WO2013154069A1 - カラーフィルター基板、およびそれを用いた画像表示装置 - Google Patents
カラーフィルター基板、およびそれを用いた画像表示装置 Download PDFInfo
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- WO2013154069A1 WO2013154069A1 PCT/JP2013/060618 JP2013060618W WO2013154069A1 WO 2013154069 A1 WO2013154069 A1 WO 2013154069A1 JP 2013060618 W JP2013060618 W JP 2013060618W WO 2013154069 A1 WO2013154069 A1 WO 2013154069A1
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- color filter
- filter substrate
- organic
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- nmp
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/201—Filters in the form of arrays
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
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- 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
- H10K59/30—Devices specially adapted for multicolour light emission
- H10K59/38—Devices specially adapted for multicolour light emission comprising colour filters or colour changing media [CCM]
Definitions
- the present invention relates to a color filter substrate and an image display device using the same.
- organic EL (electroluminescence) displays have attracted attention as one of the new thin displays, and have begun to appear on the market as display displays for mobile phones and mobile devices.
- the liquid crystal display the pioneer of thin displays, is a non-self-luminous type, whereas the organic EL display is a self-luminous display element. It is superior to liquid crystal displays in that it can realize faster and smoother video images, and is regarded as a promising candidate for next-generation thin displays.
- FIG. 9 An example of a conventional color filter type organic EL display is shown in FIG. It has a structure in which the color filter substrate 20 and one type of organic EL light emitting element 30 that emits white light are combined, and the white light emitted from the organic EL layer 9 passes through the RGB colored layers 3 to 5 of the color filter. Thus, full color display is possible by chromaticity conversion. Therefore, since only one type of organic EL layer 9 emits white light is required, the organic EL layer 9 is superior to the separate coating method in terms of cost, production yield, and ease of enlargement.
- a method of obtaining a silica film by applying polysilazane to the surface of a color filter and oxidizing it by heating Patent Document 4
- silicon nitride oxide (SiO x N y ) silicon nitride oxide
- a method of forming an inorganic barrier film by sputtering or CVD has also been studied (Patent Document 5).
- due to generation of cracks black spots (dark spots) and white spots (brightness abnormalities) are caused in organic EL elements. Defects are likely to occur, and the solution has been desired.
- the present invention has been made in view of these problems, and provides a reliable color filter substrate suitable for an image display device, particularly a color filter type organic EL display, and has a display quality that is clear and excellent in contrast.
- An object of the present invention is to provide and provide a high-quality image display device inexpensively and easily.
- the above problem can be solved by the following means. That is, (1) When a color filter substrate having red, green and blue colored layers and an inorganic barrier film used in an image display device having an organic electroluminescence element is heated to 300 ° C. in a helium atmosphere. A color filter substrate, wherein the amount of N-methylpyrrolidone generated from the color filter substrate is 0.02 to 0.5 ppm relative to the weight of the color filter substrate.
- An image display device comprising at least an organic electroluminescence element and the color filter substrate described in (1) or (2).
- the color filter substrate of the present invention By using the color filter substrate of the present invention, it is possible to stably produce a clear and high-contrast image display device with high display quality without defects such as cracks and luminance reduction.
- the amount of N-methylpyrrolidone (hereinafter abbreviated as NMP) generated from the color filter substrate when heated to 300 ° C. in a helium atmosphere is 0.02 to 0 with respect to the weight of the color filter substrate.
- the color filter substrate of the present invention appropriately contains NMP, the residual stress is relieved, and as a result, it is presumed that the occurrence of cracks in the inorganic barrier film is suppressed. Such an effect is considered to occur because NMP is contained in a certain amount with respect to the color filter substrate. Specifically, NMP is generated from the color filter substrate when heated to 300 ° C. in a helium atmosphere. It has been found that the amount may be 0.02 ppm or more with respect to the weight of the color filter substrate.
- an image display device particularly preferably an organic EL display equipped with an organic electroluminescence (EL) element, water, carbon dioxide gas, carbon monoxide gas, organic substance decomposition gas, etc. from a color filter or an insulating film
- EL organic electroluminescence
- NMP has a slightly large molecular weight and a chemically stable structure, so the effect of promoting deterioration is considered to be relatively minor.
- its content is excessive, it has been found to have an adverse effect on organic EL displays. did.
- the amount of NMP generated from the color filter substrate when heated to 300 ° C. in a helium atmosphere may be 0.5 ppm or less with respect to the weight of the color filter substrate.
- the amount of NMP generated from the color filter substrate when heated to 300 ° C. in a helium atmosphere is 0.02 to 0 with respect to the weight of the color filter substrate. It was found to be 5 ppm, and the present invention was reached.
- the amount of NMP generated from the color filter substrate is 0.02 to 0.5 ppm when heated to 300 ° C. in a helium atmosphere, the inorganic barrier film works effectively, and there are no defects such as black spots or white spots.
- a color filter substrate suitable for obtaining a display having excellent contrast can be obtained.
- a display using a color filter substrate in which the amount of NMP generated is less than 0.02 ppm is not preferable because many defects are observed and the display performance is inferior, and the color filter substrate in which the amount of NMP generated is more than 0.5 ppm is used.
- a display is not preferable because the deterioration of the organic EL element results in poor clarity and contrast.
- temperature-programmed desorption-mass spectrometry can be used as a method for measuring the amount of NMP generated.
- a color filter substrate cut to about 10 mm ⁇ 20 mm is prepared, and 50 mL / min is prepared in a helium atmosphere.
- the amount of gas generated under the condition of a heating rate of 10 ° C./minute (total 27.5 minutes) from room temperature (25 ° C.) to 300 ° C. in a helium flow atmosphere was determined, and the molecular weight was NMP. It can be observed as 99 peaks corresponding to.
- the color filter substrate is a pattern that matches the size of the liquid crystal panel on the transparent substrate at one location near the center.
- the amount of NMP generated from the color filter substrate of the present invention can be measured by cutting an arbitrary portion in the substrate on which the pattern is produced, and this is within the above range.
- the amount of NMP generated from the color filter substrate can be estimated. Cutting is performed so as to exclude out-of-plane areas where no pattern is formed.
- the term “out-of-plane” refers to a region where a black matrix or colored layer is not formed, and a region that does not enter the display area when an image display device is used even if there is a substrate number or other alignment mark. Is considered out of plane.
- cutting is performed perpendicular to the surface of the color filter substrate, and measurement is performed using 10 or more pieces of about 10 mm ⁇ 20 mm.
- the amount of NMP generated from the color filter substrate when heated to 300 ° C. in the measured helium atmosphere must be 0.02 to 0.5 ppm with respect to the weight of the color filter substrate. More preferably, it is 0.04 to 0.4 ppm.
- the amount of NMP generated from the color filter substrate when heated to 300 ° C. in a helium atmosphere is 0.003 to 0.09 ⁇ g / cm 2 per unit area of the color filter substrate. It is preferable to be 0.007 to 0.07 ⁇ g / cm 2 . By setting it as such a range, generation
- the water generation amount of the color filter substrate can be quantified by the same measurement method as the amount of NMP generation, and can be observed as 18 peaks corresponding to the molecular weight of water.
- the amount of moisture generated from the color filter substrate when heated to 300 ° C. in a helium atmosphere is preferably 1 to 20 ppm, more preferably 2 to 10 ppm based on the weight of the color filter substrate.
- the amount of water generated is less than 1 ppm, the amount of NMP generated tends to be too small, which is not preferable.
- the amount of water generated exceeds 20 ppm the amount of NMP generated tends to be too large.
- the amount of other degassing of the color filter substrate can be quantified, and the amount of NMP generated corresponding to a molecular weight of 99 and the amount of water generated of molecular weight of 18 are subtracted from the total amount of degassed components. Can be obtained.
- the amount of other degassing generated from the color filter substrate when heated to 300 ° C. in a helium atmosphere is preferably 0.1 to 10 ppm, more preferably 0.3 to 5 ppm, based on the weight of the color filter substrate. When the amount of other degassing is less than 0.1 ppm, it is not preferable because the amount of NMP generated tends to be too small.
- NMP is in the above-mentioned range so that an organic EL display having a clear and high contrast and excellent display performance can be realized, but even if the color filter substrate contains another solvent, Such a specific effect is not expressed.
- NMP having a boiling point of 204 ° C. has an appropriate boiling point for suppressing cracks due to stress relaxation, and further has a closed ring structure as the chemical structure of the solvent itself, and has high thermal stability and a decomposition gas. It is assumed that this is because it is difficult to generate.
- Such remarkable effects cannot be expected if the boiling point is too low or too high, and only other solvents that do not have a closed ring structure or lactone solvents that have an ester skeleton are used.
- the thermal stability is poor, the above effects cannot be exhibited, and the amount of NMP generated from the color filter substrate when heated to 300 ° C. in a helium atmosphere is 0.02 with respect to the weight of the color filter substrate. It is important that the content is ⁇ 0.5 ppm, and more preferably 0.04 to 0.4 ppm.
- the color filter substrate referred to in the present invention has a colored layer that can be recognized as a color when transmitting or reflecting light. Generally, red (R), green (G), blue It has three colored layers (B). In addition to the colored layer, it may have a black matrix, TFT circuit, planarizing film, transparent electrode, and other organic material, inorganic material, or colored layer other than RGB as necessary, and it can be already incorporated into the display. In rare cases, the amount of NMP generated can be measured after disassembly into an organic EL element and a color filter substrate. If disassembly is difficult, there is no problem even if the amount of NMP generated is measured while the organic EL element and the color filter substrate are integrated, and it is calculated and calculated that no NMP is generated from the organic EL element. .
- the color filter substrate of the present invention has at least a colored layer.
- the transparent substrate used for the color filter substrate is not particularly limited, and glass such as soda glass, alkali-free glass, borosilicate glass, and quartz glass, a plastic film, a sheet, and the like can be used.
- glass such as soda glass, alkali-free glass, borosilicate glass, and quartz glass, a plastic film, a sheet, and the like can be used.
- the thickness of the transparent substrate is not particularly limited, but is preferably 0.01 to 3 mm, more preferably 0.1 to 0.8 mm. If it is thinner than 0.01 mm, the strength as a support is poor, and if it is thicker than 3 mm, the image display device becomes heavy.
- a black matrix, a TFT circuit, or the like can be formed on the transparent substrate as necessary.
- a method for forming the colored layer known methods such as a dyeing method, an electrodeposition method, a printing method, and a pigment dispersion method can be used, and among these, the pigment dispersion method is preferable.
- a pigment dispersion method a non-photosensitive polyimide resin in which a coloring agent such as a pigment is dispersed is applied, and then a positive photoresist or a negative photoresist is laminated and applied, followed by exposure and development for patterning.
- a photosensitive polyimide method or a photosensitive color resist in which a pigment is dispersed in a solution containing a binder resin and a photopolymerization initiator may be used, but a non-photosensitive polyimide method capable of high-definition processing is preferably used.
- a colored paste containing at least a colorant, a polyimide resin and / or a polyimide precursor, and a solvent can be used.
- colorant used in the colored paste dyes, organic pigments, inorganic pigments and the like can be used, but organic pigments are preferable from the viewpoint of heat resistance and transparency. Among them, those having high transparency and excellent light resistance, heat resistance, and chemical resistance are preferable.
- color index (CI) numbers the following are preferably used, but the invention is not limited to these.
- yellow pigments examples include pigment yellow (hereinafter abbreviated as PY) 12, 13, 17, 20, 24, 83, 86, 93, 95, 109, 110, 117, 125, 129, 137, 138, 139, 147. 148, 150, 153, 154, 166, 168, 180, 185, etc. are used.
- orange pigments examples include pigment oranges 13, 36, 38, 43, 51, 55, 59, 61, 64, 65, 71, and the like.
- red pigments examples include pigment red (hereinafter abbreviated as PR) 9, 48, 97, 122, 123, 144, 149, 166, 168, 177, 179, 180, 192, 209, 215, 216, 217. 220, 223, 224, 226, 227, 228, 240, 254, etc. are used.
- pigment violet 19 19, 23, 29, 30, 32, 37, 40, 50, etc. are used.
- pigment blue hereinafter abbreviated as PB 15, 15: 3, 15: 4, 15: 6, 22, 60, 64, 80, and the like are used.
- pigment green (hereinafter abbreviated as PG) 7, 10, 36, 58, and the like are used.
- These pigments may be subjected to surface treatment such as rosin treatment, acidic group treatment, basic treatment, etc., if necessary.
- the pigment can be appropriately adjusted according to the color of the organic EL element used according to the target color.
- the organic EL element may be an element that emits white light, or may be a combination of RGB light emitting elements, but considering that it can be manufactured at low cost, the organic EL element emits white light. Is preferably used.
- a pigment when combined with an organic EL element that emits white light As an example of a pigment when combined with an organic EL element that emits white light, the case of R (red) is taken as an example.
- G green
- the chromaticity is toned by a combination of a selected green pigment and a yellow pigment selected from the group of PY-138, PY-139, and PY-150.
- PB15: 3 or PB15: 6 Toning is preferably performed in combination with PV23 or the like, but is not limited thereto.
- the resin used for the colored paste acrylic resin, epoxy resin, silicone resin, etc. can be used, but in view of the heat resistance, light resistance and solvent resistance of the coating film, a polyimide resin is used. It is preferable.
- the polyimide resin includes, in addition to a polyimide resin having a completely closed ring structure, a polyamic acid resin which is a precursor of a polyimide resin having a completely closed ring structure and a polyimide resin in which a part of the polyamic acid resin is closed.
- the polyimide resin can be obtained by reacting tetracarboxylic dianhydride and diamine.
- an aliphatic or alicyclic one can be used as the tetracarboxylic dianhydride, and specific examples thereof include 1,2,3,4-cyclobutanetetra.
- a polyimide resin that can be converted into a film having good heat resistance can be obtained.
- 3,3 ′, 4,4′-benzophenonetetracarboxylic acid can be obtained.
- a polyimide resin that can be converted into a film having good transparency in a short wavelength region can be obtained.
- a fluorine-based material a fluorine-based material
- a polyimide resin that can be converted into a film having good transparency in a short wavelength region can be obtained.
- 4,4 ′-(hexafluoroisopropylidene ) Diphthalic anhydride a specific example, 4,4 ′-(hexafluoroisopropylidene ) Diphthalic anhydride.
- this invention is not limited to these,
- the tetracarboxylic dianhydride is used 1 type (s) or 2 or more types.
- diamine for example, aliphatic or alicyclic ones can be used, and specific examples thereof include 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 4,4′-diamino. -3,3'-dimethyldicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexyl, and the like.
- an aromatic resin when an aromatic resin is used, a polyimide resin that can be converted into a film having good heat resistance can be obtained. Specific examples thereof include 4,4′-diaminodiphenyl ether, 3,4′-diamino.
- Diphenyl ether 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfide, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, benzidine, 3,3′-dimethylbenzidine, 3,3′-dimethoxybenzidine, o-tolidine, 4, 4 "-diaminoterphenyl, 1,5-diaminonaphthalene, 3,3'-di Til-4,4′-diaminodiphenylmethane, 4,4′-bis (4-aminophenoxy) biphenyl,
- a polyimide resin that can be converted into a film having good transparency in the short wavelength region can be obtained.
- Specific examples thereof include 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane and the like. Is mentioned.
- siloxane diamine when siloxane diamine is used as part of the diamine, the adhesion to the substrate can be improved.
- Siloxane diamine is usually used in an amount of 1 to 20 mol% in the total diamine. If the amount of siloxane diamine is too small, the effect of improving the adhesiveness is not exhibited, and if it is too large, the heat resistance is lowered.
- Specific examples of the siloxane diamine include bis-3- (aminopropyl) tetramethylsiloxane. The present invention is not limited to this, and one or more diamines are used.
- the synthesis of the polyimide resin is generally carried out by mixing tetracarboxylic dianhydride and diamine and reacting them in a polar organic solvent. At this time, the degree of polymerization of the resulting polyimide resin can be adjusted by the mixing ratio of diamine and tetracarboxylic dianhydride.
- a polyimide resin there are various methods for obtaining a polyimide resin, such as reacting tetracarboxylic acid dichloride and diamine in a polar organic solvent and then removing the hydrochloric acid and the solvent to obtain a polyimide resin.
- both acid dianhydride and diamine preferably contain an aromatic structure because of excellent heat resistance, and further, an imide structure represented by the following general formula (1), and the following general formula (2)
- An aromatic polyimide resin having either an amic acid structure represented by formula (1) or a structure formed by partially imide ring closure represented by the following general formula (3) is more preferred.
- X and Y represent a linking group
- —X— represents —O—, —CO—
- a part of H may be substituted with another atom or atomic group.
- good -CH 2 - indicates either a direct bond without the linking group
- -Y- is, -O -, - SO 2 - , - CONH-, some of H is replaced with another atom or atomic group It may be either —CH 2 — or a direct bond without a linking group.
- aromatic polyimide resin may be replaced with another aliphatic group, but the ratio of acid dianhydride and diamine containing an aromatic group is preferably 50 moles in the whole polyimide resin. % Or more, and more preferably 70 mol% or more is preferable because of high heat resistance.
- the solvent used in the colored paste preferably contains NMP, preferably 10 to 95% by mass, more preferably 30 to 90% by mass.
- NMP is indispensable as a component generated from the color filter substrate of the present invention as described above, in addition to the high solubility of polyimide resin and polyamic acid and no concern about gelation.
- Solvents other than NMP can also be preferably contained.
- the solvents it is preferable to include a solvent having a boiling point of 170 to 210 ° C. because the influence on the amount of NMP generated from the color filter substrate can be easily controlled. More preferably, the solvent at 170 to 210 ° C. contains 5 to 20% by mass.
- NMP When only a solvent having a boiling point lower than 170 ° C. is contained in addition to NMP, NMP tends to volatilize together with the low boiling point solvent volatilizing when the colored layer is cured, resulting in the NMP content of the color filter substrate. On the other hand, when only a solvent having a boiling point higher than 210 ° C. is included in addition to NMP, the remaining amount of NMP tends to be excessive, which is not preferable.
- solvents having a boiling point of 170 to 210 ° C. 3-methoxy-3-methylbutanol, 3-methoxy-3-methyl-1-butyl acetate, ⁇ from the viewpoint of solubility of polyimide resin and polyamic acid.
- -It is particularly preferred to contain butyrolactone.
- the color paste can also contain other additives, such as those that are effective in pigment dispersion such as polymer dispersants and pigment derivatives, adhesion improvers, surfactants, organic acids, organic amino compounds, Examples thereof include a polymerization inhibitor and an antioxidant.
- additives such as those that are effective in pigment dispersion such as polymer dispersants and pigment derivatives, adhesion improvers, surfactants, organic acids, organic amino compounds, Examples thereof include a polymerization inhibitor and an antioxidant.
- the polymer dispersant is not particularly limited as long as it is usually used for a color filter, and is polyester, polyalkylamine, polyallylamine, polyimine, polyamide, polyurethane, polyacrylate, polyimide, polyamideimide, or Various copolymers such as these copolymers can be used alone or in combination.
- a polyimide resin is preferable from the viewpoint of dispersion stability and compatibility.
- the adhesion improving agent can be preferably added for the purpose of improving the adhesion of the coating film to the substrate.
- N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane is particularly preferred.
- the surfactant can be added for the purpose of improving the coating property of the thermosetting coloring composition and the surface uniformity of the colored layer, or for the purpose of improving the dispersibility of the pigment.
- the amount of the surfactant added is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass, based on the pigment. If the added amount is less than this range, the effect of improving the coating property, the uniformity of the colored film surface or the pigment dispersibility is small, and if it is too much, the coating property is poor or the pigment is aggregated. It is not preferable because there is a case.
- anionic surfactants such as ammonium lauryl sulfate and polyoxyethylene alkyl ether sulfate triethanolamine
- cationic surfactants such as stearylamine acetate and lauryltrimethylammonium chloride, lauryldimethylamine oxide, laurylcarboxymethylhydroxy Amphoteric surfactants such as ethylimidazolium betaine
- nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, sorbitan monostearate, acrylic surfactants, fluorosurfactants and silicon-based interfaces
- the colored paste used for the color filter substrate of the present invention preferably contains NMP, and is preferably an acrylic surfactant that is compatible and effective in a small amount.
- the acrylic surfactant is preferably a copolymer of an acrylic monomer, may be a copolymer of an acrylic monomer, or may be a copolymer with other vinyl type, styrene type, Furthermore, when an acrylic surfactant containing a copolymer of an acrylic monomer and an alkyl vinyl ether and / or aromatic-containing vinyl ether is used, it is particularly preferable because unevenness at the time of forming a colored layer can be remarkably suppressed. .
- the weight average molecular weight of the acrylic surfactant by gel permeation chromatography (GPC method) is preferably 1,000 to 50,000, more preferably 2,000 to 5,000. If it is less than 1,000, the effect of suppressing unevenness is small, and if it is more than 50,000, the solubility in a solvent may deteriorate.
- a colored paste is applied on a transparent substrate, and is heated and dried (prebaked) using a hot plate, an oven, and vacuum drying. After pre-baking, a positive photoresist is applied and dried, followed by mask exposure, alkali development, and further peeling the photoresist with a solvent to obtain a colored layer.
- a dip method, a roll coater method, a spin coating method, a die coating method, a die coating and spin coating combined method, a wire bar coating method, and the like are preferably used.
- a die coating method that is excellent and uses the paste efficiently is preferable.
- the solvent is removed by air drying, vacuum drying, heat drying, or the like to form a coating film of the photosensitive transparent resin composition.
- the vacuum drying step is provided, additional heating and drying in an oven or a hot plate is preferable because the coating defects caused by convection are eliminated.
- a positive photoresist is applied and dried on the applied colored paste.
- coating and drying can be performed by the method similar to the case of a colored paste.
- an exposure process of photolithography is performed. A mask is placed on the top of the coating film on which the colored paste and the positive photoresist are laminated, and selectively exposed to ultraviolet rays or the like using an ultrahigh pressure mercury lamp, a chemical lamp, a high pressure mercury lamp or the like.
- an organic alkali developer either an organic alkali developer or an inorganic alkali developer can be used.
- an aqueous solution of sodium carbonate, sodium hydroxide, potassium hydroxide or the like is preferably used.
- an aqueous tetramethylammonium hydroxide solution or an amine-based aqueous solution such as methanolamine is preferably used, and an aqueous tetramethylammonium hydroxide solution is particularly preferred from the viewpoint of reducing impurities.
- the concentration of the alkaline substance in the developer is not particularly limited, but is usually 0.01 to 10% by mass, preferably 0.05 to 5% by mass. If the alkali concentration is too low, it is difficult to develop, while if it is too high, film roughness on the surface of the coating film and pattern roughness are likely to occur.
- a surfactant is also preferably used in the developer, and the pattern shape can be improved by adding 0.01 to 10% by mass, more preferably 0.1 to 3% by mass of a nonionic surfactant or the like. it can.
- Alkali development can be dip development, shower development, paddle development, etc., and these may be combined.
- shower development the shower pressure is preferably adjusted so as to obtain an optimal pixel shape, and the shower pressure is preferably 0.05 to 5 MPa.
- a washing step with pure water or the like may be appropriately added to remove the alkali developer.
- the positive photoresist After development, the positive photoresist is peeled off.
- the positive photoresist can be removed by dissolving it with a solvent or by ion etching in a vacuum.
- a solvent for dissolving the positive photoresist an organic solvent is preferably used, and acetone, ethyl acetate, butyl acetate, methyl cellosolve, and the like are preferably used, but are not limited thereto.
- the coating layer pattern of the obtained colored layer is then patterned by heat treatment (curing).
- the heat treatment is usually carried out continuously or stepwise in the air, in a nitrogen atmosphere, or in a vacuum at a temperature of 150 to 300 ° C. for 0.1 to 5 hours.
- the amount of NMP generated when heated to 300 ° C. in a helium atmosphere is required to be 0.02 to 0.5 ppm. Therefore, the curing temperature, particularly the highest temperature is the highest.
- the heat treatment temperature is important.
- the maximum heat treatment temperature during the production of the color filter substrate is preferably 200 to 270 ° C., more preferably 210 to 240 ° C.
- the maximum heat treatment temperature is higher than 270 ° C.
- the remaining amount of NMP is extremely small, which is not preferable because the effect of preventing cracking of the barrier film tends to be small.
- the maximum heat treatment temperature is lower than 200 ° C.
- the remaining amount of NMP becomes excessive, and as a result, it tends to lead to defects in the organic EL element presumed to be caused by degassing, which is not preferable.
- the colored layer can be formed by the above-mentioned non-photosensitive polyimide method, or a photosensitive colored paste can be used.
- the colored layer can be formed by using a photosensitive color resist in which a pigment is dispersed in a solution containing a binder resin and a photopolymerization initiator, in addition to the non-photosensitive polyimide method described above.
- a photosensitive color resist in which a pigment is dispersed in a solution containing a binder resin and a photopolymerization initiator, in addition to the non-photosensitive polyimide method described above.
- the color filter substrate of the present invention has at least a plurality of colored layers, and the resin used in at least one of the colored layers preferably contains a polyimide resin.
- the resin used in at least one of the colored layers preferably contains a polyimide resin.
- the color filter substrate of the present invention has at least red, green and blue colored layers, and the resins used in the red, green and blue colored layers each contain a polyimide resin. It is more preferable. As a result, a more highly reliable color filter substrate can be obtained.
- the formation of the colored layer can be performed sequentially in RGB, and the order is not particularly limited.
- an overcoat layer can be provided on the surface of the colored layer.
- the overcoat is provided to protect the black matrix and the colored layer, improve the flatness of the color filter surface, and prevent contamination from the color filter to the organic EL element.
- an overcoat may be necessary to reduce the color filter surface step based on the film thickness of the resin black matrix.
- Overcoats require a wide range of properties such as adhesion to lower and upper layers, blocking of impurities, smoothness, light resistance, moisture and heat resistance, solvent resistance, chemical resistance, toughness, transparency, and heat resistance.
- polyimide resin, epoxy resin, acrylic resin, siloxane resin precursor, silicone resin, and composite resins thereof can be used.
- a polyimide resin it is preferable to use a polyimide resin, and the same resin and solvent as those used in the colored layer can be preferably used.
- the curing temperature is preferably 200 to 270 ° C., more preferably 210 to 240 ° C.
- This overcoat layer is also included in the color filter substrate, and the above range is preferable as the maximum heating temperature.
- an inorganic barrier film can be formed as necessary.
- the color filter substrate of the present invention has an inorganic barrier film (hereinafter sometimes referred to as a barrier layer), and the barrier layer is formed of silicon oxide (SiOx), silicon nitride oxide (SiOxNy), silicon nitride (SixNy), or the like. can do. In particular, silicon oxide is preferably used.
- the refractive index of the barrier layer is preferably 1.4 to 1.6, more preferably 1.42 to 1.48. The barrier performance often varies depending on the refractive index, and if it is too high, it tends to transmit the degassed component, and if it is too low, it tends to transmit moisture, which is not preferable.
- the film thickness of the barrier layer is usually from 0.1 to 5 ⁇ m, more preferably from 0.3 to 3 ⁇ m. If it is too thin, the barrier effect tends to be small, which is not preferable. If it is too thick, defects such as cracks tend to occur in the barrier layer.
- the barrier layer can be formed by sputtering, plasma CVD, or the like, and is more preferably formed by plasma CVD.
- a compound containing Si in the presence of oxygen and / or nitrogen gas for example, methylsilane, dimethylsilane, trimethylsilane, tetramethylsilane, diethylsilane, tetraethylsilane, tetrabutylsilane, dimethyldiethyl
- a film can be formed under reduced pressure of 0.1 to 100 Pa using silane, tetraphenylsilane, methyltriphenylsilane, dimethyldiphenylsilane, trimethylphenylsilane, trimethylsilyl-trimethylsilane, trimethylsilylmethyl-trimethylsilane, or the like.
- Such a barrier film has no defects such as cracks on the surface, and surface cracks can be prevented by using the color filter substrate of the present invention.
- a surface crack occurs, moisture, impurity gas, etc. permeate from the place where the crack occurs and do not play its original role.
- Such surface cracks can be observed with an optical microscope, an electron microscope, etc., but there may be micro cracks that cannot be confirmed with normal observation. Is often found.
- the color filter substrate of the present invention may have a transparent electrode as necessary.
- a transparent electrode indium tin oxide (ITO) is preferably used for the transparent electrode.
- ITO indium tin oxide
- the transparent electrode is necessary for driving the organic EL element, but it may be either a bottom emission type or a top emission type, and can take any other configuration, such as a photolithographic etching method using ITO. May be patterned.
- a colored film is formed by air drying, heat drying, vacuum drying, or the like.
- the thickness of the colored coating is usually in the range of 0.5 to 3.0 ⁇ m. It is preferable to perform heat drying (semi-cure) in the range of 60 to 160 ° C. for 1 to 60 minutes using an oven, a hot plate or the like.
- heat drying in the range of 60 to 160 ° C. for 1 to 60 minutes using an oven, a hot plate or the like.
- a positive photoresist is applied to the colored film thus obtained, and is heated and dried at 50 to 150 ° C. for 1 to 30 minutes (prebaking) using an oven, a hot plate or the like.
- an ultraviolet ray with an h-line exposure of 20 to 300 mJ / cm 2 is irradiated to print a target pattern, and then alkali development is performed to obtain a colored layer with a desired pattern at a desired position.
- the positive photoresist is peeled off with a solvent or the like, and finally the colored layer is cured (cured) by heating at 150 to 300 ° C. for 1 minute to 3 hours.
- the image display device of the present invention is characterized by using the color filter substrate of the present invention.
- the color filter substrate of the present invention By combining the color filter substrate of the present invention with an organic EL display, a clear image display device free from defects such as dark spots and having good display performance can be obtained.
- the liquid crystal display device of the present invention includes a black matrix 2 produced as necessary on a transparent substrate 1, colored layers 3, 4, 5 corresponding to red, green, and blue as essential requirements, and as necessary.
- a color filter substrate 20 comprising an overcoat layer 6 and a barrier layer 7 to be produced; a transparent electrode 8 such as ITO; an organic electroluminescence layer (organic EL layer) 9 comprising a hole transport layer, a light emitting layer, and an electron transport layer;
- the back electrode layer 10, the insulating film 11, the substrate 12, and the organic EL element 30 including the extraction electrode 13 connected to an external power source are combined and sealed with a sealant 14, and if necessary, a desiccant 15 etc. may be installed.
- the color filter substrate and the organic EL element may be in close contact as shown in FIG. 2, and the sealant 14 is used as the overcoat layer 6 as shown in FIG. It may be formed on the top.
- the liquid crystal display device of the present invention only needs to use the color filter substrate of the present invention, and can have any configuration not shown.
- the components of the color filter substrate are as described above.
- the substrate 12 used in the organic EL element is a support substrate for producing the organic EL element.
- various transparent substrates such as glass, film, and plastic
- various metal substrates such as aluminum, chromium, and stainless steel and ceramics.
- An opaque substrate may be used.
- the insulating film can prevent energization of the transparent electrode layer and the back electrode layer, and is preferably made of an organic material.
- the resin used include a polyimide resin, an acrylic resin, an epoxy resin, and a silicone resin.
- Use of a resin containing a polyimide resin is preferable because of high reliability.
- the insulating film can be formed by photolithography using a photosensitive material.
- the back electrode layer 10 is formed between the substrate 12 and the organic EL layer 9, and has a mechanism in which the organic EL layer emits light when a voltage is applied between the transparent electrode 8.
- the material for forming the back electrode layer include metals, metal oxides and alloys, and mixtures thereof. More specifically, examples include magnesium, aluminum, indium, lithium, silver, and aluminum oxide. Mixtures of these can also be used preferably.
- the film thickness of the back electrode layer is usually 0.01 to 1 ⁇ m, and a method of patterning by photolithography after forming a thin film by vapor deposition, sputtering or the like is preferably used.
- the organic EL layer 9 usually has a structure in which organic substances such as a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer are laminated.
- organic substances such as a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer are laminated.
- the light that develops color in the light emitting layer is white light. Any wavelength distribution of white light can be used, but it is preferable to include each wavelength region of red, green, and blue.
- the organic EL layer is preferably an RGB coating method, which can be combined with the color filter substrate of the present invention, and the color reproduction range can be expanded, which is preferable.
- the light emitting material is not particularly limited as long as it emits fluorescence or phosphorescence.
- the light emitting material include a dye material, a metal complex material, and a polymer material.
- Organic compounds with various skeletons such as amine, tetraphenylbutadiene, triphenylamine, oxadiazole, pyrazoloquinoline, distyrylbenzene, distyrylarylene, silole, thiophene, pyridine, perinone, perylene, oligothiophene, and trifumanylamine Oxadiazole dimer, pyrazoline dimer, etc.
- metal complex materials include aluminum quinolinol complex, benzoquinolinol beryllium complex, benzoxazole zinc complex, benzothiazole zinc complex, azomethyl zinc complex, porphyrin zinc Body, europium complex, or a central metal having a rare earth metal such as Al, Zn, Be or Tb, Eu, or
- a method for forming the light emitting layer As a method for forming the light emitting layer, a vapor deposition method, a spin coating method, a printing method, an ink jet method, or the like can be used, and the film thickness of the light emitting layer is usually about 0.05 to 5 ⁇ m.
- the transparent electrode 8 preferably transmits light emitted from the organic EL layer, and the transmittance is preferably 80 to 99%, more preferably 90 to 99%.
- the material used for such a transparent electrode include metal oxides such as indium tin oxide (ITO), indium oxide, zinc oxide, and stannic oxide.
- the film thickness is usually 0.1 to 1 ⁇ m, and a method of patterning by photolithography after forming a thin film by vapor deposition or sputtering is preferably used.
- the extraction electrode 13 is not particularly limited as long as it is a conductive material, and materials generally used for extraction electrodes of organic EL elements can be used, for example, silver, aluminum, gold, chromium, nickel Further, metals such as molybdenum, various alloys, and the like can be used, and they may be formed as a laminated film.
- An image display device can be produced by combining a color filter substrate as described above and an organic EL display and bonding them together using a sealant or the like.
- sealant those capable of suppressing the contact of the organic EL element with moisture in the atmosphere are preferable, and known materials can be used.
- the color filter substrate of the present invention manufactured as described above and the image display device using the color filter substrate of the present invention are suitable for a display with few defects and a clear display performance.
- Example 1 A Preparation of polyimide resin solution 95.1 g of 4,4′-diaminodiphenyl ether and 6.2 g of bis (3-aminopropyl) tetramethyldisiloxane were charged together with 745 g of NMP, and 2,3 ′, 4,4′-biphenyltetracarboxylic acid After adding 144.1 g of anhydride and reacting at 70 ° C. for 3 hours, adding 3.0 g of phthalic anhydride and further reacting at 70 ° C. for 2 hours to obtain a 25 mass% polyimide resin solution (PAA) It was.
- PAA polyimide resin solution
- the red colored paste PR-1 was applied to a glass substrate (Corning, Eagle XG material, thickness 0.7 mm) with a slit coater, and semi-cured by heating on a 120 ° C. hot plate for 10 minutes. A red resin coating was formed. Apply a positive photoresist ("LC-100A", manufactured by Rohm and Haas Electronic Materials Co., Ltd.) with a slit coater so that the film thickness after pre-baking is 1.0 ⁇ m, and dry on a hot plate at 100 ° C. for 5 minutes. And pre-baked.
- LC-100A positive photoresist
- UV exposure machine PLA-501F manufactured by Canon Inc.
- mask exposure was performed at 100 mJ / cm 2 (ultraviolet intensity of 365 nm) through a photomask, and then using a 2.0% tetramethylammonium hydroxide aqueous solution, Photoresist development and resin coating etching were simultaneously performed to form a pattern, and then the resist was peeled off with methyl cellosolve acetate. Next, it was cured by heat treatment in an oven at 230 ° C. for 30 minutes to form a red colored layer having a thickness of 1.5 ⁇ m.
- a green colored layer was formed using the green colored paste PG-1, and a blue colored layer was formed using the blue colored paste.
- barrier film was prepared by plasma CVD. A film was formed under reduced pressure using tetramethylsilane in the presence of oxygen and nitrogen gas to form a silicon nitride oxide film having a thickness of 2 ⁇ m.
- Appearance inspection of color filter substrate Appearance inspection was performed on the produced color filter substrate using an optical microscope. 100 pixels each of RGB were inspected and determined by the following evaluation method. A: No defects such as cracks were found in 100 pixels. B: 1 to 3 minor cracks were observed in 100 pixels. C: 4 or more cracks were observed among 100 pixels.
- NMP generation amount was measured by temperature programmed desorption-mass spectrometry.
- the pattern part of the produced color filter substrate is cut to about 10 mm ⁇ 20 mm, and the weight is precisely weighed.
- the temperature is raised from room temperature (25 ° C.) to 300 ° C. in a helium atmosphere under a helium flow atmosphere of 50 mL / min.
- the amount of gas generated at a rate of 10 ° C./min (27.5 minutes in total) was quantified.
- the generated gas was analyzed using a gas chromatography mass spectrometer GC / MS “QP5050A” manufactured by Shimadzu Corporation, and 99 peaks whose mass number corresponds to the molecular weight of NMP were determined as the amount of NMP generated. Similarly, 18 peaks corresponding to the molecular weight of water were determined as the amount of water generation, and other degassing amounts were determined by subtracting the NMP generation amount and the water generation amount from the total degassing amount.
- a photosensitive polyimide resin was formed as an insulating film on a glass substrate by a photolithography method. After sputtering aluminum as the back electrode layer, patterning was performed by photolithography to form an opening without an insulating film. Subsequently, tris (8-quinolinolato) aluminum (hereinafter abbreviated as Alq3) was formed as an electron transporting layer by a vacuum deposition method, and then, as a light emitting layer, dicyanomethylenepyran, quinacridone, 4,4′-bis (2,2) was formed on Alq3. A white light-emitting layer doped with -diphenylvinyl) biphenyl was formed.
- N, N′-diphenyl-N, N′-bis ( ⁇ -naphthyl) -1,1′-biphenyl-4,4′-diamine was formed as a hole transport layer by a vacuum evaporation method.
- ITO was deposited as a transparent electrode by sputtering to produce an organic EL device having a white light emitting layer.
- Boiling point 202 ° C ⁇ BL ⁇ -butyrolactone (GBL manufactured by Kuraray Co., Ltd.)
- Boiling point 204 ° C MMB 3-methoxy-3-methylbutanol (Kuraray Co., Ltd. Solfit)
- Boiling point 174 ° C MMB-AC 3-methoxy-3-methyl-1-butyl acetate (Solfit AC manufactured by Kuraray Co., Ltd.)
- PMA Propylene glycol monomethyl ether acetate (Kuraray Co., Ltd. PGM-AC)
- a photosensitive color resist containing a pigment, an acrylic resin, a photopolymerization initiator, and a solvent was used.
- a green colored layer was formed using a green photosensitive color resist PG-2, and a blue colored layer was formed using a blue photosensitive color resist PB-2.
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Abstract
Description
すなわち、
(1)有機エレクトロルミネセンス素子を具備した画像表示装置に用いられる、赤、緑、青の各着色層および無機バリア膜を有したカラーフィルター基板において、ヘリウム雰囲気中で300℃まで加熱したときのカラーフィルター基板からのN-メチルピロリドンの発生量が、カラーフィルター基板の重量に対して0.02~0.5ppmであることを特徴とするカラーフィルター基板。
また、赤色顔料の例としては、ピグメントレッド(以下PRと略す)9、48、97、122、123、144、149、166、168、177、179、180、192、209、215、216、217、220、223、224、226、227、228、240、254などが使用される。
A.ポリイミド樹脂溶液の作製
4,4’-ジアミノジフェニルエーテル95.1gおよびビス(3-アミノプロピル)テトラメチルジシロキサン6.2gをNMP745gと共に仕込み、3,3’,4,4’-ビフェニルテトラカルボン酸二無水物144.1gを添加し、70℃で3時間反応させた後、無水フタル酸3.0gを添加し、更に70℃で2時間反応させ、25質量%のポリイミド樹脂溶液(PAA)を得た。
4,4’-ジアミノベンズアニリド161.3g、3,3’-ジアミノジフェニルスルホン176.7gおよびビス(3-アミノプロピル)テトラメチルジシロキサン18.6gをNMP3194gと共に仕込み、3,3’,4,4’-ビフェニルテトラカルボン酸二無水物439.1gを添加し、70℃で3時間反応させた後、無水フタル酸2.2gを添加し、更に70℃で2時間反応させ、20質量%のポリイミド樹脂溶液である高分子分散剤(PD)を得た。
PR254、3.6g(80質量%)、PR177、0.9g(20質量%)と高分子分散剤(PD)22.5gおよびNMP63gをガラスビーズ90gとともに仕込み、ホモジナイザーを用い、7000rpmで5時間分散後、ガラスビーズを濾過し、除去した。このようにしてPR254とPR177からなる分散液5%溶液(RD)を得た。
ガラス基板(コーニング製、イーグルXG材、厚み0.7mm)に上記赤色着色ペーストPR-1をスリットコーターで塗布し、120℃のホットプレートで、10分間加熱することによりセミキュア処理した赤色の樹脂塗膜を形成した。ポジ型フォトレジスト(ロームアンドハース電子材料社製、“LC-100A”)をスリットコーターでプリベーク後の膜厚が1.0μmになるように塗布し、100℃のホットプレートで、5分間乾燥し、プリベークを行った。
バリア膜の作製はプラズマCVD法で行った。酸素および窒素ガスの存在下でテトラメチルシランを用いて減圧下で成膜し、膜厚2μmの窒化酸化珪素膜を形成した。
作製したカラーフィルター基板を、光学顕微鏡を用いて外観検査を行った。RGB各々100画素について検査を行い、以下の評価方法にて判定した。
A:100画素のうち、クラックなどの欠陥は1つも見つからなかった。
B:100画素のうち、軽微なクラックが1~3個観察された。
C:100画素のうち、クラックが4個以上観察された。
NMPの発生量は昇温脱離-質量分析法にて測定を行った。作製したカラーフィルター基板のパターン部を10mm×20mm程度に切断して重さを精秤し、ヘリウム雰囲気下、50mL/分のヘリウム流の雰囲気下において、室温(25℃)より300℃まで昇温速度10℃/分の条件下(計27.5分間)で発生する気体の量を定量した。発生した気体は島津製作所製のガスクロマトグラフィー質量分析装置GC/MS“QP5050A”を使用して分析し、質量数がNMPの分子量に相当する99のピークをNMPの発生量として求めた。同様にして水分の分子量に相当する18のピークを水分発生量として求め、他の脱ガス発生量を全体の脱ガス発生量からNMP発生量と水分発生量を差し引くことで求めた。
ガラス基板上に絶縁膜として、感光性ポリイミド樹脂をフォトリソグラフィー法にて形成した。背面電極層としてアルミニウムをスパッタした後、フォトリソグラフィー法にてパターニングを行い、絶縁膜の無い開口部に形成した。続いて電子輸送層としてトリス(8-キノリノラト)アルミニウム(以下Alq3と略す)を真空蒸着法により成膜した後、発光層としてAlq3にジシアノメチレンピラン、キナクリドン、4,4’-ビス(2,2-ジフェニルビニル)ビフェニルをドーピングした白色発光層を形成した。次に正孔輸送層としてN,N’-ジフェニル-N,N’-ビス(α-ナフチル)-1,1’-ビフェニル-4,4’-ジアミンを真空蒸着法にて成膜した。最後に透明電極としてITOをスパッタリングにて成膜し、白色発光層を有する有機EL素子を作製した。
上記の方法にて作製したカラーフィルター基板と有機EL素子を対向させて封止剤により貼り合せ、画像表示装置を作製した。
A:鮮明でコントラストに優れたディスプレイである
B:一部で黒点、白点などの欠陥が見られるものの全体として表示良好なディスプレイである。
C:欠陥が多数見られ、表示性能に劣るディスプレイである
実施例2~13、比較例1、2
キュア温度、および着色ペーストの溶剤を変更した以外は実施例1と同様にしてカラーフィルター基板および画像表示装置を作製した。結果を実施例1と併せて表1および表2にまとめた。なお、表1および表2の中で使用した溶剤は以下の通りである。
NMP: N-メチルピロリドン (株式会社クラレ製 NMP)沸点202℃
γBL: γ-ブチロラクトン (株式会社クラレ製 GBL)沸点204℃
MMB: 3-メトキシ-3-メチルブタノール (株式会社クラレ製 ソルフィット)沸点174℃
MMB-AC: 3-メトキシ-3-メチル-1-ブチルアセテート (株式会社クラレ製 ソルフィットAC)沸点188℃
PMA: プロピレングリコールモノメチルエーテルアセテート (株式会社クラレ製 PGM-AC)沸点146℃
比較例3
C.着色ペーストの作製
着色ペーストとして、顔料、アクリル系樹脂、光重合開始剤、溶剤を含む感光性カラーレジストを用いた。固形分濃度20%、溶剤としてPMAを80%含む赤色感光性カラーレジスト(PR-2)、同じく緑色感光性カラーレジスト(PG-2)、同じく青色感光性カラーレジスト(PB-2)を作製した。
ガラス基板(コーニング製、イーグルXG材、厚み0.7mm)に上記赤色感光性カラーレジストPR-2をスリットコーターで塗布し、90℃のホットプレートで、10分間加熱することによりプリベーク処理した赤色の樹脂塗膜を形成した。キャノン株式会社製紫外線露光機PLA-501Fを用い、フォトマスクを介して100mJ/cm2(365nmの紫外線強度)でマスク露光し、次に0.05%の水酸化カリウム水溶液を用いて現像を行いパターン形成した。次に230℃のオーブンで、30分間熱処理することでキュアを行い、膜厚1.5μmの赤色着色層を形成した。
2 ・・・ブラックマトリクス
3 ・・・赤色着色層
4 ・・・緑色着色層
5 ・・・青色着色層
6 ・・・オーバーコート層
7 ・・・バリア層
8 ・・・透明電極
9 ・・・有機EL層
10 ・・・背面電極層
11 ・・・絶縁膜
12 ・・・基板
13 ・・・取り出し電極
14 ・・・封止剤
15 ・・・乾燥剤
20 ・・・カラーフィルター基板
30 ・・・有機EL発光素子
Claims (6)
- 有機エレクトロルミネセンス素子を具備した画像表示装置に用いられる、赤、緑、青の各着色層および無機バリア膜を有したカラーフィルター基板において、ヘリウム雰囲気中で300℃まで加熱したときのカラーフィルター基板からのN-メチルピロリドンの発生量が、カラーフィルター基板の重量に対して0.02~0.5ppmであることを特徴とするカラーフィルター基板。
- 該赤、緑、青の各着色層に使用されている樹脂が各々ポリイミド樹脂である請求項1に記載のカラーフィルター基板。
- 請求項1または2に記載のカラーフィルター基板を製造する方法であって、少なくとも着色剤、樹脂、溶剤を含む着色ペーストより赤、緑、青の各着色層が形成される工程を有し、少なくとも1色の着色ペーストが溶剤としてN-メチルピロリドンを10~95質量%含むことを特徴とするカラーフィルター基板の製造方法。
- 少なくとも1色の着色ペーストが溶剤としてN-メチルピロリドンを30~90質量%および沸点が170~210℃の溶剤を5~20質量%含む請求項3記載のカラーフィルター基板の製造方法。
- 熱処理工程を有し、最大熱処理温度が200~270℃である請求項3または4に記載のカラーフィルター基板の製造方法。
- 少なくとも有機エレクトロルミネッセンス素子と請求項1または2記載のカラーフィルター基板を具備したことを特徴とする画像表示装置。
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WO2015122284A1 (ja) * | 2014-02-14 | 2015-08-20 | 富士フイルム株式会社 | 着色樹脂組成物およびこれを用いた硬化膜、カラーフィルタおよびその製造方法、固体撮像素子ならびに画像表示装置 |
JP2016118772A (ja) * | 2014-12-18 | 2016-06-30 | 株式会社日本触媒 | 樹脂組成物及び積層体 |
CN112194793A (zh) * | 2019-07-08 | 2021-01-08 | Jnc株式会社 | 聚酰胺酸组合物 |
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- 2013-04-08 KR KR1020147024262A patent/KR101969193B1/ko active IP Right Grant
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Also Published As
Publication number | Publication date |
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KR101969193B1 (ko) | 2019-04-15 |
CN104303081A (zh) | 2015-01-21 |
TW201350930A (zh) | 2013-12-16 |
TWI570448B (zh) | 2017-02-11 |
JPWO2013154069A1 (ja) | 2015-12-17 |
CN104303081B (zh) | 2016-08-24 |
JP5360335B1 (ja) | 2013-12-04 |
KR20150005513A (ko) | 2015-01-14 |
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