JP2013104905A - Colored resin composition for die coating method, color filter, liquid crystal display device and organic el display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored resin composition capable of reducing the generation of aggregated foreign matters when a die coating method is used, and to provide a high-quality color filter, a liquid crystal display device and an organic EL display device.SOLUTION: There is provided a colored resin composition for a die coating method, which comprises (A) a pigment, (B) a solvent, (C) a binder resin and (D) a dispersant, wherein (A) the pigment contains 26 wt.% of or more and 40 wt.% or less of a red pigment in the total pigment solid content, (D) the dispersant contains a polymer and the polymer has a primary to tertiary amino group and/or a quaternary ammonium group in the side chain, the content ratio of a monomer having the primary to tertiary amino group and/or quaternary ammonium group is 20 wt.% or more in the monomer composition constituting the polymer, and the total solid content concentration of the colored resin composition is 20 wt.% or less, and (B) the solvent includes 5 wt.% or more and 14 wt.% or less of 1,3-butylene glycol diacetate in the total solvent.

Description

  The present invention resides in a colored resin composition for a die coating method, a color filter, a liquid crystal display device, and an organic EL display device.

Pixels, black matrixes, photo spacers, rib materials, overcoats, etc. used in the manufacture of display members such as liquid crystal display devices are generally applied to substrates with curable compositions for various applications. Various images are formed through the forming process.
Conventionally, spin coating has been used in the coating process, but in recent years, there has been a shift to the slit-and-spin method and the die coating method because of the need for larger substrates and reduced liquids.

However, in the slit-and-spin method and the die coating method, there is a serious problem that the aggregated foreign matter generated by drying at the tip of the dispensing nozzle becomes a peeled-off foreign matter on the coating film, thereby reducing the yield.
In order to solve this problem, for example, in Patent Document 1, a dry film formed with a colored image forming photosensitive solution is immersed in a solvent and dissolved within 5 minutes (hereinafter, this method is referred to as “re-dissolution” A property satisfying this is sometimes referred to as “re-solubility.”) A colored image forming photosensitive solution and its method are disclosed. However, in the actual manufacturing process, once the aggregated foreign matter is dispersed on the coated surface without waiting for the re-dissolution time, the reproducibility is low and it is not possible to improve the yield due to the aggregated foreign matter. It was enough.

Further, Patent Document 2 discloses a method of devising a solvent for the coloring composition in order to suppress clogging of slit nozzles, generation of dry foreign matter, and slit coating unevenness, while stably dispersing high concentration pigments. It was insufficient to improve the above problems.
Patent Document 3 discloses an apparatus for cleaning the nozzle tip. However, in the actual manufacturing process, it is difficult to completely remove the foreign matter at the sharp tip of the nozzle, and it is necessary to interrupt the coating operation for nozzle cleaning, which hinders the manufacturing tact. there were. Further, if the cleaning is not complete, a remaining liquid pool is generated at the tip of the nozzle, so that there is a problem that nonuniformity (unevenness) of the coating is caused.

JP 2002-23352 A JP 2007-219499 A JP-A-9-192666

This invention is made | formed in view of the above-mentioned prior art, and makes it a subject to provide the coloring resin composition for die coating methods with few aggregation foreign materials which generate | occur | produce when a die coating method is used.
Another object of the present invention is to provide a high-quality color filter, a liquid crystal display device and an organic EL display device which are formed from the colored resin composition for die coating.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have used a specific dispersant in a colored resin composition for a die coating method containing a red pigment in a specific amount range and containing a specific dispersant.
In addition, the above problem can be solved by setting the ratio of 1,3-butylene glycol diacetate (hereinafter sometimes referred to as “1,3BGDA”) contained as a solvent to a specific value in the total solvent. And the present invention has been reached.

  That is, the present invention is a colored resin composition for a die coating method containing (A) a pigment, (B) a solvent, (C) a binder resin, and (D) a dispersant, and the total solid content concentration of the colored resin composition Is 20 wt% or less, the (A) pigment contains a red pigment in a total pigment solid content of 26 wt% or more and 40 wt% or less, the (D) dispersant contains a polymer, The polymer has a primary to tertiary amino group and / or quaternary ammonium group in the side chain, and the content ratio of the monomer having the primary to tertiary amino group and / or quaternary ammonium group is a polymer. Is 20% by weight or more, the total solid content concentration of the colored resin composition is 20% by weight or less, and (B) the solvent is 1,3-butylene glycol diacetate. DAIKO characterized by containing 5 wt% or more and 14 wt% or less in the total solvent Preparative method for the colored resin composition (hereinafter, simply referred to as "the colored resin composition"), a color filter, resides in a liquid crystal display device and an organic EL display device.

ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the coloring resin composition for die coating methods with few aggregate foreign materials generated by the die coating method.
The present invention can also provide a high-quality color filter, liquid crystal display device, and organic EL display device.

It is a section schematic diagram showing an example of an organic EL device which has a color filter of the present invention.

Embodiments of the present invention will be described in detail below, but the following description is an example of embodiments of the present invention, and the present invention is not limited to these contents.
In the present invention, “(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 ".

Further, “total solid content” means all components of the colored resin composition for die coating method of the present invention other than the solvent components described later.
In the present invention, unless otherwise specified, the weight average molecular weight refers to a polystyrene-reduced weight average molecular weight (Mw) by GPC (gel permeation chromatography). “C.I.” means a color index (C.I.).

Furthermore, in the present invention, the “amine value” means an amine value in terms of effective solid content unless otherwise specified, and is a value represented by the amount of base and the equivalent weight of KOH per 1 g of the solid content of the dispersant. is there. The measuring method will be described later. On the other hand, the “acid value” represents an acid value in terms of effective solid content unless otherwise specified, and is calculated by neutralization titration.
In the present invention, “aromatic ring” refers to both “aromatic hydrocarbon ring” and “aromatic heterocycle”.

The colored resin composition for the die coating method of the present invention contains (A) a pigment, (B) a solvent, (C) a binder resin, and (D) a dispersant, and if necessary, additives other than these components, etc. May be contained. Further, it is particularly preferable to contain (E) a polymerizable monomer, (F) a photopolymerization initiating component and / or a thermal polymerization initiating component.
First, (A) the pigment will be described.

[(A) Pigment]
The colored resin composition for die coating method of the present invention contains a red pigment.
Examples of the chemical structure of the red pigment include organic pigments such as azo, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene. In addition to these, various inorganic pigments can also be used.
Specific examples of pigments that can be used in the present invention are shown below by pigment numbers, but are not limited to these examples.

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 and the like. Of these, C.I. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, etc., more preferably C.I. I. Pigment red 177, 209, 224, 242, 254, etc., particularly preferably C.I. I. Pigment red 177 and 254.
These red pigments are preferable in that the effect of the present invention can be obtained satisfactorily.
(Content)

In the colored resin composition for the die coating method of the present invention, the red pigment is usually 26% by weight or more, preferably 30% by weight or more, more preferably 35% by weight or more, and usually 40% by weight or less, Is 39.5% by weight or less.
When it is at least the above lower limit, the resulting pixel has high red purity, and a desired density of chromaticity is easily obtained. Further, when it is not more than the above upper limit, the coating film hardness is sufficient, the linearity is excellent, and a pixel having no residue is easily obtained.

(Other pigments)
The colored resin composition for die coating method of the present invention may contain other pigments in addition to the red pigment as the (A) pigment. Examples of other pigments include green pigments, yellow pigments, blue pigments, purple pigments, and orange pigments.

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, 58 and the like. Of these, C.I. I. Pigment green 7, 36, 58, and the like.
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, 3
6, 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, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 19 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, and a pigment defined by <Pigment Y> below (hereinafter referred to as “Pigment Y”). It is done.
<Pigment Y>
A compound obtained by inserting another compound into a 1: 1 complex of azobarbituric acid with nickel represented by the following structural formula or a compatible isomer thereof.

  Examples of the other compounds include compounds represented by the following formula (I-1).

Of these, C.I. I. Pigment yellow 83, 117, 129, 138, 139, 154, 155, 180, 185, pigment Y, and the like, more preferably C.I. I. Pigment yellow 83, 138, 139, 180, pigment Y, and the like.
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 and the like.

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 and the like. Of these, C.I. I. Pigment violet 19, 23, etc., more preferably C
. I. Pigment violet 23 and the like.

  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 and the like. Of these, C.I. I. Pigment orange 38, 71 and the like.

In addition, you may form the resin black matrix of a color filter using the colored resin composition of this invention, and a black pigment can be used in that case. In addition, a black pigment may be used independently and may mix and use pigments, such as red, green, and blue. Further, it may be an inorganic pigment or an organic pigment.
Examples of the organic pigment include the aforementioned green pigment, yellow pigment, blue pigment, purple pigment, orange pigment and the like.

Examples of the inorganic pigment include barium sulfate, lead sulfate, titanium oxide, yellow lead, bengara, and chromium oxide.
In addition, the above-mentioned various pigments can be used in combination. For example, in order to adjust the chromaticity, as the (A) pigment, a red pigment and a yellow pigment can be used in combination, or a green pigment and a yellow pigment can be used in combination.

The average primary particle size of the (A) pigment in the present invention is usually 100 nm or less, preferably 80 nm or less, more preferably 20 nm or more and 70 nm or less. Since the present invention is particularly effective in the case of a composition containing a highly atomized pigment, the case of containing a pigment having an average primary particle size of 20 nm to 60 nm is particularly preferable.
By making the average primary particle size of the pigment (A) used within the above range, the depolarization characteristics are kept good, high contrast and transmittance are realized, dispersion stability is good, heat resistance and light resistance A colored resin composition having excellent properties can be obtained.

The primary particle diameter of the pigment can be determined by the following method.
First, the pigment is ultrasonically dispersed in chloroform, dropped onto a collodion film-attached mesh, dried, and a primary particle image of the pigment is obtained by observation with a transmission electron microscope (TEM). However, in the case of organic pigments, the particle diameter of each pigment particle is the diameter corresponding to the area circle converted to the diameter of a circle having the same area, and the particle diameter of each of plural (usually about 200 to 300) pigment particles. Ask for. Using the obtained primary particle size value, the number average value is calculated according to the following formula to obtain the average particle size.

The pigment (A) thus obtained may be used alone, but may be used alone or in combination of two or more types within a range not impairing the effects of the present invention.
The content of the pigment (A) in the present invention is usually 0.1 to 80% by weight, more preferably 1 to 60% by weight, based on the total solid content.
(A) By making content of a pigment into the said range, the film thickness with respect to a color density does not become large too much, and it does not have a bad influence on the gap control etc. in the case of liquid crystal cell formation. Furthermore, sufficient image-forming properties can be obtained, and the dispersion state of the pigment is maintained, and aggregation and sedimentation are unlikely to occur. As a result, thickening of the colored resin composition and reduction in luminance and contrast of the resulting pixel are suppressed. Yes.

[(B) Solvent]
The colored resin composition for the die coating method of the present invention contains 1,3-butylene glycol diacetate as the (B) solvent.
The content of 1,3-butylene glycol diacetate in the total solvent is usually 5% by weight or more, preferably 8% by weight or more, and usually 14% by weight or less, preferably 12% by weight or less. The colored resin composition of the present invention may contain methoxybutyl acetate (hereinafter sometimes referred to as “MBA”) and / or ethyl ethoxypropionate (hereinafter sometimes referred to as “EEP”). preferable.

The content of MBA and / or EEP in the total solvent is usually 6% by weight or more, preferably 8% by weight or more, and usually 16% by weight or less, preferably 12% by weight or less.
Any of them is preferably within the above range in that the effect of the present invention can be obtained satisfactorily.
1,3-BGDA contained in the colored resin composition of the present invention, and even more preferably contained MBA and EEP are highly compatible with the components in the colored resin composition and dispersed, as estimated from the solubility parameter. The retained pigment (pigment dispersion) is stably retained.
For this reason, even if the solvent is volatilized at the tip of the dispensing nozzle and the concentration of the resist solid component is increased, the pigment dispersion is particularly difficult to agglomerate and hardly become a foreign substance.

The colored resin composition for die coating method of the present invention may contain other solvent as (B) solvent in addition to 1,3BGDA, MBA and EEP.
There is no restriction | limiting in particular as long as the effect of this invention is not impaired as long as it can dissolve or disperse | distribute each component. Examples of such solvents include the following.

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol-mono t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, methoxymethylpentanol, propylene Glycol monoalkyl ethers such as glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, tripropylene glycol monomethyl 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;

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monoethyl ether acetate, diethylene glycol Glycol alkyl ether acetates such as monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate;
Ethers such as diethyl ether, dipropyl ether, diisopropyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether;

Ketones such as 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;
Mono- or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, 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, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionic acid Linear or cyclic esters such as butyl, 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;
Nitriles such as acetonitrile and benzonitrile:
Commercially available products corresponding to these solvents include mineral spirits, valsol # 2, Apco # 18 solvent, apco thinner, and soak 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.

Of the above solvents, glycol alkyl ether acetates are preferred from the viewpoint of good dispersibility in the solvent such as the pigment (A). Furthermore, propylene glycol monomethyl ether acetate is particularly preferable from the viewpoint of solubility of various components in the colored resin composition.
The content of the solvent in the entire colored resin composition of the present invention is not particularly limited, but the upper limit is usually 99% by weight or less, preferably 50% by weight or more, considering the viscosity suitable for coating, etc. More preferably, it is 60 weight% or more, Most preferably, it is 70 weight% or more.

[(C) Binder resin]
(C) The preferred resin for the binder resin differs depending on the curing means.
When the colored resin composition for the die coating method of the present invention is a photopolymerizable resin composition, examples of (C) binder resin include JP-A-7-207211, JP-A-8-259876, and JP-A-10-300922. The polymer compounds described in JP-A-11-140144, JP-A-11-174224, JP-A-2000-56118, JP-A-2003-233179, and the like can be used. Include the following resins (C-1) to (C-5).

(C-1): With respect to a copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer, an unsaturated monobasic acid is added to at least a part of the epoxy group of the copolymer. Resin to be added, or an alkali-soluble resin (hereinafter referred to as “resin (C-1)”) obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction. .)
(C-2): Carboxyl group-containing linear alkali-soluble resin (C-2) (hereinafter sometimes referred to as “resin (C-2)”)
(C-3): a resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group portion of the resin (C-2) (hereinafter sometimes referred to as “resin (C-3)”).
(C-4): (Meth) acrylic resin (hereinafter sometimes referred to as “resin (C-4)”)
(C-5): Epoxy acrylate resin having a carboxyl group (hereinafter sometimes referred to as “resin (C-5)”)
Of these, the resin (C-1) is particularly preferable, and the resin will be described below.

The resins (C-2) to (C-5) may be anything as long as they are dissolved in an alkaline developer and are soluble to the extent that the desired development processing is performed. This is the same as that described as the same item in 2009-025813. The preferred embodiment is also the same.
(C-1): With respect to a copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer, an unsaturated monobasic acid is added to at least a part of the epoxy group of the copolymer. As one of particularly preferable resins of the alkali-soluble resin resin (C-1) obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction, or an epoxy group, Unsaturated in 10 to 100 mol% of the epoxy group of the copolymer with respect to the copolymer of 5 to 90 mol% of (meth) acrylate and 10 to 95 mol% of other radical polymerizable monomer Examples thereof include a resin obtained by adding a monobasic acid, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to 10 to 100 mol% of a hydroxyl group generated by the addition reaction.

  Examples of the epoxy group-containing (meth) acrylate include glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. ) Acrylate glycidyl ether and the like. Of these, glycidyl (meth) acrylate is preferred. These epoxy group-containing (meth) acrylates may be used alone or in combination of two or more.

The other radical polymerizable monomer copolymerized with the epoxy group-containing (meth) acrylate is not particularly limited as long as the effects of the present invention are not impaired. For example, vinyl aromatics, dienes, (meth) Examples include acrylic acid esters, (meth) acrylic acid amides, vinyl compounds, unsaturated dicarboxylic acid diesters, monomaleimides, and the like, and in particular, mono (meth) having a structure represented by the following formula (7) Acrylate is preferred.
The repeating unit derived from the mono (meth) acrylate having the structure represented by the following formula (7) contains 5 to 90 mol% among the repeating units derived from “other radical polymerizable monomers”. The content is preferably 10 to 70 mol%, more preferably 15 to 50 mol%.

In the above formula (7), R ⁸⁹ represents a hydrogen atom or a methyl group, and R ⁹⁰ represents a structure represented by the following formula (8).

The formula ^{(8), R} 91 ~R ⁹⁸ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ⁹⁶ and R ⁹⁸ may be connected to each other to form a ring.
The ring formed by connecting R ⁹⁶ and R ⁹⁸ is preferably an aliphatic ring, may be saturated or unsaturated, and preferably has 5 to 6 carbon atoms.
Among them, among the structures represented by the formula (8), those represented by the following structural formulas (8a), (8b), or (8c) are particularly preferable.

In addition, the mono (meth) acrylate which has a structure represented by the said Formula (8) may be used individually by 1 type, and may use 2 or more types together.
As "other radical polymerizable monomers" other than the mono (meth) acrylate having the structure represented by the formula (8), the heat resistance and strength excellent in the colored resin composition can be improved. , Styrene, (n-butyl) (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, benzyl (meth) acrylate , (Meth) acrylic acid-2-hydroxyethyl, N-phenylmaleimide, N-cyclohexylmaleimide.

The content ratio of repeating units derived from at least one selected from the above monomer group is preferably 1 to 70 mol%, more preferably 3 to 50 mol%.
A known solution polymerization method is applied to the copolymerization reaction between the epoxy group-containing (meth) acrylate and the other radical polymerizable monomer.
In the present invention, as a copolymer of the epoxy group-containing (meth) acrylate and the other radical polymerizable monomer, 5 to 90 mol% of repeating units derived from the epoxy group-containing (meth) acrylate, and others Is preferably composed of 10 to 95 mol% of repeating units derived from the radically polymerizable monomer, more preferably composed of 20 to 80 mol% of the former and 80 to 20 mol% of the latter. What consists of 70 mol% and the latter 70-30 mol% is especially preferable.

Within the above range, the addition amount of the polymerizable component and alkali-soluble component described later is sufficient, and the heat resistance and strength are sufficient, which is preferable.
The epoxy group portion of the epoxy group-containing copolymer synthesized as described above is reacted with an unsaturated monobasic acid (polymerizable component) and a polybasic acid anhydride (alkali-soluble component).
Here, as an unsaturated monobasic acid added to an epoxy group, a well-known thing can be used, For example, unsaturated carboxylic acid which has an ethylenically unsaturated double bond is mentioned.

Specific examples include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position substituted with a haloalkyl group, an alkoxyl group, a halogen atom, a nitro group, or a cyano group. And monocarboxylic acids such as (meth) acrylic acid. Of these, (meth) acrylic acid is preferred. These may be used alone or in combination of two or more.
By adding such components, polymerizability can be imparted to the binder resin used in the present invention.

These unsaturated monobasic acids are usually added to 10 to 100 mol% of the epoxy group of the copolymer, preferably 30 to 100 mol%, more preferably 50 to 100 mol%. It is preferable for it to be within the above range because the colored resin composition has excellent temporal stability. In addition, a well-known method is employable as a method of adding unsaturated monobasic acid to the epoxy group of a copolymer.
Furthermore, a well-known thing can be used as a polybasic acid anhydride added to the hydroxyl group produced when an unsaturated monobasic acid is added to the epoxy group of a copolymer.

  For example, dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride; trimellitic anhydride, pyromellitic anhydride, benzophenone Examples thereof include anhydrides of three or more bases such as tetracarboxylic acid anhydride and biphenyltetracarboxylic acid anhydride. Of these, succinic anhydride and tetrahydrophthalic anhydride are preferred. These polybasic acid anhydrides may be used individually by 1 type, and may use 2 or more types together.

By adding such a component, alkali solubility can be imparted to the binder resin used in the present invention.
These polybasic acid anhydrides are usually added to 10 to 100 mol% of the hydroxyl group generated by adding an unsaturated monobasic acid to the epoxy group of the copolymer, preferably 20 to 90 mol. %, More preferably 30 to 80 mol%.

Within the above range, the remaining film ratio and solubility during development are sufficient, which is preferable.
In addition, a well-known method is employable as a method of adding a polybasic acid anhydride to the said hydroxyl group.
Furthermore, in order to improve photosensitivity, after adding the polybasic acid anhydride, glycidyl (meth) acrylate or a glycidyl ether compound having a polymerizable unsaturated group is added to a part of the generated carboxyl group. Also good. Such a resin structure is described in, for example, Japanese Patent Application Laid-Open Nos. 8-297366 and 2001-89533.

  The polystyrene-reduced weight average molecular weight (Mw) of the above-described binder resin (C-1) measured by GPC (gel permeation chromatography) is preferably 3000 to 100,000, and particularly preferably 5000 to 50000. If the molecular weight is less than 3000, heat resistance and film strength may be inferior, and if it exceeds 100,000, the solubility in a developer tends to be insufficient. Moreover, as a standard of molecular weight distribution, the ratio of weight average molecular weight (Mw) / number average molecular weight (Mn) is preferably 2.0 to 5.0.

In addition, the acid value of binder resin (C-1) is 10-200 mg-KOH / g normally, Preferably it is 15-150 mg-KOH / g, More preferably, it is 25-100 mg-KOH / g. If the acid value is too low, the solubility in the developer may be reduced. Conversely, if it is too high, film roughening may occur.
[(D) Dispersant]
The colored resin composition of the present invention includes (D) a polymer as a dispersant, and the polymer has a primary to tertiary amino group and / or a quaternary ammonium group in the side chain, In the monomer composition constituting the polymer, the content ratio of the monomer having a group and / or a quaternary ammonium group is 2
0% by weight or more of a polymer (hereinafter sometimes referred to as “specific polymer”).

The content ratio of the monomer having a primary to tertiary amino group and / or a quaternary ammonium group is usually 20% by weight or more, preferably 25% by weight or more, based on the entire copolymerization monomer constituting the polymer. Preferably it is 30 weight%.
The copolymer is preferably a block copolymer containing a repeating unit having solvophilicity and a repeating unit having a primary to tertiary amino group and / or a quaternary ammonium group in the side chain.
Of these, (meth) acrylic block copolymers are preferred.
First, the repeating unit having a primary to tertiary amino group in the side chain in the (meth) acrylic block copolymer will be described.

(Repeating unit having a primary to tertiary amino group in the side chain)
The primary to tertiary amino group is preferably —NR ⁴¹ R ⁴² (wherein R ⁴¹ and R ⁴² each independently represents a hydrogen atom or a cyclic or chain-like alkyl group which may have a substituent). Represents an aryl group which may have a substituent, or an aralkyl group which may have a substituent.), And a partial structure (repeating unit) containing this is represented by the following formula, for example. Is done.

(However, R ⁴¹ and R ⁴² have the same meanings as R ⁴¹ and R ⁴² described above, R ⁴³ represents an alkylene group having 1 or more carbon atoms, and R ⁴⁴ represents a hydrogen atom or a methyl group.)
Among them, R ⁴¹ and R ⁴² are preferably a methyl group, R ⁴³ is preferably a methylene group or an ethylene group, and R ⁴⁴ is preferably a hydrogen atom or a methyl group. As such a partial structure, a structure derived from dimethylaminoethyl acrylate or dimethylaminoethyl methacrylate represented by the following formula is particularly preferably used.

(Wherein R ⁴⁴ has the same meaning as described above.)
(Repeating unit having a quaternary ammonium group in the side chain)
As a repeating unit having a quaternary ammonium group, the quaternary ammonium group may be directly bonded to the main chain, but may be bonded to the main chain via a divalent linking group. Moreover, as such a quaternary ammonium group, what contains the partial structure represented by following formula (VI) especially is preferable.

In the above formula (VI), R ³⁴ represents a hydrogen atom or a methyl group.
X ¹ represents a divalent linking group.
R ^{31 to} R ³³ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an optionally substituted aromatic hydrocarbon ring group having 6 to 15 carbon atoms, or optionally substituted. Aralkyl groups having 7 to 20 carbon atoms are preferred.

Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a benzyl group, and a phenyl group. Of these, methyl, ethyl, propyl, butyl, benzyl and the like are preferable.
In the formula (VI), examples of the divalent linking group X ¹ include an alkylene group having 1 to 10 carbon atoms, an arylene group, —CONH—R ³⁵ —, —COO—R ³⁶ — (provided that R ³⁵ and R ³⁶ are each independently a direct bond, an alkylene group having 1 to 10 carbon atoms, or an ether group having 1 to 10 carbon atoms (—R ³⁷ —O—R ³⁸ —: R ³⁷ and R ³⁸ are each Independently represents an alkylene group), and the like, preferably —COO—R ³⁶ —.
Examples of the counter anion M ⁻ include Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CH ₃ COO ⁻ , and PF ₆ ⁻ .

(Repeating unit having solvophilicity)
On the other hand, the repeating unit having a solvophilic property that constitutes the block copolymer of the dispersant does not have a primary to tertiary amino group and a quaternary ammonium group, and the above-described primary to tertiary amino groups and quaternary ammonium. If it consists of a monomer copolymerizable with the monomer which has group, there will be no restriction | limiting in particular.

Examples of the copolymerizable monomer constituting the solvophilic property include styrene monomers such as styrene and α-methylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate (propyl) (meth) acrylate, and (meth) acrylic. Isopropyl acid, butyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl ethyl acrylate, Polyethylene glycol (meth) acrylate,
(Meth) acrylate monomers such as polypropylene glycol (meth) acrylate; (meth) acrylate monomers such as (meth) acrylic chloride; vinyl acetate monomers; glycidyl such as allyl glycidyl ether and crotonic acid glycidyl ether Examples include comonomers such as ether monomers.

Among these, polyalkylene glycol (meth) acrylates such as polyethylene glycol (meth) acrylate and polypropylene glycol (meth) acrylate are preferable.
Among these partial structures derived from copolymerization monomers, a partial structure represented by the following formula (VIII) is particularly preferable.

(In the formula (VIII), n represents an integer of 1 to 5, but when there are a plurality of the units, that is, the formula (VIII) in one molecule, n may be the same or different. R ⁸¹ Represents a hydrogen atom or a methyl group, R ⁸² represents an alkyl group having 1 to 4 carbon atoms or a phenyl group, and R ⁸² is particularly preferably an ethyl group.)
The partial structure represented by the above formula (VIII) is usually 5% by weight or more, preferably 7% by weight or more and usually 40% by weight or less based on the entire copolymerization monomer constituting the polymer.
Within the above range, the affinity with the dispersion solvent is improved, and the stability of the dispersion system is increased, which is preferable.

In synthesizing such a (meth) acrylic block copolymer, JP-A-60-89452, JP-A-9-62002, P. Lutz, P. Masson et al, Polym. Bull. 12 , 79 (1984), BC Anderson, GD Andrews et al, Macromolecules, 14, 1601 (1981), K. Hatada, K. Ute, et al, Polym. J. 17, 977 (1985), K. Hatada, K Ute, et al, Polym. J.18, 1037 (1986), Koichi Right-hand, Koichi Hatada, Polymer Processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Papers, 46, 189 ( 1989), M. Kuroki, T. Aida, J. Am. Chem. Sic, 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43, 300 (1985), DY Sogoh, WR Hertler et al. , Macromolecules, 20, 1473 (1987), K. Matyaszewski et al, Chem. Rev. 2001, 101, 2921-2990, etc., can be used.

When the AB block copolymer and the ABA block copolymer according to the present invention are polymers having a primary to tertiary amino group in the side chain, the amine value in 1 g of solid content is preferably 80 mg-
KOH / g or more, more preferably 100 mg-KOH / g or more, preferably 150 mg-KOH / g or less, more preferably 140 mg-KOH / g or less.
Within the above range, it is preferable in that the adsorptive power to the pigment surface is sufficient and the dispersion stability is good.

The amine value of the dispersant (in terms of effective solid content) 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. 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 [mg-KOH / 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 acid value of the block copolymer depends on the presence and type of the acid group that is the basis of the acid value, but is generally preferably lower, usually 50 mg-KOH / g or less, preferably 40 or less, more Preferably it is 30 or less.
In the present invention, a commercially available (meth) acrylic block copolymer having the same structure as described above can also be applied.

(Acid value)
The acid value of a polymer having a primary to tertiary amino group and / or a quaternary ammonium group in the side chain depends on the presence and type of an acidic group that is the basis of the acid value, but is generally preferably lower. 100 mg-KOH / g or less, preferably 50 mg-KOH / g or less, more preferably 40 mg-KOH / g or less, and most preferably 30 mg-KOH / g or less.

(Molecular weight)
The molecular weight of the polymer having a primary to tertiary amino group and / or quaternary ammonium group in the side chain in the present invention is usually 1000 or more in terms of polystyrene-equivalent weight average molecular weight (Mw) measured by GPC, and usually 100,000. The range is as follows.
In the present invention, a commercially available (meth) acrylic block copolymer having the same structure as that described above can also be used.

When the average primary particle size of the pigment is small, the specific surface area increases, so that the amount of dispersant adsorbed per unit area decreases. In such a case, the above-described dispersant composed of the AB block copolymer or ABA block copolymer is particularly preferably used because the difference in the effect is very remarkable as compared with the dispersant having another structure. Is.
Further, even when a high concentration pigment is contained, a colored composition having excellent stability and capable of exhibiting sufficient color characteristics as a color filter can be obtained.

(Content)
The (D) dispersant in the present invention is preferably 5% by weight or more, more preferably 10% by weight or more, and preferably 200% by weight or less, more preferably 100% by weight, based on the total amount of the pigment in the colored resin composition. % Or less,
Furthermore, the content of the polymer having a primary to tertiary amino group and / or a quaternary ammonium group in the side chain is usually 10% by weight or more, preferably 30% by weight or more in the total dispersant. In addition, since it is particularly preferable to use only a polymer having a primary to tertiary amino group and / or a quaternary ammonium group in the side chain as a dispersant, the upper limit is ideally 100% by weight.

The content of the (D) dispersant in the (A) pigment is usually 10% by weight or more, and usually 100% by weight or less, preferably 50% by weight or less, more preferably 40% by weight or less.
(D) By controlling the content of the dispersant within the above range, a necessary and sufficient amount of the dispersant adheres to the pigment surface, so that aggregation can be achieved without reducing the coloring power of the colored resin composition described below. It can be effectively prevented, and high viscosity or gelation can be avoided, so that high dispersion stability can be ensured.

The colored resin composition of the present invention contains a dispersant other than the above-described polymer having a primary to tertiary amino group and / or a quaternary ammonium group in the side chain as long as the effects of the present invention are not impaired. Also good.
In addition, the dispersing agent in this invention may use individually the polymer which has a 1-3 primary amino group and / or a quaternary ammonium group in a side chain, and uses together 2 or more types from which it differs. Also good.

<Other dispersants>
(D) As a dispersing agent, the following (D-1) dispersing agent (henceforth "(D-1) dispersing agent") may be contained, for example.
(D-1) Examples of the dispersant include a urethane-based dispersant, a polyallylamine-based dispersant, a dispersant composed of a monomer having an amino group and a macromonomer, a polyoxyethylene alkyl ether-based dispersant, and a polyoxyethylene diester-based dispersant. Examples thereof include a dispersant, a polyether phosphate dispersant, a polyester phosphate dispersant, a sorbitan aliphatic ester dispersant, and an aliphatic modified polyester dispersant.

  Specific examples of such a dispersant include EFKA (manufactured by EFKA Chemicals Beebuy (EFKA)), Disperbyk (manufactured by Big Chemie), Disparon (manufactured by Enomoto Kasei), SOLPERSE (manufactured by Lubrizol), KP (manufactured by Shinetsu) Chemical products), polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), ajisper (manufactured by Ajinomoto Fine-Techno Co., Ltd.), and other series names can be mentioned.

[Dispersion resin]
The colored resin composition of the present invention may contain a part or all of the resin selected from the (C) binder resin or other binder resins as the following dispersion resin.
Specifically, the (C) binder resin is obtained by adding (C) a binder resin and dispersing together with the component (D) in the <Method for preparing colored resin composition> described later. However, it contributes to the dispersion stability of the pigment (A) by a synergistic effect with (D) the dispersant. As a result, there is a possibility that the amount of (D) dispersant added can be reduced, which is preferable. Further, it is preferable because the developability is improved, the undissolved matter does not remain in the non-pixel portion of the substrate, and the adhesion of the pixel to the substrate is improved.

Thus, the (C) binder resin used in the dispersion treatment step may be referred to as a dispersion resin. The dispersion resin is preferably used in an amount of about 0 to 200% by weight, more preferably about 10 to 100% by weight, based on the total amount of the pigment in the colored resin composition.
As the dispersion resin, various (C) binder resins described later can be used.
The acid value of the dispersion resin is preferably 0 mg-KOH / g or more, more preferably 1 mg-KOH / g or more, most preferably 5 mg-KOH / g or more, and preferably 300 mg-KOH / g or less, 200 mg-KOH / g. The following is more preferable, and 150 mg-KOH / g or less is most preferable. By controlling the acid value within the above range, the alkali developability is improved, and the handling becomes easy in synthesis and the like.

The weight average molecular weight in terms of polystyrene measured by GPC of the dispersion resin is preferably 1000 or more, more preferably 1500 or more, most preferably 2000 or more, and 200
000 or less is preferable, 50000 or less is more preferable, and 30000 or less is most preferable. By controlling the molecular weight within the above range, the alkali developability can be improved and the dispersion stability can be prevented from being lowered.

[(E) Polymerizable monomer]
The colored resin composition for die coating method of the present invention preferably contains (E) a polymerizable monomer. (E) The polymerizable monomer is not particularly limited as long as it is a polymerizable low molecular compound, but it may be an addition-polymerizable compound having at least one ethylenic double bond (hereinafter referred to as “ethylenic compound”). Is preferred).

  The ethylenic compound is a compound having an ethylenic double bond that undergoes addition polymerization and cures by the action of a photopolymerization initiation component described later when the colored resin composition for die coating method of the present invention is irradiated with actinic rays. It is. In addition, the (E) polymerizable monomer in this invention means the concept opposite to what is called a polymeric substance, and also includes a dimer, a trimer, and an oligomer other than a monomer in a narrow sense.

  (E) Examples of the ethylenic compound in the polymerizable monomer include unsaturated carboxylic acids such as (meth) acrylic acid; esters of monohydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds and unsaturated carboxylic acids; Ester of aromatic polyhydroxy compound and unsaturated carboxylic acid; esterification reaction of unsaturated carboxylic acid with polyvalent carboxylic acid and polyvalent hydroxy compound such as aliphatic polyhydroxy compound and aromatic polyhydroxy compound An ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound and a (meth) acryloyl group-containing hydroxy compound;

  Esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol di (meth) acrylate, triethylene glycol di (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) Examples include (meth) acrylic acid esters such as acrylate and glycerol (meth) acrylate. In addition, the (meth) acrylic acid portion of these (meth) acrylic acid esters is replaced with an itaconic acid portion, a crotonic acid portion replaced with a crotonic acid portion, or a maleic acid ester replaced with a maleic acid portion, etc. Is mentioned.

Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone di (meth) acrylate, resorcin di (meth) acrylate, pyrogallol tri (meth) acrylate, and the like.
The ester obtained by the esterification reaction of an unsaturated carboxylic acid with a polyvalent carboxylic acid and a polyvalent hydroxy compound is not necessarily a single substance but may be a mixture. Representative examples are condensates of (meth) acrylic acid, phthalic acid, and ethylene glycol; condensates of (meth) acrylic acid, maleic acid, and diethylene glycol; condensation of (meth) acrylic acid, terephthalic acid, and pentaerythritol A condensate of (meth) acrylic acid, adipic acid, butanediol, and glycerin.

Examples of the ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound and a (meth) acryloyl group-containing hydroxy compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; alicyclic rings such as cyclohexane diisocyanate and isophorone diisocyanate. Formula diisocyanates; aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate, and (meth) acryloyl such as 2-hydroxyethyl (meth) acrylate and 3-hydroxy [1,1,1-tri (meth) acryloyloxymethyl] propane A reaction product with a group-containing hydroxy compound is exemplified.

In addition, examples of the ethylenic compound used in the present invention include (meth) acrylamides such as ethylene bis (meth) acrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate. .
Among these, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids are preferred, pentaerythritol or (meth) acrylic acid esters of dipentaerythritol are more preferred, and dipentaerythritol hexa (meth) acrylate is particularly preferred.

  The ethylenic compound may be a monomer having an acid value. The monomer having an acid value is, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A polyfunctional monomer having a group is preferable, and 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, a mixture of two or more kinds may be used.
Moreover, you may use together the polyfunctional monomer which does not have an acid group, and the polyfunctional monomer which has an acid group as (E) polymeric monomer as needed.
A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mg-KOH / g, and particularly preferably 5 to 30 mg-KOH / g.

When it is within the above range, the development and dissolution characteristics are hardly deteriorated, and the production and handling are easy. Furthermore, it is preferable because the photopolymerization performance is hardly lowered and the curability such as the surface smoothness of the pixel is good.
In the present invention, a more preferred polyfunctional monomer having an acid group is, for example, a mixture containing succinic acid ester of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentaacrylate as a main component. It is also possible to use this polyfunctional monomer in combination with another polyfunctional monomer.

In the colored resin composition for die coating method of the present invention, the content ratio of these (E) polymerizable monomers is usually 1% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more in the total solid content. In addition, it is usually 80% 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.
The ratio of the (E) polymerizable monomer to the (A) pigment is usually 1% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, and particularly preferably 20% by weight or more. The amount is usually 200% by weight or less, preferably 100% by weight or less, and more preferably 80% by weight or less.
Within the above range, photocuring is appropriate, poor adhesion during development is difficult to place, the cross-section after development is difficult to reverse taper, and further, peeling phenomenon and omission failure due to lower solubility are difficult to place. preferable.

[(F) Photopolymerization initiation component and / or thermal polymerization initiation component]
The colored resin composition of the present invention preferably contains (F) a photopolymerization initiation component and / or a thermal polymerization initiation component for the purpose of curing the coating film. However, the curing method may be other than those using these initiators.

  In particular, when the colored resin composition of the present invention includes a resin having an ethylenic double bond as the component (C), or includes an ethylenic compound as the component (E), it directly absorbs light, or It is preferable to contain a photopolymerization initiating component that has a function of generating a polymerization active radical and / or a thermal polymerization initiating component that generates a polymerization active radical by heat. In the present invention, the component (F) as a photopolymerization initiation component refers to a photopolymerization initiator (hereinafter arbitrarily referred to as (F1) component) and a polymerization accelerator (hereinafter arbitrarily referred to as (F2) component). , Means a mixture in which an additive such as a sensitizing dye (hereinafter, arbitrarily referred to as component (F3)) is used in combination.

(Photopolymerization initiation component)
You may contain in the colored resin composition of this invention. The photopolymerization initiating component is usually used as a mixture of (F1) a photopolymerization initiator and an additive such as (F3) a sensitizing dye and (F2) a polymerization accelerator which are added as necessary. It is a component having a function of generating a polymerization active radical by directly absorbing or photosensitizing to cause a decomposition reaction or a hydrogen abstraction reaction.

  Examples of the (F1) photopolymerization initiator constituting the photopolymerization initiating component include titanocene derivatives described in JP-A Nos. 59-152396 and 61-151197; 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.

Specific examples include photopolymerization initiators described in International Publication No. 2009/107734.
Among these photopolymerization initiators, α-aminoalkylphenone derivatives, oxime ester derivatives, biimidazole derivatives, acetophenone derivatives, and thioxanthone derivatives are more preferable.

The oxime ester derivatives include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (o-benzoyloxime), ethanone, 1- [9-ethyl-6- ( 2-methylbenzoyl) -9H-carbazol-3-yl], 1- (o-acetyloxime), and the like.
In addition, benzoin alkyl ethers, anthraquinone derivatives; acetophenone derivatives such as 2-methyl- (4′-methylthiophenyl) -2-morpholino-1-propanone, 2-ethylthioxanthone, 2,4-diethylthioxanthone, etc. Examples also include thioxanthone derivatives, benzoate derivatives, acridine derivatives, phenazine derivatives, anthrone derivatives and the like.

Among these photopolymerization initiators, α-aminoalkylphenone derivatives, thioxanthone derivatives, and oxime ester derivatives are more preferable. In particular, oxime ester derivatives are preferable.
Examples of the (F2) polymerization accelerator used as necessary include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester; 2-mercaptobenzothiazole, 2-mercapto Examples thereof include mercapto compounds having a heterocyclic ring such as benzoxazole and 2-mercaptobenzimidazole; mercapto compounds such as aliphatic polyfunctional mercapto compounds.
These (F1) photopolymerization initiators and (F2) polymerization accelerators may be used alone or in combination of two or more.

  Further, (F3) sensitizing dye is used for the purpose of increasing the sensitivity as required. As the sensitizing dye, an appropriate one 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; No. 239703, JP-A-5-289335, etc. Coumarin dyes having a heterocyclic ring; JP-A-3-239703, JP-A-5-289335, etc .; 3-ketocoumarin dyes; Pyrromethene dyes described in JP-A-6-19240 and the like; 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 5-10. 761 No., JP-A-5-210240, dyes having a dialkyl aminobenzene skeleton described in JP-A 4-288818 Patent JP-like.

(F3) A sensitizing dye may also be used alone or in combination of two or more.
In the colored resin composition of the present invention, the content ratio of these (F) photopolymerization initiating components is usually 0.1% by weight or more, preferably 0.2% by weight or more, more preferably 0.8% by weight based on the total solid content. It is 5% by weight or more, usually 40% by weight or less, preferably 30% by weight or less, and more preferably 20% by weight or less. If this content is extremely low, the sensitivity to exposure light may be reduced. Conversely, if it is extremely high, the solubility of the unexposed portion in the developer may be reduced, leading to poor development.

((F) Thermal polymerization initiation component)
Specific examples of the thermal polymerization initiating component (thermal polymerization initiator) that may be contained in the colored resin composition for the die coating method of the present invention include azo compounds, organic peroxides, and hydrogen peroxide. Of these, azo compounds are preferably used. More specifically, for example, a thermal polymerization initiator described in International Publication No. 2009/107734 pamphlet or the like can be used.
These thermal polymerization initiators may be used individually by 1 type, and may use 2 or more types together.

[Optional ingredients]
In addition to the above components, the colored resin composition for die coating method of the present invention includes a surfactant, an organic carboxylic acid and / or an organic carboxylic acid anhydride, a thermosetting compound, a plasticizer, a thermal polymerization inhibitor, and a storage stability. An agent, a surface protective agent, an adhesion improver, a development improver and the like may be contained. Moreover, when a pigment is contained as a coloring matter, a dispersant or a dispersion aid may be contained. As these optional components, for example, various compounds described in JP-A-2007-113000 can be used.

[Surfactant]
The colored resin composition for die coating method of the present invention may further contain a surfactant. Various surfactants such as anionic, cationic, nonionic, and amphoteric surfactants can be used as surfactants, but they may adversely affect various properties such as voltage holding ratio and compatibility with organic solvents. It is preferable to use a nonionic surfactant in terms of low properties.

As the surfactant, for example, those described in JP-A-2009-25813 can be used.
The content of these surfactants is preferably 0.001% by weight or more, more preferably 0.005% by weight or more, and still more preferably 0.000% by weight or more in the total solid content of the colored resin composition for die coating method of the present invention. 01% by weight or more. Further, it is preferably used in the range of 10% by weight or less, more preferably 5% by weight or less, and still more preferably 1% by weight or less.

[Solid content of colored resin composition]
The total solid concentration of the colored resin composition for die coating method of the present invention is usually 20% by weight or less, preferably 19.5% by weight or less, and usually 14% by weight or more.
Within the above range, the colored resin composition adhering to the tip of the dispensing nozzle is difficult to dry and is less likely to become agglomerated foreign matter. Further, it is preferable because the end face of the base material is raised and defects such as coating uniformity are difficult to occur.

<Preparation method of colored resin composition>
In the present invention, the colored resin composition can be prepared by an appropriate method. For example, as the preparation method, (A) a solvent containing a pigment, (D) a dispersant containing a specific polymer, and if necessary In the presence of a dispersing aid to be added depending on the case, pulverization may be performed using, for example, a paint shaker, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer and the like together with a part of the binder resin (C). Mixing and dispersing while preparing a colored dispersion. (C) Binder resin, and, if necessary, (E) a polymerizable monomer and (F) an additive such as a photopolymerization initiating component and / or a thermal polymerization initiating component are added to and mixed with the colored dispersion. The method of preparing by can be mentioned.

<Application of colored resin composition>
The colored resin composition for the die coating method 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 a color filter and a component of the display device.
Hereinafter, as an application example of the colored resin composition for the die coating method of the present invention, an application as a pixel of a color filter, a liquid crystal display device (panel) and an organic EL display device using the same will be described.

<Manufacture of color filter substrates>
Next, the color filter of the present invention (hereinafter sometimes referred to as “color filter substrate”) will be described.
The color filter of the present invention is characterized by having pixels formed on the substrate using the above-described colored resin composition.

<Color filter>
The color filter of this invention has a pixel formed from the colored resin composition for die coating methods of this invention.
The method for forming the color filter of the present invention will be described below.
The pixel of the color filter can be formed by various methods. Here, although the case where it forms by the photolithographic method using a photopolymerizable colored resin composition is demonstrated to an example, a manufacturing method is not limited to this.

  First, on the surface of the substrate, if necessary, a black matrix is formed so as to define a pixel forming portion, and after applying the colored resin composition for die coating method of the present invention on this substrate, prebaking is performed. To evaporate the solvent and form a coating film. Then, after exposing this coating film through a photomask, developing with an alkali developer, dissolving and removing the unexposed portion of the coating film, and then post-baking, each of red, green, and blue A color filter can be manufactured by forming a pixel pattern.

The substrate used for forming the pixel is not particularly limited as long as it is transparent and has an appropriate strength. For example, a polyester resin, a polyolefin resin, a polycarbonate resin, an acrylic resin, or a thermoplastic resin is used. A sheet, an epoxy resin, a thermosetting resin, various glass, etc. are mentioned.
In addition, these substrates may be appropriately subjected to pretreatment as desired, such as thin film formation treatment with a silane coupling agent or urethane resin, surface treatment such as corona discharge treatment or ozone treatment, if desired.

Thereafter, a coating film is formed by a die coating method.
The die coating method is used in a coating apparatus and a coating method for display members containing organic solvents such as color filters, and achieves uniform coating film thickness formation with a coating solution used for coating, especially on large substrates, with as little amount as possible. It is a useful method as a means.
As a general principle of a coating apparatus, first, a coating liquid is supplied from a supply port of a die head and is stored in a manifold that functions as a collecting pipe. The coating liquid is supplied from the manifold into slits having a certain slit interval, and is discharged from the slit lower end opening to the surface of the substrate to be coated. When the die head and the substrate are relatively moved in accordance with the discharge, a uniform coating film is formed on the substrate.

The thickness of the coating film is usually 0.2 to 20 μm, preferably 0.5 to 10 μm, particularly preferably 0.8 to 5.0 μm as the film thickness after drying.
Within the above range, it is preferable in that the gap can be easily adjusted in the pattern development or liquid crystal cell forming step, and a desired color can be easily expressed.
For example, visible rays, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, and the like can be used as the radiation used when forming the pixels, but radiation having a wavelength in the range of 190 to 450 nm is preferable.

  The light source used for image exposure for using radiation having a wavelength of 190 to 450 nm is not particularly limited. Lamp light sources such as medium pressure mercury lamp, low pressure mercury lamp, carbon arc, fluorescent lamp; laser light sources such as argon ion laser, YAG laser, excimer laser, nitrogen laser, helium cadmium laser, semiconductor laser, and the like. An optical filter can also be used when used by irradiating light of a specific wavelength.

Exposure of radiation, 10~10,000J / ^{m 2} is preferred.
Examples of the alkaline developer include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, Inorganic alkaline compounds such as potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide; mono-di- or tri-ethanolamine, mono-di-, or tri -Methylamine, mono-, di-, or tri-ethylamine, mono-, or di-isopropylamine, n-butylamine, mono-, di-, or tri-isopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium Hydroxide (TMAH) Aqueous solution of an organic alkaline compound choline are preferred.

An appropriate amount of a water-soluble organic solvent such as isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol, or the like can be added to the alkali developer. In addition, it is usually washed with water after alkali development.
As the development processing method, any method such as an immersion development method, a spray development method, a brush development method, and an ultrasonic development method can be used. The development conditions are preferably 5 to 300 seconds at room temperature (23 ° C.).

There are no particular restrictions on the conditions of the development processing, but the development temperature is usually 10 ° C. or higher, especially 15 ° C. or higher, more preferably 20 ° C. or higher, and usually 50 ° C. or lower, especially 45 ° C. or lower, further 40 ° C. or lower. Is preferred.
The developing method can be any one of immersion developing method, spray developing method, brush developing method, ultrasonic developing method and the like.

  When the color filter thus produced is used in a liquid crystal display device, a transparent electrode such as ITO is formed on the image as it is and used as a part of a color display, a liquid crystal display device, or the like. Although used, in order to improve surface smoothness and durability, a top coat layer such as polyamide or polyimide can be provided on the image as necessary. Further, in some applications such as a planar alignment type drive system (IPS mode), the transparent electrode may not be formed. In the vertical alignment type driving method (MVA mode), ribs may be formed. Further, a column structure (photo spacer) by a photolithography method may be formed instead of the bead dispersion type spacer.

<Liquid crystal display device>
The liquid crystal display device of the present invention uses the above-described color filter of the present invention. There is no restriction | limiting in particular about the model and structure of the liquid crystal display device of this invention, It can assemble in accordance with a conventional method using the color filter of this invention.
For example, the liquid crystal display device of the present invention can be formed by the method described in “Liquid Crystal Device Handbook” (Nikkan Kogyo Shimbun, September 29, 1989, Japan Society for the Promotion of Science 142nd Committee).

<Organic EL display device>
When producing an organic EL display device having the color filter of the present invention, for example, as shown in FIG. 1, a blue pixel 20 is formed on a transparent support substrate 10 by the colored resin composition for die coating method of the present invention. A multicolor organic EL element can be produced by laminating the organic light-emitting body 500 on the color filter via the organic protective layer 30 and the inorganic oxide film 40. 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 in this manner can be applied to both a passive drive type organic EL display device and an active drive type organic EL display device.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. In addition, this invention is not limited to description of a following example, unless the summary is exceeded.
In the following examples, “part” represents “part by weight”.
[1] Resin synthesis

<Synthesis Example 1: Synthesis of Resin A>
114.0 g of propylene glycol monomethyl ether acetate was placed in a 500 ml four-necked flask and heated to 85 ° C. while performing nitrogen bubbling. To this, 114.4 g (0.65 mol) of benzyl methacrylate, 25.9 g (0.35 mol) of methacrylic acid, and 4.9263 g (0.03 mol) of 2,2′-azobis (isobutyronitrile) were added to propylene glycol 1-monomethyl. It melt | dissolved in 96.45g of ether 2-acetate, and was dripped over 4 hours. After dropping, the reaction solution was further stirred for 2 hours while maintaining the temperature at 85 ° C., and thereafter nitrogen bubbling was stopped, the temperature was raised to 100 ° C., and the mixture was stirred for 1 hour. To this, 0.6628 g (4 × 10 −3 mol) of tetraethylammonium chloride was added, stirred and dissolved at 80 ° C., and further 15.93 g (0.088 mol) of 3,4-epoxycyclohexyl-1-methyl acrylate, propylene glycol A solution mixed with 23.90 g of monomethyl ether acetate was added dropwise over 1 hour. The reaction solution was stirred for 30 hours while maintaining at 80 ° C. to obtain a resin having a weight average molecular weight of 20000 and an acid value of 90 mg-KOH / g.

<Synthesis Example 2: Synthesis of Resin B>
The mixture was stirred while replacing 130 parts by weight of propylene glycol monomethyl ether acetate with nitrogen, and the temperature was raised to 120 ° C. 10 parts by weight of styrene, 85.2 parts by weight of glycidyl methacrylate, and 66 parts by weight of monoacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were added dropwise thereto, and 2.2'-azobis-2-methyl 8.47 parts by weight of butyronitrile was added dropwise over 3 hours, and stirring was continued at 90 ° C. for 2 hours. Next, the inside of the reaction vessel was changed to air substitution, 0.7 part by weight of trisdimethylaminomethylphenol and 0.12 part by weight of hydroquinone were added to 43.2 parts by weight of acrylic acid, and the reaction was continued at 100 ° C. for 12 hours. Thereafter, 56.2 parts by weight of tetrahydrophthalic anhydride (THPA) and 0.7 parts by weight of triethylamine were added and reacted at 100 ° C. for 3.5 hours. Further, propylene glycol monomethyl ether acetate was added to adjust the solid content concentration to 60.0% by weight. The binder resin thus obtained had a weight average molecular weight Mw measured by GPC of about 8400, an acid value of 80 mg-KOH / g.

[2] Preparation of pigment dispersion [2-1] Preparation of red pigment dispersion 1
As a pigment, C.I. I. 20.0 parts by weight of Pigment Red 254, “BYK-LPN6919” (methacrylic acid AB block copolymer, amine value 121 mg-KOH / g, acid value 1 mg-KOH / g or less) as a dispersant 8.0 parts by weight in terms of the amount, 6.67 parts by weight of the resin A of Synthesis Example 1 as the binder resin were mixed, and propylene glycol monomethyl ether acetate was used as the solvent to adjust the solids concentration to 20%. . A stainless steel container was filled with 100.5 parts by weight of this mixed solution and 300 parts by weight of zirconia beads having a diameter of 0.5 mm, and dispersed in a paint shaker for 6 hours to prepare a red pigment dispersion 1.

[2-2] Preparation of red pigment dispersion 2 C.I. I. 22.0 parts by weight of Pigment Red 177, “BYK-DB2000” (methacrylic acid AB block copolymer, amine value 10 mg-KOH / g, acid value 1 mg-KOH / g or less) as a dispersant 5.5 parts by weight in terms of a component, 6.0 parts by weight of resin A of Synthesis Example 1 as a binder resin in terms of solids, and 98.2 g of propylene glycol monomethyl ether acetate and 26.8 g of propylene glycol monomethyl ether as solvents Was used to adjust the solid content concentration to 20%. A stainless steel container was filled with 100.5 parts by weight of this mixed solution and 300 parts by weight of zirconia beads having a diameter of 0.5 mm, and dispersed in a paint shaker for 6 hours to prepare a red pigment dispersion 2.

[2-3] Preparation of yellow pigment dispersion 22.0 parts by weight of E4GN-GT (manufactured by LANXESS) as a pigment, and 5.5 parts by weight of BYK-DB2000 manufactured by Big Chemie as a dispersant, 6.27 parts by weight of the binder resin A of Synthesis Example 1 as a resin was mixed as a resin, 98.7 g of propylene glycol monomethyl ether acetate as a solvent, 27.0 g of propylene glycol monomethyl ether as a solvent, Adjusted to 20%. A stainless steel container was filled with 100 parts by weight of this mixed solution and 300 parts by weight of zirconia beads having a diameter of 0.5 mm, and dispersed in a paint shaker for 6 hours to prepare a yellow pigment dispersion.

[3] Preparation of colored resin composition Pigment dispersion prepared in [2-1] to [2-3], resin B as binder resin, dipentaerythritol hexaacrylate as polymerizable monomer, and 2- (2′-chlorophenyl) -4,5-diphenylimidazole dimer, diethylaminobenzophenone, 2-mercaptobenzothiazole, “IRGACURE 907” (2-methyl-1- [4- (methylthio) phenyl], manufactured by Ciba Japan -2-morpholinopropan-1-one)
The surfactant and the surfactant were mixed with DIC F-475 (fluorinated surfactant) diluted with 1% propylene glycol monomethyl ether acetate and the solvent in the proportions shown in Table 1, and coloring of Examples and Comparative Examples A resin composition was prepared.
In addition, the numerical value of Table 1 is content (part by weight) containing a solvent.

[4] Re-solubility evaluation Using the colored resin composition obtained in the section of "[3] Preparation of colored resin composition", re-solubility was evaluated according to the following procedure.
The results are summarized in Table 2.
In addition, the numerical value of the solvent in Table 2 shows the content rate of each solvent when all the solvents are 100%.

<Resolubility evaluation procedure>
(1) Measure 2.5 g of the colored resin composition in a 5 ml glass bottle.
(2) Weigh 3.5 g of PGMEA and each colored resin composition into a 5 ml glass bottle.
(3) The washed glass substrate for liquid crystal is cut into a strip shape having a width of 5 mm and a length of 10 cm, and dipped straight into a glass bottle containing the colored resin composition and taken out.
(4) The strip-shaped glass plate to which the colored resin composition is adhered is allowed to stand for 30 minutes in a 23 ° C. and 55% humidity environment.
(5) Next, the strip-shaped glass plate on which the colored resin composition (4) is attached is immersed in PGMEA and the mixed solvent used in each colored resin composition for 5 seconds.
(6) The strip-shaped glass plate to which the colored resin composition is adhered is shaken lightly 5 times in a glass bottle containing the mixed solvent used in PGMEA and each colored resin composition.
(7) The strip-shaped glass plate to which the colored resin composition is adhered is taken out, and the state of resist elution in the glass bottle containing the mixed solvent used in PGMEA and each colored resin composition is observed.

<Judgment>
○: The adhering colored resin composition is uniformly dissolved in the mixed solvent used in PGMEA and each colored resin composition, and almost no colored resin composition remains on the glass plate. Δ: With PGMEA and each colored resin composition. The adhering colored resin composition is slightly dissolved in the mixed solvent used.
X: Colored resin composition hardly dissolves

As shown in Table 2, the dry film formed using the colored resin composition of the present invention exhibits high solubility in the mixed solvent used in PGMEA and the colored resin composition.
That is, the colored resin composition of the present invention is optimal for the die coating method because there are few aggregated foreign substances generated by the die coating method.
In addition, when a coating film is formed by the die coating method using the colored resin composition of the present invention, the generation of aggregated foreign matters is small, and therefore, coating unevenness due to the foreign matters and manufacturing yield are not likely to occur.

  Furthermore, a color filter including pixels obtained by a die coating method using the colored resin composition of the present invention, and a liquid crystal display device and an organic EL display device including the color filter are of high quality.

DESCRIPTION OF SYMBOLS 100 Organic EL element 20 Blue pixel 30 Organic protective layer 40 Inorganic oxide film 500 Organic light-emitting body 51 Hole injection layer 54 Electron injection layer

Claims (7)

A colored resin composition for a die coating method containing (A) a pigment, (B) a solvent, (C) a binder resin, and (D) a dispersant,
The total solid content concentration of the colored resin composition is 20% by weight or less,
The pigment (A) contains a red pigment in a total pigment solid content of 26% by weight to 40% by weight,
The (D) dispersant contains a polymer,
The polymer has a primary to tertiary amino group and / or a quaternary ammonium group in the side chain,
In the monomer composition constituting the polymer, the content ratio of the monomer having the primary to tertiary amino group and / or quaternary ammonium group is 20% by weight or more,
(B) A colored resin composition for a die coating method, wherein the solvent contains 1,3-butylene glycol diacetate in an amount of 5% by weight to 14% by weight in the total solvent.   2. The colored resin for die coating according to claim 1, wherein (B) the solvent further contains 6% by weight to 16% by weight of methoxybutyl acetate and / or ethyl ethoxypropionate in the total solvent. Composition   Furthermore, (E) The polymerizable monomer is contained, The coloring resin composition for die-coating methods of Claim 1 or 2 characterized by the above-mentioned.   Furthermore, (F) The photopolymerization start component and / or the thermal polymerization start component are contained, The coloring resin composition for die-coating methods as described in any one of Claims 1-3 characterized by the above-mentioned.   It has a pixel formed using the coloring resin composition for die-coating methods as described in any one of Claims 1-4, The color filter characterized by the above-mentioned.   A liquid crystal display device comprising the color filter according to claim 5. An organic EL display device comprising the color filter according to claim 5.

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