR KR1020197011897A patent/KR102613597B1/en active IP Right Grant
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030147034A1 (en) * | 1999-11-01 | 2003-08-07 | Kyoritsu Chemical & Co., Ltd | Sealing agent for LC dropping method for LCD panels |
| JP2005281493A (en) * | 2004-03-30 | 2005-10-13 | Yokohama Rubber Co Ltd:The | Resin composition |
| JP2010144092A (en) * | 2008-12-19 | 2010-07-01 | Nitto Denko Corp | Resin composition |
| CN103261280A (en) * | 2010-12-16 | 2013-08-21 | 日立化成株式会社 | Photocurable resin composition, and image display device and process for production thereof |
| CN104024356A (en) * | 2011-12-21 | 2014-09-03 | 汉高股份有限及两合公司 | Dry bonding acrylate adhesive layers |
| JP2014034169A (en) * | 2012-08-09 | 2014-02-24 | Tombow Pencil Co Ltd | Eraser |
| JP2014054812A (en) * | 2012-09-14 | 2014-03-27 | Tombow Pencil Co Ltd | Eraser |
| JP2016044187A (en) * | 2014-08-19 | 2016-04-04 | 積水化学工業株式会社 | Curable resin composition, sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element |
| CN106661410A (en) * | 2014-08-20 | 2017-05-10 | 株式会社可乐丽 | Acrylic adhesive composition and adhesive product |
| CN106462014A (en) * | 2014-10-08 | 2017-02-22 | 积水化学工业株式会社 | Sealing agent for liquid crystal dropping methods, vertically conducting material and liquid crystal display element |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110168440B (en) | 2022-10-18 |
| JP7088833B2 (en) | 2022-06-21 |
| KR20200019842A (en) | 2020-02-25 |
| KR102613597B1 (en) | 2023-12-13 |
| WO2018230655A1 (en) | 2018-12-20 |
| JPWO2018230655A1 (en) | 2020-04-16 |
| TW201906989A (en) | 2019-02-16 |
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