JP2013195973A - Coloring resin composition, color filter, liquid crystal display device, and organic el display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring resin composition which is capable of reducing residues on a substrate and yet highly resoluble, and to provide a color filter having pixels formed using the coloring resin composition, and a high quality liquid crystal display device and a high quality organic EL display device.SOLUTION: A coloring resin composition contains (A) a coloring material, (B) a solvent, and (C) a binder resin, where (C) the binder resin contains a specific unsaturated-group-containing resin and (B) the solvent contains a high boiling point solvent whose boiling point at 1013.25 hPa and 23°C is between 170°C and 240°C, inclusive.

Description

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

  In recent years, color filters tend to be used not only for monitors but also for televisions in liquid crystal display (LCD) applications. With the trend of the expansion of applications and energy saving, color filters are required to have high color characteristics in terms of chromaticity and contrast. In addition, color filters for image sensors (solid-state imaging devices) are also required to have high color characteristics such as reduction of color unevenness and improvement of color resolution, and high definition is also desired. ing.

  As described above, in recent years, the demand for high color reproducibility of color filters has increased, and colored resin compositions tend to have high pigment concentrations. However, when a colored pattern is formed by a photolithographic method using a colored resin composition having a high pigment concentration, since the pigment hinders or absorbs the transmission of ultraviolet rays, the underexposure is remarkable and the sensitivity becomes insufficient. , There is a tendency that sufficient deep curability cannot be obtained upon exposure.

In order to solve this problem, it has been proposed to use a highly sensitive resin (see, for example, Patent Documents 1 to 3), but a residue may be generated on the substrate of the non-pixel portion to be removed by development. There was a case.
In order to solve this problem, for example, Patent Document 4 discloses a colored photosensitive resin composition containing a specific resin and at least one compound selected from the group consisting of a triazine compound, an acetophenone compound and a biimidazole compound. Yes.

JP-A-8-262221 JP 2001-337450 A JP 2001-89533 A JP 2004-361455 A

However, in Patent Document 4, re-dissolvability of the colored resin composition sometimes becomes a problem. The re-solubility of the colored resin composition means that the aggregated foreign matters of the colored resin composition are dissolved again in the colored resin composition.
Conventionally, the spin coating method has been used in the coating step of the colored resin composition. However, in recent years, the shift to the slit-and-spin method and the die coating method has been performed due to the necessity of increasing the size of the substrate and saving liquid.
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 other words, when the re-solubility is low, there is a problem in that the production yield is lowered and the quality of the product is lowered due to the aggregated foreign matter.

Then, this invention makes it a subject to provide the colored resin composition with high re-dissolution property of a colored resin composition, maintaining the effect of the residue reduction on a board | substrate.
Another object of the present invention is to provide a color filter having pixels formed using the colored resin composition, a high-quality liquid crystal display device, and an organic EL display device.

As a result of intensive studies, the present inventors have found that (C) the binder resin can solve the above problems by including a specific resin, and have reached the present invention.
That is, the present invention contains (A) a pigment, (B) a solvent, and (C) a binder resin, and the (C) binder resin copolymerizes the following (C-1) to (C-3). The resulting copolymer is further reacted with (C-4) and then with (C-5) to obtain an unsaturated group-containing resin (hereinafter referred to as “specific unsaturated group-containing resin”). And (B) the solvent contains 101.25 hPa, a high boiling point solvent whose boiling point at 23 ° C. is 170 ° C. or higher and 240 ° C. or lower (hereinafter sometimes simply referred to as “high boiling point solvent”). A colored resin composition, a color filter, a liquid crystal display device and an organic EL display device.
(C-1); compound having an unsaturated bond and an epoxy group in one molecule (C-2); at least one skeleton selected from the group consisting of a tricyclodecane skeleton and a dicyclopentadiene skeleton in one molecule And a compound (C-3) having an unsaturated bond; a compound (C-4) having an unsaturated bond copolymerizable with the above (C-1) and (C-2); an unsaturated carboxylic acid ( C-5); succinic anhydride

The present invention can provide a colored resin composition having a higher resolubility of the colored resin composition while maintaining the effect of reducing residues on the substrate.
The present invention can also provide a color filter having pixels formed using the colored resin composition, a high-quality liquid crystal display device, and an 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 of the present invention other than the solvent components described later.
Furthermore, “aromatic ring” means both “aromatic hydrocarbon ring” and “aromatic heterocycle”.
Moreover, terms such as “CI Pigment Green” mean a color index (CI).

The colored resin composition of the present invention contains (A) a pigment, (B) a solvent, and (C) a binder resin, the solvent contains a high-boiling solvent, and the (C) binder resin is a specific unsaturated. It contains a group-containing resin, preferably (D) a polymerizable monomer, (E) a photopolymerization initiating component and / or a thermal polymerization initiating component, and may further contain other components as required.
First, (C) the binder resin will be described in detail.

[(C) Binder resin]
In the colored resin composition of the present invention, (C) the binder resin is obtained by further reacting (C-4) with a copolymer obtained by copolymerizing the following (C-1) to (C-3): Subsequently, the unsaturated group containing resin obtained by making (C-5) react is included.
(C-1); compound having an unsaturated bond and an epoxy group in one molecule (C-2); at least one skeleton selected from the group consisting of a tricyclodecane skeleton and a dicyclopentadiene skeleton in one molecule And a compound (C-3) having an unsaturated bond; a compound (C-4) having an unsaturated bond copolymerizable with the above (C-1) and (C-2); an unsaturated carboxylic acid ( C-5); succinic anhydride

  Specific examples of the compound (C-1) having an unsaturated bond and an epoxy group in one molecule include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and methyl glycidyl (meth) acrylate. Is mentioned. Preferably, it is glycidyl (meth) acrylate. These can be used alone or in combination of two or more.

  As the compound (C-2) having an unsaturated bond and a tricyclodecane skeleton and / or a dicyclopentadiene skeleton in one molecule, specifically, dicyclopentanyl (meth) acrylate, dicyclopentenyl ( And (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate. These can be used alone or in combination. Specific examples of the compound (C-3) having an unsaturated bond copolymerizable with the above (C-1) and (C-2) include methyl (meth) acrylate, ethyl (meth) acrylate, and butyl. Unsubstituted or substituted alkyl esters of unsaturated carboxylic acids such as (meth) acrylate, 2-hydroxyethyl (meth) acrylate and aminoethyl (meth) acrylate;

Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylate, menthyl (meth) acrylate, cyclopentenyl (meth) acrylate, cyclohexenyl (meta) ) Acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, mentadienyl (meth) acrylate, isobornyl (meth) acrylate, pinanyl (meth) acrylate, adamantyl (meth) acrylate, norbornenyl (meth) acrylate, pinenyl (meth) acrylate An ester compound containing an alicyclic group of an unsaturated carboxylic acid such as
Monosaturated carboxylic acid ester compounds of glycols such as oligoethylene glycol monoalkyl (meth) acrylate;

Ester compounds containing an aromatic ring of an unsaturated carboxylic acid such as benzyl (meth) acrylate and phenoxy (meth) acrylate;
Aromatic vinyl compounds such as styrene, α-methylstyrene and vinyltoluene;
Carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate;
Vinyl cyanide compounds such as (meth) acrylonitrile and α-chloroacrylonitrile;
And maleimide compounds such as N-phenylmaleimide. These can be used alone or in combination.

  Specifically, the unsaturated carboxylic acid (C-4) is preferably acrylic acid or methacrylic acid, and particularly preferably methacrylic acid. Acrylic acid and methacrylic acid can be used alone or in combination. In addition to these acrylic acid and methacrylic acid, other acids can be used. Specifically, as the other acid, at least one carboxylic acid selected from other unsaturated carboxylic acids such as crotonic acid, itaconic acid, maleic acid and fumaric acid can be used in combination. A monomer containing a hydroxy group and a carboxyl group in the same molecule, such as α- (hydroxymethyl) acrylic acid, can also be used in combination.

In the copolymer obtained by copolymerizing (C-1) to (C-3) in the present invention, the ratio of the components derived from each of (C-1) to (C-3) is as described above. It is preferable to be in the following range in terms of mole fraction with respect to the total number of moles of the constituent components constituting the copolymer.
Structural units derived from (C-1); 2-98 mol%
Structural units derived from (C-2); 1 to 90 mol%
Structural units derived from (C-3); 1 to 65 mol%
Moreover, it is more preferable in the ratio of the said structural component being the following ranges.
Structural units derived from (C-1); 40 to 80 mol%
Structural units derived from (C-2); 5 to 40 mol%
Structural units derived from (C-3); 5 to 30 mol%

Further, next, (C-4) and (C-5) are added to the copolymer to give the resin solubility in a developer and light / thermosetting.
The addition amount of (C-4) is 0.5 to 1.0 equivalent with respect to 1.0 equivalent of epoxy group in the resin obtained by polymerizing (C-1) to (C-3). Preferably it is 0.7-1.0 equivalent. When the composition ratio of (C-4) is within the above range, sufficient photocurability and thermosetting properties can be obtained, and sensitivity and reliability are excellent. The addition amount of (C-5) is 50 to 100%, preferably 60 to 100%, in terms of a molar fraction with respect to the amount of hydroxyl group produced when (C-4) is reacted.
When the composition ratio of (C-5) is within the above range, it is preferable because it is excellent in solubility in an alkali developer and hardly generates a residue.

The specific unsaturated group-containing resin preferably has a polystyrene-equivalent weight average molecular weight measured by GPC in the range of 4,000 to 100,000, and more preferably in the range of 4,500 to 20,000.
Within the above range, it is preferable because film loss is unlikely to occur during development, and the non-pixel portion tends to be easily removed during development.
The molecular weight distribution (weight average molecular weight Mw / number average molecular weight Mn) of the specific unsaturated group-containing resin is preferably 1.5 to 6.0, and more preferably 2.0 to 4.0. The molecular weight distribution (weight average molecular weight Mw / number average molecular weight Mn) is preferably from 1.5 to 6.0 because the developability is excellent.

(Other resins)
The colored resin composition of the present invention may contain other binder resins in addition to the specific unsaturated group-containing 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, etc. can do.

(Content)
The binder resin (C) used in the colored resin composition of the present invention is usually contained in the range of 5 to 90% by weight, preferably 10 to 70% by weight, based on the total solid content in the colored resin composition. . If it is within the above range, the solubility in the developer is sufficient, development residue is not easily generated on the substrate of the non-pixel portion, and the film thickness of the pixel portion of the exposed portion is difficult to occur during development. This is preferable because the slipperiness tends to be good.
In the present invention, it is preferable that all of the resins contained as the binder resin (C) are specific unsaturated group-containing resins, that is, the specific unsaturated group-containing resin is contained within the above range. preferable.

[(A) Pigment]
As the (A) pigment in the present invention, pigments of various colors such as a red pigment, a green pigment, a yellow pigment, a violet pigment, an orange pigment, and a brown pigment can be used.
Examples of the chemical structure of various pigments 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.

  First, as a red pigment, 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, and the like.

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, 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, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 17 , 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, and pigments described in JP-A-2005-325350 and JP-A-2007-25687.
Of these, C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 154, 155, 180, 185, and the pigment, pigment Y and the like described in the above-mentioned 2 publications, more preferably C.I. I. Pigment yellow 83, 138, 139, 180, and the pigment, pigment Y and the like described in the above-mentioned 2 publications.

  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 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. 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.

Alternatively, the pigment dispersion of the present invention may be used to prepare a colored resin composition as will be described later to form a resin black matrix of a color filter. In that case, a black pigment can be used. . 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.
As the pigment used in the present invention, red to yellow pigments are preferable from the viewpoint of the color of the pigment dispersion, and diketopyrrolopyrrole pigments and anthraquinone pigments that are pigmented mainly by hydrogen bonds are particularly preferable.

  The pigment in the present invention is preferably C.I. I. (Color Index) Pigment Red 177, Pigment Red 242, Pigment Red 254, Pigment Yellow 138, Pigment Yellow 139, Pigment Yellow 180, Pigment Blue 15: 6, Pigment Blue 15: 3, Pigment Violet 23, Pigment Pigment Green 7, Pigment It is preferable to use at least one pigment selected from the group consisting of Green 36, Pigment Green 58 and Pigment Y.

Examples of inorganic pigments that can be used in the present invention include barium sulfate, lead sulfate, titanium oxide, yellow lead, red iron oxide, and chromium oxide.
In addition, the above-mentioned various pigments can be used in combination. For example, in order to adjust chromaticity, 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 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 keeping the average primary particle size of the pigment used in the above range, the depolarization characteristics are kept good, high contrast and transmittance are realized, dispersion stability is good, and heat resistance and light resistance are also improved. An excellent pigment dispersion and colored resin composition 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 thus obtained may be used alone, but one or two or more pigments can be mixed and used within a range not impairing the effects of the present invention.
The content of the pigment (A) in the present invention is usually 80% by weight or less, preferably 70% by weight or less, more preferably 60% by weight or less, and usually 0.1% by weight or more based on the total solid content. , Preferably 0.5% by weight or more, more preferably 1% by weight or more.

  (A) By setting the pigment content within the above range, the film thickness with respect to the color density does not become too large, and there is no adverse effect on the gap control during the formation of a liquid crystal cell, and sufficient image formability is obtained. In addition, the dispersed state of the pigment is maintained, and aggregation and sedimentation are unlikely to occur. As a result, problems such as thickening and lowering of brightness and contrast can be solved.

[(B) Solvent]
In the colored resin composition of the present invention, (B) the solvent contains a high boiling point solvent having a boiling point of 1013.25 hPa and a boiling point at 23 ° C of 170 ° C or higher and 240 ° C or lower.
Examples of the high boiling point solvent include ethyl diglycol acetate, 1,3-butylene glycol diacetate, diethylene glycol monobutyl ether acetate, and diethylene glycol mono-n-butyl ether.
The other solvent is not particularly limited as long as it dissolves or disperses each component constituting the colored resin composition and the viscosity becomes appropriate, and examples thereof 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, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monoethyl Glycol alkyl ether acetates such as ether acetate, diethylene glycol 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:
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 of the (A) pigment in the present invention in the solvent. Furthermore, propylene glycol monomethyl ether acetate is particularly preferable from the viewpoint of solubility of various components in the colored resin composition.
In addition, it is more preferable to use a glycol monoalkyl ether as a solvent by mixing from the viewpoints of good balance such as applicability and surface tension and relatively high solubility of the components in the composition.
(B) The proportion of glycol monoalkyl ethers in the solvent is preferably 5 to 50% by weight and more preferably 5 to 30% by weight in terms of good storage stability.

In the colored resin composition of the present invention, the content of the high boiling point solvent is usually 10% by weight or more, preferably 20% by weight or more, more preferably 15% by weight or more, and usually 50% by weight in the total solvent (B). % Or less, preferably 35% by weight or less.
In the colored resin composition of the present invention, the content of the (B) solvent is not particularly limited as long as the effect of the present invention is not impaired, but is usually 75% by weight or more, preferably 80% by weight or more, and more preferably 82%. % By weight or more, and usually 99% by weight or less.
Within the above range, the colored resin composition is preferable in that it has a viscosity suitable for application and can form a coating film satisfactorily.

<Reason for effect>
By setting it as the structure of this invention, the reason which residue reduction and re-dissolution property improve is estimated as follows.
In the specific resin in the present invention, (C-5) succinic anhydride is added to the side chain. Therefore, the adsorptive power with respect to the pigment is strong and the pigment is dissolved in the developer together with the pigment, so that the residue after development is reduced.
On the other hand, since the specific unsaturated group-containing resin of the present invention has (C-5) succinic anhydride added to the side chain, the resin easily aggregates.
That is, in the case of a colored resin composition, aggregated foreign matters due to the specific unsaturated group-containing resin are likely to be generated, that is, re-solubility tends to be a problem.
In the colored resin composition of the present invention, by including the high boiling point solvent, for example, the drying rate of the colored resin composition attached to the tip of the nozzle is reduced, and the re-solubility is improved.

[Dispersant]
The dispersant in the present invention is not particularly limited as long as the pigment is dispersed and can maintain stability. For example, cationic, anionic, nonionic or amphoteric dispersants can be used, but polymer dispersants are preferred. Specifically, a modified acrylic copolymer, an acrylic copolymer, polyurethane, polyester, a polymer copolymer alkylammonium salt or phosphate ester salt, a cationic comb graft polymer, and the like can be given. Among these dispersants, modified acrylic copolymers, polyurethane, and cationic comb graft polymers are preferable. In particular, a modified acrylic copolymer is preferable. Among these, a block copolymer composed of an A block having a solvophilic property and a B block having a functional group containing a nitrogen atom has an amine value of 80 mg-KOH / g or more and 150 mg. What is -KOH / g or less (effective solid content conversion) is especially preferable. More preferably, it is 100-140 mg-KOH / g.
Within the above range, the adsorptive power to the pigment surface is sufficient and the dispersion stability is good.

Of these, the (meth) acrylic block copolymer described in JP-A-2009-025813 is preferable. The acrylic block copolymer can disperse the pigment (A) very efficiently. This is presumably because the molecular arrangement is controlled, so that there are few structures that obstruct the dispersant when adsorbing to the pigment.
In the present invention, the acrylic block copolymer is preferably an AB block comprising an A block and a B block and / or an ABA block copolymer.

The B block constituting the acrylic block copolymer has an amino group, and the amino group is preferably —NR ⁴¹ R ⁴² (provided that R ⁴¹ and R ⁴² each independently have a substituent). A cyclic or chain alkyl group which may be substituted, an aryl group which may have a substituent, or an aralkyl group which may have a substituent. A preferable example is represented by the following formula, for example.

^{(However, R 41} and ^{R 42} has the same meaning as above ^{R 41} and ^{R 42, R 43} is one or more alkylene groups having a carbon ^{number, R 44} represents a hydrogen atom or a methyl group.)
Among them, R ⁴¹ and R ⁴² are preferably methyl groups, R ⁴³ is preferably a methylene group or an ethylene group, and R ⁴⁴ is preferably a methyl group. Examples of such a compound include a partial structure represented by the following formula.

  Two or more kinds of the partial structure containing an amino group as described above may be contained in one B block. In that case, two or more amino group-containing partial structures may be contained in the B block in any form of random copolymerization or block copolymerization. In addition, a partial structure not containing an amino group may be partially contained in the B block within a range not impairing the effects of the present invention. Examples of such a partial structure include (meth) acrylic acid esters. And a partial structure derived from a monomer.

On the other hand, in the present invention, the A block of the dispersant is not particularly limited as long as the A block is solvophilic and is composed of a monomer copolymerizable with the monomer constituting the B block described above.
Examples of the A block include polymer structures obtained by copolymerizing comonomers such as styrene monomers, (meth) acrylate monomers, (meth) acrylate monomers, vinyl acetate monomers, glycidyl ether monomers, and the like. It is done.

The dispersant in the present invention is an AB block or ABA block copolymerized polymer compound composed of an A block and a B block as described above. Of these, AB block copolymers are preferred. Such a block copolymer is prepared, for example, by a living polymerization method.
The living polymerization method includes an anion living polymerization method, a cation living polymerization method, and a radical living polymerization method. Specifically, for example, a method described in JP-A-2007-270147 can be mentioned.
In addition, the amine value (in terms of effective solid content) of the dispersant is 1 solid content excluding the solvent in the dispersant sample.
Expressed by the weight of KOH equivalent to the amount of base per g, and 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.)
Further, the acid value of this block copolymer is preferably lower, although it depends on the presence and type of acidic groups that form the acid value, and is usually 50 mg-KOH / g or less, preferably 40 or less, more preferably. Is 30 or less.
When the average primary particle size of the pigment is small, the specific surface area increases and the amount of adsorbing dispersant per unit area decreases. In this case, the dispersant made of the copolymer is preferably used because it is more effective than the other dispersants.

The dispersant in the present invention is preferably 5% by weight or more, more preferably 10% by weight or more, and usually 200% by weight or less, more preferably 100% by weight or less, based on the total amount of the pigment (A) in the colored resin composition. It is.
The colored resin composition of the present invention may contain other dispersants as long as the effects of the present invention are not impaired. Examples of other dispersants include those described in JP-A-2006-343648, for example.

[Dispersion aid]
The colored resin composition of the present invention may further contain a dispersion aid. The dispersion aid here may be a pigment derivative. Examples of the pigment derivative include JP-A Nos. 2001-220520, 2001-271004, 2002-179976, and 2007-. Various compounds described in Japanese Patent Application Publication No. 113000 and Japanese Patent Application Publication No. 2007-186681 can be used.

The content of the dispersion aid in the colored resin composition of the present invention is usually 0.1% by weight or more, usually 30% by weight or less, preferably 20% by weight or less, based on the total (A) pigment. More preferably, it is 10 weight% or less, More preferably, it is 5 weight% or less.
Within the above range, the effect as a dispersion aid is effectively obtained, and this is preferable in terms of good dispersibility and dispersion stability.

[Dispersion resin]
In the colored resin composition of the present invention, a part or all of the resin selected from the binder resin (C) including the resin synthesized in the above (C-1) to (C-5) is used as the following dispersion resin. You may contain.
Specifically, in [Preparation Method of Colored Resin Composition], which will be described later, by adding (C) binder resin together with the components such as the above-mentioned dispersant, the (C) binder resin is combined with the dispersant. It contributes to the dispersion stability of the pigment (A) by a synergistic effect. As a result, the amount of dispersant added may 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 pigment in the pigment dispersion.
As the dispersion resin, the above-mentioned various (C) binder resins can be used.
The acid value of the dispersion resin is preferably 0.5 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 or less 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, more preferably 200000 or less, more preferably 50000 or less, and 30000 or less. Most preferred. 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.

[(D) Polymerizable monomer]
The colored resin composition of the present invention preferably contains (D) a polymerizable monomer. (D) 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 the photopolymerization initiation system described later when the colored resin composition of the present invention is irradiated with actinic rays. It is. In addition, the (D) 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.

  (D) 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; Esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; Esterification of unsaturated carboxylic acids with polyvalent carboxylic acids and polyhydric hydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds described above An ester obtained by the reaction; 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 group. The monomer having an acid group is, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid. 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 (D) 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 of the present invention, the content of the polymerizable monomer (D) 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. Further, 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 (D) polymerizable monomer to the total 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. % By weight or less, preferably 150% by weight or less, more preferably 110% 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.

[(E) Photopolymerization initiation component and / or thermal polymerization initiation component]
The colored resin composition of the present invention preferably contains (E) 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 (D), 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 (E) as a photopolymerization initiation component refers to a photopolymerization initiator (hereinafter also referred to as “(E1) component”), a polymerization accelerator (hereinafter, optionally referred to as “(E2) component”). ")" And a sensitizing dye (hereinafter also referred to as "(E3) component").

[(E) Photopolymerization initiation component]
The (E) photopolymerization initiating component in the present invention is usually a mixture of (E1) a photopolymerization initiator and, if necessary, (E2) a polymerization accelerator and (E3) an additive such as a sensitizing dye. And is a component having a function of generating a polymerization active radical by directly absorbing light or being photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction.

  Examples of (E1) photopolymerization initiator constituting the photopolymerization initiating component 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.

Specific examples include photopolymerization initiators described in International Publication No. 2009/107734 pamphlet and the like.
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 a compound represented by the following formula (XI).

(In formula (XI), R ¹⁰¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or 2 to 25 carbon atoms.
An alkenyl group, a C 3-20 heteroaryl group or a C 4-25 heteroarylalkyl group, any of which may have a substituent. Alternatively, R ¹⁰¹ may be bonded to X or Z to form a ring.
R ¹⁰² represents an alkanoyl group having 2 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 4 to 8 carbon atoms, an aryloyl group having 7 to 20 carbon atoms, or an alkoxycarbonyl group having 2 to 10 carbon atoms. , An aryloxycarbonyl group having 7 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, a heteroaryloyl group having 3 to 20 carbon atoms, or an alkylaminocarbonyl group having 2 to 20 carbon atoms, It may have a substituent.
X represents a divalent aromatic hydrocarbon ring group and / or an aromatic hetero group formed by condensation of two or more rings which may have a substituent.
Z represents an aromatic ring group which may have a substituent. )
Of the compounds represented by the formula (XI), compounds in which X is a carbazole ring which may have a substituent are preferable. Specifically, compounds represented by the following formula (XII) Among them, the compound represented by the following formula (XIII) is particularly preferable.

(Wherein R ¹⁰¹ , R ¹⁰² and Z have the same meanings as in formula (XI), R ^103.
To R ¹⁰⁹ is a hydrogen atom or an arbitrary substituent independently. )

(In the formula, R ^101a represents an alkyl group having 1 to 3 carbon atoms or a group represented by the following formula (XIIIa).

(Wherein R ¹⁰³ and R ¹⁰⁴ each independently represent a hydrogen atom, a phenyl group or an N-acetyl-N-acetoxyamino group.
* Represents a binding site. )
R ^102a represents an alkanoyl group having 2 to 4 carbon atoms, and X ^a represents a 3,6-carbazolyl group in which the nitrogen atom may be substituted with an alkyl group having 1 to 4 carbon atoms. Za represents ^a phenyl group which may be substituted with an alkyl group or a naphthyl group which may be substituted with a morpholino group. )
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 (E2) 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.
Each of these (E1) photopolymerization initiator and (E2) polymerization accelerator may be used alone or in combination of two or more.

  Further, (E3) 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.

(E3) 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 of these (E) photopolymerization initiating components is usually 0.1% by weight or more, preferably 0.2% by weight or more, more preferably 0.8% by weight in 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.
Within the above range, the sensitivity to the exposure light beam is good, the solubility of the unexposed part in the development station is good, and it is preferable in that it is difficult to induce poor development.

((E) Thermal polymerization initiation component)
Specific examples of the (E) thermal polymerization initiating component that may be contained in the colored resin composition 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 initiating component described in International Publication No. 2009/107734 can be used.
These thermal polymerization initiating components may be used alone or in combination of two or more.

[Other optional ingredients]
In addition to the above components, the colored resin composition of the present invention comprises a surfactant, an organic carboxylic acid and / or an organic carboxylic acid anhydride, a thermosetting compound, a plasticizer, a thermal polymerization inhibitor, a storage stabilizer, a surface It may contain a protective agent, an adhesion improver, a development improver, and the like. As these optional components, for example, various compounds described in JP-A-2007-113000 can be used.

[Preparation Method of Colored Resin Composition]
In the present invention, the colored resin composition can be prepared by an appropriate method. For example, the colored resin composition includes (A) a pigment, (C) a binder resin containing a specific unsaturated group-containing resin, and an acid group-containing monomer ( D) The polymerizable monomer can be prepared by mixing with (B) a solvent and optional components used as necessary.
Preferably, (A) a pigment is added in (B) a solvent, in the presence of a dispersing agent and, if necessary, a dispersing aid, optionally with (C) a part of a binder resin, for example, a paint shaker, Using a sand grinder, ball mill, roll mill, stone mill, jet mill, homogenizer or the like, a pigment dispersion is prepared by mixing and dispersing while grinding. The pigment dispersion contains (C) a binder resin containing a specific unsaturated group-containing resin, and (D) a polymerizable monomer containing an acid group-containing monomer, and (E) a photopolymerization initiating component and / or heat, if necessary. The method of preparing by adding a polymerization start component, another component, etc., and mixing can be mentioned.

[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. Such a colored resin composition is supplied onto a substrate to form components such as a color filter, a liquid crystal display device, and an organic EL display device.
Hereinafter, as an application example of the colored resin composition 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 them will be described.

<Color filter>
The color filter of the present invention has a pixel formed from the colored resin composition of the present 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 partition a portion for forming pixels, and after applying the colored resin composition of the present invention on this substrate, pre-baking is performed. The solvent is evaporated to 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 pixels is not particularly limited as long as it is transparent and has an appropriate strength. For example, polyester resin, polyolefin resin, polycarbonate resin, acrylic resin, thermoplastic resin Examples thereof include a sheet made, an epoxy resin, a thermosetting resin, and various glasses.
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.

When applying the colored resin composition to the substrate, a spinner method, a wire bar method, a flow coating method, a slit and spin method, a die coating method, a roll coating method, a spray coating method, and the like can be given. Of these, the slit and spin method and the die coating method are preferable.
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.
As the radiation used in the exposure, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used, and radiation having a wavelength in the range of 190 to 450 nm is preferable.

A light source for using radiation having a wavelength of 190 to 450 nm used for image exposure is not particularly limited. 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, 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, more preferably 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 component such as a color display or a liquid crystal display device. 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, on a blue color filter in which pixels 20 are formed on a transparent support substrate 10 by the colored resin composition of the present invention. A multicolor organic EL element is manufactured by laminating the organic light-emitting body 500 through 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 as described above can be applied to both a passive drive type organic EL display device and an active drive type organic EL display device.

Next, although a synthesis example, 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.
In the following examples, “part” represents “part by weight”.
<Resin synthesis>
(Synthesis Example 1: Synthesis of Resin P-1)
145 parts by weight of propylene glycol monomethyl ether acetate was stirred while purging 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 FA-513M (manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton 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, 19.2 parts by weight of succinic anhydride and 0.7 parts by weight of triethylamine were added and reacted at 100 ° C. for 3.5 hours.
The weight average molecular weight Mw in terms of polystyrene measured by GPC of the obtained resin P-1 is about 9
000, and the acid value was 81 mg-KOH / g.

(Reference Synthesis Example 1: Synthesis of Resin P-2)
145 parts by weight of propylene glycol monomethyl ether acetate was stirred while purging 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 FA-513M (manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton 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. The weight average molecular weight Mw in terms of polystyrene measured by GPC of the obtained resin P-2 was about 8400, and the acid value was 80 mg-KOH / g.

(Reference Synthesis Example 2: Synthesis of Resin Q-1)
50 parts by weight of polyethyleneimine having a molecular weight of about 5000 and 40 parts by weight of polycaprolactone with n = 5 are mixed with 300 parts by weight of propylene glycol monomethyl ether acetate, stirred at 150 ° C. for 3 hours in a nitrogen atmosphere, and an amine value of 40 mgKOH / G, resin Q-1 having an acid value of 10 mg-KOH / g was obtained.

<Preparation of pigment dispersion>
[1] Preparation of blue pigment dispersion (1) 80 parts by weight of propylene glycol monomethyl ether acetate, pigment C.I. I. Pigment Blue 15: 6 (abbreviated as B 15: 6) 13.33 parts by weight, 2.22 parts by weight of the resin Q-1 synthesized in Reference Synthesis Example 2, and 4. the resin P-2 synthesized in the above Reference Synthesis Example 4. 44 parts by weight were mixed and stirred with a stirrer for 3 hours to prepare a mill base having a solid content concentration of 20% by weight.

[2] Preparation of purple pigment dispersion (1) 80 parts by weight of propylene glycol monomethyl ether acetate, pigment C.I. I. 13.33 parts by weight of Pigment Violet 23, 2.22 parts by weight of Resin Q-1 synthesized in Reference Synthesis Example 2, and 4.44 parts by weight of Resin P-2 synthesized in the above Reference Synthesis Example were mixed and stirred. Was stirred for 3 hours to prepare a mill base having a solid concentration of 20% by weight.

<Preparation of colored resin composition>
The pigment dispersion prepared in <Preparation of Pigment Dispersion> is mixed with a surfactant as a binder resin, a polymerizable monomer, a photopolymerization initiation component, and other components so as to have the composition shown in Table 1 below. Then, a solvent was added so that the solid content concentration was 20% by weight to obtain a colored resin composition.
Table 1 shows the weight ratio of each composition.
Table 2 shows the composition of the solvent.
In addition, finally, it filtered with the 5 micrometers piece filter, and removed the foreign material.

Each compound in Table 1 is as follows.
BCIM: 2- (2-chlorophenyl) -4,5-diphenylimidazole dimer (Hodogaya Chemical Co., Ltd.)
DPHA: Dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd.)
EABF: 4,4′-bis (diethylamino) benzophenone (Hodogaya Chemical Co., Ltd.)
2MBI: 2-mercaptobenzimidazole Irg907: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one

The numbers in Table 2 represent parts by weight, and are values when the total solvent is 100.
Each compound in Table 2 is as follows.
PGMEA: Propylene glycol monomethyl ether acetate EEP: Ethyl-3-ethoxypropionate 1,3-BGDA: 1,3-butylene glycol diacetate

<Evaluation method>
[1] Residue Evaluation Each colored resin composition was spin-coated on a cleaned glass substrate AN100 (manufactured by Asahi Glass Co., Ltd.), and prebaked for 3 minutes on an 80 ° C. hot plate.
This was spray developed using a 0.04 wt% aqueous potassium hydroxide solution at a developer temperature of 23 ° C. and a pressure of 0.25 MPa. The development time was 1.5 times the dissolution time.
In the same manner as described above, the dissolution time is the time when the colored resin composition is completely dissolved in the developer and the substrate is exposed when the colored resin composition is applied, dried and developed. Dissolution time.
An operation of wiping 10 reciprocations of a 30 × 100 mm portion of the obtained substrate with a Toraysee MK clean cloth impregnated with ethanol (manufactured by Toray Industries, Inc.) was performed. The Toraysee MK clean cloth was fixed to the tip of a 1 cm × 1 cm resin square and impregnated with 0.1 cc of ethanol using a dropper.

The amount of pigment adhering to Toraysee was confirmed visually and evaluated according to the following five levels.
A: No pigment adhesion to Toraysee was observed.
B: Slight adhesion of pigment to Toraysee was observed.
C: Pigment adhesion to Toraysee was slightly observed, and the color was darker than B.
D: Pigment adhesion to Toraysee was clearly observed.
E: Pigment adhesion to Toraysee is very dark, and the color is darker than D.
The results are summarized in Table 3.

[2] Re-solubility evaluation A colored resin layer of a colored resin composition having a predetermined thickness was formed as a coating film on a glass rod having a predetermined size with a clean surface, and dried for a predetermined time in a constant temperature and humidity environment. . Next, after the glass rod adhered and dried with the above colored resin composition was immersed in a certain amount of re-dissolving solvent for a certain period of time, the glass rod was shaken lightly and stirred, and then re-dissolved in the re-dissolving solvent. The re-solubility was evaluated according to the following criteria.

A: Re-solubility is good. The colored resin composition adhering to the glass rod is completely dissolved, or the peeled colored pieces are dissolved within 5 minutes. B: Most of the colored resin composition adhering to the glass rod is dissolved and not partially dissolved. Remain in.
C: Most of the colored resin composition adhered to the glass rod remains undissolved and partially dissolves.
D: The re-solubility is poor. The colored resin composition adhering to the glass rod does not dissolve even if it peels off.
The results are summarized in Table 3.

As shown in Table 3, the colored resin composition of the present invention has both a residue and re-solubility. That is, a color filter having pixels formed using the colored resin composition of the present invention, and a liquid crystal display device and an organic EL display device having the color filter are of high quality.

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

Claims (8)

(A) a pigment, (B) a solvent and (C) a binder resin,
The (C) binder resin is reacted with the copolymer obtained by copolymerizing the following (C-1) to (C-3) with (C-4) and then with (C-5). An unsaturated group-containing resin obtained by
And (B) a colored resin composition, wherein the solvent contains a high-boiling solvent having a boiling point of 1013.25 hPa at 23 ° C. of 170 ° C. or higher and 240 ° C. or lower.
(C-1); compound having an unsaturated bond and an epoxy group in one molecule (C-2); at least one skeleton selected from the group consisting of a tricyclodecane skeleton and a dicyclopentadiene skeleton in one molecule And a compound (C-3) having an unsaturated bond; a compound (C-4) having an unsaturated bond copolymerizable with the above (C-1) and (C-2); an unsaturated carboxylic acid ( C-5); succinic anhydride   2. The colored resin composition according to claim 1, wherein the content of the high boiling point solvent is 10% by weight or more and 50% by weight or less in all the solvents.   (C-4) The colored resin composition according to claim 1 or 2, wherein the unsaturated carboxylic acid is methacrylic acid.   Furthermore, (D) polymerizable monomer is contained, The colored resin composition as described in any one of Claims 1-3 characterized by the above-mentioned.   The colored resin composition according to claim 1, further comprising (E) a photopolymerization initiating component and / or a thermal polymerization initiating component.   It has a pixel formed using the colored resin composition as described in any one of Claims 1-5, The color filter characterized by the above-mentioned.   A liquid crystal display device comprising the color filter according to claim 6.   An organic EL display device comprising the color filter according to claim 6.

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