JP2009198904A - Colored resin composition, color filter, and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a color filter formed by an inkjet method and having a high flatness pixel. <P>SOLUTION: The color filter includes at least a plurality of the pixels and a black matrix between the adjacent pixels, and the maximum film thickness of the pixel portion is ≤70% of the film thickness of the black matrix portion. A liquid crystal display device and an organic EL display using the same are disclosed. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a color filter, a liquid crystal display device using the same, and an organic EL display. Specifically, the present invention relates to a color filter that is formed by an inkjet method and includes pixels having high flatness, a liquid crystal display device that includes the color filter, and an organic EL display.

A color filter in which a pixel is formed by driving a colored resin composition (hereinafter sometimes referred to as “color ink”) in a pixel bank, that is, in a substantially rectangular recessed area surrounded by a black matrix by an inkjet method. Manufacturing technology is in practical use.
The color filter manufactured by the ink jet method has an advantage that the cost is low compared with the case of manufacturing by the conventional photolithography method, but the shape of the color portion (pixel portion) becomes convex. Has drawbacks. As a result, color unevenness occurs in the pixel, and the optical characteristics as a color filter tend to be insufficient.

  In general, the film thickness of the pixel portion is designed to be substantially the same as the film thickness of the black matrix (hereinafter sometimes referred to as “BM”) portion after drying. This is because in the conventional pixel formation by the photolithography method, such a configuration is preferable in the process, and the configuration has been used as it is also in the color filter by the ink jet method.

Therefore, the film thickness of the pixel portion immediately after the color ink is discharged into the pixel, that is, the film thickness of the pixel portion before drying is higher than that of the BM portion. For example, if the solid content concentration of the ink-jet color ink is 20%, the height of the color ink liquid surface in the pixel bank immediately after ejection from the substrate is five times higher than the BM portion.
Therefore, in order to prevent color mixture between pixels, it is necessary to perform a liquid repellent process on the black matrix portion. As a result, the shape before drying becomes a convex shape as shown in FIG. When this is dried, the droplets gradually become smaller with the color ink droplets pinned on the upper end of the BM in the initial stage. (Refer to FIG. 1 (b)) As the drying further proceeds, the color ink gradually loses its fluidity, and after that, the shape changes so as to reduce the overall film thickness while maintaining the convex shape. ). That is, the minimum film thickness is determined by how much the color ink contracts from the timing when it loses fluidity.

Therefore, the minimum film thickness of the pixel portion is not the same as the height of the BM portion, and is generally about 50% of the film thickness of the BM portion after drying. As a result, when the average film thickness of the pixel after drying is matched with the film thickness of the BM part, the minimum film thickness is smaller than the BM part, the maximum film thickness is larger than the BM part, and it becomes a convex shape. (See FIG. 2).
On the other hand, Patent Document 1 proposes to improve the adhesion between the BM side surface and the ink and solve the surface flatness defect of the pixel portion. Specifically, in the method described in the publication, the above-mentioned problem is solved by roughening the BM side surface by dry etching or discharging the color ink into the pixel bank with the BM portion uncured. It is said. However, even if this method can improve the local shape in the vicinity of the BM side surface in the pixel, it is difficult to flatten the shape of the entire pixel. As described above, the color ink gradually loses fluidity as the drying progresses, and thereafter changes in shape so that the overall film thickness becomes small while maintaining the convex shape. Therefore, even if the adhesion between the BM side surface and the color ink is improved, the pixel shape excluding the vicinity of the BM side surface remains convex.
Japanese Patent Laid-Open No. 2002-148429

  As a result of intensive studies to solve the above problems, the present inventors have designed the color filter so that the maximum film thickness of the pixel portion is 70% or less of the film thickness of the BM portion. It has been found that the flatness can be obtained. It has been found that a configuration in which the film thickness of the pixel portion is smaller than that of the BM portion as shown in FIG. 3 is suitable for a color filter manufactured by an inkjet method.

That is, the present invention is as follows.
[1] A color filter in which at least a plurality of pixels and a black matrix located between adjacent pixels are provided on a support substrate, and the maximum film thickness of the pixel portion is equal to the film thickness of the black matrix portion. A color filter characterized by being 70% or less.
[2] The color filter as described in [1] above, wherein the minimum film thickness of the pixel portion is 30% or more of the film thickness of the black matrix portion.
[3] A colored resin composition in which the pixel portion of the color filter according to [1] or [2] contains at least (a) a color material, (b) a binder resin, and (c) a solvent. A color filter characterized by being formed.
[4] The color filter according to [3], wherein the color material (a) in the colored resin composition is 40% by weight or more in terms of the concentration in the solid content.
[5] The color filter according to [3] or [4], wherein the colored resin composition further contains (d) a surfactant.
[6] The color filter according to [5], wherein (d) the surfactant contains a compound represented by the following general formula (0).

(In the above formula, substituent A represents a fluorinated alkyl group having 1 to 5 carbon atoms, and n represents an integer of 2 to 100.)
[7] The color filter according to any one of [3] to [6], wherein the colored resin composition further contains a monomer.
[8] The color filter according to any one of [3] to [7], wherein the colored resin composition further contains a photopolymerization initiation system and / or a thermal polymerization initiation system. filter.
[9] The color filter according to any one of [1] to [8], wherein the thickness of the black matrix portion is 1.5 μm or more.
[10] The color filter according to any one of [3] to [9], wherein the pixel portion is formed by an inkjet method using the colored resin composition. .
[11] A liquid crystal display device manufactured using the color filter according to any one of [1] to [10].
[12] An organic EL display produced using the color filter according to any one of [1] to [10].

In the color filter, in order to reduce the film thickness while sufficiently maintaining the optical characteristics of the pixel portion, it is preferable that the ratio of the color material in the pixel is relatively large. That is, it is preferable that the ratio of the color material in the solid content of the color ink is relatively large.
Further, it is possible to realize further planarization by adding a surfactant. In general, the addition of a surfactant tends to lower the ejection stability by inkjet, but the compound represented by the general formula (0) (surfactant) does not impair the ejection stability of inkjet. This is preferable because of the effect of flattening the shape of the pixel portion.

  According to the present invention, it is possible to produce a high-performance color filter with a flat pixel portion and low cost by an inkjet method. By using such a color filter, it is possible to provide a high-quality liquid crystal display device or organic EL display at low cost.

Embodiments of the present invention will be described in detail below, but the description of the constituent elements described below is an example (representative example) of the embodiments of the present invention, and the present invention does not exceed the gist thereof. It is not limited to the contents of.
The color filter of the present invention is provided with at least a plurality of pixels and a black matrix located between adjacent pixels on a support substrate, and the maximum film thickness of the pixel portion is 70% of the film thickness of the black matrix portion. % Or less.
The pixel portion is suitably formed using a colored resin composition containing at least (a) a color material, (b) a binder resin, and (c) a solvent.

[Colored resin composition]
Hereinafter, the colored resin composition will be described first, but “(meth) acryl”, “(meth) acrylate” and the like mean “acryl and / or methacryl”, “acrylate and / or methacrylate”, and the like. For example, “(meth) acrylic acid” means “acrylic acid and / or methacrylic acid”. In addition, “(co) polymer” means “single polymer (homopolymer) and / or copolymer (copolymer)”.
In the following, “total solid content” refers to all components in the colored resin composition of the present invention other than the solvent components described later.
Moreover, below, the weight average molecular weight (Mw) of resin ((co) polymer) is the value of polystyrene conversion measured by GPC (gel permeation chromatography).

[(A) Color material]
(A) Although a dye / pigment can be used as the coloring material, a pigment is preferable from the viewpoint of heat resistance, light resistance, and the like. As the pigment, pigments of various colors such as a blue pigment, a green pigment, a red pigment, a yellow pigment, a purple pigment, an orange pigment, a brown pigment, and a black pigment can be used. In addition to organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene, various inorganic pigments can be used. It is. Specific examples of pigments that can be used are shown below by pigment numbers. Note that “CI” described below means a color index (CI).

  Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 , 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267 268, 269, 270, 271, 272, 273, 274, 275, 276. Of these, C.I. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment red 177, 209, 224, 254.

  Examples of blue pigments include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79. Of these, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, more preferably C.I. I. Pigment blue 15: 6.

Examples of green pigments include C.I. I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55. Of these, C.I. I. And CI Pigment Green 7 and 36.
Examples of yellow pigments include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207, 208. Of these, C.I. I. Pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably C.I. I. Pigment yellow 83, 138, 139, 150, 180.

  Examples of orange pigments include C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79. Of these, C.I. I. And CI pigment oranges 38 and 71.

  Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50. Of these, C.I. I. Pigment violet 19, 23, more preferably C.I. I. And CI Pigment Violet 23.

A plurality of the above-described various pigments can be used in combination. For example, in order to adjust the chromaticity, a green pigment and a yellow pigment can be used in combination, or a blue pigment and a violet pigment can be used in combination.
These pigments are used after being subjected to a dispersion treatment so that the average particle size is usually 1 μm or less, preferably 0.5 μm or less, more preferably 0.3 μm or less. The particle diameter is a value measured by dynamic light scattering DLS for a sufficiently diluted pigment dispersion (described later) or color ink.

Examples of the dye that can be used as the coloring material include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.
Examples of the azo dye include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse Blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Molded Red 7, C.I. I. Moldant Yellow 5, C.I. I. Examples thereof include Moldant Black 7.

Examples of anthraquinone dyes include C.I. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disper thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60 etc. are mentioned.
Other examples of the phthalocyanine dye include C.I. I. Pad Blue 5 and the like are quinone imine dyes such as C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like are quinoline dyes such as C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like are nitro dyes such as C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like.

Among these, it is preferable to use a pigment for the colorant (a) mainly in that light resistance and / or weather resistance and fastness of the coating film finally obtained are excellent. Further, in terms of color tone adjustment, pigments and dyes may be used in combination as necessary.
In the colored resin composition of the present invention, the ratio of the color material (a) to the total solid content is preferably 40% by weight or more, more preferably 45% by weight or more, particularly preferably 50% by weight or more, and usually 90%. % By weight or less, preferably 80% by weight or less, more preferably 60% by weight or less.

  (A) If the content ratio of the color material is too small, the target color density may not be obtained with a predetermined film thickness. Conversely, if the content ratio of (a) the coloring material is too large, the dispersion stability of the pigment may be deteriorated, and problems such as re-aggregation and thickening may occur. There is a possibility.

[(B) Binder resin]
(B) The binder resin can be used without particular limitation, such as an existing thermosetting resin or photopolymerizable resin. For example, JP-A-7-207211, JP-A-8-259876, JP-A-10 -300922, JP-A-11-140144, JP-A-11-174224, JP-A-2000-56118, JP-A-2003-233179, JP-A-2007-270147, etc. Molecular compounds can be used.

  (B) The content ratio of the binder resin is usually 1% by weight or more, preferably 10% by weight or more, and usually 80% by weight or less, preferably 60% by weight or less in the total solid content of the colored resin composition. is there. When the content of the binder resin is less than this range, the film becomes brittle and the adhesion to the substrate may be lowered. On the other hand, if it exceeds this range, the film hardness may be insufficient or the coloring power may be insufficient.

[(C) Solvent]
(C) The solvent has a function of adjusting the viscosity by dissolving or dispersing each component.
The solvent (c) may be any solvent that can dissolve or disperse each component constituting the colored resin composition.
Specifically, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether , Propylene glycol mono-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxy Butanol, triethylene glycol monomethyl ether Triethylene glycol monoethyl ether, glycol monoalkyl ethers such as tripropylene glycol methyl ether;
Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether;
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl Acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol Roh ether acetate, triethylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate, glycol alkyl ether acetates such as ethylene glycol diacetate;
Ethers such as amyl ether, propyl ether, diethyl ether, dipropyl ether, diisopropyl ether, butyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether;
Like acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxymethyl pentanone Ketones;
Mono- or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, benzyl alcohol, ethylene glycol, propylene glycol, butanediol, triethylene glycol, methoxymethylpentanol, diethylene glycol, dipropylene glycol, glycerin;
aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;
Cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;
Aromatic hydrocarbons such as benzene, toluene, xylene, cumene;
Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-methoxypropionic acid Linear or cyclic esters such as propyl, butyl 3-methoxypropionate, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;
Halogenated hydrocarbons such as butyl chloride and amyl chloride;
Ether ketones such as methoxymethylpentanone;
Examples thereof include nitriles such as acetonitrile and benzonitrile.

  Commercially available solvents corresponding to the above include mineral spirit, Barsol # 2, Apco # 18 Solvent, Apco thinner, Soal Solvent No. 1 and no. 2, Solvesso # 150, Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (all trade names) and the like.

These solvents may be used alone or in combination of two or more.
The boiling point of the solvent is usually 130 ° C. or higher and 300 ° C. or lower (under a pressure of 101.25 [hPa]. The same applies to the boiling points hereinafter), and preferably 150 ° C. or higher and 280 ° C. or lower. If the boiling point is too low, the uniformity of the resulting coating film will be poor. Also, if the boiling point is too high, the effect of inhibiting drying of the curable resin composition is high as described later, but there are many residual solvents in the coating film even after heat firing, which may cause quality problems. In some cases, the drying time in vacuum drying or the like becomes long, resulting in problems such as an increase in tact time.

The solvent vapor pressure is usually 10 mmHg or less, more preferably 5 mmHg or less, and still more preferably 1 mmHg or less, from the viewpoint of the uniformity of the resulting coating film.
In addition, in the production of color filters by the ink jet method, the ink emitted from the nozzle is very fine, from several to several tens of pL, so the solvent evaporates and concentrates before landing on the periphery of the nozzle opening or in the pixel bank.・ Tends to dry. In order to avoid this, it is preferable that the solvent has a high boiling point. Specifically, it is preferable that the solvent (c) includes a solvent having a boiling point of 180 ° C. or higher. More preferably, it contains a solvent having a boiling point of 200 ° C. or higher, particularly preferably a boiling point of 220 ° C. or higher. Moreover, it is preferable that the high boiling point solvent whose boiling point is 180 degreeC or more is 50 weight% or more in (c) solvent. When the high boiling point solvent is less than 50% by weight, the effect of preventing evaporation of the solvent from the ink droplets may not be sufficiently exhibited.

Preferred examples of the high boiling point solvent include diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, and 1,6-hexanol diester. Examples include acetate and triacetin.
It is also effective to partially contain a solvent having a boiling point lower than 180 ° C. in order to adjust the viscosity of the ink and the solubility of the solid content. As such a solvent, a solvent having low viscosity, high solubility, and low surface tension is preferable, and ethers, esters, ketones, and the like are preferable. Of these, cyclohexanone, dipropylene glycol dimethyl ether, cyclohexanol acetate, and the like are particularly preferable.

On the other hand, when the solvent contains alcohols, there may be a problem that ejection stability in the ink jet method is deteriorated. Therefore, the alcohol is preferably 20% by weight or less in the total solvent, more preferably 10% by weight or less, and particularly preferably 5% by weight or less.
The proportion of the solvent (c) in the entire colored resin composition of the present invention is not particularly limited, but is usually 50% by weight or more, preferably 60% by weight or more, and usually 99% by weight or less, preferably 95% by weight. % Or less. (C) If there is too much solvent, the solid content concentration becomes too low and it becomes unsuitable for forming a coating film, or the viscosity of the ink becomes too high, which hinders the stability of the composition. Problems such as playing may occur, and when applied to the ink jet method, the ejection stability may be reduced.

[(D) Surfactant]
The (d) surfactant in the colored resin composition of the present invention preferably contains a compound represented by the following general formula (0).

(In the above formula, substituent A represents a fluorinated alkyl group having 1 to 5 carbon atoms, and n represents an integer of 2 to 100.)
In the compound represented by the general formula (0), the substituent A represents a fluorinated alkyl group having 1 to 5 carbon atoms, preferably 1 to 4 carbon atoms. When the number of carbon atoms is 6 or more, the substituent portion becomes too bulky, and the orientation to the interface may be impaired.

Of these, a perfluoroalkyl group in which all of the hydrogen atoms are substituted with fluorine atoms is preferred. Further, the number of fluorine-substituted carbon atoms is preferably 1 to 3, and more preferably 1 or 2. When four or more carbon atoms are fluorine-substituted, they may show harmful effects accumulated in the human body.
Specific examples of such a substituent A include —CF ₃ , —CF ₂ CF ₃ , —CF ₂ C ₂ F _5, etc. Among them, —CF ₃ or —CF ₂ CF ₃ is particularly preferable.

N in the general formula (0) represents an integer of 2 to 100, preferably an integer of 5 to 30. If n exceeds 100, the molecular weight becomes too large, and the solubility may be impaired. On the other hand, when n is less than 2, the molecular weight becomes too small and the stability in the solution may be impaired.
Of the compounds represented by the general formula (0), more preferable compounds are, for example, the following compounds.

The compound represented by the general formula (0) is commercially available, and for example, PF-636, PF-656, PF-6320, PF-6520 (all trade names) manufactured by OMNOVA may be used. it can.
In addition, from the viewpoint of spreading in the pixel bank, the colored resin composition preferably has a small contact angle with a transparent substrate of a color filter described later. For example, in the case of the colored resin composition of the present invention, glass ( It is preferable that the contact angle with respect to the (clean glass) surface is less than 5 degrees. In terms of easily achieving such a contact angle, for example, (ii), (iii) and (iv) are particularly preferable among the above four compounds.

The compound represented by general formula (0) may be used individually by 1 type, or may use 2 or more types together.
The content of the compound represented by the general formula (0) in the colored resin composition of the present invention is generally 0.005 to 5% by weight, preferably 0.02 to 1% by weight, more preferably in the total solid content. 0.05 to 0.5% by weight. If the content of the compound is too large, it may be precipitated or the surface tension may be excessively lowered. If the content is too small, the pixel flatness may be poor.

(D) The surfactant may contain a surfactant other than the compound represented by the general formula (0) as long as the effects of the present invention are not impaired. In this case, it is preferable to use it in the form of replacing a part of the content of the compound represented by the general formula (0).
As the surfactant that can be used in combination, for example, various surfactants such as anionic, cationic, nonionic, and amphoteric surfactants can be used. A nonionic surfactant is preferably used because it is less likely to adversely affect various properties such as solubility.

[Monomer]
The colored resin composition used in the present invention preferably contains a monomer. The monomer is not particularly limited as long as it is a polymerizable low-molecular compound, but it can be an addition-polymerizable compound having at least one ethylenic double bond (hereinafter sometimes referred to as “ethylenic compound”). Is preferred.
Examples of the ethylenic compound include unsaturated carboxylic acid such as (meth) acrylic acid, ester of monohydroxy compound and unsaturated carboxylic acid, ester of aliphatic polyhydroxy compound and unsaturated carboxylic acid, aromatic polyhydroxy Esters obtained by esterification reaction of an ester of a compound with an unsaturated carboxylic acid, an unsaturated carboxylic acid and a polyvalent carboxylic acid and a polyvalent hydroxy compound such as the above-mentioned aliphatic polyhydroxy compound or aromatic polyhydroxy compound, poly Examples thereof include an ethylenic compound having a urethane skeleton obtained by reacting an isocyanate compound and a (meth) acryloyl group-containing hydroxy compound.

  Among them, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferable. Specifically, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, Trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerol (meth) acrylate, triglycerol di Meth) acrylate, isopropyloxy of diglycerol di (meth) acrylate, etc. (meth) acrylic acid ester.

  A polyfunctional monomer obtained by reacting an unreacted hydroxyl group with a non-aromatic carboxylic anhydride in an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is also preferable. Particularly preferably, in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. These monomers may be used alone, but since it is difficult to obtain a single compound in production, two or more kinds may be used in combination. Moreover, you may use together the polyfunctional monomer which does not have an acid group as a monomer, and the polyfunctional monomer which has an acid group as needed. Commercially available products include, for example, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentaacrylate succinic acid ester, which are commercially available as “TO1382” manufactured by Toagosei Co., Ltd.

  When the colored resin composition is used for the production of an ink jet color filter, the monomer is preferably a linear monomer or a monomer having a relatively small molecular weight. For example, ethoxylated trimethylolpropane tri (meth) acrylate, triglycerol diglycerol is preferable. (Meth) acrylate, isopropyloxylated diglycerol di (meth) acrylate and the like are preferable. Such compounds are commercially available as “70PA”, “80MFA” (both trade names, manufactured by Kyoeisha Chemical Co., Ltd.), “A-TMPT-3EO” (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.), etc. Has been.

In the colored resin composition of the present invention, the content ratio of these monomers is usually 0% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more in the total solid content, and usually 80% or more. % By weight or less, preferably 70% by weight or less, more preferably 50% by weight or less, and particularly preferably 40% by weight or less.
[Photopolymerization initiation system and thermal polymerization initiation system]
The colored resin composition used in the present invention preferably contains a photopolymerization initiation system or a thermal polymerization initiation system in order to be cured by exposure or heating during pixel formation.

The photopolymerization initiating system is usually used as a mixture of (h1) a photopolymerization initiator and an additive such as (h3) a sensitizing dye and (h2) a polymerization accelerator which are added as necessary. It is a component having a function of generating a polymerization active radical by absorbing or photosensitizing to cause a decomposition reaction or a hydrogen abstraction reaction.
Examples of the photopolymerization initiator constituting the photopolymerization initiation system (h1) include titanocene derivatives described in JP-A Nos. 59-152396 and 61-151197, etc .; JP-A-10-300922 Hexaarylbiimidazole derivatives described in JP-A-11-174224, JP-A-2000-56118, etc .; halomethylated oxadiazole derivatives described in JP-A-10-39503, etc., halomethyl-s -Radical activators such as triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives And oxime ester derivatives described in JP-A No. 2000-80068 and the like.

  Examples of the (h2) polymerization accelerator used as necessary include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester; 2-mercaptobenzothiazole, 2-mercapto Mercapto compounds having a heterocyclic ring such as benzoxazole and 2-mercaptobenzimidazole; or mercapto compounds such as aliphatic polyfunctional mercapto compounds.

Each of these photopolymerization initiators and polymerization accelerators may be used alone or in combination of two or more.
In the colored resin composition of the present invention, the content ratio of these (h) photopolymerization initiation systems is usually 0.1% by weight or more, preferably 0.5% by weight or more, and usually 40% by weight in the total solid content. % Or less, preferably 30% by weight or less. If this content is extremely low, the sensitivity to exposure light may be reduced. On the other hand, if it is extremely high, the solubility of the unexposed portion in the developer may be reduced, leading to poor development.

  Further, (h3) sensitizing dye is used for the purpose of increasing the sensitivity as required. (H3) As the sensitizing dye, an appropriate dye is used according to the wavelength of the image exposure light source. For example, xanthene dyes described in JP-A-4-221958 and JP-A-4-219756; Coumarin dyes having a heterocyclic ring described in Kaihei 3-239703, JP-A-5-289335, etc .; 3-ketocoumarin dyes described in JP-A-3-239703, JP-A-5-289335, etc. Pyrromethene dyes described in JP-A-6-19240, etc .; JP-A 47-2528, JP-A 54-155292, JP-B 45-37377, JP-A 48-84183, JP-A 52-112681, JP 58-15503, JP 60-88005, JP 59-56403, JP 2-69, JP 57-168088, JP No. -107761, JP-A-5-210240, it may be mentioned dyes having a dialkyl aminobenzene skeleton described in JP-A 4-288818 Patent JP-like. A sensitizing dye may also be used individually by 1 type, and may use 2 or more types together.

  In the colored resin composition of the present invention, the content ratio of these (h3) sensitizing dyes is usually 0% by weight or more, preferably 0.2% by weight or more, more preferably 0.5% by weight in the total solid content. In addition, the range is usually 20% by weight or less, preferably 15% by weight or less, and more preferably 10% by weight or less.

[Thermal polymerization initiation system]
Specific examples of the thermal polymerization initiation system (thermal polymerization initiator) used in the present invention include azo compounds, organic peroxides, and hydrogen peroxide. Of these, azo compounds are preferably used.
In addition, some of the compounds listed as (h1) photopolymerization initiators in the section of [Photopolymerization initiator] can be used as thermal polymerization initiators. For example, 2-methyl-2-morpholino-1- An α-aminoalkylphenone derivative such as (4-methylthiophenyl) propan-1-one is also suitable as a thermal polymerization initiator.
The thermal polymerization initiator is preferably used in the range of usually 0.5 to 30% by weight, preferably 1 to 20% by weight in the total solid content of the colored resin composition of the present invention.

[Other ingredients]
In addition to the above-described components, the colored resin composition used in the present invention includes a dispersant, a dispersion aid, a plasticizer, a dye, a thermal polymerization inhibitor, a storage stabilizer, a surface protective agent, an adhesion improver, and development improvement. An agent or the like may be contained.

[Dispersant]
As the dispersant, an existing polymer dispersant or the like can be used. Among them, a polymer dispersant having a basic functional group is preferable. For example, a nitrogen atom-containing graft copolymer such as a polyethyleneimine-based dispersant, a tertiary amino group, a quaternary ammonium base, a nitrogen-containing heterocycle, etc. in the side chain. Examples thereof include a nitrogen atom-containing acrylic block copolymer and a urethane polymer dispersant having a functional group.

  Such dispersants are, for example, Disperbyk-160, 161, 162, 163, 164, 165, 166, 182, 2000, 2001, BYK-LPN-6919 (above, Big Chemie Japan Manufactured by the same company), Solsperse S13240, S13940, S17000, S20000, S20000, S24000GR, S26000, S28000 (above, manufactured by Abyssia), EFKA46, 47, 48, 4055, It is commercially available as EFKA Polymer 400, 401, 402, 450, 451, 453 (manufactured by Fuka Chemicals Co., Ltd.).

The amine value (effective solid content conversion) of the polymer dispersant having a basic functional group is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, further preferably 50 mgKOH / g or more, particularly preferably 80 mgKOH / g. The above is usually 300 mgKOH / g or less.
The amine value of the dispersant is represented by the weight of KOH equivalent to the amount of base per gram of solid content excluding the solvent in the dispersant sample, and is measured by the following method. Disperse 0.5-1.5 g of the dispersant sample in a 100 mL beaker and dissolve with 50 mL of acetic acid. This solution is neutralized with a 0.1 mol / L HCLO ₄ acetic acid solution using an automatic titrator equipped with a pH electrode. The inflection point of the titration pH curve is taken as the titration end point, and the amine value is determined by the following formula.

Amine value [mgKOH / g] = (561 × V) / (W × S)
(W represents the amount of the dispersant sample weighed [g], V represents the titration amount at the end of titration [mL], and S represents the solid content concentration [wt%] of the dispersant sample.)
The dispersant is usually used when the above-mentioned (a) colorant contains a pigment, and is preferably used in an amount of about 5 to 200% by weight, more preferably about 10 to 100% by weight based on the total amount of the pigment. preferable.

[Dispersion aid]
The dispersion aid is used for improving the dispersibility of the pigment in the colorant (a), improving the dispersion stability, and the like. For example, azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, Examples thereof include derivatives of isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, dioxazine pigments and the like.
Examples of the substituent of these pigment derivatives include a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a phthalimidomethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, and an amide group. These substituents may be directly bonded to the pigment skeleton, or may be bonded via an alkyl group, an aryl group, a heterocyclic group or the like. Of the substituents, a sulfonamide group, a quaternary salt thereof, and a sulfonic acid group are preferable, and a sulfonic acid group is more preferable.

A plurality of these substituents may be substituted on one pigment skeleton, or a mixture of compounds having different numbers of substitutions.
Specific examples of pigment derivatives include sulfonic acid derivatives of azo pigments, sulfonic acid derivatives of phthalocyanine pigments, sulfonic acid derivatives of quinophthalone pigments, sulfonic acid derivatives of anthraquinone pigments, sulfonic acid derivatives of quinacridone pigments, diketo Examples include sulfonic acid derivatives of pyrrolopyrrole pigments and sulfonic acid derivatives of dioxazine pigments.
The content ratio of these dispersion aids is usually 0.1% by weight or more, and usually 30% by weight or less, preferably 20% by weight or less, based on the total amount of the pigment contained in the color material (a). More preferably, it is 10 weight% or less, Most preferably, it is 5 weight% or less.

[Plasticizer]
Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin and the like. The content of these plasticizers is preferably in the range of 10% by weight or less based on the total solid content in the colored resin composition.

[Thermal polymerization inhibitor]
Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-t-butyl-p-cresol, β-naphthol and the like. The content of these thermal polymerization inhibitors is preferably in the range of 3% by weight or less based on the total solid content in the colored resin composition.

[Preparation Method of Colored Resin Composition]
Next, a method for preparing the colored resin composition of the present invention will be described.
First, (a) a coloring material, (c) a solvent, and (a) when the coloring material contains a pigment, a predetermined amount of a dispersant, which is an optional component, is weighed, and in the dispersion treatment step, (a) the pigment in the coloring material Is dispersed to obtain a pigment dispersion. In this dispersion treatment step, a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like can be used. By carrying out this dispersion treatment, the pigment is made fine, so that the coating characteristics of the colored resin composition are improved and the transmittance of the product color filter substrate and the like is improved.

  When dispersing the pigment, it is preferable to use (b) a part of the binder resin and a dispersion aid as appropriate. Moreover, when performing a dispersion process using a sand grinder, it is preferable to use glass beads or zirconia beads having a diameter of 0.1 to several mm. The temperature during the dispersion treatment is usually set to 0 ° C. or higher, preferably room temperature or higher, and usually 100 ° C. or lower, preferably 80 ° C. or lower. The dispersion time needs to be appropriately adjusted because the appropriate time varies depending on the composition of the pigment dispersion, the size of the sand grinder apparatus, and the like.

  In addition to the pigment dispersion obtained by the above dispersion treatment, (d) a surfactant and (b) a binder resin, (c) a solvent, and optionally a monomer that is an optional component, photopolymerization start. A colored resin composition is obtained by mixing the system and / or the thermal polymerization initiation system and other components to obtain a uniform dispersion solution. In addition, since fine dust may be mixed in each of the dispersion treatment step and the mixing step, the obtained pigment dispersion is preferably filtered with a filter or the like.

[Application of colored resin composition]
The colored resin composition of the present invention is usually in a state where all the constituent components are dissolved or dispersed in a solvent. This is supplied onto the substrate to form the color filter and the constituent members of the liquid crystal display device.
Hereinafter, a method for producing a color filter using the colored resin composition of the present invention, a liquid crystal display device (panel) and an organic EL display using the same will be described.

[Color filter]
The manufacturing method of the color filter by the inkjet method using the colored resin composition of this invention is demonstrated.
In the inkjet method, a partition pattern (black matrix) is first provided on a substrate, and pixel forming ink is directly applied in the pattern to produce a color filter. Since ink droplets can be drawn at a desired position, high productivity and cost reduction of the color filter can be achieved.
The black matrix (BM) of the color filter by the ink jet method not only functions as a light shielding function that is conventionally required, but also functions as a partition wall for preventing RGB inks that are driven into the pixels from being mixed, so that the conventional photo Compared to the case of a color filter by lithography, the film thickness is thick (usually a film thickness of 1.5 μm or more, preferably about 1.8 to 2.5 μm, more preferably about 2.0 to 2.3 μm. There is a feature. Further, in order to prevent color mixing of RGB ink, liquid repellent treatment is often applied to the upper surface of the black matrix.

Therefore, it was formed using a photosensitive material including a black color material from a conventionally used chromium compound such as chromium, chromium oxide and chromium nitride, and a black matrix made of a light-shielding metal material such as nickel and tungsten alloy. A resin black matrix (BM) is preferred.
In the color filter of the present invention, the resin black matrix (BM) may be formed by a general photolithography method. The obtained resin BM is made hydrophilic on the surface of the transparent substrate and lyophobic on the BM pattern by chemical treatment or physical treatment, respectively.

Next, in the substantially rectangular recessed area surrounded by the resin BM pattern, the colored resin composition of the present invention is used to draw with an ink jet apparatus, and the composition is completely removed by drying, photocuring and / or thermosetting. A color filter is obtained by curing and forming pixels.
The color filter of the present invention is a color filter in which at least a plurality of pixels and a black matrix positioned between adjacent pixels are provided on a support substrate, and the maximum film thickness of the pixel portion is a black matrix portion. The film thickness is 70% or less, more preferably 65% or less, and still more preferably 60% or less. Further, the minimum film thickness of the pixel portion is preferably 30% or more of the film thickness of the black matrix portion, and more preferably 40% or more.

As described above, the minimum film thickness of the pixel portion formed by the ordinary ink jet method is smaller than the film thickness of the BM portion. Therefore, in the color filter of the present invention, the maximum film thickness of the pixel portion is set to the film thickness of the BM portion. By making it smaller than the thickness, the film thickness difference in the pixel is reduced, and the flatness of the pixel portion can be obtained.
In many cases, the pixel is provided with three colors of R (red), G (green), and B (blue), but the present invention is not limited to these.

  The material of the transparent substrate used in the color filter of the present invention is not particularly limited. For example, polyester such as polyethylene terephthalate, polypropylene, polyolefin such as polyethylene, thermoplastic such as polycarbonate, polymethyl methacrylate, polysulfone, etc. Examples thereof include a thermosetting plastic sheet such as a plastic sheet, an epoxy resin, a polyester resin, and a poly (meth) acrylic resin, or various glass plates. In particular, a glass plate and a heat-resistant plastic plate are preferably used from the viewpoint of heat resistance.

  For drying the coating film of the colored resin composition, heat drying such as a hot plate, IR oven, convection oven or the like can be used. Preferred drying conditions are 40 to 150 ° C., and drying time is in the range of 10 seconds to 60 minutes. is there. Also, reduced pressure (vacuum) drying can be used, and preferable drying conditions are 10 to 200 Pa, and drying time is in the range of 10 seconds to 60 minutes. Furthermore, both can be used together and can also be performed sequentially or simultaneously.

  When the colored resin composition of the present invention is cured by photocuring, the light source used for exposure is, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, etc. And a laser light source such as an argon ion laser, a YAG laser, an excimer laser, and a nitrogen laser. In the case where only the wavelength of specific irradiation light is used, an optical filter can also be used.

  In addition, when the colored resin composition of the present invention is cured by heat curing, it may be heated usually at about 200 ° C. for 0.5 to 1 hour using an oven or a hot plate.

[Liquid Crystal Display]
The liquid crystal display device according to the present invention has, for example, a structure in which the above-described color filter (hereinafter sometimes referred to as a “color filter substrate”) and a driving substrate made of a thin film transistor (TFT) are opposed to each other through a liquid crystal layer. Can be configured. More specifically, a color filter substrate coated with an alignment film material and subjected to an alignment process is bonded to a TFT drive substrate through a peripheral sealing material, and a liquid crystal material is injected into the gap, thereby liquid crystal. It can be a display device.

The liquid crystal display device according to the present invention is generally formed by forming an alignment film on the color filter according to the present invention, spraying spacers on the alignment film, and then bonding to a counter substrate to form a liquid crystal cell. The liquid crystal cell is manufactured by injecting liquid crystal and connecting to the counter electrode.
The alignment film is preferably a resin film such as polyimide. For the formation of the alignment film, a gravure printing method and / or a flexographic printing method is usually employed, and the thickness of the alignment film is several tens of nm. After the alignment film is cured by thermal baking, it is surface-treated by irradiation with ultraviolet rays or a rubbing cloth to be processed into a surface state in which the tilt of the liquid crystal can be adjusted.

As the spacer, a spacer having a size corresponding to a gap (gap) with the counter substrate is used, and a spacer of 2 to 8 μm is usually preferable. A photo spacer (PS) of a transparent resin film can be formed on the color filter substrate by photolithography, and this can be used instead of the spacer.
As the counter substrate, an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly preferable. Further, the bonding gap with the counter substrate varies depending on the use of the liquid crystal panel, but is usually selected in the range of 2 μm or more and 8 μm or less. After being bonded to the counter substrate, portions other than the liquid crystal injection port are sealed with a sealing material such as an epoxy resin. The sealing material is cured by UV irradiation and / or heating, and the periphery of the liquid crystal cell is sealed.

The liquid crystal cell whose periphery is sealed is cut into panel units, then decompressed in a vacuum chamber, the liquid crystal injection port is immersed in liquid crystal, and then the liquid crystal is injected into the liquid crystal cell by leaking in the chamber. . The degree of vacuum in the liquid crystal cell is usually in the range of 1 × 10 ⁻² Pa or more, preferably 1 × 10 ⁻³ Pa or more, and usually 1 × 10 ⁻⁷ Pa or less, preferably 1 × 10 ⁻⁶ Pa or less. . The liquid crystal cell is preferably heated at reduced pressure, and the heating temperature is usually 30 ° C. or higher, preferably 50 ° C. or higher, and usually 100 ° C. or lower, preferably 90 ° C. or lower. The warming holding at the time of depressurization is usually in the range of 10 minutes or more and 60 minutes or less, and then immersed in the liquid crystal.

  In the liquid crystal cell into which liquid crystal is injected, the liquid crystal injection device is completed by sealing the liquid crystal injection port by curing the UV curable resin. The type of liquid crystal is not particularly limited, and is a conventionally known liquid crystal such as an aromatic, aliphatic, or polycyclic compound, and may be any of lyotropic liquid crystal, thermotropic liquid crystal, and the like. As the thermotropic liquid crystal, nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal and the like are known, but any of them may be used.

[Organic EL display]
When an organic EL display is produced using the color filter of the present invention, for example, as shown in FIG. 11, an organic light-emitting body 500 is laminated on the color filter with an organic protective layer 30 and an inorganic oxide film 40 interposed therebetween. A colored organic EL element can be produced. As a method for laminating the organic light emitter 500, a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 are sequentially formed on the upper surface of the color filter. For example, a method of adhering the organic light-emitting body 500 formed on another substrate onto the inorganic oxide film 40 can be used. The organic EL element 100 manufactured as described above can be applied to both a passive drive type organic EL display and an active drive type organic EL display.

EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to a following example, unless the summary is exceeded.
(Synthesis Example 1)
“XD1000” manufactured by Nippon Kayaku Co., Ltd. (polyglycidyl ether of dicyclopentadiene / phenol polymer, weight average molecular weight 700, epoxy equivalent 252) 300 parts, 87 parts of acrylic acid, 0.2 parts of p-methoxyphenol, tri 5 parts of phenylphosphine and 255 parts of propylene glycol monomethyl ether acetate were charged into a reaction vessel and stirred at 100 ° C. until the acid value became 3.30 mgKOH / g. It took 9 hours for the acid value to reach the target (acid value 2.5). Subsequently, 145 parts of tetrahydrophthalic anhydride was further added and reacted at 120 ° C. for 4 hours to obtain a binder resin solution 1 having an acid value of 100 and a weight average molecular weight of 2600 in terms of polystyrene measured by GPC.

(Synthesis Example 2)
The following compound was obtained according to the synthesis method described in JP-A-2006-36750.

(Synthesis Example 3)
Prepare a separable flask with a cooling tube as a reaction tank, charge 400 parts by weight of propylene glycol monomethyl ether acetate, purge with nitrogen, and heat in an oil bath while stirring to raise the temperature of the reaction tank to 90 ° C. did.
Meanwhile, 10 parts by weight of dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, 15 parts by weight of methacrylic acid, 20 parts by weight of methyl methacrylate, 55 parts by weight of benzyl methacrylate, t- 2.6 parts by weight of butyl peroxy-2-ethylhexanoate and 40 parts by weight of propylene glycol monomethyl ether acetate were charged, and 5.2 parts by weight of n-dodecyl mercaptan and 27 parts by weight of propylene glycol monomethyl ether acetate were added to the chain transfer agent tank. After the temperature of the reaction vessel was stabilized at 90 ° C., dropping was started from the monomer tank and the chain transfer agent tank to initiate polymerization.

  While maintaining the temperature at 90 ° C., dropping was carried out over 135 minutes each, and 60 minutes after the dropping was finished, the temperature was raised and the reaction vessel was brought to 110 ° C. After maintaining at 110 ° C. for 3 hours, the mixture was cooled to room temperature to obtain a 30 wt% polymer solution 3 having a weight average molecular weight of 9200 and an acid value of 107 mg KOH / g.

[Production of black matrix substrate]
(Preparation of titanium black dispersion a)
100 parts by weight of titanium black ("13M-C" manufactured by Mitsubishi Materials), 20 parts by weight of the polymer dispersant "Disperbyk-161" manufactured by Big Chemie, and propylene so that the solid concentration is 36% by weight Glycol monomethyl ether acetate (PGMEA) was added. This was sufficiently stirred with a stirrer and premixed, and then dispersed with a disperser. As beads, zirconia beads having a diameter of 0.5 mm were used, and the same weight as the dispersion was added. After the dispersion was completed, the beads and the dispersion were separated by a filter to prepare a titanium black dispersion a.

(Preparation of titanium black dispersion b)
PGMEA is added so that 100 parts by weight of titanium black (“Tilack” manufactured by Ako Kasei Co., Ltd.), 20% by weight of the polymer dispersant “Disperbyk-161” manufactured by Big Chemie, and a solid content concentration of 34% by weight are added. It was. This was sufficiently stirred with a stirrer and premixed, and then dispersed with a disperser. As beads, zirconia beads having a diameter of 0.5 mm were used, and the same weight as the dispersion was added. After the dispersion was completed, the beads and the dispersion were separated by a filter to prepare a titanium black dispersion b.

(Preparation of black resist)
Using the titanium black dispersions a and b obtained above, add each component to the following blending ratio as solid content, stir with a stirrer to disperse or dissolve each component, and adjust the black resist did.

<Combination ratio>
Titanium black dispersion a: 45 g as solid content
Titanium black dispersion b: 15 g as solid content
Binder resin solution 3 obtained in Synthesis Example 1: 30.3 g as a solid content
Monomer (U-6LPA): 3.8 g as a solid content
Monomer (dipentaerythritol hexaacrylate): 1.3 g as a solid content
Compound obtained in Synthesis Example 2: 4.0 g
Solvent (PGMEA): 334 g
Surfactant (F-475): An amount in which the concentration in the resist solution is 200 ppm. * However, “U-6LPA”: trade name. New Nakamura Chemical Co., Ltd. urethane acrylate compound.
“F-475”: trade name. Fluorosurfactant manufactured by Sumitomo 3M.

(Formation of black matrix)
The black resist is applied to a 10 cm square 0.7 mm non-alkali glass substrate ("AN635" manufactured by Asahi Glass Co., Ltd.) with a spin coater, and the coating film is exposed with a high-pressure mercury lamp through a photomask. Then, spray development was performed with an aqueous solution of sodium carbonate having a concentration of 0.8% by weight, and post baking was performed in an oven to prepare a black matrix pattern having a rectangular opening with a film thickness of 2 μm and 700 μm × 220 μm.

The black matrix pattern was subjected to plasma treatment in the order of the following conditions (1) and (2) using “PC-300” manufactured by Samco Co., Ltd., and liquid-repellent treatment was performed.
<Plasma treatment conditions>
(1) Gas: O ₂ , pressure: 25 Pa, RF power: 100 W, processing time: 2 minutes
(2) Gas: CF ₄ , pressure: 80 Pa, RF power: 300 W, processing time: 10 minutes

(Preparation of pigment dispersion A)
17 g of Pigment Red 254 as a pigment, 5.7 g of “BYK-LPN6919” manufactured by BYK-Chemie as a dispersant, 6.8 g of the resin obtained in Synthesis Example 3 as a dispersion resin (in terms of effective solid content), and a solvent After 118 g of diethylene glycol mono-n-butyl ether acetate was mixed and stirred and homogenized, 300 g of zirconia beads having a particle diameter of 0.5 mm was added, and the mixture was shaken with a paint conditioner for 5 hours for dispersion treatment to prepare pigment dispersion A. .

(Pigment dispersion B)
10.2 g of Pigment Red 177 as a pigment, 6.8 g of Pigment Yellow 150, 5.7 g of “BYK-LPN6919” manufactured by Big Chemie, as a dispersant, and 6.8 g of the resin obtained in Synthesis Example 3 as a dispersion resin. After mixing 118 g of diethylene glycol mono-n-butyl ether acetate as a solvent (in terms of effective solid content) and stirring and homogenizing, 300 g of zirconia beads having a particle diameter of 0.5 mm are added and dispersed by shaking for 5 hours with a paint conditioner. The pigment dispersion B was prepared by the treatment.
* BYK-LPN6919 manufactured by Big Chemie:
A methacrylic AB block copolymer having a tertiary amino group. The weight average molecular weight Mw is 9000, the amine value is 121 mgKOH / g, the acid value is almost 0 mgKOH / g, and the “repeating unit having an amino group in the side chain” in the A block has the structure represented by the following formula (i): Yes, the proportion of the repeating unit represented by the following formula (ii) in the B block is 11 mol%.

The amine value was measured by the following method.
<Measurement of amine value>
In a 100 mL beaker, 0.5 to 1.5 g of a dispersant sample (note: the dispersant itself (or a solution is acceptable)) is precisely weighed and dissolved in 50 mL of acetic acid. This solution is neutralized with a 0.1 mol / L HCLO ₄ acetic acid solution using an automatic titrator equipped with a pH electrode. Using the inflection point of the titration pH curve as the end point of titration, the amine value is determined by the following formula.

Amine value [mgKOH / g] = (561 × V) / (W × S)
(W: Dispersant sample weighed [g], V: Titration amount at the end of titration [mL], S: Dispersant sample solid content concentration [wt%].)

[Example 1]
While stirring Pigment Dispersion Liquid A: 5.3 g and Pigment Dispersion Liquid B: 9.8 g, 0.5 g of epoxy resin “EHPE3150” manufactured by Daicel Chemical Co., Ltd. was used as a solid content, and “Irga” manufactured by Ciba Geigy Co., Ltd. was used as a polymerization initiator. After adding 0.2 g of Cure 907 ”(2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one) and 4.2 g of diethylene glycol mono-n-butyl ether acetate and mixing, 5 μm And a uniform colored resin composition 1 was obtained. In addition, the ratio of the coloring material in the solid content of the colored resin composition 1 was 47% by weight.

In the substrate provided with the black matrix and subjected to the liquid repellent treatment as described above, the amount of the colored resin composition 1 corresponding to 1400 pl by the inkjet method is applied to the center of each pixel bank formed by the black matrix pattern. Application was performed. The application range was 28.8 mm square.
Thereafter, drying under reduced pressure was performed at 50 Pa for 10 minutes, and further a thermosetting treatment was performed at 240 ° C. for 40 minutes to obtain a pixel. The cross-sectional shape of the obtained pixel in the cross section and vertical section shown in FIG. 4 was measured with a laser microscope. The measurement results are shown in FIGS.

The maximum film thickness of the pixel was 1.2 μm, and the minimum film thickness was 0.9 μm.
Further, as an evaluation index of flatness, when the average value of the standard deviation of the pixel film thickness in the cross section (from the black matrix wall surface to the center of the pixel and the length of 250 μm) and the vertical cross section was obtained, the average of the standard deviation was 0.09. The standard deviation value indicates that the smaller the value, the flatter the shape. If the value is 0.1 or less, it is considered that the flatness is practically sufficient. It can be seen that the pixels obtained in Example 1 have sufficiently good flatness.

[Example 2]
While stirring Pigment Dispersion A: 5.3 g and Pigment Dispersion B: 9.8 g, 0.5 g of epoxy resin “EHPE3150” manufactured by Daicel Chemical Co., Ltd. was used as a solid content, and Irgacure manufactured by Ciba Geigy Co., Ltd. as a polymerization initiator. 0.2 g of 907, 0.4 g of a compound represented by the following structural formula (surfactant “PF-6520” manufactured by OMNOVA) as a surfactant, and 3.8 g of diethylene glycol mono-n-butyl ether acetate Then, the mixture was filtered through a 5 μm membrane filter to obtain a uniform colored resin composition 2. In addition, the ratio of the coloring material in the solid content of the colored resin composition 2 was 47% by weight.

In the same manner as in Example 1, 1400 pl of the colored resin composition 2 was applied to the center of the pixel bank on the above-described substrate subjected to the liquid repellent treatment by providing the black matrix. In addition, the influence on inkjet discharge stability by surfactant addition was not recognized.
Thereafter, drying under reduced pressure was performed at 50 Pa for 10 minutes, and further a thermosetting treatment was performed at 240 ° C. for 40 minutes to obtain a pixel. The cross-sectional shape of the obtained pixel in the cross section and vertical section shown in FIG. 4 was measured with a laser microscope. The measurement results are shown in FIGS.

The obtained pixel had a maximum film thickness of 1.2 μm, a minimum film thickness of 1.0 μm, and an average standard deviation of 0.05. It can be seen that by adding the surfactant, better flatness was obtained as compared with Example 1.
[Comparative Example 1]
While stirring 4.3 g of pigment dispersion A and 7.9 g of pigment dispersion B, 1.0 g of epoxy resin “EHPE3150” manufactured by Daicel Chemical Co., Ltd. as a solid content and Irgacure manufactured by Ciba Geigy as a polymerization initiator 0.3 g of 907 and 6.4 g of diethylene glycol mono-n-butyl ether acetate were added and mixed, and then filtered through a 5 μm membrane filter to obtain uniform colored resin composition 3. In addition, the ratio of the coloring material in the solid content of the colored resin composition 3 was 38% by weight.

  In the same manner as in Example 1, an amount equivalent to 1800 pl of the colored resin composition 3 was applied to the center of the pixel bank on the above-described substrate subjected to the liquid repellent treatment by providing the black matrix. It was. Since the ratio of the color material in the solid content is lower in Comparative Example 1 than in Examples 1 and 2, in order to compare with the same optical characteristics, adjustment was made so that the amount of liquid was increased accordingly.

Thereafter, drying under reduced pressure was performed at 50 Pa for 10 minutes, and further a thermosetting treatment was performed at 240 ° C. for 40 minutes to obtain a pixel. The cross-sectional shape of the obtained pixel in the cross section and vertical section shown in FIG. 4 was measured with a laser microscope. The measurement results are shown in FIG. 9 and FIG.
The obtained pixel had a maximum film thickness of 1.8 μm, a minimum film thickness of 1.1 μm, and an average standard deviation of 0.14. It can be seen that the flatness was insufficient.

It is a figure explaining the drying process of a colored resin composition in the pixel formation process by the conventional inkjet method. It is a figure explaining the state of the colored resin composition struck in the pixel bank in the pixel formation process by the conventional inkjet method. It is a figure explaining the shape of the pixel formed by this invention. It is a figure explaining the film thickness measurement site | part (a cross section and a longitudinal cross section) of a pixel in an Example and a comparative example. It is a figure showing the cross-sectional shape in a cross section of the pixel obtained in Example 1. FIG. It is a figure showing the cross-sectional shape in the longitudinal cross-section of the pixel obtained in Example 1. FIG. It is a figure showing the cross-sectional shape in a cross section of the pixel obtained in Example 2. FIG. It is a figure showing the cross-sectional shape in the longitudinal cross-section of the pixel obtained in Example 2. FIG. It is a figure showing the cross-sectional shape in a cross section of the pixel obtained in the comparative example 1. It is a figure showing the cross-sectional shape in the longitudinal cross-section of the pixel obtained in the comparative example 1. It is an example of the cross-sectional schematic diagram of the organic EL element in the organic EL display provided with the color filter of this invention.

Explanation of symbols

10 Transparent support substrate
50 transparent anode
52 Hole transport layer
53 Light emitting layer
55 Cathode
100 Organic EL device
20 Color filter
30 Organic protective layer
40 Inorganic oxide film
500 Organic light emitter
51 Hole injection layer
54 Electron injection layer

Claims (12)

  A color filter comprising at least a plurality of pixels and a black matrix located between adjacent pixels on a support substrate, wherein the maximum film thickness of the pixel portion is 70% or less of the film thickness of the black matrix portion A color filter characterized by being.   2. The color filter according to claim 1, wherein the minimum film thickness of the pixel portion is 30% or more of the film thickness of the black matrix portion.   The pixel portion of the color filter according to claim 1 or 2 is formed using a colored resin composition comprising at least (a) a color material, (b) a binder resin, and (c) a solvent. Characteristic color filter.  4. The color filter according to claim 3, wherein (a) the color material in the colored resin composition is 40% by weight or more in terms of solid content.   5. The color filter according to claim 3, wherein the colored resin composition further contains (d) a surfactant. 6. The color filter according to claim 5, wherein (d) the surfactant contains a compound represented by the following general formula (0).

(In the above formula, substituent A represents a fluorinated alkyl group having 1 to 5 carbon atoms, and n represents an integer of 2 to 100.)   The color filter according to any one of claims 3 to 6, wherein the colored resin composition further contains a monomer.   The color filter according to any one of claims 3 to 7, wherein the colored resin composition further contains a photopolymerization initiation system and / or a thermal polymerization initiation system.   9. The color filter according to claim 1, wherein the thickness of the black matrix portion is 1.5 [mu] m or more.   10. The color filter according to claim 3, wherein the pixel portion is formed by an ink jet method using the colored resin composition. 11.   A liquid crystal display device manufactured using the color filter according to claim 1.   The organic electroluminescent display produced using the color filter as described in any one of Claims 1 thru | or 10.