CN101193752A - Substrate and display element - Google Patents

Substrate and display element Download PDF

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Publication number
CN101193752A
CN101193752A CNA2006800200938A CN200680020093A CN101193752A CN 101193752 A CN101193752 A CN 101193752A CN A2006800200938 A CNA2006800200938 A CN A2006800200938A CN 200680020093 A CN200680020093 A CN 200680020093A CN 101193752 A CN101193752 A CN 101193752A
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Prior art keywords
resin bed
layer
substrate
resin
display element
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Inventor
山本恭子
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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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
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/38—Polymers
    • C09K19/3804—Polymers with mesogenic groups in the main chain
    • C09K19/3809—Polyesters; Polyester derivatives, e.g. polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/38—Polymers
    • C09K19/3833—Polymers with mesogenic groups in the side chain
    • C09K19/3838—Polyesters; Polyester derivatives
    • 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
    • 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
    • G02F1/133305—Flexible substrates, e.g. plastics, organic film
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
    • H10K77/10—Substrates, e.g. flexible substrates
    • H10K77/111—Flexible substrates
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/301—Details of OLEDs
    • H10K2102/302—Details of OLEDs of OLED structures
    • H10K2102/3023—Direction of light emission
    • H10K2102/3026—Top emission
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/301—Details of OLEDs
    • H10K2102/311—Flexible OLED
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/87—Passivation; Containers; Encapsulations
    • H10K59/873—Encapsulations
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Nonlinear Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Mathematical Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Liquid Crystal (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)

Abstract

Disclosed are a substrate and a display device. The substrate comprises a resin layer (1) and a resin layer (2). The resin layer (1) is composed of a liquid crystal polyester A and a polymer B having a functional group reactive with liquid crystal polyesters, and the resin layer (2) is composed of a resin other than liquid crystal polyesters. The display device sequentially comprises the following (a)-(e): (a) the resin layer (1); (b) the resin layer (2); (c) a conductive layer; (d) an organic layer which absorbs, diffuses, rotates or emits light when an electric field is applied thereto; and (e) a transparent conductive layer.

Description

Substrate and display element
Technical field
The present invention relates to a kind of substrate and display element.In particular to the display element of a kind of flexible display (flexible display) and so on and the substrate that uses therein.
Background technology
In display element, flexible display has pliability, can be set at the curved surface of instrument etc., so get most of the attention.As flexible display, for example known organic EL, liquid crystal cell.
As the substrate that uses in the display element, for example knownly stack gradually the substrate (spy opens the 1st page～the 3rd page in 2003-89163 communique) that the oxidation prevention layer that is made of inorganic oxide and resin bed form in base material.
Display element requires to improve durability, and the substrate that uses in display element in addition requires to have high resistance oxygen.
Summary of the invention
The inventor concentrates on studies in order to solve above-mentioned problem, and the result is so that finish the present invention.
That is, the invention provides a kind of substrate that comprises resin bed 1 and resin bed 2.
At this, resin bed 1 comprises liquid-crystal polyester resin, and resin bed 2 comprises the resin beyond the liquid-crystal polyester resin.
In addition, the present invention also provides a kind of display element that contains following (a)～(e) successively.
(a) described resin bed 1,
(b) described resin bed 2,
(c) conductive layer,
(d) when applying electric field, demonstrate light absorption, light scattering, optically-active or luminous organic layer,
(e) transparent conductivity layer.
The specific embodiment
Substrate
Substrate of the present invention contains resin bed 1 and resin bed 2.Resin bed 1 is generally 1, also can be for more than 2.Resin bed 2 can be more than 1 or 2 any one.And then substrate also can contain the resin bed beyond resin bed 1 or the resin bed 2.
[resin bed 1]
Resin bed 1 comprises liquid-crystal polyester resin, in fact, comprises: liquid crystal polyester A and comprising has the polymer B with reactive functional group of liquid crystal polyester.
Liquid crystal polyester A
Liquid crystal polyester A is the material for aromatic hydroxy-carboxylic, aromatic dicarboxylic acid and aromatic diol polymerization are obtained for example; Make material of the same race or that the polymerization of xenogenesis aromatic hydroxy-carboxylic obtains; Make material that pet reactions such as aromatic hydroxy-carboxylic and PETG obtain etc.
Except aromatic hydroxy-carboxylic, aromatic dicarboxylic acid aromatic diol, the material that liquid crystal polyester A also can obtain for the ester formation property derivative that uses them.
The ester of carboxylic acid forms the property derivative and for example promotes the acid chloride, acid anhydrides etc. of polyester reaction of formation and so on to become the material of reactive high derivative, alcohols that carboxyl generation ester exchange reaction generates polyester and so on for carboxyl or with the material of ethylene glycol formation ester etc.
In addition, as long as aromatic hydroxy-carboxylic, aromatic dicarboxylic acid, aromatic diol also can be for using halogen atoms such as chlorine atom, fluorine atom, alkyl such as methyl, ethyl, the material that replacements such as aryl such as phenyl form for not hindering the degree of ester formation property.
The constitutional repeating unit that derives from aromatic dicarboxylic acid that the constitutional repeating unit of liquid crystal polyester is for example shown below; Derive from the constitutional repeating unit of aromatic diol; Derive from the constitutional repeating unit of aromatic hydroxy-carboxylic.
Derive from the constitutional repeating unit of aromatic dicarboxylic acid:
Figure S2006800200938D00031
Above-mentioned constitutional repeating unit also can be replaced by halogen atom, alkyl or aryl.
Derive from the constitutional repeating unit of aromatic diol:
Figure S2006800200938D00032
Above-mentioned constitutional repeating unit also can be replaced by halogen atom, alkyl or aryl.
Derive from the constitutional repeating unit of aromatic hydroxy-carboxylic:
Figure S2006800200938D00041
Above-mentioned constitutional repeating unit also can be replaced by halogen atom, alkyl or aryl.
From the stable on heating viewpoint of substrate, liquid crystal polyester A preferably contains constitutional repeating unit that 25～10 moles of % derive from aromatic dicarboxylic acid, 35～10 moles of % and derives from the constitutional repeating unit that the constitutional repeating unit of aromatic diol, 30～80 moles of % derive from aromatic hydroxy-carboxylic.Wherein, these construction unit sum totals are 100 moles of %.
In addition, viewpoint from the balance of the hear resistance of substrate, mechanical property, machinability, the preferred constitutional repeating unit total mole number of liquid crystal polyester A relatively of liquid crystal polyester A contains above, the 99 moles of constitutional repeating units that the following formula (1-1) of % is represented of 30 moles of %.Liquid crystal polyester with constitutional repeating unit of formula (1-1) expression has following (I), (II), (III), (IV), (V) or (VI) usually as constitutional repeating unit, preferably have (I), (II), (III), (V) or (VI), and then preferably have (I), (II) or (III), especially preferably have (I) or (II).
Figure S2006800200938D00051
Figure S2006800200938D00061
Any one the liquid crystal polyester A of constitutional repeating unit that contains formula (I)～(VI) is the standard preparation as long as for example open the method for putting down in writing in the flat 2-51523 communique with the public clear 47-47870 communique of spy, special public clear 63-3888 communique, special public clear 63-3891 communique, special public clear 56-18016 communique, spy.
Polymer B
Polymer B contains the reactive functional group that has with liquid crystal polyester.With liquid crystal polyester have reactive functional group for the functional group of liquid crystal polyester reaction, You Xuan Wei oxazolyl or epoxy radicals, amino, and then be preferably epoxy radicals.The part that these functional groups also can be used as other functional groups exists, and as such example, can enumerate glycidyl etc.
To have reactive functional group in order in polymer B, importing, for example when synthetic polymer, can to make monomer polymerization, also can make monomer and polymer generation glycerol polymerization with functional group with functional group with liquid crystal polyester.The monomer that use this moment contains for example glycidyl.The monomer that contains glycidyl is preferably following formula
Figure S2006800200938D00062
(in the formula, the carbon number that R represents to have the ethene unsaturated bond is 2～13 alkyl, X represents-C (O) O-,-CH 2-O-or
Figure S2006800200938D00063
) expression unsaturated carboxylic acid ethylene oxidic ester, unsaturated glycidol ether.
The unsaturated carboxylic acid ethylene oxidic ester for example is glycidyl acrylate, GMA, itaconic acid 2-glycidyl ester, butylene tricarboxylic acids three-glycidyl ester, to styrene carboxylic acid ethylene oxidic ester.
Unsaturated glycidol ether for example is vinyl glycidyl ether, allyl glycidyl ether, 2-methacrylic glycidol ether, methylpropenyl glycidol ether, styrene-to glycidol ether.
Polymer B preferably contains 0.1～30 weight % unsaturated carboxylic acid glycidol ester units and/or unsaturated glycidol ether unit.
As polymer B, for example have rubber, the thermoplastic resin of above-mentioned functional group.They can be for alone or in combination.Heat endurance or flexible viewpoint from resin bed 1 preferably are made of rubber.
Polymer B is under the situation of rubber, for example during synthetic rubber, can make the monomer polymerization with functional group, also can make monomer and grafting rubbers polymerization with functional group.
Rubber for example can be enumerated the rubber with epoxy radicals of (methyl) acrylate-styrene-(unsaturated carboxylic acid ethylene oxidic ester and/or unsaturated glycidol ether) polymer rubber and so on.
The ester of (methyl) acrylate for obtaining from acrylic or methacrylic acid and alcohol.It is 1～8 alcohol that alcohol is preferably carbon number.(methyl) acrylate for example is methyl acrylate, methyl methacrylate, n-butyl acrylate, n-BMA, tert-butyl acrylate, metering system tert-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid 2-ethylhexyl.(methyl) acrylate can be for separately or any one of their combination.
Viewpoint from heat endurance or engineering properties, (methyl) acrylic ester unit of the rubber of polymer B surpasses 40 weight % usually, be preferably more than the 45 weight %, usually less than 97 weight %, be preferably below the 70 weight %, ethylene unit is generally more than the 3 weight %, be preferably more than the 10 weight %, usually less than 50 weight %, be preferably below the 49 weight %, unsaturated carboxylic acid glycidol ether unit and/or unsaturated glycidol ether unit are generally more than the 0.1 weight %, are preferably more than the 0.5 weight %, be generally below the 30 weight %, be preferably below the 20 weight %.Wherein, their sum total is 100 weight %.
Rubber for example utilizes polymerisation in bulk, emulsion polymerisation, the polymerisation in solution manufacturing of radical initiator to get final product.As the spy open clear 48-11388 communique, the spy opens clear 61-127709 communique and puts down in writing, rubber is as long as in the presence of the polymerization initiator that produces free radical, at pressure 500kg/cm 2More than, prepare under the condition of 40～300 ℃ of temperature and get final product.
Polymer B also can be for having the rubber of above-mentioned other functional groups in addition.Other rubber are for example for to have the acrylic rubber that has reactive functional group with liquid crystal polyester, or have the vinyl aromatic hydrocarbon compound one conjugated diene compound block copolymer rubber that has reactive functional group with liquid crystal polyester.
Acrylic rubber is preferably with formula (2-1), (2-2) or (2-3)
CH 2＝CH-C(O)-OR 1 (2-1)
CH 2＝CH-C(O)-OR 2OR 3 (2-2)
CH 2＝CR 4H-C(O)-O(R 5(C(O)O)nR 6 (2-3)
(in the formula, R 1The expression carbon number is 1～18 alkyl or cyanoalkyl.R 2The expression carbon number is 1～12 alkylidene, R 3The expression carbon number is 1～12 alkyl.R 4Expression hydrogen atom or methyl, R 5The expression carbon number is 3～30 alkylidene, R 6The expression carbon number is 1～20 alkyl or derivatives thereof, and n represents 1～20 integer.) expression polymer of monomers.Monomer can be for independent or two or more.
With the alkyl acrylate of formula (2-1) expression for example be methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, acrylic acid pentyl ester, Hexyl 2-propenoate, 2-ethyl hexyl acrylate, 2-ethylhexyl acrylate, acrylic acid ester in the ninth of the ten Heavenly Stems, decyl acrylate, dodecylacrylate, acrylic acid cyanoethyl ester,
Alkoxyalkyl acrylate with formula (2-2) expression for example is acrylic acid methoxy ethyl ester, acrylic acid ethoxyethyl group ester, butoxyethyl acrylate, acrylic acid ethoxycarbonyl propyl ester.
Acrylic rubber can be for containing independent or two or more any one in them.
In addition, acrylic rubber also can for can with the mixture of the unsaturated monomer of at least a combined polymerization of from the compound of formula (2-1)～(2-3) expression, selecting or their copolymer.
Unsaturated monomer for example is styrene, AMS, acrylonitrile, halogenated styrenes, methacrylonitrile, acrylamide, Methacrylamide, vinyl naphthalene, N hydroxymethyl acrylamide, vinyl acetate, vinyl chloride, vinylidene chloride, acrylic acid benzyl ester, methacrylic acid, itaconic acid, fumaric acid, maleic acid.
Acrylic rubber for example is at least a monomer of selecting in the compound of 40～99.9 weight % formulas (2-1)～(2-3) expression;
0.1～30 weight % unsaturated carboxylic acid ethylene oxidic ester and/or unsaturated glycidol ethers;
0～30 weight % can with the copolymer of the unsaturated monomer of at least a combined polymerization of from the compound of formula (2-1)～(2-3) expression, selecting.Wherein, their sum total is 100 weight %.If acrylic rubber satisfies described making, hear resistance, resistance to impact, the shaping processability that resin bed 1 can be good then.
Open clear 59-113010 communique, spy as the spy and open that clear 62-64809 communique, spy are opened flat 3-160008 communique, WO95/04764 puts down in writing, acrylic rubber utilizes emulsion polymerisation, suspension polymerisation, polymerisation in solution or polymerisation in bulk preparation to get final product for example as long as in the presence of polymerization initiator.
The rubber that the rubber that the block copolymer that vinyl aromatic hydrocarbon compound-conjugated diene compound block copolymer rubber for example constitutes based on the sequence of vinyl aromatic hydrocarbon compound and sequence based on conjugated diene compound for epoxidation obtains, the hydrogenation thing of epoxidized block copolymer obtain.
The vinyl aromatic hydrocarbon compound is styrene, vinyltoluene, divinylbenzene, AMS, p-methylstyrene, vinyl naphthalene for example, is preferably styrene.
Conjugated diene compound for example is butadiene, isoprene, 1,3-pentadiene, 3-butyl-1, and the 3-octadiene is preferably butadiene, isoprene.
Vinyl aromatic hydrocarbon compound-conjugated diene compound block copolymer or its hydrogenation thing are for example prepared as long as open the method for putting down in writing in the clear 59-133203 communique with special public clear 40-23798 communique, spy.
Polymer B preferably contains (methyl) acrylate-styrene-(unsaturated carboxylic acid ethylene oxidic ester and/or unsaturated glycidol ether) copolymer rubber.
Polymer B also can be the polymer that has vulcanized.The sulfuration of (methyl) acrylate-styrene-(unsaturated carboxylic acid ethylene oxidic ester and/or unsaturated glycidol ether) copolymer rubber is for example as long as use multi-functional organic acid, multi-functional amines, imidazolium compounds.
Polymer B is under the situation of thermoplastic resin, and thermoplastic resin preferably has epoxy radicals.Thermoplastic resin for example is
More than the ethylene unit 50 weight %, below the 99 weight %,
Unsaturated carboxylic acid glycidol ester units and/or more than the unsaturated glycidol ether unit 0.1 weight % is preferably more than the 0.5 weight %, below the 30 weight %, is preferably below the 20 weight %,
Ethene is that beta-unsaturated esters compound unit 0 weight % is above, 50 weight % are following contains the epoxy radicals ethylene copolymer.The sum total of these unit is 100 weight %.
Ethene is that the beta-unsaturated esters compound for example is vinyl esters of carboxylic acids such as vinyl acetate, propionate, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, EMA, butyl methacrylate; α, beta-unsaturated carboxylic acid Arrcostab are preferably vinyl acetate, methyl acrylate, ethyl acrylate.
Contain the copolymer that copolymer, ethylene unit and methyl propenoic acid glycidyl base ester units that copolymer, ethylene unit and methyl propenoic acid glycidyl base ester units that the epoxy radicals ethylene copolymer for example constitutes for the copolymer that is made of ethylene unit and methyl propenoic acid glycidyl base ester units, by ethylene unit and methyl propenoic acid glycidyl base ester units and methyl acrylate unit and ethyl acrylate unit constitute and vinyl acetate unit constitute.Containing the epoxy radicals ethylene copolymer utilizes the high-pressure free radical polymerization usually (in the presence of radical initiator, under 500～4000 air pressure, 100～300 ℃, making its saturated rings oxygen compound and ethylene copolymerization in the presence of appropriate solvent or the chain-transferring agent or not) preparation gets final product.In addition, contain the epoxy radicals ethylene copolymer and also can utilize mixing unsaturated epoxy compound and radical initiator in polyethylene, in extruder, make the method preparation of its fusion-grafting combined polymerization.
Resin bed 1 preferably contains liquid crystal polyester A as continuous phase, contains polymer B as decentralized photo.The resin bed 1 that satisfies these has high gas barrier property, hear resistance.
The liquid crystal polyester A of resin bed 1 is generally more than 56 weight portions, be preferably more than 65 weight portions, and then be preferably more than 70 weight portions, be generally below 99.9 weight portions, be preferably below 98 weight portions, polymer B is generally more than 0.1 weight portion, be preferably more than 2 weight portions, be generally below 44 weight portions, be preferably below 35 weight portions, and then be preferably below 30 weight portions.
The resin bed 1 that satisfies these has high water-vapor barrier, hear resistance.
Resin bed 1 is for example as long as mixing liquid crystal polyester A and polymer B are prepared.Device, the preferred two-way mixing roll of the unidirectional or two-way extruder of mixing use or unidirectional or two-way kneader and so on get final product.Mixing cylinder design temperature: 200～360 ℃, be preferably under 230～350 ℃ the condition and get final product at device.
Before mixing, the device that also can use deflecting roller, Henschel mixer (Henschel mixer) and so on is mixed liquid crystal polyester A and polymer B equably in advance, to the unit feeding mixture, so that mixing.In addition, also can in device, distinguish weight feed liquid crystal polyester A and polymer B, so mixing.
When preparation resin bed 1, as required, also can use various additives such as demoulding modifying agent such as organic filler, antioxidant, heat stabilizer, light stabilizer, fire retardant, lubricant, antistatic agent, inorganic or organic system colouring agent, corrosion inhibiter, crosslinking agent, blowing agent, fluorescer, surface smoothing agent, lustrous surface modifying agent, fluororesin.Additive adds when mixing liquid crystal polyester A and polymer B or when operation (for example processing) thereafter.
Resin bed 1 is the blow molding preparation of biaxial tension simultaneously preferably.Resin bed 1 is for example by supplying with the mixture of liquid crystal polyester A and polymer B to the die head that possesses annular slot, at the cylinder design temperature: 200～360 ℃, be preferably melting mixing under 230～350 ℃ the condition, from the annular slot of extruder upward or below extrusion molten resin, then, after the circumference of the resin that air cooling or water-cooled have expanded, make it pass through mip rolls (nip roll) and get and prepare.The direction of extrusion (major diameter direction) is the MD direction, and the direction with its craspedodrome in pellicular front is the TD direction.Die lip is generally more than the 0.1mm at interval, is preferably more than the 0.5mm, is generally below the 5mm, is preferably below the 2mm, and typically having a diameter from more than the 20mm of annular slot is preferably more than the 50mm, is generally below the 1000mm, is preferably below the 300mm.In addition, the blowing of blow molding ratio is generally 1.5～10, and pressure differential (draw down) is than being generally 1.5～40.If be shaped, then can obtain not having the high-intensity resin bed 1 of wrinkle with the thickness of homogeneous with this condition.Blow molding needs only the composition of corresponding resin, selects to make molten resin become the condition of the state of surface smoothing to get final product with the thickness swelling of homogeneous.
From satisfying good gas-barrier properties and flexible viewpoint, the thickness of resin bed 1 is generally more than the 3 μ m, and be preferably more than the 5 μ m, and then be preferably more than the 8 μ m, usually less than 500 μ m, preferably less than 300 μ m, and then preferably less than 200 μ m.
[resin bed 2]
Resin bed 2 comprises: the resin beyond the liquid-crystal polyester resin.Resin bed 2 comprises heat-resistant resin, for example, comprises vitrification point (Tg) and is more than 150 ℃, is preferably more than 180 ℃ and then is preferably resin more than 190 ℃.Resin bed 2 for example can be enumerated polyolefin-based resins such as ethylene-norbornene copolymer, ethene-multi-door (De モ Application) copolymer; Polyester based resins such as PETG, polybutylene terephthalate (PBT), PEN; Nylon-6, nylon-6,6, m-xylene diamine-adipic acid condensation polymer; Acid amides such as poly-methyl acrylimide are resin; Acrylic resins such as polymethyl methacrylate; Styrene-acrylonitriles such as polystyrene, SAN, ABS, polyacrylonitrile are resin; The cellulose-based resin of hydrophobization such as cellulose triacetate, cellulose diacetate; Halogen-containing resins such as polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, polytetrafluoroethylene (PTFE); Hydrogen bond resins such as polyvinyl alcohol, ethylene-vinyl alcohol copolymer, cellulose derivative; Polycarbonate resin, polysulfone resin, polyethersulfone resin, polyether-ether-ketone resin, polyphenylene oxide resin, acetal resin.In addition, in these resins, constitute by ethylene-norbornene copolymer, ethene-multi-door (De モ Application) copolymer, PEN, polycarbonate resin, polysulfone resin, polyethersulfone resin.They are used alone or in combination and get final product.
The thickness of resin bed 2 is generally more than the 3 μ m, and be preferably more than the 5 μ m, and then be preferably more than the 8 μ m, usually less than 500 μ m, preferably less than 300 μ m, and then preferably less than 200 μ m.
The surface average roughness Ra of resin bed 2 is generally below the 5nm, is preferably below the 3nm.Surface average roughness Ra is equivalent to the arithmetic average roughness of record in the paragraph [4.2.1] of JIS B 0601 (putting down into revision on January 20th, 13) of Japanese specification consonance distribution, can try to achieve from the average line of the cross section curve on the surface of resin bed 2.The mensuration of surface average roughness Ra uses commercially available device to get final product.
[inorganic layer 3]
Preferable substrate and then contain inorganic layer 3.
Inorganic layer 3 for example is metal (aluminium, copper, nickel etc.), metal oxide (silica, aluminium oxide, titanium white, indium oxide, tin oxide, titanium oxide, zinc oxide etc.), metal nitride (aluminium nitride, silicon nitride etc.), metal carbides (carborundum etc.), metal oxynitrides (silicon oxynitride etc.), be preferably aluminium oxide, aluminium nitride, silicon nitride, silicon oxynitride, and then the preferred oxygen silicon nitride.They are used alone or in combination and get final product.
The thickness of inorganic layer 3 is generally more than the 1nm, is preferably more than the 10nm, is generally below the 1000nm, is preferably below the 500nm.
Inorganic layer 3 preferably contacts (connecing the The Ru) with resin bed 2.
[resin bed 4 that contains inorganic layered compounds]
Substrate also can and then contain the resin bed 4 of inorganic layered compounds.
Layer 4 contains resin C and inorganic layered compounds.Resin C is the high resin of hear resistance, for example is polyolefin-based resins such as ethylene-norbornene copolymer, ethene-multi-door (De モ Application) copolymer; Polyester based resins such as PETG, polybutylene terephthalate (PBT), PEN; Nylon-6, nylon-6,6, m-xylene diamine-adipic acid condensation polymer; Acid amides such as poly-methyl acrylimide are resin; Acrylic resins such as polymethyl methacrylate; Styrene-acrylonitriles such as polystyrene, SAN, ABS, polyacrylonitrile are resin; The cellulose-based resin of hydrophobization such as cellulose triacetate, cellulose diacetate; Halogen-containing resins such as polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, polytetrafluoroethylene (PTFE); Hydrogen bond resins such as polyvinyl alcohol, ethylene-vinyl alcohol copolymer, cellulose derivative; Merlon, polysulfones, polyether sulfone are (hereinafter referred to as " PES ".), polyether-ether-ketone, polyphenylene oxide, polyformaldehyde.They are used alone or in combination and get final product.
Inorganic layered compounds is generally clay mineral.Clay mineral for example is kaolin, dickite, nacrite, galapectite, antigorite, chrysotile, pyrophyllite, montmorillonite, hectorite, tetramethyl silylation mica (ラ ト ラ シ リ リ Star Network マ イ カ), sodium taincolite (natrium taeniolite), muscovite, emerylite, mica, vermiculite, phlogopite, holmesite (xanthophyllite), chlorite, preferred kaolin, montmorillonite, hectorite, mica.
The average grain diameter L of inorganic layered compounds is generally more than the 50nm, is preferably more than the 100nm, is generally below the 5 μ m, is preferably below the 3 μ m, and then is preferably below the 2 μ m.Average grain diameter L utilizes light scattering determining in solvent.
In addition, the aspect ratio of inorganic layered compounds is generally more than 50, is preferably more than 100, is generally below 5000, is preferably below 2000, and then is preferably below 1000.Aspect ratio Z tries to achieve from formula Z=L/a.L is an average grain diameter, and a is the mean value of the unit thickness calculated of the diffraction maximum of the inorganic layered compounds that utilizes powder x-ray diffraction to measure to obtain.
And then, the inorganic layered compounds preferred orientation becomes the face that area is big relatively in each face of particle (for example inorganic layered compounds is under the situation of tabular particle, with the rectangular face of the thickness direction of plate) and rectangular the almost parallel of thickness direction of resin bed 4 that contains inorganic layered compounds (hereinafter referred to as " being orientated on the face direction ".)。
Containing the inorganic layered compounds of resin bed 4 of inorganic layered compounds and the weight ratio (inorganic layered compounds/resin) of resin is 5 weight portions/95 weight portions～90 weight portions/10 weight portions, is preferably 5 weight portions/95 weight portions～50 weight portions/50 weight portions.
The thickness that contains the resin bed 4 of inorganic layered compounds is generally more than the 0.01 μ m, is preferably more than the 0.1 μ m, is generally below the 5 μ m, is preferably below the 3 μ m.
The resin bed 4 that contains inorganic layered compounds also can contact with resin bed 1.
[conductive layer 5]
Substrate also can and then contain conductive layer 5.
Inorganic matter or the organic matter of conductive layer 5 for having electric conductivity.Inorganic matter with electric conductivity for example is metal oxide (indium oxide, zinc oxide, tin oxide, indium tin oxide (ITO), indium-zinc oxide etc.), metal (gold, platinum, silver, copper etc.).For example utilize vacuum vapour deposition, sputtering method, ion plating method, plating method to form and get final product by the conductive layer 5 that inorganic matter constitutes.In addition, the organic matter with electric conductivity for example is polyaniline or derivatives thereof, polythiophene or derivatives thereof.Conductive layer 5 can contact with resin bed 2, perhaps also can be patterned.In addition, conductive layer also can be as the male or female of display element.
The thickness of conductive layer 5 is generally more than the 0.05 μ m, is preferably more than the 0.1 μ m, is generally below the 0.5 μ m, is preferably below the 0.4 μ m.
Substrate of the present invention contains resin bed 1, resin bed 2, contains inorganic layer 3, the resin bed 4 that contains inorganic layered compounds, conductive layer 5 arbitrarily, and the layer structure example of substrate is as being
(L1) resin bed 1/ resin bed 2,
(L2) resin bed 1/ resin bed 2/ inorganic layer 3,
(L3) resin bed 1/ contain inorganic layered compounds resin bed 4/ resin bed 2,
(L4) resin bed 1/ contains resin bed 4/ resin bed 2/ inorganic layer 3 of inorganic layered compounds.
In addition, substrate also can contain anti-reflection layer or erasibility layer.
And then, substrate also can contain the layer of the additive of ultra-violet absorber, colouring agent, antioxidant and so on, and resin bed 1, resin bed 2, inorganic layer 3, the resin bed 4 that contains inorganic layered compounds, conductive layer 5, anti-reflection layer, erasibility layer also can contain additive.
Substrate has high gas barrier property, and steam permeability is generally 0.2g/m 2Below/the sky, be preferably 0.1g/m 2Below/the sky, the oxygen permeability is generally 0.1g/m 2Below/the sky, be preferably 0.05g/m 2Below/the sky.In addition, the evenly heat linear expansion coefficient of substrate in 20 ℃～150 ℃ temperature range be generally-more than the 10ppm/ ℃, be preferably-more than the 5ppm/ ℃, be generally below 25ppm/ ℃, be preferably below 20ppm/ ℃.
As long as described have the substrate of a layer structure (L1) for example the method manufacturing that operation (1a) below utilizing or operation (1b) constitute.
(1a) on resin bed 1, utilize coating form resin bed 2,
(1b) stacked resin bed 2 on resin bed 1.
Have a layer structure (L2) if substrate for example utilize operation (1a) and (2a) or operation (1b) and the method manufacturing that (2a) constitutes.
(2a) on resin bed 2, form inorganic layer 3.
Have a layer structure (L3) if substrate for example utilize operation (3a) and (3c), operation (3a) and (3d), operation (3b) and (3c) or operation (3b) and the method manufacturing that (3d) constitutes.
(3a) resin bed 4 that on resin bed 1, utilizes coating to form to contain inorganic layered compounds,
(3b) stacked resin bed 1 and contain inorganic layered compounds resin bed 4,
(3c) on the resin bed 4 that contains inorganic layered compounds, utilize coating to form resin bed 2.
(3d) stacked resin bed 2 on the resin bed 4 that contains inorganic layered compounds.
In addition, have a layer structure (L4) if substrate utilize operation (3a), (3c) and (2a), operation (3a), (3d) and (2a), operation (3b), (3c) and (2a) or operation (3b), (3d) and the method manufacturing that (2a) constitutes get final product.
As long as coating is by coating, dry, the resinous layer 2 of heat treatment or contain the coating liquid of the resin that contains in the resin bed 4 of inorganic layered compounds, for example utilize direct intaglio (direct gravure) method, oppositely intaglio method (reverse gravure), nick plate print process, rolling method (2 rollers strike (PVC one ト) coating process, 3 coating process etc. that overturn are supplied with in the bottom), scrape the skill in using a kitchen knife in cookery, metal mold coating process, dip coating, excellent Tu Fa etc. and get final product.They can be alone or in combination.Usually coating liquid contains solvent.
Formation contains under the situation of resin bed 4 of inorganic layered compounds, preferred solvent is split the inorganic layered compounds swelling, become dispersion liquid, for example preferred water, alcohols (methyl alcohol etc.), dimethyl formamide, methyl-sulfoxide, carrene, chloroform, toluene, acetone, N-methyl pyrrolidone.In addition, in this case, thus coating liquid adds inorganic layered compounds and its swelling is split and the method 3 of mixing simultaneously or melting mixing resin C and inorganic layered compounds obtain mixing thing and then make it and the method for solvent 4, preferably utilize 1,2,3 manufacturings as long as utilize to mix the solution that makes described resin C be dissolved in the solvent gained with the method 2 of method 1, mixed dispersion liquid and the resin of dispersion liquid, in solution.From the viewpoint of the dispersiveness that improves inorganic layered compounds, inorganic layered compounds also can be by surface treatment.Surface conditioning agent for example is a quaternary ammonium salt.
From improving the viewpoint of cementability, stacked also can be at surface treatment resin bed 1, resin bed 2, carry out after containing the binding face of resin bed 4 of inorganic layered compounds.As surface treatment, for example can enumerate Corona discharge Treatment, plasma treatment, flame treatment, sputter process, solvent processing, UV treatment, milled processed, infra red treatment, ozone treatment.
As long as the formation of inorganic layer 3, conductive layer 5 for example utilizes vacuum vapour deposition, CVD method, sputtering method, sol-gal process.
Display element
Display element of the present invention contains aforesaid substrate, contains successively usually following (a)～(e).
(a) resin bed 1
(b) resin bed 2,
(c) conductive layer,
(d) when applying electric field, demonstrate from light absorption, light scattering, optically-active and luminous at least a function selected organic layer,
(e) transparent conductivity layer.
Resin bed 1 is made of the material identical with the resin bed 1 of described substrate.
Resin bed 2 is made of the material identical with the resin bed 2 of described substrate.
Conductive layer is made of the material identical with the conductive layer 5 of described substrate.
Organic layer so long as demonstrate when applying electric field from the material of light absorption, light scattering, optically-active or luminous function gets final product.
The material that demonstrates the function of light absorption when applying electric field for example is the liquid-crystal composition that contains the dichroism pigment.
The material that demonstrates the function of light scattering when applying electric field for example is polymer dispersion type liquid crystal.
The material that demonstrates the function of optically-active when applying electric field for example is cholesterol type liquid crystal composite.
In addition, the material luminescent layer that demonstrates luminous function when applying electric field is made of low molecular compound or macromolecular compound, and the viewpoint of easiness from coating preferably is made of macromolecular compound.For example the spy opens clear 57-51781 communique, the spy opens in the clear 59-194393 communique and puts down in writing, low molecular compound is pigments such as naphthalene derivatives, anthracene or derivatives thereof, perylene or derivatives thereof, polymethine system, xanthene system, coumarin series, anthocyanin system, the metal complex of oxine or derivatives thereof, aromatic amine, tetraphenyl cyclopentadiene or derivatives thereof.In addition, macromolecular compound for example is poly-(to phenylene vinylidene), poly-fluorenes (Japanese applicating physical magazine (JapaneseJournalofAppliedPhysics) is the 30th volume, L1941 page or leaf (1991) (Jpn.J.Appl.Phys.)), poly radical derivative (advanced material (AdvancedMaterials) is the 4th volume, 36 pages (1992 years) (Adv.Mater.)).
Luminescent layer for example needs only method, ink-jet method, the spin-coating method formation of the solution of the vacuum vapour deposition, coating and dry macromolecular compound or the macromolecular compound that utilize the powder that uses macromolecular compound or macromolecular compound.
In addition, also can in luminescent layer, make up electron supplying layer and/or hole transporting layer.
Hole transporting layer for example by PVK or derivatives thereof, polysilane or derivatives thereof, side chain or main chain have the aromatic amines compound base polyorganosiloxane ramification, polyaniline or derivatives thereof, polythiophene or derivatives thereof, poly-styrene support or derivatives thereof or poly-(2, the inferior thienyl ethenylidene of 5-) or derivatives thereof are constituted.Hole transporting layer is as long as utilize the method for the solution that coating, dry mixed they and polymer binder obtain to form.
Electron supplying layer is You oxadiazole derivative for example, anthraquinone bismethane (ア Application ト ラ キ ノ ジ メ Application) or derivatives thereof, the benzoquinones or derivatives thereof, the naphthoquinones or derivatives thereof, the anthraquinone or derivatives thereof, four cyano anthraquinone bismethane or derivatives thereof, fluorenone derivatives, diphenyl dicyano ethene or derivatives thereof, the metal complex of connection 1,4-benzoquinone derivative or oxine or derivatives thereof, the poly quinoline or derivatives thereof, the polyquinoxaline or derivatives thereof, poly-fluorenes or derivatives thereof constitutes.The method that electron supplying layer needs only the vacuum vapour deposition, coating and their solution of drying that utilize the powder that uses them forms.
The transparent conductivity layer has the transparency and electric conductivity, also can be patterned.The transparent conductivity layer is as long as for example utilize vacuum vapour deposition, CVD method, sputtering method, sol-gal process to form.In addition, the transparent conductivity layer of patterning needs only and utilizes sputter or resist work (work) formation of using mask.
In addition, when conductive layer was used as the negative electrode of display element, the transparent conductivity layer can be used as anode.The transparent conductivity layer of this moment is for example by the metal of lithium, sodium, potassium, rubidium, caesium, beryllium, magnesium, calcium, strontium, barium, aluminium, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, an ancient unit of weight equal to 20 or 24 *taels of silver and so on, two or more alloy in these metals, in these metals more than one and more than one the alloy of selecting from gold, silver, copper, manganese, titanium, cobalt, nickel, tungsten, tin, perhaps graphite or compound between graphite layers constitute.As long as the transparent conductivity layer for example utilizes vacuum vapour deposition, sputtering method, the layered manner by thermocompression bonding to form.From improving the viewpoint of the transparency, the transparent conductivity layer also can reduce bed thickness.And then from reducing the viewpoint of resistance value, the transparent conductivity layer also can be for being laminated with the layer of the material that becomes anode.
As the layer structure of display element, for example can enumerate
Resin bed 1/ resin bed, 2/ anode (conductive layer)/luminescent layer/negative electrode (transparent conductivity layer),
Resin bed 1/ resin bed, 2/ anode (conductive layer)/luminescent layer/electron supplying layer/negative electrode (transparent conductivity layer),
Resin bed 1/ resin bed, 2/ anode (conductive layer)/hole transporting layer/luminescent layer/negative electrode (transparent conductivity layer),
Resin bed 1/ resin bed, 2/ anode (conductive layer)/hole transporting layer/luminescent layer/electron supplying layer/negative electrode (transparent conductivity layer),
Resin bed 1/ resin bed, 2/ negative electrode (conductive layer)/luminescent layer/anode (transparent conductivity layer),
Resin bed 1/ resin bed, 2/ negative electrode (conductive layer)/electron supplying layer/luminescent layer/anode (transparent conductivity layer),
Resin bed 1/ resin bed, 2/ negative electrode (conductive layer)/luminescent layer/hole transporting layer/positive negative electrode (transparent conductivity layer) or
Resin bed 1/ resin bed, 2/ negative electrode (conductive layer)/electron supplying layer/luminescent layer/hole transporting layer/anode (transparent conductivity layer).
Preferred resin layer 1/ resin bed, 2/ anode (conductive layer)/hole transporting layer/luminescent layer/electron supplying layer/negative electrode (transparent conductivity layer), resin bed 1/ resin bed, 2/ negative electrode (conductive layer)/electron supplying layer/luminescent layer/hole transporting layer/anode (transparent conductivity layer).
In addition, display element contains duplexer and the encapsulant that is made of described layer structure, part or all of sealing duplexer usually.
Encapsulant is for the transparency, preferably clear and give the material of fully gentle threading property to the display element that obtains.Encapsulant for example is polyolefin-based resins such as polyethylene (low-density, high density), ethylene-propylene copolymer, ethylene-butene copolymer, ethene-hexene copolymer, ethylene-octene copolymer, ethylene-norbornene copolymer, ethene-multi-door (De モ Application) copolymer, polypropylene, ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate methyl terpolymer, ionomer resin; Polyester based resins such as PETG, polybutylene terephthalate (PBT), PEN; Nylon-6, nylon-6,6, m-xylene diamine-adipic acid condensation polymer; Acid amides such as poly-methyl acrylimide are resin; Acrylic resins such as polymethyl methacrylate; Styrene-acrylonitriles such as polystyrene, SAN, ABS, polyacrylonitrile are resin; The cellulose-based resin of hydrophobization such as cellulose triacetate, cellulose diacetate; Halogen-containing resins such as polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, polytetrafluoroethylene (PTFE); Hydrogen bond resins such as polyvinyl alcohol, ethylene-vinyl alcohol copolymer, cellulose derivative; Engineering plastics such as polycarbonate resin, polysulfone resin, polyethersulfone resin, polyether-ether-ketone resin, polyphenylene oxide resin, acetal resin are resin.Encapsulant is the film shape, and thickness is generally more than the 20 μ m, below the 1000 μ m, is preferably below the 500 μ m, and then is preferably below the 300 μ m.
Sealing utilizes coating process, layered manner to get final product.Coating process is coating on duplexer, dry, method that heat treatment contains the coating process of described encapsulant, for example, utilize direct intaglio (direct gravure) method, oppositely intaglio method (reverse gravure), nick plate print process, rolling method (for example 2 rollers strike coating process, 3 reverse coating process are supplied with in the bottom), scrape the skill in using a kitchen knife in cookery, metal mold coating process, dip coating, rod and be coated with method and get final product.They can be used alone or in combination.
Layered manner is the method for applying duplexer and film shape encapsulant.In layered manner, also can carry out sided corona treatment, utilize tackifier to handle at binding face.
And then in order to protect the transparent conductivity layer, display element also can have protective layer.Protective layer is as long as formed before with the encapsulant sealing.
Display element of the present invention has pliability, and gas barrier property is better, can be preferred for flexible display (flexible display).As flexible display, for example be used to the view finder of computer, television set, portable terminal device, portable phone, navigator, video camera.In addition, display element can be emissive type and attenuate, so be preferably used as the flat light source that the backlight of liquid crystal indicator uses, planar illumination light source.
And then display element also can change configuration, the shape of anode and negative electrode, makes it luminous with various patterns.For example, obtain planarly when luminous, be configured to planar anode and overlap with negative electrode and get final product.Obtaining under the luminous situation of specific pattern-like, be provided with the method for mask of the window of this specific pattern-like on planar display element surface, any one party of male or female or both sides' electrode is being formed specific pattern-like get final product.Form pattern with these any one methods,, can obtain to show segmented (segment type) display element of simple mark etc. by several electrodes being configured to ON/OFF independently.Under the situation that becomes the dot matrix element, anode and negative electrode are all formed striated, be configured to quadrature and get final product.Divide method or colour filter or the fluorescence conversion color filter that is coated with the different a plurality of luminescent layers of illuminant colour as long as use, partial colour shows, multicolor displaying becomes possibility.The dot matrix element can carry out passive driving, also can carry out active drive with combinations such as TFT.
As long as display element is according to the order of described layer structure, for example utilizes the method manufacturing that comprises following operation (a ')～(d ') to get final product.
(a ') on resin bed 1, form resin bed 2,
(b ') on resin bed 2, form conductive layer 5,
(c ') on conductive layer 5, be formed on demonstrate when applying electric field light absorption, light scattering, optically-active or luminous organic layer,
(d ') formation transparent conductivity layer on organic layer.
Display element with electron supplying layer, hole transporting layer is for example as long as utilize the method that comprises operation (a '), (b '), (e1 '), (c1 '), (d ') successively, comprises the method for operation (a '), (b '), (c '), (f1 '), (d1 ') successively or comprises that successively the method manufacturing of operation (a '), (b '), (e1 '), (c1 '), (f1 '), (d ') gets final product.At this, (a '), (b '), (d ') same as described above, (e1 ') goes up the operation that forms electron supplying layer at the layer that utilizes operation (h ') to form, (c1 ') is formed on the operation that demonstrates light absorption, light scattering, optically-active or luminous organic layer when applying electric field on the layer that forms in last operation, (f1 ') be the operation that forms hole transporting layer on the layer that in last operation, forms, (d1 ') be the operation that forms the transparent conductivity layer on the layer that in last operation, forms.
In addition, contain the display element of encapsulant and then comprise following operation (g ').
Seal all or part of of duplexer (constituting) with encapsulant by resin bed 1, resin bed 2, conductive layer, organic layer, transparent conductivity layer and electron supplying layer as required, hole transporting layer.
Embodiment
Utilize embodiment that the present invention is described, but the present invention is not limited by these embodiment.
Surface roughness Ra: use Seiko instrument (Seiko Instruments) corporate system Nanopics to try to achieve.
The Production Example 1 of liquid-crystal polyester resin layer (resin bed 1)
[preparation of liquid crystal polyester A]
In the polymerization tank of band comb type agitator, add P-hydroxybenzoic acid 16.6Kg (12.1 moles), 6-hydroxyl-2-naphthoic acid 8.4Kg (4.5 moles) and acetic anhydride 18.6Kg (18.2 moles), warming while stirring under nitrogen atmosphere, under 320 ℃, make its polymerization 1 hour, and then make its polymerization 1 hour under the decompression of 2.0torr, under 320 ℃.Continue outside system, to distillate the acetic acid of by-product therebetween.Then, cooling is lentamente taken out down at 180 ℃, obtains polymer.
Hammer crusher with thin river ミ Network ロ Application (strain) system is pulverized, and obtains the following particle of particle diameter 2.5mm, then, in adding rotary kiln, under nitrogen atmosphere, heat-treats 5 hours with 240 ℃, obtains liquid crystal polyester A.Liquid crystal polyester A is the particle shape, and repetitive and ratio are as follows, and flow starting temperature is 270 ℃.
Figure S2006800200938D00211
In addition, liquid crystal polyester A is with the result of polarized light microscope observing, demonstrates optical anisotropy adding to depress more than 280 ℃.
[preparation of polymer B]
Open the method for putting down in writing among the embodiment 5 of clear 61-127709 communique according to the spy, obtain the rubber of methyl acrylate/ethylene/methacrylic acid glycidyl esters=59.0/38.7/2.3 (weight ratio).
[formation of liquid-crystal polyester resin layer (resin bed 1)]
Use the two-way extruder of Japan's system steel (strain) system TEX-30 type, set mean temperature at cylinder: under 300 ℃, the condition of spiral rotation number: 250rpm, melting mixing liquid crystal polyester A (95 weight %) and polymer B (5 weight %) obtain composition.Composition is depressed, is demonstrated optical anisotropy more than 265 ℃ adding.
Use possesses the one-way stretcher of 60mm Φ of the cylinder die head of diameter 50mm, at the cylinder design temperature: 290 ℃, spiral rotation number: 60rpm, die lip at interval: 1.0mm, die head design temperature: under 305 ℃ the condition, the melt extruded composition, obtain the tubular molten resin, hollow part to this tubular molten resin is pressed into dry air, makes its expansion, then makes its cooling, by niproll, obtain the liquid-crystal polyester resin layer then.Blowing is than being 2.5, and pressure differential (draw down) is than being 10, and the average thickness of liquid-crystal polyester resin layer is 40 μ m.
The surface average roughness of liquid-crystal polyester resin layer (Ra) is 8.6nm (10 μ m).The evaluation result of the gas barrier property of liquid-crystal polyester resin layer (at the steam permeability under 40 ℃, oxygen permeability under 23 ℃) is as shown in table 2.
Comparative example 1
At thickness is on the PES film of 200 μ m, utilizes sputter, and forming thickness is the silicon oxynitride layer of 150nm, obtains substrate 1.For substrate 1, layer structure is as shown in table 1, and the evaluation result of gas barrier property is as shown in table 2.
Embodiment 1
At side pipe threeway plug valve and the happy (Dimroth of Jim are installed, ジ system ロ one ト), in the 100mL there-necked flask of being responsible for the fluororesin system of joint agitator, add PES (trade name " PES5200p ", Sumitomo Chemical system, Tg:230 ℃) 15g and N-methyl pyrrolidone 45g, stirred 3 hours down at 80 ℃, obtain resin bed 2 and form with coating liquid.
On the superincumbent liquid-crystal polyester resin layer, use rod to be coated with device (" SA-203 type ", ラ ス one industry system), application of resin layer 2 forms with coating liquid, and forming thickness is the PES layer (resin bed 2) of 15 μ m, obtains having flexible substrate 2.The surface average roughness (Ra) of the PES layer of substrate 2 is 0.2nm (10 μ m), the average coefficient of linear expansion under 20 ℃～150 ℃ temperature range is-and 1.8ppm/ ℃
Embodiment 2
On the substrate 2 that obtains in embodiment 1, utilize sputter, under 120 ℃ condition, forming thickness is the Al of 150nm 2O 3Layer (inorganic layer 3) obtains having flexible substrate 3.For substrate 3, layer structure is as shown in table 1, and the evaluation result of gas barrier property is as shown in table 2.
Embodiment 3
In ion exchange water 3000g, add polyvinyl alcohol (trade name " PVA117H ", (strain) Network ラ レ system) 100g, (wing rotation number: 1500rpm under stirring condition, wing circular velocity: about 4m/ second), be warming up to 95 ℃, and then stirred 1 hour, dissolving obtains solution.Limit agitating solution, limit are cooled to 65 ℃, drippage pure water (mixture of ion exchange water 1600g and 1-butanols 376g) in coating liquid.After drippage finishes, in solution, be added on 65 ℃ and as inorganic layered compounds be highly purified natural montmorillonite (trade name " Network ニ ピ ア G ", Network ニ ミ ネ industry (strain) system, outward appearance: powder, aspect ratio 200～1000) 50g, (wing rotation number 3000rpm, wing circular velocity: about 8m/ second) stirred 90 minutes down under stirring condition, disperse, obtain mixed liquor.In super-pressure homogenizer (" M1 10-E/H type ", Microfluidics Corporation system), 1,750kgf/cm 2Condition under, by 1 mixed liquor, the resin bed that obtains containing inorganic layered compounds forms with coating liquid.
On the superincumbent liquid-crystal polyester resin layer, use rod to be coated with device (" SA-203 type ", ラ ス one industry system), the resin bed that coating, dry also heat treatment contain inorganic layered compounds forms with coating liquid, what form thickness and be 1.4 μ m contains inorganic layered compounds layer 4, obtains substrate 4.
On substrate 4, use rod to be coated with device (ラ ス one industry system, SA-203 type), coating, resin bed 2 dry and that heat treatment is prepared in embodiment 1 form with coating liquid, and forming thickness is the PES layer (resin bed 2) of 15 μ m, obtains having flexible substrate 5.The surface average roughness (Ra) of the PES layer of substrate 5 is 1.7nm (10 μ m), the average coefficient of linear expansion under 20 ℃～150 ℃ temperature range is-and 1.1ppm/ ℃
Embodiment 4
On the substrate 5 that obtains in embodiment 3, utilize sputter, under 120 ℃ condition, forming thickness is the Al of 150nm 2O 3Layer (inorganic layer 3) obtains having flexible substrate 6.For substrate 6, layer structure is as shown in table 1, and the evaluation result of gas barrier property is as shown in table 2.
Embodiment 5
On the substrate 2 that obtains in embodiment 1, utilize sputter, under 120 ℃ condition, forming thickness is the SiON layer of 150nm, obtains having flexible substrate 7.For substrate 7, layer structure is as shown in table 1, and the evaluation result of gas barrier property is as shown in table 2.
The layer structure of table 1 substrate
Layer structure
Production Example 1 Resin bed 1 (LCP)
Comparative example 1 Resin bed 2 (PES)/inorganic layer 3 (SiON)
Embodiment 1 Resin bed 1 (LCP)/resin bed 2 (PES)
Embodiment 2 Resin bed 1 (LCP)/resin bed 2 (PES)/inorganic layer 3 (Al 2O 3)
Embodiment 3 Resin bed 1 (LCP)/contain resin bed 4/ resin bed 2 (PES) of inorganic layered compounds
Embodiment 4 Resin bed 1 (LCP)/contain resin bed 4/ resin bed 2 (the PES)/inorganic layer 3 (Al of inorganic layered compounds 2O 3)
Embodiment 5 Resin bed 1 (LCP)/resin bed 2 (PES)/inorganic layer 3 (SiON)
The gas barrier property of table 2 substrate
Steam permeability [g/m under 40 ℃ 2/ day] Oxygen permeability [cc/m under 23 ℃ 2/ day]
Production Example 1 Resin bed 1 0.29 0.84
Comparative example 1 Substrate 1 0.60 2.9
Embodiment 2 Substrate 3 0.12 ＜0.01
Embodiment 4 Substrate 6 0.16 ＜0.01
Embodiment 5 Substrate 7 0.22 ＜0.01
Utilizability on the industry
Substrate of the present invention has pliability, and gas barrier property is better, can be preferred for the display element of flexible display illumination and so on.
In addition, display element of the present invention has pliability, gas barrier property, and durability is outstanding.

Claims (20)

1. substrate, it is the substrate that comprises resin bed 1 and resin bed 2, wherein,
Resin bed 1 comprises: liquid crystal polyester A and comprising has the polymer B with reactive functional group of liquid crystal polyester,
Resin bed 2 comprises: the resin beyond the liquid crystal polyester.
2. substrate according to claim 1, wherein,
In the resin bed 1, the weight ratio of liquid crystal polyester A and polymer B (liquid crystal polyester A/ polymer B) is 56～99.9 weight portions/44～0.1 weight portions.
3. substrate according to claim 2, wherein,
Resin bed 1 contacts with resin bed 2.
4. substrate according to claim 1, wherein,
The average surface roughness Ra of resin bed 2 is below the 6nm.
5. substrate according to claim 1, wherein,
Resin bed 2 comprises: vitrification point Tg is the resin more than 150 ℃.
6. substrate according to claim 1, wherein,
Substrate also comprises inorganic layer 3.
7. substrate according to claim 6, wherein,
Inorganic layer 3 comprises: that selects from the group that metal, metal oxide, metal nitride, metal carbides and metal oxynitrides constitute is at least a.
8. substrate according to claim 6, wherein,
Inorganic layer 3 contacts with resin bed 2.
9. substrate according to claim 1, wherein,
Substrate also comprises: the resin bed 4 that contains inorganic layered compounds.
10. substrate according to claim 9, wherein,
The average grain diameter of the inorganic layered compounds that contains in the resin bed 4 that contains inorganic layered compounds is below the 5 μ m, and aspect ratio is 50～5000.
11. substrate according to claim 9, wherein,
The resin bed 4 that contains inorganic layered compounds contacts with resin bed 1.
12. substrate according to claim 1, wherein,
Substrate also comprises conductive layer 5.
13. substrate according to claim 12, wherein,
Conductive layer 5 contacts with resin bed 2.
14. substrate according to claim 1, wherein,
The mean coefficient of linear thermal expansion of 20 ℃～150 ℃ temperature range is-10ppm/ ℃～25ppm/ ℃.
15. a display element, it is the display element that comprises following (a)～(e) successively, that is:
(a) described resin bed 1,
(b) described resin bed 2,
(c) conductive layer,
(d) display light absorption when applying electric field, light scattering, optically-active or luminous organic layer,
(e) transparent conductivity layer.
16. display element according to claim 15, wherein,
Display element also contains: sealing comprises part or all encapsulant of the duplexer of described (a)～(e).
17. display element according to claim 15, wherein,
Display element is a flexible display.
18. the manufacture method of a display element, it is the manufacture method that comprises the display element of following operation (a ')～(d '), that is:
(a ') on resin bed 1, form resin bed 2,
(b ') on resin bed 2, form conductive layer 5,
(c ') on conductive layer 5, be formed on display light absorption when applying electric field, light scattering, optically-active or luminous organic layer,
(d ') formation transparent conductivity layer on organic layer.
19. manufacture method according to claim 18, wherein,
Also comprise following operation (g '), that is:
(g ') is with all or part of of the duplexer of the resinous layer 1 of encapsulant sealed packet, resin bed 2, conductive layer, organic layer, transparent conductivity layer.
20. a use, it is the use as display element of the described substrate of claim 1.
CNA2006800200938A 2005-04-18 2006-04-17 Substrate and display element Pending CN101193752A (en)

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KR101411022B1 (en) * 2011-12-30 2014-06-24 제일모직주식회사 Polarizer plate and optical display device comprising the same
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CN102782619A (en) * 2010-03-04 2012-11-14 木本股份有限公司 Functional laminated sheet, and transparent electrically conductive laminated sheet for touch panel and touch panel produced using same
CN103351872A (en) * 2013-06-20 2013-10-16 深圳市华星光电技术有限公司 High-molecular liquid crystal material for liquid crystal display (LCD) frame, frame and manufacturing method of frame
CN103351872B (en) * 2013-06-20 2016-02-03 深圳市华星光电技术有限公司 For the Liquid Crystalline Polymeric Materials of liquid-crystal display frame, frame and manufacture method
US9617374B2 (en) 2013-06-20 2017-04-11 Shenzhen China Star Optoelectronics Technology Co., Ltd High-molecular liquid crystal material for frame of liquid crystal display, frame and manufacturing method

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WO2006112525A1 (en) 2006-10-26
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KR20080011192A (en) 2008-01-31
GB0722560D0 (en) 2007-12-27
GB2440096B (en) 2010-06-30

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