CN100501521C - Color filter substrate - Google Patents

Color filter substrate Download PDF

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Publication number
CN100501521C
CN100501521C CNB2005101249953A CN200510124995A CN100501521C CN 100501521 C CN100501521 C CN 100501521C CN B2005101249953 A CNB2005101249953 A CN B2005101249953A CN 200510124995 A CN200510124995 A CN 200510124995A CN 100501521 C CN100501521 C CN 100501521C
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substrate
film
polyimide
color filter
filter substrate
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CN1769978A (en
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木原秀太
毛户耕
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Mitsubishi Gas Chemical Co Inc
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Mitsubishi Gas Chemical Co Inc
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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices

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  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Polymers & Plastics (AREA)
  • Optics & Photonics (AREA)
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Abstract

To provide a color filter substrate having a color filter part formed excellently and directly on a base material plate of a flexible plastic film which is colorless and transparent, and also excellent in heat resistance, non-coloring property, and adhesion to obtain a thin, lightweight, and hard-to-crack panel display device at low cost. Disclosed is the color filter substrate having the color filter part formed on the base material plate made of a film of polyimide having repetiting units shown by a specific formula.

Description

Filter substrate
Technical field
The present invention relates to the filter substrate that the transparency and thermotolerance are good, be formed with color filter portions on the film substrate that is made of polyimide, be used in the display device such as liquid crystal indicator, organic EL display.
Background technology
In recent years the filter substrate that uses in the panel display apparatus of popularizing gradually, glass substrate is provided with blue or green (B) dyed layer of etc.ing of red (R) green (G) is important composition parts of realizing colorize, has obtained use widely.
Color filter portions that filter substrate constitutes by water white substrates such as glass, by versicolor pixel portions etc. and the transparent conducting film that is provided with as required constitute.The conventional method that forms filter substrate is as follows.At first, the surface of glass substrate is cleaned.Next, utilize the black-matrix material film of method comprehensive formation chromium, black resins etc. on the single side surface of glass substrate such as sputter.On the surface of this black-matrix material film, coat resist then, utilize the pattern of photomask exposure, development and formation resist after the oven dry.Then, carry out etching, resist is peeled off, and only stays the necessary part of black-matrix material film, form black matrix".
Then, form pixel portions of all kinds such as RGB.For example, be coated with red pixel material, prebake in the occasion that forms red pixel.Next on the surface of this haematochrome material membrane, apply resist, utilize photomask exposure, development after the oven dry, form the pattern of haematochrome material membrane., carry out etching, resist is peeled off, and only stays the necessary part of haematochrome material membrane thereafter, through after oven dry form red pixel portion.Residual versicolor pixel portions such as G, B also forms by repeating same operation.
Next, for the flattening surface of color pixel portion and the purpose of protection, on color pixel portion surface, form external coating as required.By above operation, on substrate, form color filter portions.At last, form transparent conducting film as required, thereby finished the making of filter substrate.
As the substrate of filter substrate, if adopt plastic sheeting to come instead of glass, can be approached, gently, be difficult to broken filter substrate.And, by utilizing the pliability of plastic sheeting, adopt so-called roller to roller (roll to roll) method for making, greatly improved the production efficiency of filter substrate and panel display apparatus.
But the treatment temperature in the color filter portions forming method of above-mentioned standard is generally more than 180 ℃, and is significantly not enough because normally used transparent plastic is the thermotolerance of polyethylene terephthalate and polycarbonate, thereby can not use.
Material as the higher plastic base of thermotolerance, also consider to use for example polyarylate resin and polyethersulfone resin. still, because the thermotolerance of these resins is also insufficient, the bake out temperature of the dye material of above-mentioned black-matrix material and each color pixel is hanged down to about 150 ℃, because can not carry out enough solidifying fully handles, look characteristic, thermotolerance, resistance to chemical reagents are all insufficient.And, the occasion of additional transparent conductive membrane in final operation, because need in the low temperature below 150 ℃, form transparent conducting film, thus exist the crystallinity of transparent conducting film low, the shortcoming that sheet resistance value is high.And the substrate that filter substrate uses need and be kept water white transparency when making under long-term environment for use.But if use these plastic bases, when making and in the long-term use, resin can painted (flavescence), the very big problem of existence in the use.
Except that above-mentioned resin, the method (opening flat 5-61026 communique with reference to the spy) that transparent resin that the alicyclic olefin polymerization is obtained uses as the substrate of panel display apparatus is disclosed.But, because the surface polarity of this resin is low, thus the poor adhesion of the dye material of existence and black-matrix material, each color pixel, the shortcoming that color filter portions is peeled off easily.
On the other hand, as thermotolerance and the good resin of dimensional stability, known all aromatic polyimide resin.The all aromatic polyimide resin that is obtained by the polycondensation reaction of aromatic tetracarboxylic acid's dianhydride and aromatic diamines can use under the high temperature more than 400 ℃, have good characteristics such as thermal expansivity is little, dimensional stability is good, raw material as the film that uses under the high temperature, electric wire coating, cementing agent, coating etc. uses in the various fields that with universe Aerobiz, electronic industry are the center.But all aromatic polyimide resin can not use in the substrate of filter substrate because from faint yellow painted to bronzing.
As solution to this problem, after disclosing on the heat resistant substrates such as in a single day color filter portions being formed on glass, be transferred on the plastic base by the color filter portions that will form, obtain having the method (opening the 2000-47023 communique) of the filter substrate of plastic base referring to the spy.
But the production efficiency of this method is low, and existence can not be produced the shortcoming of the filter substrate with glass substrate more cheaply.
Summary of the invention
Problem of the present invention is to address the above problem, provide a kind of and can produce panel display apparatus thin, light, that be difficult to fragmentation cheaply, water white transparency and thermotolerance, non-staining, good adhesion, the soft filter substrate that comprises film substrate that constitutes by plastics and the color filter portions that on this substrate, forms.
Present inventors specialize in order to address the above problem, and obtain the present invention.Promptly the present invention relates to comprise the filter substrate of film substrate of making by polyimide and the color filter portions that on this film substrate, forms with repetitive of representing by following general formula I.
Figure C200510124995D00051
(in the formula, R is the 4 valency groups of deriving from cyclohexane, and Φ is that carbon number is 2～39 divalent fatty group, alicyclic group, aromatic series base or these the group that constitutes, in the main chain of Φ, can insert from by-O-,-SO 2-,-CO-,-CH 2-,-C (CH 3) 2-,-OSi (CH 3) 2-,-C 2H 4O-and-at least one group of selecting in the group that S-constitutes.)
According to the present invention, can obtain water white transparency, thermotolerance, non-staining, good adhesion, and the soft filter substrate that comprises the film substrate that constitutes by plastics and utilize the color filter portions that common film build method forms.This filter substrate can utilize in the manufacturing of thin, light, as to be difficult to fragmentation panel display apparatus.
Description of drawings
The infrared absorption spectrum of the film of the polyimide that [Fig. 1] obtained by embodiment 1.
Embodiment
The polyimide that uses among the present invention has by following general formula I:
Figure C200510124995D00052
The repetitive of expression.In the formula, R is the 4 valency groups of deriving from cyclohexane.Φ is that carbon number is 2～39 divalent fatty group, alicyclic group, aromatic series base or these the group that constitutes, in the main chain of Φ, can insert from by-O-,-SO 2-,-CO-,-CH 2-,-C (CH 3) 2-,-OSi (CH 3) 2-,-C 2H 4O-and-at least one group of selecting in the group that S-constitutes.
As preferred Φ, can list fatty groups such as polyolefin, polyoxyalkylene, xylylene and their alkyl substituent, halogen substituent; Cyclohexane, dicyclo ethyl methane, dimethyl cyclohexane, isophorone, norbornane and the divalent alicyclic group of deriving from their alkyl substituent, halogen substituent etc.; With benzene,
Figure C200510124995D0008163924QIETU
, biphenyl, diphenyl methane, diphenyl ether, diphenylsulphone, benzophenone and the divalent aromatic series base of deriving from their alkyl substituent, halogen substituent etc.More particularly, enumerate by following structural formula:
Figure C200510124995D00061
The divalent group of expression.
The content of the repetitive of being represented by general formula I is 10～100 moles of % of all repetitives, more preferably 50～100 moles of % preferably.And preferably 10～2000 of the numbers of the repetitive of being represented by general formula I in 1 molecule of polyimide are more preferably 20～200.
Above-mentioned polyimide (hereinafter referred to as polyimide A) obtains by making tetrabasic carboxylic acid composition and diamines constituents (diamines and derivant thereof) reaction. as the tetrabasic carboxylic acid composition, can enumerate cyclohexane tetrabasic carboxylic acid, cyclohexane tetrabasic ester class, cyclohexane tetracarboxylic dianhydride etc., preferred cyclohexane tetracarboxylic dianhydride.And above-mentioned tetrabasic carboxylic acid composition comprises position isomer.
Have the polyimide A of the cyclohexane tetrabasic carboxylic acid skeleton that comes from above-mentioned tetrabasic carboxylic acid composition because macromolecule quantizes easily, be easy to obtain soft film substrate, also enough big to the solubleness of solvent, so help the shaping processing of film substrate.
At the solvent soluble that does not injure polyimide A, the transparency of film substrate, in the scope of flexibility, the tetrabasic carboxylic acid composition can comprise at least a compound of selecting from following material: other tetrabasic carboxylic acid or its derivant, for example, pyromellitic acid, 3,3 ', 4,4 '-biphenyltetracarboxyacid acid, 2,3,3 ', 4 '-biphenyltetracarboxyacid acid, 2,2-two (3,4-dicarboxyl phenyl) propane, 2,2-two (2,3-dicarboxyl phenyl) propane, 2,2-two (3,4-dicarboxyl phenyl)-1,1,1,3,3, the 3-HFC-236fa, 2,2-two (2,3-dicarboxyl phenyl)-1,1,1,3,3, the 3-HFC-236fa, two (3,4-dicarboxyl phenyl) sulfone, two (3,4-dicarboxyl phenyl) ether, two (2,3-dicarboxyl phenyl) ether, 3,3 ', 4,4 '-benzophenone tetrabasic carboxylic acid, 2,2 ', 3,3 '-benzophenone tetrabasic carboxylic acid, 4,4-(to the phenylene dioxy) two phthalic acids, 4,4-(metaphenylene dioxy) two phthalic acids, ethene tetrabasic carboxylic acid, 1,2,3, the 4-BTCA, 1,2,3,4-cyclo-butane tetrabasic carboxylic acid, 1,2,4,5-cyclopentane tetrabasic carboxylic acid, 3-carboxyl methyl isophthalic acid, 2,4-cyclopentane tricarboxylic acids, dicyclo [2.2.2] suffering-7-alkene-2,3,5, the 6-tetrabasic carboxylic acid, dicyclohexyl tetrabasic carboxylic acid, 1,1-two (2,3-dicarboxyl phenyl) ethane, two (2,3-dicarboxyl phenyl) methane, two (3,4-dicarboxyl phenyl) methane and their derivant.
As the diamines constituents, can list diamines, diisocyanate resin, diamido disilane class etc., preferred diamines.Diamine contents in the diamines constituents preferably (comprises 100 moles of %) at 50 moles more than the %.
Above-mentioned diamines can be aliphatic diamine or aromatic diamine, also can be their potpourri, but from the angle of the water white transparency of the film substrate that keeps constituting by polyimide, preferred aliphat diamines.As the reason of painted (flavescence) of the film substrate that is made of polyimide, the variation of the phenyl that contains in the polymer backbone etc. is one of reason, from this point, preferably uses the amine that contains the aromatic series base in the molecular structure less.Also with the occasion of aromatic diamine, the fit rate of optimization aromatic diamines is 80 moles of % following (comprising 0) of diamines constituents in aliphatic diamine.And, in the present invention, what " aromatic diamine " represented is the amino diamines that directly is attached on the aromatic ring, can contain fatty group, alicyclic group, other substituting group in the part of its structure. " fatty amine " refers to the amino diamines that directly is attached on fatty group or the alicyclic group, also can contain aromatic series base, other substituting group in the part of its structure.
And, also consider from the terminal amino group of polymkeric substance as one of reason of painted flavescence, utilize acid anhydrides to wait to handle the amido of polyimide end also can prevent painted effectively.
In general,, form firm complex compound, be difficult to obtain the polyimide of high molecular because intermediate product is polyamic acid and aliphatic diamine if aliphatic diamine is used as constituent.Therefore, need to use dissolubility to complex compound, for example utilize the method for cresols etc. than higher solvent.But, if cyclohexane tetrabasic carboxylic acid or its derivant and aliphatic diamine are used as composition, because form the more weak complex compound of combination of polyamic acid and aliphatic diamine, so can easily realize the macromolecule quantification of polyimide.
As above-mentioned aliphatic diamine, for example enumerate 4,4 '-diamino bicyclic hexyl methane, ethylenediamine, 1,6-diamines, polyglycol two (3-aminopropyl) ether, polypropylene glycol two (3-aminopropyl) ether, 1,3-two (aminomethyl) cyclohexane, 1,4-two (aminomethyl) cyclohexane, m-xylene diamine, the p dimethylamine, isophorone diamine, norbornane diamines, siloxane diamine etc.
As above-mentioned aromatic diamine, for example can list 4,4 '-diaminodiphenyl ether, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl sulfone, m-phenylene diamine, p-phenylenediamine (PPD), diaminobenzophenone, 2,6-diamido
Figure C200510124995D0008163924QIETU
, 1, the 5-diamido
Figure C200510124995D0008163924QIETU
Deng.
In the present invention, polyimide A is manufactured to organic solvent solution usually.As organic solvent, can list for example N-N-methyl-2-2-pyrrolidone N-, N, the N-dimethyl acetamide, N, dinethylformamide, dimethyl sulfoxide (DMSO), hexamethyl phosphoramide, tetramethylene sulfone, parachlorophenol, m-cresol, 2-chloro-4-hydroxy-methylbenzene, gamma-butyrolacton, propylene carbonate, dioxolanes etc.
The method of the organic solvent solution of polyimide A by following (i)～(iii) obtains.
(i) in the organic solvent solution of diamines constituents, add the tetrabasic carboxylic acid composition, perhaps in the organic solvent solution of tetrabasic carboxylic acid composition, add the diamines constituents, preferably below 80 ℃, particularly near room temperature～kept 0.5～3 hour in the temperature below it.In the polyamic acid solution of the reaction intermediate that obtains, add azeotropic dehydration solvents such as toluene or dimethylbenzene, the water that generates is discharged to the system outside, carry out dehydration simultaneously, obtain the organic solvent solution of polyimide A by azeotropic.
Thereby (ii) in the polyamic acid solution of reaction intermediate, add after the dewatering agent imidizate such as acetic anhydride, add methyl alcohol etc. for the dissolving of polyimide A can be low solvent, make polyimide A precipitation.By filtering after clean dry separates as solid, in the N,N-dimethylacetamide equal solvent, dissolve the organic solvent solution that just obtains polyimide A.
(iii) utilize high boiling solvent modulation polyamic acid solutions such as cresols, after in 150～220 ℃, directly keeping making its polyimideization in 3～12 hours, interpolation methyl alcohol etc. are for the low solvent of dissolving energy of polyimide A, make polyimide A precipitation. after separating as solid by the filtration clean dry, in the N,N-dimethylacetamide equal solvent, dissolve the organic solvent solution that just obtains polyimide A.
The polyimide A concentration of above-mentioned organic solvent solution is preferably 5～50 weight %, more preferably 10～40 weight %.
Make by following step by the film substrate that the polyimide that uses among the present invention constitutes, the organic solvent solution of the polyimide A that the method by above-mentioned (i)～(iii) that is about to obtains is coated to films such as glass plate, sheet metal and forms with on the support, be heated to 100 ℃～350 ℃ and make solvent evaporation, the film of formation is peeled off from support.In addition, be coated to film by organic solvent solution and form, be heated to 200 ℃～350 ℃ methods, also can make the film substrate that constitutes by polyimide with the imidization reaction of dewatering with on the support with polyamic acid.The thickness of the film substrate that is made of polyimide is preferably 20～400 μ m.
Utilize solution-cast manufactured thin film based inverse time at this, be easy to remove foreign material by filtering the polyimide amine aqueous solution.In addition, the film substrate that constitutes by the polyimide that obtains with compare by the film substrate that dissolves the extrusion molding manufacturing commonly used, have the more superior feature of isotropy of surface smoothing, optics.
The glass transition temperature of the film substrate that is made of polyimide A is roughly 250 ℃～350 ℃ according to the difference of the diamines of selecting and inequality, has sufficient thermotolerance as the substrate that uses in the filter substrate.
Color filter portions among the present invention can adopt the known method identical with the occasion of using glass substrate to make.
At first, the surface of the film substrate that will be made of polyimide A is cleaned.Secondly, utilize the black-matrix material film of method comprehensive formation chromium, black resins etc. on a side surface of film substrate such as sputter.On the surface of this black-matrix material film, coat resist then, utilize photomask exposure, development after the oven dry, form the pattern of resist.Then, carry out etching, resist is peeled off, and only stays the necessary part of black-matrix material film, form black matrix".The thickness of black matrix" is preferably 0.05～2 μ m, more preferably 0.12～1.2 μ m.
Then, form the pixel portions of all kinds of RGB etc.For example, apply red pixel material, prebake in the occasion that forms red pixel.Next on the surface of this haematochrome material membrane, apply resist, utilize photomask exposure, development after the oven dry, form the pattern of haematochrome material membrane., carry out etching, resist peel off, only stay the necessary part of haematochrome material membrane, form red pixel portion by the back oven dry thereafter.Remaining versicolor pixel portions such as G, B also forms by repeating same operation.The thickness of pixel portions of all kinds is preferably 0.5～5 μ m, more preferably 1～3 μ m.
Pattern forming method as black matrix" and pixel portions of all kinds, except that the method for using above-mentioned photoresist, also can adopt to use to have photosensitive black-matrix material, each dye material, without resist but directly form method of patterning by photomask.In addition, can form the pattern of black matrix" and pixel portions of all kinds by print processes such as serigraphy, photogravure, ink jet printings.
And as black-matrix material and each dye material, photo anti-corrosion agent material, using acrylic resin and polyimide is resin.After applying these resins, make its curing by the above-mentioned thermal treatment of curing that is called with liquid condition.If use the film substrate that constitutes by polyimide A of the present invention, because substrate has high-fire resistance, so can in the high temperature more than 180 ℃, dry processing, black-matrix material and each dye material, photo anti-corrosion agent material are hardened fully, therefore preferred.
By suitably adding the insoluble solvent of separating polyimide A etc., the solvent that can be used in the solution of modulation black-matrix material and each dye material, photo anti-corrosion agent material etc. does not dissolve the film substrate that is made of polyimide A.Shown good adaptation between black matrix" that obtains by said method and pixel portions of all kinds and the film substrate that constitutes by polyimide A or the gas-barrier layer that forms as required.
Next, for the flattening surface of color pixel portion and the purpose of protection, on color pixel portion surface, form external coating as required.The main resin that adopts epoxies and acrylic compounds in the external coating, its thickness is generally 1～10 μ m.By above operation, on film substrate, form color filter portions.
At last, form transparent conducting film as required, for example form known metal oxide film etc.As metal oxide film, enumerate indium oxide, cadmium oxide and the tin oxide of the tin that for example added as impurity, tellurium, cadmium, molybdenum, tungsten, fluorine, zinc, germanium etc., added the metal oxide film such as zinc paste, titanium dioxide of impurity aluminum.The transparent conducting film that wherein contains the indium oxide (ITO) of the tin oxide of 2～15 weight % has the good transparency and electric conductivity, so preferential the use.The thickness of above-mentioned transparent conducting film layer is set according to targeted sheet resistance, preferred 5nm～10 μ m.By color filter portions just these transparent conducting films be stacked in occasion on the Kapton layer by layer, can adopt vapour deposition processes such as sputtering method, vacuum vapour deposition, ion plating, plasma CVD method.For the resistivity that makes the transparent conducting film layer below 1m Ω cm, the temperature of film substrate is 20 ℃～400 ℃, is preferably 180 ℃～350 ℃.
In the occasion that filter substrate of the present invention is used as the filter substrate of organic EL and liquid crystal display cells, preferably on the single face of the film substrate that constitutes by polyimide or two sides, be laminated to the gas-barrier layer of few one deck.As the material of gas-barrier layer, enumerate the one or more kinds of metals that from the group that silicon, aluminium, magnesium and zinc constitute, to select metal oxide or metal nitride as principal ingredient.These are known barrier properties for gases excellent material. these oxide skin(coating)s and nitride layer can be made by vapour deposition processes such as sputtering method, vacuum vapour deposition, ion plating, plasma CVD methods.The thickness of above-mentioned gas barrier layer is set according to the object gas transmitance, but in order to obtain 23 ℃, OTR oxygen transmission rate during 60%RH at 1.0cc/m 2Below it, and be 1.0g/m at 40 ℃, moisture-vapor transmission during 90%RH 2The filter substrate that it is following, preferred 10nm～10 μ m.
Through above-mentioned operation, can access the filter substrate of the present invention that on the transparent film substrate that constitutes by polyimide, is formed with color filter portions.
And, when on the film substrate that polyimide constitutes, forming gas-barrier layer, color filter portions, transparent conducting film as mentioned above, can adopt and use individual same processing of occasion of glass substrate, also can utilize the characteristic of film substrate to adopt the continuous processing of roller to roller.
Embodiment
Below, according to embodiment the present invention is carried out specific description.But the present invention is not subjected to any restriction of these embodiment.
Reference example
1,2,4,5-cyclohexane tetracarboxylic dianhydride's is synthetic
Add pyromellitic acid 552g in Chlorimet system (HC22) autoclave of 5 liters of internal volumes, be loaded with catalyzer (エ ヌ イ-ケ system キ ヤ Star ト (strain) makes) 200g of Rh on the activated charcoal, water 1656g charges into nitrogen to inside reactor while stirring.Next, replace inside reactor with hydrogen, making the hydrogen pressure of reactor is 5.0MPa, is warmed up to 60 ℃.Make hydrogen-pressure remain 5.0MPa, the reaction that it was taken place two hours.With the hydrogen in the nitrogen replacement reactor, take out reaction liquid by autoclave, this reaction liquid of filtered while hot is isolated catalyzer.Utilize the rotary cylinder type rapid steamer under reduced pressure, from filtered fluid, to remove moisture to concentrate, to separate out crystallization.Separation of Solid and Liquid, the drying crystallization of separating out at room temperature obtains 1,2,4,5-cyclohexane tetrabasic carboxylic acid 481g (yield 85.0%).
Next, in the separable flask of 5 liters glass (ジ system ロ-ト cooling tube is installed), add obtain 1,2,4,5-cyclohexane tetrabasic carboxylic acid 450g and acetic anhydride 4000g use the nitrogen replacement inside reactor while stirring.Under nitrogen atmosphere, be elevated to the reflux temperature of solvent, made solvent refluxing 10 minutes.While stirring cool to room temperature, crystallization is separated out.The crystallization that Separation of Solid and Liquid, drying are separated out obtains primary crystallization.Further utilize rotary cylinder type rapid steamer concentrating and separating mother liquor under reduced pressure, crystallization is separated out.Separation of Solid and Liquid, dry this crystallization obtain secondary crystallization.Mixing primary crystallization, secondary crystallization obtain 1,2,4,5-cyclohexane tetracarboxylic dianhydride 375g (yield 96.6% of no aquation).
Embodiment 1
Possess thermometer, stirrer, nitrogen import ring, be equipped with side pipe addition funnel, have in 5 mouthfuls of flasks of 500mL of cooling tube of dephlegmator, adding by reference example synthetic 1,2,4,5-cyclohexane tetracarboxylic dianhydride 11.2g (0.05 mole) and as the N-N-methyl-2-2-pyrrolidone N-37.7g of solvent, make it dissolving, utilize ice-water bath to be cooled to 5 ℃.Remain on identical temperature on one side, drip 4 of 7.1g (0.05 mole) with 30 minutes by addition funnel on one side, 4 '-diamino bicyclic hexyl methane is dissolved in the solution that obtains in the N-N-methyl-2-2-pyrrolidone N-of 40.0g, and dropping is taken ice-water bath away after finishing, and at room temperature stirs 2 hours.Add 30.0g then as the m-xylene of azeotropic dehydration solvent and be warmed up to 170 ℃,,, finish reaction Yi Bian be warmed up to 200 ℃ with 4 hours Yi Bian distillate is distillated.In air, make internal temperature be cooled to 60 ℃, take out reactant liquor (organic solvent solution of polyimide).The weight of the organic solvent solution of this polyimide is 87.9g, and the general assembly (TW) of distillate is 37.7g.On glass plate, apply the organic solvent solution of the polyimide obtain, after on 50 ℃ the hot plate dry 1 hour, peel off from glass plate and to obtain independently film.With this independently film be fixed on the stationary fixture that stainless steel makes, in hot-air drier,, obtain the film of soft thickness 200 μ m 200 ℃ of dryings 1 hour.The IR spectrum of this film as shown in Figure 1.Utilize γ (C=0) 1772,1700 (cm -1) confirm imido generation.The Film Fractionation that further makes 0.5g is 0.44 in the limiting viscosity [η] of 30 ℃ of mensuration in the 10ml concentrated sulphuric acid, and the glass transition temperature of measuring with DSC is 256 ℃.In addition, measure the total light transmittance of this film with haze meter (Japanese electric look (strain) system Z-Σ 80), show value up to 90% according to JIS K7105.
In air, heat-treat with 4 hours films (film substrate that constitutes by polyimide) at 220 ℃ this polyimide, measure the total light transmittance before and after the thermal treatment, be 90% not change, promptly use eyes to observe can not to see painted.And, the film of this polyimide is placed air (temperature: 60 ℃), with the high-pressure mercury-vapor lamp of 200W as light source irradiation 1000 hours with after carrying out high energy light and handling, measure total light transmittance equally, be 90% not change, promptly use eyes to observe to see painted.
With the length of side that obtains be the film of the square polyimide of 200mm clean and drying after, utilize sputtering method on a side surface, to form silicon oxide layer as the thick 500nm of gas-barrier layer.Next, on the reverse side of the gas-barrier layer of this Kapton, on whole, form the chromium film with sputtering method.Utilize the photoresist of eurymeric to expose, carry out etching after the development treatment, form the black matrix" (thickness: about 0.2 μ m) of regulation shape.
Next, utilize spin coating method behind the pigment-dispersing type dye material (acrylic acid series negative-type photosensitive) of coated red on whole, on hot plate, carry out prebake.Afterwards, develop after utilizing photoresist exposure, remove part not, form the red pixel part.And then, in clean baking oven, handle 200 ℃ of back oven dry of carrying out 20 minutes, dye material is solidified.Carry out same operation repeatedly, form the pixel of green and cyan.
On pixel formation face, utilize spin coating method to apply outside the epoxy resin and be coated with material, on substrate, form uniform coat film.Form external coating by in clean baking oven, handling, form color filter portions 200 ℃ of oven dry that this substrate was carried out 20 minutes.External coating has good flatness.On this external coating, utilize sputter equipment, form by the thick tin indium oxide of about 100nm (ITO, In:Sn=9:1) transparent conducting film of Gou Chenging down at 200 ℃.Measure sheet resistance value, obtain the good value of 50 Ω/.
And when observing color filter portions, each color pixel does not depart from, and also inviolateness can form pixel well.
And, the good adhesion of color filter portions, transparent conducting film, the filter substrate that obtains has shown sufficient pliability, does not also produce and peels off even carry out bending with 30mmR.
Through above-mentioned operation, can access the flexible filter substrate that utilizes common film build method on the film substrate that constitutes by polyimide, to be formed with color filter portions.

Claims (6)

1. filter substrate, the color filter portions that comprises film substrate and on this film substrate, form, described film substrate is to be made by the polyimide with repetitive that general formula I represents,
Figure C200510124995C00021
In the formula, R is a cyclohexane ring, and Φ is that carbon number is 2～39 divalent alicyclic group.
2. according to the filter substrate of claim 1 record, wherein, the divalent alicyclic group in the above-mentioned formula is the divalent alicyclic group derived from cyclohexane, double-hexyl methane, dimethyl cyclohexane, isophorone or norbornane.
3. according to the filter substrate of claim 1 record, wherein, above-mentioned color filter portions constitutes by the black-matrix layer that begins to have successively from this film substrate side with in the color pixel portion that this black-matrix layer forms.
4. according to the filter substrate of claim 3 record, wherein, the single face of above-mentioned film substrate or two-sided on have gas-barrier layer.
5. according to the filter substrates of claim 3 or 4 records, wherein, also has external coating in the above-mentioned color pixel portion.
6. according to the filter substrate of claim 5 record, it also has transparent conducting film.
CNB2005101249953A 2004-05-26 2005-05-26 Color filter substrate Expired - Fee Related CN100501521C (en)

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KR102119426B1 (en) 2013-06-26 2020-06-08 도레이 카부시키가이샤 Polyimide precursor, polyimide, flexible substrate prepared therewith, color filter and production method thereof, and flexible display device
WO2015012339A1 (en) 2013-07-24 2015-01-29 ユニチカ株式会社 Laminate, method for processing same, and method for manufacturing flexible device
KR102236562B1 (en) * 2013-09-27 2021-04-06 도레이 카부시키가이샤 Heat-resistant resin film and method for manufacturing same, heating furnace and process for producing image display device
JP6331314B2 (en) * 2013-10-03 2018-05-30 東レ株式会社 Flexible color filter, manufacturing method thereof, and flexible light-emitting device using the same
WO2016052323A1 (en) 2014-09-30 2016-04-07 東レ株式会社 Support substrate for display, color filter employing same and method for manufacturing same, organic led element and method for manufacturing same, and flexible organic el display
KR102611196B1 (en) * 2016-03-31 2023-12-06 동우 화인켐 주식회사 Flexible Color Filter and Fabrication Method for the Same
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KR102315129B1 (en) 2021-03-22 2021-10-19 동우 화인켐 주식회사 Flexible Color Filter, Flexible Display Device Including the Same, and Fabrication Method Thereof

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