CN103240936A - Transparent flexible laminate and laminate roll - Google Patents

Transparent flexible laminate and laminate roll Download PDF

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Publication number
CN103240936A
CN103240936A CN201310049356XA CN201310049356A CN103240936A CN 103240936 A CN103240936 A CN 103240936A CN 201310049356X A CN201310049356X A CN 201310049356XA CN 201310049356 A CN201310049356 A CN 201310049356A CN 103240936 A CN103240936 A CN 103240936A
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Prior art keywords
polyimide resin
resin layer
duplexer
glass
film
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CN103240936B (en
Inventor
片山正和
平石克文
须藤芳树
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Nippon Steel Chemical and Materials Co Ltd
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Nippon Steel Chemical Co Ltd
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    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • 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
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/10—Batteries
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • 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

Abstract

The invention provides a laminate and a laminate roll. The laminate has excellent flexibility and transparency, is applicable to displays, solar cells, and the like; warping of the laminate itself is inhibited; and the laminate has excellent heat resistance and gas barrier properties. The transparent flexible laminate is characterized in that the laminate comprises a glass film with a thick ness of 20-200 microns, and a polyimide resin layer; the polyimide resin layer has a coefficient of thermal expansion of below 10 ppm/K, and has a light transmittance of more than 80% at a wavelength of 500 nm. In addition, a laminate roll formed by rolling the transparent flexible laminate is provided.

Description

Clear flexible duplexer and duplexer volume
Technical field
The present invention relates to have the glass-film of film shape and clear flexible duplexer and the duplexer volume of polyimide resin layer.
Background technology
In recent years, the multifunction progress of display, solar cell is to the baseplate material as one of its parts, except as in the past the gas barrier property that requires characteristic, the hear resistance, to the also raising gradually of requirement of lightweight, softnessization.Existing baseplate material uses glass mostly, but these require the raising of characteristic for reply, has carried out the trial of replacing glass with resin, and the resin that is carrying out the glass substrate material replaces.
Yet, resin and glassy phase relatively because its hear resistance is low, gas barrier property is poor, so the problem of being pointed out that manufacture method to display, solar cell has caused restriction, can't give full play to its performance, cost rises and so on.Therefore, to using resin to be still purposes and the scale that rests on restrictions such as flexible solar battery as the practicability present situation of this purposes of baseplate material.
As the replacement example from glass to the resin, for example, the duplexer of resin and glass has been proposed as the baseplate material of gas barrier property excellence in the patent documentation 1.Yet, technology disclosed herein since the resin that makes poor heat resistance with glass laminated, so on the whole the time, have the problem of hear resistance reduction as duplexer.In addition, as the suitable example of the high resin of hear resistance, polyimide resin is also disclosed in the patent documentation 1, but because general polyimide resin demonstrates yellow, even so use this polyimide resin separately, require transparent purposes also insufficient for being used for.
In addition, proposed to make the high polyimide resin layer of hear resistance to fold method in glass in the patent documentation 2.Yet, in this invention, for making substrate have the purpose of rigidity and inhibition thermal expansion, partly use glass.And, in patent documentation 2 in the concrete disclosed experimental example, have only and use the experimental example that does not have flexible or flexible extremely low thicker glass.It is difficult utilizing wherein disclosed technology to make baseplate material itself have flexible (flexibility).Therefore, be difficult in as the display of end article, solar cell, give flexibility.
The prior art document
Patent documentation
Patent documentation 1: No. 4122139 communiques of special permission communique
Patent documentation 2: the spy opens the 2002-297054 communique
Summary of the invention
The present invention In view of the foregoing finishes, its purpose is, provide flexible (flexibility) and the transparency excellent, applicable to purposes such as display, solar cell and suppressed the warpage of duplexer itself and duplexer and the duplexer of hear resistance and gas barrier property excellence rolled up.
The inventor etc. further investigate in order to solve above-mentioned problem, found that if the glass-film that uses shape as thin as a wafer as glass baseplate, the stacked polyimide resin that satisfies predetermined characteristic on this glass-film, then obtain having the duplexer of aforesaid any performance, and then finish the present invention.
That is, the present invention is the clear flexible duplexer, it is characterized in that, has glass-film and the polyimide resin layer of thickness 20 ~ 200 μ m, and the thermal coefficient of expansion of above-mentioned polyimide resin layer is below the 10ppm/K, and the light transmittance at wavelength 500nm place is more than 80%.
In addition, the present invention is that above-mentioned clear flexible duplexer is wound into the duplexer volume that web-like forms.
In clear flexible duplexer of the present invention, the glass-film of used thickness 20 ~ 200 μ m.This glass-film itself is because coming from glass but transparent, and has flexible.If the thickness deficiency of glass-film 20 μ m, the manufacturing difficulty of glass-film itself then is so be not easy to obtain.On the other hand, if the thickness of glass-film surpasses 200 μ m, then flexible reduction, becoming is easy to generate the crackle of glass-film.From taking into account flexible and viewpoint operability, the scope of preferred 30 ~ 100 μ m of the thickness of glass-film, the more preferably scope of 50 ~ 100 μ m.
Such glass-film can use commercially available glass-film, for example, can use the OA-10G of Nippon Electric Glass Co., Ltd's system, the AF32 of Schott AG corporate system.
Usually, if at the glass-film of aforesaid film shape resin bed is set, the characteristic hear resistance because of resin itself, the problem that the transparency reduces are arranged then.In addition, because to glass-film applying foreign material, so the warpage that causes because of both characteristic difference becomes problem.Therefore, in the present invention, solve these problems by stacked polyimide resin with particular characteristics.
That is, the polyimide resin layer that is laminated in glass-film among the present invention use in its construction unit, have imide bond, thermal coefficient of expansion as 10ppm/K below and the light transmittance at wavelength 500nm place be polyimide resin more than 80%.Wherein, for keep with stackedization of glass-film after the hear resistance of duplexer, the preferred high polyimide resin of hear resistance.From such viewpoint, the glass transition temperature of preferred polyimide resin is more than 300 ℃, more preferably more than 350 ℃.
Satisfy the polyimide resin of above-mentioned characteristic, particularly, can be formed as follows.Namely, if to use glass-film to illustrate as example as the situation of base material, then at first prepare the glass-film of regulation, the coating of this glass-film as the polyimide precursor resin solution of the precursor of polyimide resin (below, be called polyamic acid solution), make solvent seasoning by heat treated, under higher temperature, heat again, make the polyimide precursor imidizate thus, obtain being laminated with on the glass-film the flexible duplexer of polyimide resin.
Then, as the preferred polyimide resin that forms at glass-film, can enumerate the polyimide resin of the construction unit with following general formula (1) expression, more preferably contain the polyimide resin of construction unit of this general formula (1) expression of 80 ~ 100 moles of %.
Figure BDA00002831145400031
(in the formula, Ar 1Expression has 4 valency organic groups of aromatic rings, Ar 2It is the divalent organic group of following general formula (2) or (3) expression.）
Figure BDA00002831145400041
General formula (2)
Figure BDA00002831145400042
General formula (3)
(wherein, the R in general formula (2) or the general formula (3) 1~ R 8Be alkyl or alkoxyl or the fluorine substituted hydrocarbon radical of hydrogen atom, fluorine atom, carbon number 1 ~ 5 independently of each other, the R in the general formula (2) 1~ R 4In, at least one is fluorine atom or fluorine substituted hydrocarbon radical, in addition, and the R in the general formula (3) 1~ R 8In, at least one is fluorine atom or fluorine substituted hydrocarbon radical.）
Except the polyimide resin of general formula (1), to being not particularly limited by other polyimide resin of maximum 20 moles of % interpolation, can use general acid anhydrides and diamines, wherein, as the acid anhydrides of preferred use, can enumerate pyromellitic acid anhydride, 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride, 1,4-cyclohexane cyclohexanedimethanodibasic, 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 2,2 '-two (3,4-dicarboxyl phenyl) hexafluoropropane dianhydride etc. in addition, can enumerate 4 as diamines, 4 '-DADPS, anti-form-1, the 4-DACH, 4,4 '-the diaminourea cyclohexyl-methane, 2,2 '-two (4-aminocyclohexyl)-HFC-236fas, 2,2 '-two (trifluoromethyl)-4,4 '-the diamino bicyclic hexane etc.
As mentioned above, the part of polyimide resin in its chemical constitution that is preferred for polyimide resin layer has fluorine atom or fluorine substituted hydrocarbon radical.Therefore, fluorine atom or fluorine substituted hydrocarbon radical can be contained in the Ar in the general formula (1) 1In, also can be contained in Ar 2In, also can be contained among both.As more preferred form, can be the R in the above-mentioned general formula (2) 1~ R 4Or the R in (3) 1~ R 8At least one is fluorine atom or fluorine substituted hydrocarbon radical.
As R 1~ R 8Preferred concrete example, can enumerate-H ,-CH 3,-OCH 3,-F ,-CF 3Deng, R more preferably 1~ R 8At least one be-F or-CF 3Any.
In addition, as the Ar in the general formula (1) 1Concrete example, for example can enumerate 4 following valency acid anhydrides residues.
Figure BDA00002831145400051
In addition, as the Ar that provides in the general formula (1) 2Concrete diamines residue, for example can enumerate following residue.
Figure BDA00002831145400061
From the reductionization of thermal coefficient of expansion, stable on heating viewpoint, in the above-mentioned illustrative polyimide resin, preferably contain the construction unit of following formula (4) or (5) expression with 80 moles of ratios more than the %.
Figure BDA00002831145400071
Various polyimide resins as described above, the polyamic acid imidizate can be obtained, here, the resin solution of polyamic acid can be by using equimolar in fact aromatic diamine and aromatic acid dianhydride as raw material, it is reacted in organic solvent and obtains.More specifically, can make aromatic diamine be dissolved in N by flowing down at nitrogen, in the organic polar solvents such as N-dimethylacetylamide after, add aromatic tetracarboxylic acid's dianhydride, room temperature reaction is about 5 hours and obtain.The viewpoint of the mechanical strength of the uniform film thicknessization during from coating and the polyimide film that obtains, the weight average molecular weight of the polyamic acid that preferably obtains is 10,000 ~ 300,000.Should illustrate that the preferred molecular weight ranges of polyimide resin layer also is the molecular weight ranges identical with polyamic acid.
In addition, in order to make glass-film and polyimide resin layer stacked, after being coated on polyamic acid solution on the glass-film, carry out beyond the so-called casting method of drying, curing, can also enumerate be coated on polyamic acid solution on the base material of regulation after, dry solvent is peeled off uncured film, be cured by heat treatment and make polyimide film, this polyimide film and glass-film are added the method that hot pressing forms polyimide resin layer; Or after polyamic acid solution being coated on the base material of regulation, make its drying, till solidifying, make polyimide film, peel off from base material then, this polyimide film and glass-film are added the method for hot pressing etc.
Among the present invention, can use the arbitrary method in these methods, in addition, not limited by these methods, from with the cementability of glass-film and the control easness of thermal coefficient of expansion, and surface roughness, the reduction of phase difference, the easy degree of manufacturing process etc. set out, and most preferably carry out the casting method of dry solidification after constituting on the glass-film of the present invention direct coating polyamic acid solution.Here, if the surface roughness Ra of polyimide resin surpasses 5nm, and phase difference surpasses 10nm, and then the thickness of the element of the display on the substrate, solar cell and so on, optical characteristics become inhomogeneous, and performance may reduce.Therefore, the surface roughness Ra that preferably makes polyimide resin layer respectively is below the 5nm, and in addition, making the phase difference of the face direction in the polyimide resin layer of the duplexer that obtains is below the 10nm.And then from the viewpoint of the easy degree of dry, the manufacturing process of solidifying, preferably the polyimide resin layer thickness that forms by casting method is 1 ~ 50 μ m.Should illustrate that surface roughness Ra is represented arithmetic average roughness (JIS B0601-1994).
The Production Example of duplexer of the present invention more specifically is shown, for example, can followingly obtain: use applicator etc. will be coated on by the polyamic acid solution that above-mentioned reaction obtains on the glass-film that becomes supporter, in the temperature below 150 ℃ after predrying 2 ~ 20 minutes, usually in the heat treatment about 130 ~ 360 ℃ about 2 ~ 30 minutes, imidizate is carried out in desolventizing.
Among the present invention, the thickness of polyimide resin layer is not particularly limited, but the scope of preferred 1 ~ 100 μ m, the more preferably scope of 1 ~ 50 μ m.If the thickness deficiency of polyimide resin layer 1 μ m, the control difficulty of applicator then, it is inhomogeneous that thickness becomes easily, on the contrary, if surpass 100 μ m, then may cause hear resistance, light transmittance to reduce.Especially, when the thickness that the thickness of glass-film is made as Gt, polyimide resin layer is made as Pt, preferably there is the relation of 2≤Pt≤Gt/10.Thereby can provide thickness uniform clear flexible duplexer by satisfying this relation.
But as mentioned above, for clear flexible duplexer of the present invention, its polyimide resin layer need be more than 80% at the light transmittance at wavelength 500nm place.For making light transmittance in this scope, importantly select the chemical constitution of polyimide resin, make the high polyimide resin layer of transmissivity.In addition, be the also flexible duplexer of bendable transparent below the 150mm in order to make radius of curvature, the thickness of importantly selecting glass-film is the glass-film of 20 μ m ~ 200 μ m, forms to have flexible glassy layer.
Namely, by selecting the polyimide resin of suitable chemical constitution unit, adopt the glass-film of creating conditions with stipulating of regulation stacked, thereby can be as mentioned above when improving light transmittance, the thermal coefficient of expansion that makes polyimide resin layer is below the 10ppm/K, in addition, the coefficient of thermal expansion differences that can make glass-film and polyimide resin layer is the scope of 0 ~ 3ppm/K, further reduces the warpage of duplexer.And then, be below the 0.2mm by the thickness that makes glass-film, thereby can further improve flexiblely, be strip by making the clear flexible duplexer, thereby can be wound into web-like, can and provide as the duplexer volume.
Therefore, satisfy the preferably following manufacturing of clear flexible duplexer of these characteristics: use the polyimides raw material of the construction unit that constitutes above-mentioned general formula (4) to make polyamic acid solution, this polyamic acid solution thickness in accordance with regulations is coated on the glass-film, after making its drying about through 2 ~ 20 minutes below 150 ℃, in the heat treatment about 130 ~ 360 ℃ about 2 ~ 30 minutes.
Here, the viewpoint of the thickness when using applicator etc. to be coated with from control equably, when the degree of polymerization that is used to form the polyamic acid of polyimide resin layer and polyimides was represented with the range of viscosities of polyamic acid solution, preferred solution viscosity was in the scope of 500 ~ 200000cP.The mensuration of solution viscosity can be undertaken by the cone and plate viscometer of band Water Tank with Temp.-controlled.
Clear flexible duplexer of the present invention, because the transparency is excellent, no warpage, and have hear resistance and gas barrier property concurrently is so be useful as flexible baseplate material.For example, utilize as the flexible base, board in the display equipment that as organic EL, Electronic Paper etc., shows image, or utilize as the transparency carrier of solar cell and all to be fit to, in addition, in addition to these, for example also can be used for illumination, lithium ion battery etc.Therefore, utilize clear flexible duplexer of the present invention as the substitute material of the main glass substrate that uses up to now etc., can use in field widely, this industry is had huge contribution.
Embodiment
Below wait based on embodiment and to be described more specifically content of the present invention, but the invention is not restricted to the scope of these embodiment.
Below represent the abbreviation of employed polyimides raw materials such as embodiment
TFMB:2, two (trifluoromethyl)-4 of 2'-, 4'-benzidine
PMDA: pyromellitic acid anhydride
6FDA:2,2 '-two (3,4-dicarboxyl phenyl) hexafluoropropane dianhydride
BPDA:3,3', 4,4'-bibenzene tetracarboxylic dianhydride
BAPP:2, two (4-(4-amino-benzene oxygen) phenyl of 2-) propane
M-TB:2,2 '-dimethyl-4, the 4'-benzidine
DMAc:N, the N-dimethylacetylamide
Assay method and the condition of the various rerum naturas among the embodiment below are shown in addition.
(viscosity)
For viscosity, with the cone and plate viscometer (TOKIMEC corporate system) of band Water Tank with Temp.-controlled the polyamic acid solution that obtains in the synthesis example is measured at 25 ℃.
(thermal coefficient of expansion (CTE))
With thermo-mechanical analysis (TMA) on one side device applies the load of 5.0g to the polyimide film of the size of 3mm * 15mm, on one side with certain programming rate (20 ℃/min) carry out tension test 30 ℃ ~ 260 ℃ temperature range are measured thermal coefficient of expansion (ppm/K) by polyimide film with respect to the elongation of temperature.
(light transmittance)
(50mm * 50mm) obtains the light transmittance at 500nm place to polyimide film with U4000 type self-recording spectrophotometer.
(warpage)
The clear flexible duplexer is placed on the smooth plate, measure the distance at 4 angles of plate and duplexer.Should illustrate, when the clear flexible duplexer curls to a side, the inboard of curling be placed towards top.
(surface roughness)
For the surface roughness Ra of the polyimide resin layer in the clear flexible duplexer, use the AFM (AFM) " Multi Mode8 " of Bruker corporate system to carry out surface observation, in the square visual field of 10 μ m, measure 4 points, average.
(phase difference)
Use the spectropolarimeter " Poxi-spectra " of Tokyo instruments corporate system to obtain the phase difference of direction in the face in the polyimide resin layer of clear flexible duplexer.
(flexible)
The clear flexible duplexer is cut out the square of 10cm, defective such as whether crack when making the roller that it is sealed at radius 150mm by Visual Confirmation.
(synthesis example 1 ~ 4)
At first, for synthesizing polyamides acid A, flow down at nitrogen, the limit is stirred with the diamines shown in the table 1 in the limit in the detachable flask of 200mL be dissolved among the solvent DMAc it.Then, add the acid dianhydride shown in the table 1.Then, room temperature continues agitating solution and carried out polymerisation in 5 hours, keeps diel.Obtain the polyamic acid solution of thickness, confirm to have generated the polyamic acid of high polymerization degree.Solid constituent and the solution viscosity of the solution (hereinafter referred to as polyamic acid solution A) of the polyamic acid A that obtains are shown in table 1.Here, solid constituent is polyamic acid concentration.To the results are summarized in table 1.
In addition, with the example that uses polyamic acid A as synthesis example 1, below, except according to the composition of the synthesis example 2 ~ 4 shown in the table 1 than, similarly carry out the synthetic of polyamic acid B ~ D with the situation of polyamic acid A.For their solid constituent and solution viscosity, gather and be shown in table 1.
Table 1
Figure BDA00002831145400111
(embodiment 1)
The mode that thickness after using applicator with heat treatment is about 5 μ m is coated on the polyamic acid solution A shown in the table 1 on the commercially available glass-film of thickness 50 μ m, be warming up to 360 ℃ with 1 minute speed of 22 ℃ from 90 ℃, obtain having on the glass-film duplexer of the polyimide layer of individual layer.The thermal coefficient of expansion of glass-film used herein is 3.8ppm/K, and the transmissivity at 500nm place is 90%, and elastic modelling quantity is 30GPa.
For the duplexer of the above-mentioned embodiment that obtains 1, measure warpage, surface roughness and flexible.In addition, peel off polyimide film from the glass-film of the duplexer that obtains, measure light transmittance, phase difference and the thermal coefficient of expansion (CTE) of the polyimide film that obtains.Summarized results is shown in table 2.
Table 2
Figure BDA00002831145400121
(embodiment 2)
Except using the polyamic acid solution B shown in the table 1, carry out similarly to Example 1, obtain the duplexer of embodiment 2.For the duplexer that obtains, carry out various evaluations similarly to Example 1.Show the result in table 2.
(comparative example 1)
Except using the polyamic acid solution C shown in the table 1, carry out similarly to Example 1, obtain the duplexer of comparative example 1.For the duplexer that obtains, carry out various evaluations similarly to Example 1.Show the result in table 2.
(comparative example 2)
Except using the polyamic acid solution D shown in the table 1, carry out similarly to Example 1, obtain the duplexer of comparative example 2.For the duplexer that obtains, carry out various evaluations similarly to Example 1.Show the result in table 2.
The result who is obtained by above-described embodiment 1 ~ 2 and comparative example 1 ~ 2 as can be known, the clear flexible duplexer that is constituted by the glass-film that satisfies condition of the present invention and polyimide resin layer, the transparency is excellent, no warpage, and the roughness on polyimide resin layer surface, the value of phase difference are low.On the other hand, by the duplexer that the polyimide resin layer of the condition of discontented unabridged version invention constitutes, the transparency low (comparative example 1) in addition, when stacked with thin glass-film, produces big warpage (comparative example 1, comparative example 2).

Claims (8)

1. a clear flexible duplexer is characterized in that, has glass-film and the polyimide resin layer of thickness 20 ~ 200 μ m, and the thermal coefficient of expansion of described polyimide resin layer is below the 10ppm/K, and the light transmittance at wavelength 500nm place is more than 80%.
2. clear flexible duplexer according to claim 1, wherein, the difference of the thermal coefficient of expansion of described glass-film and polyimide resin layer is the scope of 0 ~ 3ppm/K.
3. clear flexible duplexer according to claim 1 and 2 wherein, is flexible to below the radius of curvature 150mm.
4. clear flexible duplexer according to claim 1 and 2, wherein, described polyimide resin layer is made of the polyimide resin of the construction unit of following general formula (1) expression that contains 80 ~ 100 moles of %,
Figure FDA00002831145300011
In the formula (1), Ar 1Expression has 4 valency organic groups of aromatic rings, Ar 2Be the divalent organic group of following general formula (2) or (3) expression,
Figure FDA00002831145300012
General formula (2)
Figure FDA00002831145300013
Wherein, the R in general formula (2) or the general formula (3) 1~ R 8Be alkyl or alkoxyl or the fluorine substituted hydrocarbon radical of hydrogen atom, fluorine atom, carbon number 1 ~ 5 independently of each other, the R in the general formula (2) 1~ R 4In, at least one is fluorine atom or fluorine substituted hydrocarbon radical, and, the R in the general formula (3) 1~ R 8In, at least one is fluorine atom or fluorine substituted hydrocarbon radical.
5. according to each described clear flexible duplexer in the claim 1 ~ 4, wherein, the phase difference of the face direction of polyimide resin layer is below the 10nm.
6. according to each described clear flexible duplexer in the claim 1 ~ 5, wherein, described polyimide resin layer is that the polyimide precursor resin solution that will form this polyimide resin layer is coated on the glass-film, carrying out drying and heat cure handles, form thickness 1 ~ 50 μ m and, the surface roughness Ra of this polyimide resin layer is below the 5nm.
7. according to each described clear flexible duplexer in the claim 1 ~ 6, be used for showing the display equipment of image or the transparency carrier of solar cell.
8. duplexer volume is that each described clear flexible duplexer is wound into web-like and forms in the claim 1 ~ 7.
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CN104507263A (en) * 2014-09-15 2015-04-08 横店集团东磁股份有限公司 Preparation method for two-layer flexible copper clad lamination
CN105118963A (en) * 2015-07-21 2015-12-02 广州有色金属研究院 Lithium ion battery transparent anode material and preparation method thereof
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