TW201350930A - Color filter substrate and image display device using the same - Google Patents

Abstract

The object of the present invention is to provide a color filter substrate with high reliability, which is suitable for an image display device, especially suitable for a color filter type of an organic EL displayer, and an image display device with high display quality, which can be accomplished cheaply and simply to have excellent vividness and contract degree. A color filter substrate of the present invention is characterized in that is used for an image display device including an organic electroluminescence element and comprising a coloring layer with each color of red, green, blue, and a overcoat layer, a inorganic barrier film, and the generation rate of N-methylpyrrolidone of the color filter substrate, respect to quality of the color filter substrate, is 0.02 to 0.5 ppm when is heated to 300 DEG C under an atmosphere of helium gases.

Description

Color filter substrate, and image display device using the same

The present invention relates to a color filter substrate and an image display device using the same.

In recent years, organic EL (electroluminescence) displays, which are one of the new types of thin displays, have attracted attention, and display displays such as mobile phones and mobile devices have begun to flow in the market. Since the liquid crystal display of the pioneer of the thin display is a non-self-illuminating type, since the organic EL display is a self-luminous display element, it is possible to vividly develop color over a wide range of color reproduction, and it is possible to achieve faster response and Smooth video transmission, etc., based on this, is expected to be regarded as the best candidate for the next generation of thin display that is better than the liquid crystal display.

As a method of fully coloring an organic EL display, development of RGB coating methods in which each of red (R), green (G), and blue (B) luminescent materials is formed has been developed, but with the large display In addition, there are disadvantages such as increased cost and high definition due to the enlargement of the film forming apparatus, and various methods are being reviewed. Wherein, color filtering is performed by combining a white light-emitting organic EL element and a color filter substrate having each colored layer of RGB The film method has attracted attention, and various proposals have been made (Patent Documents 1 to 3).

An example of an organic EL display in the form of a conventional color filter is shown in FIG. A structure in which the color filter substrate 20 and the organic EL light-emitting element 30 which emits white light are combined, and the organic EL layer 9 emits white light through the RGB colored layers 3 to 5 of the color filter to change colors. Degree, thereby enabling full color display. Therefore, the organic EL layer 9 is only one type that can emit white light. Therefore, it is superior to the respective coating methods in terms of cost surface, manufacturing yield, ease of large screen, and the like.

However, in the organic EL display in the form of such a color filter, in principle, the conversion of electric energy into an organic EL element of light is liable to cause a problem due to impurities, moisture, etc., when the previous color filter is used. In the case of a substrate, it is difficult to stabilize the manufacturing or image display, and it is desirable to be able to solve it.

In order to reduce such a problem, it is proposed to add a top coat (planarization layer) 6 on the surface of the RGB colored layers 3 to 5 of the color filter as shown in FIG. 2, and to provide a mask layer 7 and the like, for example, also in color. The surface of the filter is coated with polyazane, which is heated and oxidized to obtain a cerium oxide film (Patent Document 4), or cerium oxide (SiO _x ) or nitridation is formed on the outermost surface by sputtering or CVD. In the case of an inorganic masking film such as cerium oxide (SiO _x N _y ) (Patent Document 5), defects such as dark spots or white spots (abnormal brightness) are likely to occur in the organic EL element due to the occurrence of cracks and the like. Still expect it to be solved.

[Previous Technical Literature] [Patent Document]

Patent Document 1: Japanese Patent Laid-Open No. Hei 11-260562

Patent Document 2: Japanese Laid-Open Patent Publication No. 2004-227853

Patent Document 3: Japanese Laid-Open Patent Publication No. 2007-273327

Patent Document 4: Japanese Laid-Open Patent Publication No. 2002-222691

Patent Document 5: Japanese Patent Laid-Open Publication No. 2004-277317

The present invention has been made in view of the above problems, and an object thereof is to provide a highly reliable color filter substrate suitable for an image display device, particularly an organic EL display in the form of a color filter, which is inexpensive and simple. It realizes and provides an image display device with high display quality and excellent contrast.

The above problems can be solved by the following means.

that is,

(1) A color filter substrate characterized in that, in a color filter substrate having red, green, and blue colored layers and an inorganic masking film for use in an image display device including an organic electroluminescence device, When heated to 300 ° C in a helium atmosphere, the amount of N-methylpyrrolidone generated from the color filter substrate is 0.02 to 0.5 ppm with respect to the weight of the color filter substrate.

(2) The color filter substrate according to (1), wherein the resin used in each of the red, green, and blue colored layers is a polyimide resin.

(3) A method of producing a color filter substrate, which is characterized in that the method of producing a color filter substrate according to (1) or (2) is characterized in that it has a color paste containing at least a coloring agent, a resin, and a solvent. a step of forming each of the colored layers of red, green, and blue, and at least one color paste contains 10 to 95% by mass of N-methyl Pyrrolidone is used as a solvent.

(4) The method for producing a color filter substrate according to (3), wherein the solvent of the color paste of at least one color contains 30 to 90% by mass of N-methylpyrrolidone and a boiling point of 5 to 20% by mass is Solvent at 170~210 °C.

(5) The method for producing a color filter substrate according to (3) or (4), which has a heat treatment step and a maximum heat treatment temperature of 200 to 270 °C.

(6) An image display device comprising at least an organic electroluminescence device and the color filter substrate according to (1) or (2).

By using the color filter substrate of the present invention, it is possible to stably produce an image display device having high display quality with high contrast and excellent resolution without defects such as cracks or brightness reduction.

1‧‧‧Transparent substrate

2‧‧‧Black matrix

3‧‧‧Red colored layer

4‧‧‧Green color layer

5‧‧‧Blue colored layer

6‧‧‧Skin coating

7‧‧‧shading layer

8‧‧‧Transparent electrode

9‧‧‧Organic EL layer

10‧‧‧Back electrode layer

11‧‧‧Insulation film

12‧‧‧Substrate

13‧‧‧Extraction electrode

14‧‧‧Sealant

15‧‧‧Drying agent

20‧‧‧Color filter substrate

30‧‧‧Organic EL light-emitting elements

Fig. 1 is a schematic cross-sectional view showing an example of a video display device of the present invention.

Fig. 2 is a schematic cross-sectional view showing an example of the image display device of the present invention.

Fig. 3 is a schematic cross-sectional view showing an example of the image display device of the present invention.

[Formation of the Invention]

Hereinafter, embodiments of the present invention will be described.

The color filter substrate of the present invention is N-methylpyrrolidone from a color filter substrate when heated to 300 ° C in a helium atmosphere (hereinafter referred to as The amount of NMP generated is 0.02 to 0.5 ppm with respect to the weight of the color filter substrate, and by using such a color filter substrate, defects such as cracks of the inorganic mask film formed on the surface of the color filter can be prevented. At the same time, defects such as dark spots when the image display device is used can be suppressed.

By setting the content of NMP to the above range, it is surprisingly possible to prevent defects such as cracks and dark spots, and the reason is considered as follows. In other words, in order to satisfy the reliability such as solvent resistance and light resistance, the coloring layer of the color filter is often subjected to a thermosetting reaction at the time of curing, and as a result, residual stress is generated on the surface of the film. Then, in the case where an inorganic shielding film such as cerium oxide (SiOx) or cerium nitride oxide (SiOxNy) is formed on the surface thereof, cracks or the like may occur due to residual stress.

However, it is presumed that in the color filter substrate of the present invention, since NMP is moderately contained, the residual stress is alleviated, and as a result, cracking of the inorganic mask film is suppressed. It is considered that this effect is exhibited because a certain amount of NMP is contained with respect to the color filter substrate. Specifically, it is found that NMP from the color filter substrate is heated as long as it is heated to 300 ° C in a helium atmosphere. The amount of production may be 0.02 ppm or more based on the weight of the color filter substrate.

On the other hand, in the case of an image display device, particularly an organic EL display having an organic electroluminescence (EL) element, moisture or carbon dioxide gas, carbon monoxide gas, or organic matter from a color filter or an insulating film is known. It is well known that degassing due to decomposition of gases or the like causes deterioration of the element itself. Regarding NMP, although it is considered to be a chemically stable structure because of its slightly larger molecular weight, the effect of promoting deterioration is relatively slight, but it is found to be a content. When it is excessive, it will adversely affect the organic EL display. Specifically, it is found that the amount of NMP generated from the color filter substrate is 0.5 ppm or less with respect to the weight of the color filter substrate when heated to 300 ° C in a helium atmosphere.

That is, it has been found that a color filter substrate suitable for combination with an organic EL display is heated in an xenon atmosphere to 300 ° C, and the amount of NMP generated from the color filter substrate is relative to the weight of the color filter substrate. The present invention has been completed in the range of 0.02 to 0.5 ppm. When heated to 300 ° C in a helium atmosphere, when the amount of NMP generated from the color filter substrate is 0.02 to 0.5 ppm, the inorganic masking film acts effectively, and is applicable to defects such as no dark spots or white spots. A color filter substrate for a display that is sharp and has excellent contrast. A display using a color filter substrate having a production amount of NMP less than 0.02 ppm, because many defects are found, which is not good for poor display performance; a display using a color filter substrate having an NMP generation ratio of more than 0.5 ppm, It may be poor in sharpness or contrast due to deterioration of the organic EL element.

For the method for measuring the amount of NMP produced, a temperature-rise desorption-mass analysis method can be used. For example, a color filter substrate cut to about 10 mm × 20 mm can be prepared, and a turbulent gas at 50 mL/min can be prepared in a helium atmosphere. In the environment, the amount of gas generated was quantified from room temperature (25 ° C) at a temperature increase rate of 10 ° C / min (27.5 minutes) to 300 ° C, and the observed mass was a peak corresponding to the molecular weight of NMP 99. .

Moreover, in general, the color filter substrate is formed in a pattern conforming to the size of the liquid crystal panel on the transparent substrate at a position near the center. In the case where the sheet transparent substrate has six truncated angles and eight truncated angles, the amount of NMP generated from the color filter substrate of the present invention can be cut by any position in the patterned substrate. To determine, these are within the above range, so that the amount of NMP produced from the color filter substrate can be estimated. The pattern is cut out except for the out-of-plane (the portion other than the truncated portion). The term "outer surface" as used herein refers to a range in which a black matrix or a colored layer or the like is not formed. Even when a substrate number or other sorting mark is present, when the image display device is formed, an area that is not in the display range is regarded as an out-of-plane. Further, in order to eliminate the unevenness due to the measurement, the cutting was performed perpendicularly on the surface of the color filter substrate, and measurement was carried out using 10 or more pieces of about 10 mm × 20 mm.

In this manner, in the measured helium atmosphere, the amount of NMP generated from the color filter substrate when heated to 300 ° C must be 0.02 to 0.5 ppm, more preferably 0.04, with respect to the weight of the color filter substrate. ~0.4ppm.

Moreover, when the color filter substrate of the present invention is heated to 300 ° C in a helium atmosphere, the amount of NMP generated from the color filter substrate is preferably 0.003 to 0.09 μg/cm per unit area of the color filter substrate. ² , more preferably 0.007 to 0.07 μg/cm ² . In this range, it is possible to suppress the occurrence of defects such as cracks in the inorganic mask film, and to obtain a color filter substrate excellent in display performance.

The amount of water generated by the color filter substrate can be quantified by the same measurement method as that of NMP, and a peak corresponding to the molecular weight of water of 18 can be observed. In the helium atmosphere, when heated to 300 ° C, the amount of moisture generated from the color filter substrate is preferably from 1 to 20 ppm, more preferably from 2 to 10 ppm, based on the weight of the color filter substrate. When the amount of moisture produced is less than 1 ppm, The tendency for the amount of NMP to be generated is too small, and the amount of NMP generated tends to be excessive when it is more than 20 ppm.

Further, the amount of other degassing generated by the color filter substrate can be quantified by the same method, and the amount of NMP generated corresponding to the molecular weight of 99 and the amount of generated water having a molecular weight of 18 can be obtained by subtracting the amount of the entire degassing component. In the helium atmosphere, when heated to 300 ° C, the amount of other degassing generated from the color filter substrate is preferably from 0.1 to 10 ppm, more preferably from 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, the amount of NMP generated is too small, and when the amount of NMP is too small, the amount of NMP is more than 10 ppm, and the amount of NMP is too large, which may cause an organic EL element or even an image. The performance of the display device has an adverse effect and is therefore not good.

According to the present invention, an organic EL display having excellent display performance with a sharp and high contrast can be realized with NMP within the above range, and the color filter substrate does not exhibit such a special effect even if it contains other solvents. It is considered that this NMP having a boiling point of 204 ° C has a moderate boiling point in terms of crack suppression due to stress relaxation, and it is presumed that the chemical structure of the solvent itself has a closed-loop structure, so that the heat stability is high and it is not easy to decompose and generate gas. It is considered that such a remarkable effect cannot be expected if the boiling point is too low or too high, and even if only other solvents having no closed-loop structure or lactone-based solvents such as an ester skeleton are used, the thermal stability is not good and the above-described effects cannot be exhibited. The effect is that when the temperature is raised to 300 ° C in a helium atmosphere, the amount of NMP generated from the color filter substrate is 0.02 to 0.5 ppm with respect to the weight of the color filter substrate, and more preferably 0.04~ 0.4ppm.

Further, the color filter substrate referred to in the present invention refers to a coloring layer capable of recognizing a color when at least transmitted or reflected light is present, and generally has three colors of red (R), green (G), and blue (B). Layer. In addition to the colored layer, it may have a black matrix or a TFT circuit, a planarizing film, a transparent electrode, other organic components as needed, an inorganic member, or a coloring layer other than RGB, and may be incorporated into a display. After the organic EL element and the color filter substrate were disassembled, the amount of NMP produced was measured. When it is difficult to disintegrate, it is possible to directly measure the amount of NMP generated by the organic EL element and the color filter substrate as a whole, and it is also possible to calculate it as a generator without NMP from the organic EL element.

Next, the configuration of the color filter substrate of the present invention will be described.

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 a glass such as soda glass, alkali-free glass, borosilicate glass, or quartz glass, or a plastic film, a sheet, or the like can be used. Among these transparent substrates, the use of the alkali-free glass is preferable because the impurities are eluted less and the reliability is high. 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. When it is thinner than 0.01 mm, the strength as a support is lacking, and when it is thicker than 3 mm, the image display device becomes heavy. Further, a black matrix, a TFT circuit, or the like may be formed on the transparent substrate as needed.

As a method of forming the coloring layer, a known method such as a dyeing method, a plating method, a printing method, or a pigment dispersion method can be used, and a pigment dispersion method is preferred. The pigment dispersion method may be followed by coating a color paste obtained by dispersing a colorant such as a pigment on a non-photosensitive polyimide film, and coating a positive resist or a negative photoresist. a non-photosensitive polyimide process which is patterned by exposure and development; or a photosensitive color resist which is obtained by dispersing a pigment in a solution containing a binder resin and a photopolymerization initiator, but can be highly processed by use. The non-photosensitive polyimine method is preferred.

As the coloring layer used in the non-photosensitive polyimide process, a color paste containing at least a colorant, a polyimide resin, and/or a polyimide precursor and a solvent can be used.

As the coloring agent used in the coloring paste, a dye, an organic pigment, an inorganic pigment or the like can be used, but in terms of heat resistance and transparency, an organic pigment is preferred. Among them, those having high transparency, light resistance, heat resistance, and chemical resistance are preferred. When a specific example of a representative organic pigment is displayed by a color index (CI) number, it is preferably used as follows, but is not limited thereto.

As an example of the yellow pigment, pigment yellow (hereinafter abbreviated as PY) 12, 13, 17, 20, 24, 83, 86, 93, 95, 109, 110, 117, 125, 129, 137, 138, 139 may be used. 147, 148, 150, 153, 154, 166, 168, 180, 185, and the like.

Further, as an example of the orange pigment, Pigment Orange 13, 36, 38, 43, 51, 55, 59, 61, 64, 65, 71 and the like can be used.

Further, as an example of the red pigment, pigment red (hereinafter abbreviated as PR) 9, 48, 97, 122, 123, 144, 149, 166, 168, 177, 179, 180, 192, 209, 215, 216, 217 may be used. , 220, 223, 224, 226, 227, 228, 240, 254, and the like.

Further, as an example of the violet pigment, Pigment Violet 19, 23, 29, 30, 32, 37, 40, 50 and the like can be used.

Further, as an example of the blue pigment, pigment blue (hereinafter abbreviated as PB) 15, 15:3, 15:4, 15:6, 22, 60, 64, 80, or the like can be used.

Further, as an example of the green pigment, pigment green (hereinafter abbreviated as PG) 7, 10, 36, 58, and the like can be used.

These pigments may also be subjected to surface treatment such as rosin-coating, acid-based treatment, alkaline treatment, etc., as needed.

The above pigment can be appropriately adjusted depending on the color tone of the object depending on the color tone of the organic EL element to be used. The organic EL element may be a white light-emitting element or a combination of RGB light-emitting elements. However, in consideration of low-cost production, it is preferable to use an organic EL element that emits white light.

When an example of the pigment in combination with an organic EL element that emits white light is R (red), it is preferably a combination of PR-254 and PR-177, and a combination of PR-254 and PY-138. , the combination of PR-254 and PY-139, the combination of PR-254 and PR-150, etc., and the color of G (green) is preferably selected from PG-7, PG-36, The green pigment of the group of PG-58 is combined with the yellow pigment selected from the group of PY-138, PY-139, and PY-150, and the case of B (blue) is preferably PB15:3 or PB15. :6 is combined with PV23 or the like, but is not limited thereto.

As the resin to be used for the coloring paste, a transparent resin such as an acrylic, epoxy or polyoxygen can be used, and from the viewpoint of heat resistance, light resistance and solvent resistance of the coating film, it is preferred to use a polyfluorene. Imine resin. The term "polyimine resin" as used herein, in addition to a polyimine resin having a completely closed-loop structure, comprises a polyamine resin having a precursor of a poly-imine resin having a completely closed-loop structure and a poly-proline. The resin is a partially closed polyimine resin.

The polyimine resin can be obtained by reacting a tetracarboxylic dianhydride with a diamine.

In the synthesis of the polyimine resin, as the tetracarboxylic dianhydride, for example, an aliphatic or alicyclic type may be used, and specific examples thereof include 1,2,3,4-cyclobutanetetracarboxylic dianhydride. 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,3,5-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-dicyclohexenetetracarboxylic acid Anhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furan Base)-naphthalene [1,2-C]furan-1,3-dione. Further, when an aromatic type is used, a polyimine resin which can be converted into a film having good heat resistance can be obtained, and specific examples thereof include 3,3',4,4'-benzophenonetetracarboxylic acid Anhydride, 1,2,4,5-benzenetetracarboxylic dianhydride, 3,4,9,10-decanetetracarboxylic dianhydride, 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride , 4,4'-oxydiphthalic anhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,3", 4,4"-paired triphenyltetracarboxylic dianhydride, 3,3",4,4"-orthotriphenyltetracarboxylic dianhydride. Further, when a fluorine-based one is used, a polyimide resin which can be converted into a film having good transparency in a short wavelength range can be obtained, and specific examples thereof include 4,4'-(hexafluoroisopropylidene). Dicarboxylic anhydride and the like. In addition, the present invention is not limited thereto, and one type or two or more types of tetracarboxylic dianhydride may be used.

Further, as the diamine, for example, an aliphatic or alicyclic system can be used, and specific examples thereof include 1,3-diaminocyclohexane and 1,4-diaminocyclohexane. 4'-Diamino-3,3'-dimethyldicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexyl, and the like. Further, when an aromatic system is used, a polyimine resin which can be converted into a film having good heat resistance can be obtained, and specific examples thereof include 4,4'-diaminodiphenyl ether and 3,4'- Diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylanthracene, 3,3 '-Diaminodiphenylphosphonium, 4,4'-diaminodiphenyl sulfide, M-phenylene diamine, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, benzidine, 3,3' - dimethyl benzidine, 3,3'-dimethoxybenzidine, o-tolidine, 4,4"-diaminotriphenyl, 1,5-diaminonaphthalene, 3,3' -Dimethyl-4,4'-diaminodiphenylmethane, 4,4'-bis(4-aminophenoxy)biphenyl, 2,2-bis[4-(4-aminobenzene) Oxy)phenyl]propane, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(4-aminophenoxy)phenyl]indole, bis[4-(3 -Aminophenoxy)phenyl]anthracene, etc. Further, when a fluorine-based one is used, a polyimine resin which can be converted into a film having good transparency in a short-wavelength region can be obtained, and specific examples thereof include 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane or the like.

Further, when a nonoxyldiamine is used as a part of the diamine, the adhesion to the substrate can be improved. The oxane diamine is usually used in an amount of from 1 to 20 mol% in all diamines. When the amount of the nonoxyldiamine is too small, the adhesion improving effect cannot be exhibited, and if it is too large, the heat resistance is lowered. Specific examples of the oxirane diamine include bis-3-(aminopropyl)tetramethyl decane and the like. The present invention is not limited to these, and the diamine may be used alone or in combination of two or more.

The synthesis of the polyimine resin is usually carried out by mixing a tetracarboxylic dianhydride and a diamine in a polar organic solvent. At this time, the degree of polymerization of the obtained polyimine resin can be adjusted by the mixing ratio of the diamine and the tetracarboxylic dianhydride.

Further, a method in which a tetracarboxylic acid dichloride and a diamine are removed in a polar organic solvent, and then hydrochloric acid and a solvent are removed, thereby obtaining various polyiminoimine resins such as a polyimide resin are obtained.

Among these polyimine resins, both of the acid dianhydride and the diamine have an aromatic structure and are excellent in heat resistance, and therefore, more preferably, they have the following Any one of the quinone imine structure represented by the general formula (1), the proline structure shown by the following general formula (2), and the partial quinone imine ring structure represented by the following general formula (3). Aromatic polyimine resin.

In the above general formulas (1) to (3), X and Y represent a linking group, -X- represents -O-, -CO-, a moiety H may be substituted by another atom or a group of atoms -CH ₂ -, no linking group Any of the direct bonds, -Y- represents -O-, -SO ₂ -, -CONH-, part H can be replaced by other atoms or groups of atoms -CH ₂ -, direct bond without linkage One.

Further, it is also possible that a part of such an aromatic polyimide resin can be exchanged with other aliphatic groups, but the ratio of the aromatic acid-containing acid dianhydride and the diamine is preferably 50% in the entire polyimide resin. When the amount of the ear is more than 70% by volume, more preferably 70% by mole or more, it is preferable because of high heat resistance.

The solvent used for the coloring paste preferably contains NMP in an amount of 10 to 95% by mass. Preferably, it is preferably 30 to 90% by mass.

In addition to the doubt that the solubility of the polyimine resin and the polyaminic acid is high and there is no gelation, the NMP is an essential component of the color filter substrate of the present invention as described above. Further, a solvent other than NMP may be preferably contained, and examples thereof include methyl sirolius, ethyl sirolius, methyl carbitol, ethyl carbitol, ethylene glycol monomethyl ether, and ethylene glycol single a (poly)alkylene glycol ether solvent such as diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether or diethylene glycol monomethyl ether, or propylene glycol monoethyl ether acetate, ethyl acetate ethyl acetate, methyl-3- Methoxy propionate, 3-methoxy-3-methyl-1-butyl acetate, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, malonic acid An ester of diethyl ester, propylene glycol diacetate, 1,3-butanediol diacetate, or ethanol, 1-octanol, 1-nonanol, benzyl alcohol, 3-methoxy-3 - an alcohol such as methyl butanol, a ketone such as cyclopentanone or cyclohexanone, or β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-hexan Lactones such as lactones, ε-caprolactone, and the like, benzyl ether, dihexyl ether, acetone acetone, isophorone, caproic acid, octanoic acid, ethyl carbonate, propyl carbonate, benzene Kesailusu acetate, methyl benzoate, ethyl benzoate, diacetone alcohol, tripropyl Alcohol methyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol dimethyl ether, dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, propylene glycol phenyl ether, cyclohexanol acetate, etc. These solvents may be used in combination of two or more kinds.

Among these solvents, a solvent having a boiling point of 170 to 210 ° C is preferred because it is easy to control the amount of NMP generated from the color filter substrate. More preferably, it is a solvent containing 5 to 20% by mass of 170 to 210 °C.

In the case of a solvent containing only a boiling point lower than 170 ° C except NMP When the colored layer is hardened, the low-boiling solvent volatilizes, and it is easy to induce NMP to volatilize together. As a result, the NMP content of the color filter substrate becomes less and less, and conversely, only the boiling point is higher than 210 ° C except NMP. In the case of a solvent, there is a tendency that the residual amount of NMP is excessive.

Further, among these solvents having a boiling point of 170 to 210 ° C, 3-methoxy-3-methylbutanol is particularly preferred from the viewpoint of solubility of the polyimine resin and polylysine. , 3-methoxy-3-methyl-1-butyl acetate, γ-butyrolactone.

The coloring paste may contain other additives, and examples thereof include those having a pigment dispersion effect such as a polymer dispersant or a pigment derivative, or a adhesion improver, a surfactant, an organic acid, or an organic amine compound. A polymerization inhibitor or an antioxidant or the like.

The polymer dispersant is not particularly limited as long as it is generally used for a color filter, and polyester, polyalkylamine, polyallylamine, polyimine, polyamine, polyamine can be used. Each of the urethane, polyacrylate, polyimide, polyamidimide, or the like may be used singly or in combination. In the case of the color paste used in the non-photosensitive polyimide process, among these, the polyimide resin is preferred from the viewpoint of dispersion stability or compatibility.

In order to enhance the adhesion of the coating film to the substrate, a adhesion improving agent can be preferably added. For example, vinyl trimethoxy decane, vinyl triethoxy decane, vinyl ginate (2-methoxyethoxy) decane, N-(2-aminoethyl)-3-aminopropyl Methyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-epoxypropoxy Propyltrimethoxydecane, 3-glycidoxypropylmethyldimethyl Oxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methyl a decane coupling agent such as acryloxypropyltrimethoxydecane or 3-mercaptopropyltrimethoxydecane, wherein a decane coupling agent having an amine group has a high adhesion enhancement effect, and is preferably N. -(2-Aminoethyl)-3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-amino Propyltriethoxydecane.

A surfactant may be added for the purpose of improving the coatability of the thermosetting coloring composition and the surface uniformity of the coloring layer, or for improving the pigment dispersibility. The amount of the surfactant to be added is preferably 0.001 to 10% by mass, and more preferably 0.01 to 1% by mass based on the pigment. When the amount of addition is less than this range, the coating property, the improvement of the uniformity of the surface of the colored film, or the effect of improving the pigment dispersibility are small. On the other hand, when the amount is too large, the coating property is deteriorated, and the pigment is aggregated. Not good.

Specific examples thereof include cationic surfactants such as ammonium lauryl sulfate, polyoxyethylene alkyl ether triethanolamine sulfate, stearyl mercaptoacetate, and lauryl trimethyl ammonium chloride. Agent, lauryl dimethylamine oxide, amphoteric carboxymethyl hydroxyethyl imidazolium betaine and the like, amphoteric surfactant, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, sorbitan A nonionic surfactant such as monostearate or the like, an acrylic surfactant, a fluorine-based surfactant or a quinone-based surfactant. In particular, the coloring paste used in the substrate for a color filter of the present invention is preferably an N-based epoxy-based surfactant which is excellent in compatibility and has a small amount of effect.

The acrylic surfactant is preferably a copolymer of an acrylic monomer, and may be a copolymer of an acrylic monomer or a copolymer with other vinyl or styrene. When an acrylic surfactant containing a copolymer of an acrylic monomer and an alkyl vinyl ether and/or an aromatic vinyl ether is used, coating at the time of formation of a colored layer can be remarkably suppressed Uneven, so it is especially good. The weight average molecular weight obtained by gel permeation chromatography (GPC method) of the acrylic surfactant is preferably from 1,000 to 50,000, more preferably from 2,000 to 5,000. When it is less than 1,000, the effect of suppressing the unevenness is small, and when it is more than 50,000, the solubility in a solvent may be deteriorated.

Regarding the method of forming a colored layer by a non-photosensitive polyimide process, a colored paste can be applied onto a transparent substrate, and dried by heating (prebaking) using a hot plate, an oven, and vacuum drying. After prebaking, a dry positive photoresist is applied, followed by exposure to a reticle, followed by alkali development, and the photoresist is stripped with a solvent to obtain a colored layer.

As a method of applying the coloring paste, a dipping method, a roll coater method, a spin coating method, a die coating method, a die coating method, a spin coating method, a wire bar coating method, or the like can be suitably used, and the film thickness uniformity is excellent. The die coating method in which the paste is used efficiently is preferred.

After the photosensitive transparent resin composition is applied onto the substrate, the solvent is removed by air drying, drying under reduced pressure, heat drying, or the like to form a coating film of the photosensitive transparent resin composition. In particular, after the vacuum drying step is provided, it is more preferable to perform additional heat drying by an oven or a hot plate to eliminate coating defects caused by convection. Then, in the color of the coating The coating and drying of the positive photoresist are performed on the paste. The method of coating and drying can be carried out in the same manner as in the case of color paste. The exposure step of the photolithography process is then performed. A photomask is placed on the upper portion of the coating film in which the colored paste and the positive photoresist are laminated, and is 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.

The alkali developer may be any of an organic alkali developer or an inorganic alkali developer. As the inorganic alkali developing solution, an aqueous solution of sodium carbonate, sodium hydroxide or potassium hydroxide is preferably used. The organic alkali developer is preferably an aqueous solution of an aqueous solution of tetramethylammonium hydroxide or methanolamine, and is preferably an aqueous solution of tetramethylammonium hydroxide from the viewpoint of reducing impurities.

The concentration of the basic substance in the developing solution is not particularly limited, but is usually 0.01 to 10% by mass, preferably 0.05 to 5% by mass. When the alkali concentration is too low, development is difficult, and if it is too high, the film on the surface of the coating film is likely to be cracked or the pattern is not jagged. Further, it is preferable to use a surfactant as the developer, and it is preferable to add 0.01 to 10% by mass of a nonionic surfactant or the like, more preferably 0.1 to 3% by mass, to improve the pattern shape.

The alkali development may be a method such as immersion development, spray development, stirring development, or the like, or may be combined. The spray development is preferably adjusted to the optimum pixel shape, and the spray pressure is preferably 0.05 to 5 MPa. After the development, in order to remove the alkali developer, a step of washing with pure water or the like may be appropriately added.

The positive photoresist was peeled off after development. The positive photoresist can be removed by solvent dissolution or ion etching in a vacuum. The solvent for dissolving the positive photoresist is preferably an organic solvent, and acetone, ethyl acetate, butyl acetate, methyl sarbuta acetate or the like is preferably used, but is not limited thereto.

The coating film pattern of the obtained colored layer is then patterned by heat treatment (hardening). The heat treatment is usually carried out in air, in a nitrogen atmosphere, or in a vacuum, at a temperature of 150 to 300 ° C, continuously or in stages for 0.1 to 5 hours. When the color filter substrate of the present invention is heated to 300 ° C in a helium atmosphere, the amount of NMP generated must be 0.02 to 0.5 ppm. For this reason, the curing temperature, especially the maximum heat treatment temperature at which the maximum temperature is employed, is important.

Specifically, the maximum heat treatment temperature at the time of manufacture of the color filter substrate is preferably 200 to 270 ° C, more preferably 210 to 240 ° C. When the maximum heat treatment temperature is higher than 270 ° C, the residual amount of NMP is relatively small, and the effect of preventing cracks of the mask film tends to be small, which is not preferable. When the maximum heat treatment temperature is lower than 200 ° C, the residual amount of NMP becomes excessive. As a result, it is presumed that the defects of the organic EL element are likely to be generated depending on the influence of the degassing, and thus it is not preferable.

The formation of the colored layer may be carried out by a photosensitive coloring paste in addition to the above non-photosensitive polyimide process.

The formation of the colored layer may be carried out by using a photosensitive color resist obtained by dispersing a pigment in a solution containing a binder resin and a photopolymerization initiator in addition to the above non-photosensitive polyimide process. In this case, the positive photoresist may be applied, and after the photosensitive color resist is applied and dried, the patterning is directly performed by photolithography, but it is difficult to perform high-precision processing.

The color filter substrate of the present invention forms at least a plurality of colored layers, and it is preferred that the resin used in at least one of the colored layers contains a polyimide resin. By containing a polyimide resin, a high-performance and highly reliable color filter substrate can be obtained. Furthermore, the color filter substrate of the present invention is formed to In the case of less red, green, and blue color layers, the resins used in the respective colored layers of red, green, and blue respectively contain a polyimide resin. Thereby, a color filter substrate having higher reliability can be obtained.

The formation of the colored layer can be performed in the order of RGB, and the order is not particularly limited.

A surface coating may be provided on the surface of the colored layer as needed. The surface coating is for protecting the black matrix or the colored layer, and improving the flatness of the surface of the color filter and preventing contamination from the organic EL element by the color filter. In particular, when a resin black matrix is used as the black matrix, in order to reduce the surface difference of the color filter due to the film thickness of the resin black matrix, it is necessary to perform surface coating. Surface coating requirements and the lower layer. A wide range of properties such as adhesion of the upper layer, insulation of impurities, smoothness, light resistance, heat and humidity resistance, solvent resistance, chemical resistance, toughness, transparency, heat resistance, etc. An imide resin, an epoxy resin, an acrylic resin, a decane resin precursor, a polyoxyn epoxide, and a composite resin thereof.

Among these, a polyimide resin is preferably used, and as the resin and solvent to be used, it is preferable to use the same one as the user of the coloring layer. In particular, as a solvent for the transparent paste used in the surface coating layer, it is preferably contained in an amount of 10 to 95% by mass of NMP, further preferably 30 to 90 parts by weight of NMP, and more preferably 5 to 20% by mass of a boiling point of 170 to 210. Solvent for °C.

When the surface coating is hardened, the hardening temperature is preferably 200 to 270 ° C, more preferably 210 to 240 ° C. The surface coating is also contained in the color filter substrate, and the maximum heating temperature is preferably in the above range.

Further, an inorganic masking film can be formed as needed.

The color filter substrate of the present invention has an inorganic masking film (hereinafter sometimes referred to as a shielding layer), and the shielding layer can be formed using yttrium oxide (SiOx), cerium nitride oxide (SiOxNy), tantalum nitride (SixNy) or the like. . It is particularly preferred to use bismuth oxynitride. The refractive index of the shielding layer is preferably from 1.4 to 1.6, more preferably from 1.42 to 1.48. Depending on the refractive index, the difference in shielding performance is large. If it is too high, the degassing component tends to penetrate easily. If it is too low, it tends to penetrate water, which is not preferable. The film thickness of the shielding layer is usually 0.1 to 5 μm, more preferably 0.3 to 3 μm. If it is too thin, the tendency of the shadowing effect to be reduced is not preferable. On the other hand, if it is too thick, the masking layer tends to have defects such as cracks.

The shielding layer can be formed by a sputtering method, a plasma CVD method, or the like, and more preferably formed by a plasma CVD method. Regarding the method of film formation by the plasma CVD method, a Si-containing compound such as methyl decane, dimethyl decane, trimethyl decane, tetramethyl decane, or the like may be contained in the presence of oxygen and/or a nitrogen gas. Ethyl decane, tetraethyl decane, tetrabutyl decane, dimethyl diethyl decane, tetraphenyl decane, methyl triphenyl decane, dimethyl diphenyl decane, trimethyl phenyl decane, three Methyl decyl-trimethyl decane, trimethyl decylmethyl-trimethyl decane, and the like are formed under reduced pressure of 0.1 to 100 Pa.

It is important that such a masking film has no defects such as cracks on the surface, and surface cracks can be prevented by the color filter substrate of the present invention. In the case where surface cracks are generated, water, impurity gas, and the like are transmitted from the position where the crack is generated, and the original function cannot be exhibited. Such surface cracks can also be observed by an optical microscope, an electron microscope, etc., but there are cases where extremely small cracks which cannot be confirmed by general observation are generated, and the number of defects is found after the final assembly of the image display device.

Furthermore, the color filter substrate of the present invention may have a transparent electrode as needed. Transparent electrodes are usually preferably made of indium. Tin oxide (ITO). The transparent electrode is required for driving the organic EL element, and may be either a bottom emission type or a top emission type, and any other structure may be employed, and ITO may be patterned by photolithography etching or the like.

The manufacturing steps of the color filter of the present invention will be briefly described below.

On the transparent substrate, a non-photosensitive colored paste containing at least a coloring agent, a resin, and a solvent is applied onto a transparent substrate by a spin coater, a die coater, or the like, and then dried by air drying, heat drying, and vacuum drying to form a colored film. The thickness of the colored film is usually in the range of 0.5 to 3.0 μm. It is preferred to use an oven, a hot plate, etc., for heating and drying (semi-hardening) for 1 to 60 minutes in the range of 60 to 160 °C. Next, a positive photoresist is applied onto the colored film thus obtained, and dried by heating in an oven or a hot plate at a temperature of 50 to 150 ° C for 1 to 30 minutes (prebaking). Next, ultraviolet rays having an h-line exposure amount of 20 to 300 mJ/cm ² are irradiated with a photomask and a proximity exposure device to imprint the target pattern, and then alkali development is performed to obtain a coloring layer of a desired pattern at a desired position. The positive photoresist is peeled off by 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 above steps are carried out in accordance with the required red, green and blue pixels.

The image display device of the present invention is characterized by using the color filter substrate of the present invention. By combining the color filter substrate of the present invention with an organic EL display, it is possible to obtain a display device which has no display performance such as a dark spot and has a good display performance and a clear image.

The image display device of the present invention will be described with reference to FIG. 1.

In the liquid crystal display device of the present invention, the black matrix 2 which is produced as needed, and the colored layers 3, 4, and 5 which are equivalent to red, green, and blue, which are necessary components, and the like are prepared as needed. The color filter substrate 20 composed of the top coat layer 6 and the shielding layer 7, an organic electroluminescent layer (organic EL layer) composed of a transparent electrode 8 such as ITO, a hole transport layer, a light-emitting layer, and an electron transport layer 9. The organic EL element 30 composed of the back electrode layer 10, the insulating film 11, the substrate 12, and the extraction electrode 13 connected to the external power source is sealed with a sealant 14, and a desiccant 15 or the like may be provided as needed.

Further, another configuration may be provided. Alternatively, as shown in FIG. 2, the color filter substrate may be in close contact with the organic EL element, or as shown in FIG. 3, the sealant 14 may be formed on the top coat layer 6. The liquid crystal display device of the present invention may be any structure not shown, as long as it is a color filter substrate of the present invention.

The respective constituent elements of the color filter substrate are as described above.

The substrate 12 used for the organic EL element is a support substrate for producing an organic EL element, and may be various metal substrates such as aluminum, chromium, stainless steel, or the like, in addition to various transparent substrates such as glass, film, and plastic. Opaque substrate.

The insulating film prevents energization of the transparent electrode layer and the back electrode layer, and is preferably made of an organic material. Examples of the resin to be used include a polyimide resin, an acrylic resin, an epoxy resin, and a polyoxymethylene resin. When a polyimide-containing resin is used, reliability is high, which is preferable. The insulating film is made of a photosensitive material and can be formed by photolithography.

The back electrode layer 10 is a structure in which a voltage is applied between the substrate 12 and the organic EL layer 9 and a voltage is applied between the transparent electrode 8 and the organic EL layer. Examples of the material for forming the back electrode layer include a metal, a metal oxide, an alloy, and a mixture thereof. More specifically, magnesium, aluminum, indium, lithium, silver, alumina, etc. may be mentioned, and this can be preferably used. And other mixtures. The film thickness of the back electrode layer is usually 0.01 to 1 μm, and a method of forming a film by vapor deposition, sputtering, or the like, and then patterning by photolithography is preferably employed.

The organic EL layer 9 is usually formed of an organic material such as a laminated hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer. In the image display device of the present invention, since a color filter substrate having a color layer of RGB or the like is used, the light emitted from the light-emitting layer is preferably white light. Any wavelength distribution of white light may be used, and it is preferable to include wavelength fields of red, green, and blue. The color tone of the color layer used for the color filter substrate can be appropriately changed in accordance with the wavelength distribution of the white light to become a video display device having a desired color reproduction range. Further, the organic EL layer is formed by RGB coating, and it is preferable to combine with the color filter substrate of the present invention or to expand the color reproduction range.

The luminescent material is not particularly limited as long as it can be fluorescent or fluorinated, and examples of the pigment-based material include a metal-based compound material and a polymer-based material, and more specifically, as a pigment-based material. Examples thereof include cyclopentenylamine, tetraphenylbutadiene, triphenylamine, oxadiazole, pyrazoloquinoline, distyrylbenzene, distyryl extended aryl, silole, and thiophene. An organic compound having a skeleton, a pyridine, a perinone, a hydrazine, an oligothiophene, a tri-n-butylene decylamine, or an oxadiazole dimer, a pyrazoline II Examples of the metal complex compound material include an aluminum quinolol complex, a benzoquinolinol ruthenium complex, a benzoxazole zinc complex, and a benzothiazole zinc complex. An oxamethylzinc complex, a zinc porphyrin complex, a ruthenium complex, or a rare earth metal such as Al, Zn, Be or the like, or Tb, Eu, Dy or the like in the central metal a metal complex such as an azole, a thiadiazole, a phenylpyridine, a phenylbenzimidazole or a quinoline structure, and the like, and examples of the polymer material include a polyparaphenylene vinyl derivative and a polythiophene derivative. A polyparaphenylene derivative, a polydecane derivative, a polyacetylene derivative, a polyfluorene derivative, or a polyvinylcarbazole derivative, and a polymer material or a metal complex material is polymerized.

As a method of forming the light-emitting layer, a vapor deposition method, a spin coating method, a printing method, an inkjet method, or the like can be used, and the thickness of the light-emitting layer is usually about 0.05 to 5 μm.

The transparent electrode 8 is preferably a light that transmits light emitted from the organic EL layer, and the transmittance is preferably from 80 to 99%, more preferably from 90 to 99%. Examples of the material used for these transparent electrodes include metal oxides, and examples thereof include indium tin oxide (ITO), indium oxide, zinc oxide, and stannous oxide. The film thickness is usually 0.1 to 1 μm, and it is preferably a method of forming a film by a vapor deposition method or a sputtering method and then patterning it by photolithography.

The material for the conductivity of the extraction electrode 13 is not particularly limited, and a material generally used for the extraction electrode of the organic EL element can be used. For example, a metal such as silver, aluminum, gold, chromium, nickel, molybdenum or the like can be used. An alloy or the like can also be formed as a laminated film.

By combining the color filter substrate and the organic EL display as described above, and bonding them with a sealant or the like, an image display device can be produced.

As the sealant, it is preferable to prevent contact of the organic EL element with moisture or the like in the atmosphere, and a known material 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 displays having few defects and excellent display performance.

[Examples]

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited thereto.

(Example 1)

A. Production of polyimine resin solution

95.1 g of 4,4'-diaminodiphenyl ether and 6.2 g of bis(3-aminopropyl)tetramethyldioxane were charged together with NMP 745g, and 3,3',4,4 was added. 144.1 g of '-biphenyltetracarboxylic dianhydride was reacted at 70 ° C for 3 hours, and 3.0 g of phthalic anhydride was added, and further reacted at 70 ° C for 2 hours to obtain a 25% by mass polyienimine resin solution (PAA).

B. Synthesis of polymer dispersant

161.3 g of 4,4'-diaminobenzimidamide, 176.7 g of 3,3'-diaminodiphenylphosphonium and 18.6 g of bis(3-aminopropyl)tetramethyldioxane NMP 3194g was charged together, and 439.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride was added, and after reacting at 70 ° C for 3 hours, 2.2 g of phthalic anhydride was added, and further reacted at 70 ° C for 2 hours. A polymer dispersant (PD) of a 20% by mass polyimine resin solution was obtained.

C. Production of coloring paste

PR254, 3.6 g (80% by mass), PR177, 0.9 g (20% by mass) 22.5 g of polymer dispersant (PD) and 63 g of NMP were placed together with 90 g of glass beads, and dispersed by a homogenizer at 7000 rpm for 5 hours, and then the glass beads were removed by filtration. In this manner, a 5% solution (RD) of a dispersion composed of PR254 and PR177 was obtained.

To 45.6 g of the dispersion (RD), 18.2 g of a mixed polyimine resin solution (PAA), 0.1 g of 3-aminopropyltriethoxydecane as a adhesion modifier, and an acrylic resin as a surfactant were added. 0.03 g of a surfactant, and an appropriate amount of NMP, a red coloring paste (RP-1) containing a pigment/resin ratio of 25/75 and a solid content concentration of 6% containing NMP as a solvent of 94% was obtained. In the same manner, a weight-to-mix ratio (G/Y) of PG36 and PY150 of 60/40, a pigment/resin ratio of 25/75, a solid content concentration of 6%, and a green coloring paste containing NMP 94% as a solvent were obtained. -1) and PB15:6, a pigment/resin ratio of 25/75, a solid content concentration of 6%, and a blue coloring paste (BP-1) containing 94% of NMP as a solvent.

D. Production of colored layer

The red colored paste PR-1 was applied to a glass substrate (manufactured by CORNING, EAGLE XG material, thickness: 0.7 mm) by a slit coater, and heated at 120 ° C for 10 minutes to form a semi-hardened red resin coating film. . A positive photoresist ("LC-100A" manufactured by Rohm and Haas Electronic Materials Co., Ltd.) was applied by a slit coater so that the film thickness after prebaking was 1.0 μm, and dried on a hot plate at 100 ° C for 5 minutes. Pre-bake.

Using a UV exposure machine PLA-501F manufactured by Canon Inc., the mask was exposed through a mask at 100 mJ/cm ² (UV intensity at 365 nm), followed by development of a photoresist with a 2.0% aqueous solution of tetramethylammonium hydroxide. Etching with a resin coating film, forming a pattern, and then stripping the photoresist with methyl sesaphate acetate. Subsequently, it was heat-treated in an oven at 230 ° C for 30 minutes to be hardened to form a red colored layer having a film thickness of 1.5 μm.

Similarly, 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.

E. Production of masking film

The production of the masking film is carried out by a plasma CVD method. A film was formed under reduced pressure with tetramethyl decane in the presence of oxygen and a nitrogen gas to form a cerium nitride film having a thickness of 2 μm.

F. Visual inspection of the color filter substrate

The produced color filter substrate was visually inspected with an optical microscope. The 100 pixels of each of RGB are inspected and judged according to the following evaluation method.

A: Among the 100 pixels, no defects such as cracks were found.

Among the B: 100 pixels, 1 to 3 minor cracks were observed.

Among the C: 100 pixels, more than 4 cracks were observed.

G. Determination of NMP production

The amount of NMP produced was measured by a temperature rise-off-mass method. The pattern portion of the produced color filter substrate was cut into a size of about 10 mm × 20 mm, and the weight thereof was weighed, and in a helium atmosphere, under a turbulent atmosphere of 50 mL/min, at a temperature rising rate of 10 ° C / min. The amount of gas generated from room temperature (25 ° C) to 300 ° C (27.5 minutes) was quantified. The generated gas is analyzed by a gas chromatography mass spectrometer GC/MS "QP5050A" manufactured by Shimadzu Corporation, and the mass is equivalent to NMP. The peak of 99 of the sub-quantity is used as the amount of NMP production. Similarly, a peak corresponding to the molecular weight of water 18 was obtained as the amount of generated water, and the amount of generation of degassing was subtracted from the amount of generated NMP and the amount of generated water.

H. Production of organic EL elements

A photosensitive polyimide resin was formed as an insulating film by photolithography on a glass substrate. After sputtering aluminum as a back electrode layer, it is patterned by photolithography to form an opening having no insulating film. Then, ginseng (8-quinoline) aluminum (hereinafter abbreviated as Alq3) as an electron transport layer is formed by a vacuum deposition method to form a light-emitting layer which is doped with Alq3 doped dicyanomethylenepyran and quinine. A white light-emitting layer of anthrone and 4,4'-bis(2,2-diphenylvinyl)biphenyl. Next, N,N'-diphenyl-N,N'-bis(α-naphthyl)-1,1'-biphenyl-4,4'-di as a transport layer of the hole was vacuum-deposited. Amine is formed into a film. Finally, ITO as a transparent electrode was sputter-deposited to form an organic EL device having a white light-emitting layer.

I. Production of image display device

The color filter substrate produced by the above method was opposed to the organic EL element, and bonded together with a sealant to prepare a video display device.

A: Display with sharp and excellent contrast

B: Although some of the defects such as dark spots and white spots are seen, the display is good overall.

C: Most defects are observed, showing poor performance display

(Examples 2 to 13, Comparative Examples 1, 2)

A color filter substrate and a video display device were produced in the same manner as in Example 1 except that the curing temperature and the solvent of the color paste were changed. The results were summarized in Table 1 and Table 2 together with Example 1. Also, in Tables 1 and 2 The solvent used is as follows.

NMP: N-methylpyrrolidone (NMP made by KURARAY Co., Ltd.) boiling point 202 ° C

γBL: γ-butyrolactone (GBL manufactured by KURARAY Co., Ltd.) Boiling point 204 ° C

MMB: 3-methoxy-3-methylbutanol (SOLFIT manufactured by KURARAY Co., Ltd.) 154 °C

MMB-AC: 3-methoxy-3-methyl-1-butyl acetate (SOLFITAC, manufactured by KURARAY Co., Ltd.) 188 °C

PMA: propylene glycol monomethyl ether acetate (PGM-AC manufactured by KURARAY Co., Ltd.) boiling point 146 ° C

(Comparative Example 3)

C. Production of coloring paste

A photosensitive color resist containing a pigment, an acrylic resin, a photopolymerization initiator, and a solvent is used as a coloring paste. A red photosensitive color resist (PR-2) having a solid concentration of 20% and a PMA of 80% as a solvent was produced, and a green photosensitive color resist (PG-2) was produced in the same manner, and a blue photosensitive color was produced in the same manner. Photoresist (PB-2).

D. Production of colored layer

The red photosensitive color resist PR-2 was applied onto a glass substrate (manufactured by CORNING, EAGLE XG material, thickness: 0.7 mm) by a slit coater, and heated at 90 ° C for 10 minutes to form a prebaked treatment. Red resin coating. The mask was exposed to light at 100 mJ/cm ² (ultraviolet intensity of 365 nm) through a mask by a UV exposure machine PLA-501F manufactured by Canon Co., Ltd., and then developed with a 0.05% potassium hydroxide aqueous solution to form a pattern. Subsequently, it was heat-treated in an oven at 230 ° C for 30 minutes to be hardened to form a red colored layer having a film thickness of 1.5 μm.

In the same manner, a green colored layer was formed using the green photosensitive color resist PG-2, and a blue colored layer was formed using the blue photosensitive color resist PB-2.

E to I is a color filter substrate and a video display device produced in the same manner as in the first embodiment. The results are summarized in Tables 1 and 2.

As shown in Tables 1 and 2, in any of the examples, the NMP production amount is 0.02 to 0.5 ppm, and an image display device having good display performance can be obtained. In contrast, in Comparative Examples 1 to 3 which are outside the above range, , you can't get vivid images.

1‧‧‧Transparent substrate

2‧‧‧Black matrix

3‧‧‧Red colored layer

4‧‧‧Green color layer

5‧‧‧Blue colored layer

6‧‧‧Skin coating

8‧‧‧Transparent electrode

9‧‧‧Organic EL layer

10‧‧‧Back electrode layer

11‧‧‧Insulation film

12‧‧‧Substrate

13‧‧‧Extraction electrode

14‧‧‧Sealant

20‧‧‧Color filter substrate

30‧‧‧Organic EL light-emitting elements

Claims (6)

A color filter substrate characterized in that in a color filter substrate having red, green, and blue colored layers and an inorganic masking film for an image display device including an organic electroluminescence device, in a xenon environment When heated to 300 ° C, the amount of N-methylpyrrolidone generated from the color filter substrate is 0.02 to 0.5 ppm with respect to the weight of the color filter substrate. The color filter substrate according to claim 1, wherein the resin used in each of the red, green and blue colored layers is a polyimide resin. A method of manufacturing a color filter substrate, which is characterized in that the method for producing a color filter substrate according to claim 1 or 2, characterized in that it has a red, green color formed by a color paste containing at least a colorant, a resin, and a solvent. And a step of each of the blue colored layers, and at least one color paste contains 10 to 95% by mass of N-methylpyrrolidone as a solvent. The method for producing a color filter substrate according to claim 3, wherein the solvent of the at least one color paste contains 30 to 90% by mass of N-methylpyrrolidone and 5 to 20% by mass of a boiling point of 170 to 210. Solvent for °C. The method for producing a color filter substrate according to claim 3 or 4, which has a heat treatment step and has a maximum heat treatment temperature of 200 to 270 °C. An image display device comprising at least an organic electroluminescence device and a color filter substrate according to claim 1 or 2.