JP2012025943A - Coloring material dispersion, colored curable resin composition, color filter, liquid crystal display device, and organic el(electroluminescent) display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring material dispersion meeting both of the effects regarding trade-off-related flatness and dispersibility in forming the pixel for a color filter by an ink-jet technique, and having high viscosity stability, and to provide a colored curable resin composition using the dispersion.SOLUTION: The coloring material dispersion includes: (a) a coloring material; (c) an organic solvent; (d) a dispersant; and (e) an aromatic or aliphatic carboxylic acid; wherein (d) the dispersant is characterized by including a block copolymer and a graft copolymer. Uses of the coloring material dispersion are also provided.

Description

  The present invention relates to a color material dispersion, a colored curable resin composition, a color filter, a liquid crystal display device, and an organic EL display. Specifically, in the production of a color filter, a colored curable resin composition having long-term ejection stability suitable for pixel formation by an inkjet method, and a color filter having a highly flat pixel formed using this composition And a liquid crystal display device and an organic EL display having the color filter.

  2. Description of the Related Art In recent years, a color filter manufacturing technique in which a coloring material (ink) is driven (discharged and landed) in a pixel bank, that is, a substantially rectangular recessed area surrounded by a black matrix by an ink jet method has been put into practical use. The basic quality required for the color filter is that the coating film in the pixel bank (hereinafter sometimes simply referred to as a pixel) has good flatness, that is, there is no unevenness or uneven color, wrinkles or cracks. It is important that there are no coating film defects. In order to stabilize the manufacturing process and improve the yield, the wetting and spreading of the impacted droplets is good in the liquid-repellent bank, that is, the required amount of droplets is avoided while avoiding color mixing between pixels. It is important that it can be filled.

  In particular, insufficient pixel flatness causes color unevenness and is inappropriate for high-quality display applications. Until now, various conditions such as the temperature of wetting and spreading, the drying conditions, and the types of ink constituent materials have been studied in order to improve the flatness of the pixels, but the flattening mechanism has not been fully elucidated. Even if the conditions are adjusted empirically and through trial and error, sufficient flatness cannot be obtained.

JP 2009-258619 A

Regarding the flatness of the pixel, the type of the ink constituent material affects the surface shape. Among these, the type of dispersant used has a great influence on the flatness, that is, the surface shape of the pixel, and in particular, the graft copolymer type polymer dispersant has a high effect of improving the flatness of the coating film.
However, when a graft copolymer type dispersant is used, the dispersibility of the pigment is not sufficient, and in order to obtain the target contrast value, the dispersion strength of the pigment is increased, the dispersion time is increased, etc. Therefore, it is necessary to input more dispersion energy, the increase in viscosity due to the fine powder of the pigment and the accompanying increase in specific surface area is unavoidable, and the viscosity stability over time of the ink also deteriorates. It is very difficult to fit in range.

On the other hand, the block copolymer type polymer dispersant has high pigment dispersibility and can obtain a high contrast value, but hardly contributes to improvement of the flatness of the pixel.
Further, when the amine species contained in the block copolymer is made highly polar, the dispersibility is further improved, but it is necessary to use an organic solvent having a relatively low boiling point and a sufficiently high polarity. There is a tendency that the ink jet head is easily dried and the coating stability (ejection stability) is lowered. On the other hand, when a block copolymer containing a less polar amine species is used, the need to use a low-boiling solvent is reduced, and the above problem is solved. May be insufficient, the contrast value may be lowered, and it may be difficult to adjust the viscosity of the colorant dispersion or the colored curable resin composition to an appropriate viscosity range as an inkjet ink.

An object of the present invention is to solve the above-mentioned problems, particularly when forming pixels of a color filter by an ink jet method, satisfying both the effects relating to flatness and dispersibility in a trade-off relationship, and The object is to provide a colorant dispersion having high viscosity stability and a colored curable resin composition.
Another object of the present invention is to provide a high-quality color filter and a liquid crystal display device having pixels formed using such a colored curable resin composition.

As a result of intensive studies, the present inventors have satisfied both flatness and dispersibility by using both a block copolymer type dispersant and a graft copolymer type dispersant together with a carboxylic acid. The present inventors have found that pigment dispersions and colored curable resin compositions that exhibit high viscosity stability and good coating stability by the inkjet method can be obtained.
That is, the gist of the present invention includes (a) a color material, (c) an organic solvent, (d) a dispersant and (e) an aromatic or aliphatic carboxylic acid, and (d) the dispersant is a block copolymer. And a colorant dispersion characterized by containing at least one or more graft copolymers, and a colored curable resin composition using the same.

Another gist of the present invention includes (a) a color material, (b) a binder resin, (c) an organic solvent, (d) a dispersant and (e) an aromatic or aliphatic carboxylic acid, and (d) a dispersion. The colorant curable resin composition is characterized in that the agent contains at least one block copolymer and graft copolymer.
Another gist of the present invention resides in a color filter having pixels formed using the colored curable resin composition, a liquid crystal display device having the color filter, and an organic EL display.

In the color material dispersion and the colored curable resin composition, the pixel (coating film) flatness and the color material dispersibility can be achieved by using a block copolymer and a graft copolymer together as a dispersant. Furthermore, by containing an aromatic or aliphatic carboxylic acid, it is possible to suppress an increase in viscosity and improve the viscosity stability with time.
As a result, it is possible to provide a colored curable resin composition having good viscosity stability and high contrast, which is suitable for the production of an ink-jet color filter. By using the composition, pixel flatness is improved. A good color filter can be obtained. Further, since such a color filter can be manufactured with high quality yield, a liquid crystal display device can be provided in a large amount at a low cost.

It is the enlarged photograph which looked at the pixel from the upper surface. It is the model showing the shape of the cross section (however, the cross section in FIG. 1) of the pixel and BM pattern which were formed in the Example and the comparative example. It is sectional drawing which shows an example of the organic EL element which has the color filter of this invention. In an Example and a comparative example, it is a figure showing the emission spectrum of the light source used when measuring a contrast value. (A), (b) is a schematic diagram for demonstrating the method to measure the chromaticity of the parallel transmitted light and orthogonal transmitted light of a colored plate in an Example and a comparative example of this application. In an Example and a comparative example, it is a spectrum figure which shows the optical characteristic of the polarizing plate used for the measurement of contrast value.

Embodiments of the present invention will be described in detail below, but the description of the constituent elements described below is an example (representative example) of the embodiments of the present invention, and the present invention does not exceed the gist thereof. It is not limited to the contents of.
[1] Color material dispersion The color material dispersion of the present invention contains at least (a) a color material, (c) an organic solvent, (d) a dispersant, and (e) an aromatic or aliphatic carboxylic acid. d) The dispersant contains at least one block copolymer and one graft copolymer.

  The constituents of the colorant dispersion of the present invention and the colored curable resin composition will be described below. “(Meth) acryl”, “(meth) acrylate” and the like are “acrylic and / or methacrylic”. ”,“ Acrylate and / or methacrylate ”, and the like, for example,“ (meth) acrylic acid ”means“ acrylic acid and / or methacrylic acid ”. In addition, “(co) polymer” means “single polymer (homopolymer) and / or copolymer (copolymer)”.

“Amine value” and “acid value” mean values in terms of effective solids unless otherwise specified. Both are determined by a titration method, and the amine value will be described later in detail.
In the following, “total solid content” refers to all components in the colorant dispersion or colored curable resin composition of the present invention other than the solvent components described later.
Moreover, below, the weight average molecular weight (Mw) of resin ((co) polymer) is the value of polystyrene conversion measured by GPC (gel permeation chromatography).

In the following, the colored curable resin composition may be simply referred to as “ink”.
[1-1] (a) Color material
(A) A coloring material means what colors the coloring material dispersion of this invention and the coloring curable resin composition mentioned later. As the coloring material, dyes and pigments can be used, but pigments are preferable from the viewpoint of heat resistance, light resistance and the like. As the pigment, various color pigments such as a blue pigment, a green pigment, a red pigment, a yellow pigment, a purple pigment, an orange pigment, a brown pigment, and a black pigment can be used. In addition to organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene, various inorganic pigments can be used. It is.

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

Examples of green pigments include C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 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 a pigment defined by <Pigment Y> below (hereinafter referred to as “Pigment Y”).

<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.

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 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 oranges 38 and 71, 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 and the like, more preferably C.I. I. And CI Pigment Violet 23.

The above-mentioned various pigments can be used in combination. For example, in order to adjust the chromaticity, a green pigment and a yellow pigment can be used in combination, or a blue pigment and a violet pigment can be used in combination.
The average primary particle size of these pigments is usually 1 μm or less, preferably 0.5 μm or less, more preferably 0.25 μm or less.

The primary particle diameter of the pigment is determined by the following method. That is, 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). From the obtained primary particle image The particle size of each pigment particle is determined for a plurality of (usually about 200 to 300) pigment particles, with the diameter corresponding to the area circle converted to the diameter of a circle having the same area. 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 particle diameter of each pigment _{particle: X 1, X 2, X} 3, X 4, ····, X i, ······ X m

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

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

Among these, it is preferable to use a pigment for the color material (a) in that the light resistance and / or weather resistance and fastness of the coating film finally obtained are excellent. Further, in terms of color tone adjustment, pigments and dyes may be used in combination as necessary.
In the present invention, when a blue color material is used as the color material (a), an effect such as a decrease in viscosity is particularly remarkable.

In the color material dispersion of the present invention, the ratio of the color material (a) to the total solid content is usually 90% by weight or less, preferably 85% by weight or less, more preferably 80% by weight or less, and usually 20% by weight. % Or more, preferably 30% by weight or more, more preferably 40% by weight or more.
In the colored curable resin composition of the present invention to be described later, the proportion of the (a) coloring material to the total solid content is usually 10% by weight or more, preferably 20% by weight or more, and usually 90% by weight or less. Preferably it is 80 weight% or less, More preferably, it is 60 weight% or less.

  (A) When the content ratio of the color material is too small, the coloring power becomes low, and the film thickness necessary for realizing the desired color density becomes too thick, which adversely affects the gap control at the time of forming the liquid crystal cell. There is. On the other hand, if the content ratio of (a) the color material is too large, it is difficult to maintain a good dispersion state, and (a) the color material aggregates and settles, resulting in a problem of increased viscosity, brightness, and contrast. In addition, the crosslink density of the colored curable resin composition decreases, the film strength tends to decrease, and it tends to fall off.

[1-2] (c) Organic solvent
The color material dispersion and the colored curable resin composition of the present invention contain (c) an organic solvent as an essential component. (C) The organic solvent has a function of adjusting the viscosity by dissolving or dispersing the respective components.
The organic solvent (c) may be any organic solvent that can dissolve or disperse the components constituting the colorant dispersion and the colored curable resin composition.

Specifically, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether , Propylene glycol mono-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxy Butanol, triethylene glycol monomethyl ether Triethylene glycol monoethyl ether, glycol monoalkyl ethers such as tripropylene glycol methyl ether;
Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether;
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl Acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol Roh ether acetate, triethylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate, glycol alkyl ether acetates such as ethylene glycol diacetate;
Glycol diacetates such as 1,3-butylene glycol diacetate, propylene glycol diacetate, 1,6-hexanediol diacetate;
Ethers such as amyl ether, propyl ether, diethyl ether, dipropyl ether, diisopropyl ether, butyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether;
Like acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxymethyl pentanone Ketones;
Mono- or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, benzyl alcohol, ethylene glycol, propylene glycol, butanediol, triethylene glycol, methoxymethylpentanol, diethylene glycol, dipropylene glycol, glycerin;
aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;
Cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;
Aromatic hydrocarbons such as benzene, toluene, xylene, cumene;
Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-methoxypropionic acid Linear or cyclic esters such as propyl, butyl 3-methoxypropionate, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;
Halogenated hydrocarbons such as butyl chloride and amyl chloride; ether ketones such as methoxymethylpentanone; nitriles such as acetonitrile and benzonitrile, and the like.

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

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

The solvent vapor pressure is usually 10 mmHg or less, more preferably 5 mmHg or less, and still more preferably 1 mmHg or less, from the viewpoint of the uniformity of the resulting coating film.
In addition, in the production of color filters by the ink jet method, the ink emitted from the nozzle is very fine, from several to several tens of pL, so the solvent evaporates and concentrates before landing on the periphery of the nozzle opening or in the pixel bank.・ Tends to dry. In order to avoid this, it is preferable that the solvent has a high boiling point. Specifically, it is preferable that (c) the organic solvent contains a solvent having a boiling point of 180 ° C. or higher. More preferably, it contains a solvent having a boiling point of 200 ° C. or higher, particularly preferably a boiling point of 220 ° C. or higher. The solvent having a boiling point of 180 ° C. or higher (hereinafter referred to as “high boiling solvent”) is preferably 50% by weight or more, more preferably 70% by weight or more, and 90% by weight or more in the organic solvent (c). Is most preferred. When the high boiling point solvent is less than 50% by weight, the effect of preventing evaporation of the solvent from the ink droplets may not be sufficiently exhibited.

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

On the other hand, when the organic solvent contains a highly polar solvent such as alcohols, there may be a problem that ejection stability in the ink jet method is deteriorated. Therefore, the alcohol is preferably 20% by weight or less in the total solvent, more preferably 10% by weight or less, and particularly preferably 5% by weight or less.
The proportion of the organic solvent (c) in the colorant dispersion of the present invention is not particularly limited, but is usually 50% by weight or more, preferably 70% by weight or more, and usually 90% by weight or less, preferably 85% by weight. % Or less. (C) If there is too much organic solvent, the dispersant will be detached from the pigment surface and pigment aggregation will easily occur. The final ink will be less than the appropriate solid content range, and an appropriate film thickness cannot be obtained unless a large amount of ink is applied. In some cases, the final ink falls below the lower limit of the appropriate viscosity range, making it difficult to apply the ink jet. If the amount is too small, the viscosity becomes high when dispersed and the pigment is difficult to disperse. Problems such as being difficult to handle and being likely to generate abnormal heat due to high viscosity in the dispersion apparatus may occur.

  Further, the proportion of the organic solvent (c) in the entire colored curable resin composition of the present invention described later is not particularly limited, but is usually 50% by weight or more, preferably 60% by weight or more, and usually 99% by weight. % Or less, preferably 95% by weight or less. (C) If there is too much organic solvent, the solid concentration becomes too low and it becomes unsuitable for forming a coating film, or the viscosity of the ink becomes too high, which hinders the stability of the composition. In some cases, the discharge stability may be lowered when the ink jet method is applied.

[1-3] (d) Dispersant
The color material dispersion and the colored curable resin composition of the present invention must contain at least one type of block copolymer and graft copolymer as the dispersant (d). The graft copolymer is particularly effective for improving the flatness of the coating film formed using the colored curable resin composition containing the graft copolymer, and the block copolymer is particularly effective for improving the dispersibility of the colorant. Therefore, a high contrast pixel can be obtained by using a colored curable resin composition containing the same.

Although there is no restriction | limiting in particular in the kind of a block copolymer and a graft copolymer, (d-1) (meth) acrylic block copolymer containing a nitrogen atom, (d-2) nitrogen atom more specifically It is preferable to contain one or more dispersants each selected from graft copolymers containing
(D-1) a (meth) acrylic block copolymer containing a nitrogen atom and (d-2) a graft copolymer containing a nitrogen atom, where the nitrogen atom contained therein is a color material surface such as a pigment It is estimated that the portion other than the nitrogen atom has an affinity for the medium, and the affinity for the medium is enhanced, thereby contributing to the improvement of the dispersion stability as a whole.

The performance of the dispersant is greatly influenced by its adsorption behavior on the solid surface. Regarding the relationship between the molecular architecture and the adsorption behavior, it is known that when the same unit is used, the adsorption behavior is superior in the order of random copolymerization <graft copolymer <block copolymer. (Eg Jones and Richards, “Polymers at Surfaces and Interfaces”
p281).

Although the detailed mechanism is unknown, the following can be inferred.
That is, in the case of a normal random copolymer, the monomer constituting the copolymer has a high probability of being stably arranged in the copolymer sterically and / or electrically during the formation of the polymer. . Since the portion (molecule) in which the monomer is stably arranged is sterically and / or electrically stable, it may become an obstacle when adsorbing to the coloring material. On the other hand, a resin whose molecular arrangement is controlled, such as a graft copolymer or a block copolymer, disposes a portion that prevents the adsorption of the dispersant at a position away from the adsorption portion of the coloring material and the dispersant. be able to. That is, an optimal portion for adsorption can be arranged in the adsorbing portion between the coloring material and the dispersant, and a portion suitable for it can be arranged in a portion requiring solvent affinity. It is speculated that this molecular arrangement affects the good dispersibility particularly for the dispersion of the colorant having a small crystallite size.

(D-1) a (meth) acrylic block copolymer having a nitrogen atom
A (meth) acrylic block copolymer having a nitrogen atom (hereinafter sometimes referred to as “(d-1) copolymer”) is preferable in that (a) the colorant can be dispersed very efficiently. The reason is not clear, but it is presumed that because the molecular arrangement is controlled, there are few structures that obstruct the dispersant when adsorbing to the colorant.

As the (meth) acrylic block copolymer having a nitrogen atom, a copolymer composed of a B-block having a functional group containing a nitrogen atom and an A-block having no functional group containing a nitrogen atom is preferable.
The B-block has a functional group containing a nitrogen atom, and examples of the functional group include nitrogen-containing heterocyclic groups such as an amino group, an amide group, and an imidazolyl group. Among them, a primary to tertiary amino group is preferable. . In addition, by having a tertiary amino group as a functional group containing a nitrogen atom, unlike the case of having a polar group such as a quaternary ammonium base, (c) the necessity of including a highly polar solvent as the organic solvent is reduced. That is, a tertiary amino group is more preferable as the nitrogen atom-containing functional group from the viewpoint that high colorant dispersibility can be obtained without containing a highly polar solvent.

In particular, the (meth) acrylic block copolymer having a nitrogen atom includes (d1) an A- block consisting of a B-block having an amino group in the side chain and an A-block having no amino group in the side chain. A B block copolymer and / or an ABA block copolymer (hereinafter sometimes referred to as “(d1) copolymer”) are preferred.
(D1) In the monomer composition constituting the copolymer, the proportion of the monomer having a primary to tertiary amino group is preferably 20 mol% or more, more preferably 50 mol% or more. By setting the amount of amino group to the above lower limit value or more, sufficient adsorptivity of the dispersant to the pigment can be ensured and high dispersion stability can be obtained. As the primary to tertiary amino group, preferably —NR ⁴¹ R ⁴² (wherein R ⁴¹ and R ⁴² are each independently a cyclic or chain alkyl group or substituent which may have a substituent). The aryl group optionally having a substituent or an aralkyl group optionally having a substituent is preferably represented by the following formula (VIII). ).

(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 (meth) acrylate is particularly preferably used.

  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. A partial structure not containing an amino group may be partially contained in the B-block, and examples of such a partial structure include a partial structure derived from a (meth) acrylate monomer. . The content of such a partial structure not containing an amino group in the B-block is preferably 0 to 50% by weight, more preferably 0 to 20% by weight. Most preferably it is not included.

On the other hand, the A-block constituting the (meth) acrylic block copolymer having a nitrogen atom does not have a nitrogen atom-containing functional group such as the amino group described above, and is co-polymerized with the monomer constituting the B-block described above. There is no particular limitation as long as it is composed of a polymerizable monomer, but it is usually selected from solvophilic monomers.
Examples of the A-block include styrene monomers such as styrene and α-methylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate (propyl) (meth) acrylate, isopropyl (meth) acrylate, (meth) Butyl 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; allyl glycidyl ether, croto Polymer structure obtained by copolymerizing comonomers including glycidyl ether monomers such as glycidyl ether.

Among these, (meth) acrylic acid ester monomers are more preferable, and it is particularly preferable that the monomers constituting the A-block and B-block are all (meth) acrylate monomers.
Among them, in particular, it is derived from a (meth) acrylic acid ester monomer represented by the following general formula (IX) in terms of improving the familiarity with the nonpolar part of the solvent by imparting appropriate hydrophobicity to the A-block. It is preferable that the partial structure is included.

(In the general formula (IX), R ⁹¹ represents a hydrogen atom or a methyl group. R ⁹² may have a cyclic or chain alkyl group which may have a substituent, or a substituent. Represents a good aryl group or an aralkyl group which may have a substituent.)
In addition, it is preferable that R ⁹² is a cyclic group in terms of high affinity with the color material and good compatibility.

  The A-block contains a polyalkylene glycol (meth) acrylate such as polyethylene glycol (meth) acrylate and polypropylene glycol (meth) acrylate as a copolymerization component (that is, a partial structure derived from polyalkylene glycol (meth) acrylate). In particular, an A-block having a partial structure represented by the following formula (X) is preferable.

(In the general formula (X), n ¹⁰ represents an integer of 1 to 5, R ¹⁰ represents a hydrogen atom or a methyl group, and V ¹⁰ represents an alkyl group or a phenyl group having 1 to 4 carbon atoms.)
In addition, when there are a plurality of the above units, that is, the general formula (X) in one molecule, n ¹⁰ may be the same or different. V ¹⁰ is particularly preferably an ethyl group.
The partial structure represented by the general formula (X) is preferably contained in an amount of 3 to 20 mol% in terms of the monomer constituting the (meth) acrylic copolymer, It is most preferable that 10 mol% is contained.

Although the detailed mechanism of action is unknown, it has a partial structure derived from polyalkylene glycol (meth) acrylate, in particular, a partial structure represented by the above formula, so that it is possible to increase hydrogen bonding properties, It is thought that the affinity for the dispersion improves and the stability of the dispersion increases.
The partial structure derived from the (meth) acrylic acid ester monomer represented by the general formula (IX), (X) or the like may be contained in one A-block in two or more.

Of course, the A-block may further contain a partial structure other than these.
When a partial structure derived from two or more kinds of monomers is present in the A-block, each partial structure may be contained in the A-block in any form of random copolymerization or block copolymerization.
When the A-block contains a partial structure other than the partial structure derived from the (meth) acrylic acid ester monomer represented by the general formula (IX) or (X), other than the (meth) acrylic acid ester monomer The content of the partial structure in the A-block is preferably 0 to 99% by weight, more preferably 0 to 85% by weight.

In the present invention, the (meth) acrylic block copolymer having a nitrogen atom is an AB block or ABA block copolymer type polymer composed of such an A block and a B block. Compounds are preferred. Among these, an AB block copolymer is preferable. Such a block copolymer is prepared, for example, by the living polymerization method shown below.
The living polymerization method includes an anion living polymerization method, a cation living polymerization method, and a radical living polymerization method. In the anion living polymerization method, the polymerization active species is an anion, and is shown, for example, in the scheme described in JP-A-2009-52010.

In the radical living polymerization method (nitroxyl method, ATRP method), a polymerization active species is a radical, and is shown by a scheme described in, for example, JP-A-2009-52010.
For the synthesis of such a (meth) acrylic block copolymer, a known method such as that incorporated in JP-A-2009-52010 can be employed.
The amine value in 1 g of solid content of the AB block copolymer and the ABA block copolymer according to the present invention is preferably 80 to 150 mgKOH / g, more preferably 100 to 140 mgKOH / g. It is.

If the amine value is too low, the adsorptive power on the surface of the colorant becomes insufficient, and sufficient dispersion stability may not be obtained. On the other hand, if the amine value is too high, it means that the molecular weight of the A-block is insufficient, and thus the dispersion stability tends to be inferior. In other words, it is preferable that the amine value for expressing the optimum dispersibility is in the above range.
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 [mgKOH / g] = (561 × V) / (W × S)
(W: represents the amount of the dispersant sample weighed [g], V: represents the titration amount at the end of titration [mL], and S represents the solid content concentration [wt%] of the dispersant sample.)
The 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 generally it is preferably lower, usually 50 mgKOH / g or less, preferably 40 or less, more preferably 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.
When the average primary particle size of the color material is small, the specific surface area increases, so that the amount of dispersant adsorbed per unit area decreases. In such a case, the difference in the effect of the dispersant composed of the AB block copolymer or the ABA block copolymer described above is very remarkable as compared with the dispersant having another structure. Are particularly preferably used.

(D-2) Graft copolymer containing nitrogen atom
A graft copolymer containing nitrogen atoms (hereinafter sometimes referred to as “(d-2) copolymer”) is preferable in that (a) the colorant can be dispersed very efficiently. The reason for this is not clear, but it has a structure that can positively eliminate the part (molecule) that obstructs the adsorption of the coloring material and the dispersing agent around the adsorption part to the coloring material. It is assumed that this is because.

Specific examples of (d-2) copolymers include those having a repeating unit containing a nitrogen atom in the side chain and those having a repeating unit containing a nitrogen atom in the main chain.
(D-2-1) Graft copolymer having a repeating unit containing a nitrogen atom in the side chain The graft copolymer having a repeating unit containing a nitrogen atom in the side chain is not particularly limited. A part of the amino group has a structure obtained by acid amidation with 1) a polyester having a carboxyl group at one end, 2) a polyamide having a carboxyl group at one end, or 3) a polyester amide having a carboxyl group at one end. Things.

Specifically, the following (d2) polyallylamine derivatives represented by the general formula (VII) (hereinafter sometimes referred to as “(d2) copolymer”) can be mentioned.

(In the formula, R ⁷¹ is a group represented by —NHCOR ⁷² or —NH ₃ ⁺ OCOR ⁷² —, and X ⁷ and Y ⁷ are each independently a hydrogen atom, a polymerization initiator residue, or a chain transfer catalyst residue. N ⁷ represents an integer of 2 to 1000, wherein R ⁷² is a carboxyl from any of a polyester having a free carboxylic acid, a polyamide having a free carboxylic acid, or a polyester amide having a free carboxylic acid. Represents a residue excluding a group, provided that at least one of n ⁷ R ⁷¹ represents a group represented by —NHCOR ^72. )
In the above general formula (VII), the “residue obtained by removing a carboxyl group from a polyester having a free carboxylic acid” represented by R ⁷² is “a carboxyl group from a polyester derived from a hydroxycarboxylic acid and / or a lactone”. Examples include “residues removed” and “residues obtained by removing a carboxyl group from a polyester derived from a dibasic acid (dicarboxylic acid) and a diol”.

Here, the polyester derived from hydroxycarboxylic acid is usually a polyester obtained by dehydration condensation of an aliphatic hydroxycarboxylic acid having 3 to 20, preferably 3 to 10, more preferably 3 to 8 carbon atoms. As the polyester derived from the corresponding lactone, a polyester usually obtained by ring-opening polymerization of a lactone having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 3 to 8 carbon atoms can be mentioned. The polyester derived from a dibasic acid (dicarboxylic acid) and a diol has an aliphatic or aromatic dicarboxylic acid having 4 to 24 carbon atoms, preferably 4 to 10 carbon atoms, and 2 to 20 carbon atoms, preferably 2 to 2 carbon atoms. Polyester obtained by dehydration condensation with 10 alkylene glycols or polyalkylene glycols.

  The degree of polymerization (polyester unit) of the polyester is usually about 2 to 100. Moreover, molecular weight is 300-20,000 normally, Preferably it is 1,000-10,000. If the molecular weight is too small, the dispersing agent side chain may be too short and sufficient dispersion may not be obtained.If the molecular weight is too large, the dispersing agent side chain may be too long, causing aggregation of pigments and reducing fluidity. May bring.

In the above general formula (VII), the “residue obtained by removing a carboxyl group from a polyamide having a free carboxylic acid” represented by R ⁷² is “residue obtained by removing a carboxyl group from a polyamide derived from an aminocarboxylic acid” Specifically, the carboxyl group was usually removed from the polyamide obtained by dehydration condensation of an aliphatic aminocarboxylic acid having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 3 to 8 carbon atoms. Residue. The degree of polymerization (polyamide unit) is usually about 2 to 100, and the molecular weight is the same as that of the polyester.

In the above general formula (VII), the “residue obtained by removing the carboxyl group from the polyesteramide having a free carboxylic acid” represented by R ⁷² is “polyesteramide derived from dibasic acid (dicarboxylic acid) and diamine”. A residue obtained by removing a carboxyl group from Here, as a polyesteramide derived from a dibasic acid (dicarboxylic acid) and a diamine, an aliphatic or aromatic dicarboxylic acid having 4 to 24 carbon atoms, preferably 4 to 10 carbon atoms, and 2 to 20 carbon atoms, preferably Examples include polyester amides obtained by dehydration condensation with 2 to 10 diamines. The degree of polymerization of the polyester amide (polyester amide unit) is usually about 2 to 100, and the molecular weight is about the same as that of the polyester.

Among the above, R ⁷¹ is preferably —NHCOR ⁷² , and among R ⁷¹ , when it is “residue obtained by removing a carboxyl group from a polyester derived from hydroxycarboxylic acid and / or lactone”, it corresponds to the main chain. By having no nitrogen atom other than the nitrogen atom derived from polyallylamine, the role sharing between the adsorbing group in the molecule and the other structure becomes clear, and high pigment dispersibility and dispersion stability are obtained, which is preferable. .

X ⁷ and Y ⁷ each independently represent a hydrogen atom, a polymerization initiator residue, or a chain transfer catalyst residue. Here, the polymerization initiator residue or chain transfer catalyst residue is a polymerization initiator or chain transfer catalyst used when synthesizing a polyamine corresponding to the main chain of the copolymer represented by the general formula (VII). Means a residue derived from
N ⁷ represents an integer of 2 to 1000, and among n ⁷ R ⁷¹ , at least one represents a group represented by —NHCOR ⁷² . Among them, in n ⁷ R ⁷¹ , a residue bonded by an acid amide bond (a bond in which R ⁷¹ is —NHCOR ⁷² in the general formula (VII)) is 60 to
It is preferably 95 mol%, particularly preferably 65 to 90 mol%. If this value is too small, the pigments may agglomerate, which may cause an insufficient viscosity reduction effect and a disadvantage in the appearance of the coating film. On the other hand, if it is too large, the functional group adsorbing to the pigment is reduced, making it difficult to contribute to pigment dispersion, resulting in an insufficient viscosity reduction effect or inconvenience in the appearance of the coating film.

In addition, the number average molecular weight of the polyallylamine used as the raw material of the (d2) copolymer is usually about 150 to 100,000, preferably 600 to 20,000. If this value is too small, the adsorptive power with respect to the pigment may be insufficient and dispersion may be insufficient, and if it is too large, aggregation of pigments may occur and dispersion may become difficult.
(D2) amine value of the polyallylamine derivative represented by the general formula (VII) (mgKO)
H / g) is preferably about 5 to 30. If this value is too small, the adsorptive power with respect to the pigment may be insufficient and dispersion may be insufficient, and if it is too large, aggregation of pigments may occur and dispersion may become difficult. The acid value (mgKOH / g) is preferably about 2.5 to 50 from the viewpoint of pigment dispersibility. Furthermore, the number average molecular weight of the (d2) copolymer is usually about 2000 to 100,000.

The (d2) copolymer can be produced, for example, according to the method described in JP-A-9-169821.
(D-2-2) Graft copolymer having a repeating unit containing a nitrogen atom in the main chain The graft copolymer having a repeating unit containing a nitrogen atom in the main chain is not particularly limited. (D3) a graph and a copolymer (hereinafter referred to as “(d3) copolymer”) having at least one of the repeating unit represented by the general formula (II) and the repeating unit represented by the general formula (III) May be called).

^{Wherein, R 51} represents an alkylene group having 1 to 5 carbon atoms, A represents either a hydrogen atom or the following formula (IV) ~ (VI).
In the formula (II), R ⁵¹ represents a linear or branched alkylene group having 1 to 5 carbon atoms such as a methylene group, an ethylene group, or a propylene group, preferably 2 to 3 carbon atoms, and more preferably Is an ethylene group. A represents a hydrogen atom or any one of the following formulas (IV) to (VI), preferably formula (IV).

Wherein ^{(III), R 51} and A have the same meanings as ^{R 51} and A in the formula (II).

In Formula (IV), W ₁ represents a linear or branched alkylene group having 2 to 10 carbon atoms, and among them, an alkylene group having 4 to 7 carbon atoms such as a butylene group, a pentylene group, and a hexylene group is preferable. p represents an integer of 1 to 20, preferably an integer of 5 to 10.

In formula (V), Y ₁ represents a divalent linking group, and in particular, an alkylene group having 1 to 4 carbon atoms such as an ethylene group or a propylene group, or an alkylene group having 1 to 4 carbon atoms such as an ethyleneoxy group or a propyleneoxy group. An alkyleneoxy group is preferred. W ₂ represents a linear or branched alkylene group having 2 to 10 carbon atoms such as an ethylene group, a propylene group or a butylene group, and among them, an alkylene group having 2 to 3 carbon atoms such as an ethylene group or a propylene group is preferable. Y ₂ represents a hydrogen atom or —CO—R ⁵² (
R ⁵² represents an alkyl group having 1 to 10 carbon atoms such as an ethyl group, a propyl group, a butyl group, a pentyl group, or a hexyl group, and among them, an alkyl group having 2 to 5 carbon atoms such as an ethyl group, a propyl group, a butyl group, or a pentyl group. Alkyl groups are preferred. ). q represents an integer of 1 to 20, preferably an integer of 5 to 10.

In the formula (VI), W ₃ represents an alkyl group having 1 to 50 carbon atoms or a hydroxyalkyl group having 1 to 50 carbon atoms having 1 to 5 hydroxyl groups, among which an alkyl group having 10 to 20 carbon atoms such as a stearyl group, A C10-20 hydroxyalkyl group having 1-2 hydroxyl groups such as a monohydroxystearyl group is preferred.
(D3) The content of the repeating unit represented by the formula (II) or (III) in the copolymer is preferably as high as possible, usually 50 mol% or more, and preferably 70 mol% or more. The repeating unit represented by the formula (II) and the repeating unit represented by the formula (III) may both be present, and the content ratio is not particularly limited, but the repeating unit represented by the formula (II) It is preferable to contain a large amount of. The total number of repeating units represented by formula (II) or formula (III) is usually 1 to 100, preferably 10 to 70, more preferably 20 to 50 in one molecule.

Moreover, repeating units other than Formula (II) and Formula (III) may be included, and examples of other repeating units include an alkylene group and an alkyleneoxy group. The graft copolymer of the present invention preferably has a terminal of —NH ₂ or —R ⁵¹ —NH ₂ (R ⁵¹ is synonymous with R ⁵¹ ).
The (d3) copolymer may have a main chain that is linear or branched.

(D3) The amine value of the copolymer is usually 5 to 100 mgKOH / g, preferably 10 to 70 mgKOH / g, and more preferably 15 to 40 mgKOH / g. If the amine value is too high or too low, the dispersion stability may be lowered and the viscosity may become unstable, and if it is too high, the electrical characteristics after the liquid crystal panel is formed may be lowered.
(D3) The polystyrene-reduced weight average molecular weight measured by GPC of the copolymer is preferably 3000 to 50000, particularly preferably 5000 to 20000. If the weight average molecular weight is less than 3000, aggregation of the coloring material cannot be prevented and the viscosity or gelation may occur. When the weight average molecular weight exceeds 50,000, the viscosity itself becomes high, and (c) the solubility in an organic solvent may be insufficient. In addition, due to the steric hindrance of the molecule itself, (a) adsorption to the coloring material is hindered, so that dispersibility may be reduced.

(D3) As a method for synthesizing the copolymer, a known method can be adopted. For example, a method described in JP-B-63-30057 can be used.
In the present invention, a commercially available graft copolymer having the same structure as described above can also be applied.
(D-3) Other dispersant
The (d) dispersant used in the color material dispersion and colored curable resin composition of the present invention may contain a dispersant other than the above-mentioned various dispersants as long as the effects of the present invention are not impaired. .

  Other dispersants include urethane resin dispersants described in JP-A-2009-52031, various dispersants described in JP-A-2006-343648, such as polyethyleneimine-based dispersants, polyoxyethylene Examples thereof include alkyl ether dispersants, polyoxyethylene diester dispersants, polyether phosphoric acid, polyester phosphoric acid, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.

  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) It can be selected from commercially available products with series names such as “Chemical Industry Co., Ltd.” and “Polyflow” (manufactured by Kyoeisha Chemical Co., Ltd.) These polymer dispersants may be used alone or in combination of two or more.

  In the color material dispersion and colored curable resin composition of the present invention, the content ratio of (d) dispersant is usually 150% by weight or less, preferably 100% by weight or less, more preferably, based on (a) the color material. Is not more than 50% by weight, usually not less than 5% by weight, preferably not less than 7% by weight, particularly preferably not less than 10% by weight. (D) When the content ratio of the dispersant is too small, (a) the adsorption to the coloring material is insufficient, aggregation cannot be prevented, and the viscosity may be increased or gelled. It may worsen and problems such as re-aggregation and thickening may occur. On the other hand, if the amount is too large, the ratio of the coloring material is relatively reduced, so the coloring power is low, and the film thickness is too thick for the color density. A gap control failure may occur.

(D-2) Among copolymers, a graft copolymer having a repeating unit containing a nitrogen atom in a side chain from the viewpoint of a high effect of suppressing thickening of a colorant dispersion or a colored curable resin composition In particular, (d2) a polyallylamine derivative represented by the general formula (VII) is more preferable. The (d) dispersant in the colorant dispersion and colored curable resin composition of the present invention comprises (d-1) the acrylic block copolymer containing a nitrogen atom and (d-2) the nitrogen atom. The graft copolymer is contained, and the ratio is preferably in the range of 5/95 to 95/5 by weight. By controlling the content ratio within the above range, the advantages of both dispersants can be utilized, and both pixel flatness and color material dispersibility can be achieved at a higher level.

[1-4] (e) Aromatic or aliphatic carboxylic acid The coloring material dispersion and the colored curable resin composition of the present invention contain (e) an aromatic or aliphatic carboxylic acid as an essential component. (E) By containing an aromatic or aliphatic carboxylic acid (hereinafter sometimes referred to as “(e) carboxylic acid”), the viscosity of the colorant dispersion or the colored curable resin composition is lowered, and the viscosity over time Stability can be increased.

(E) The carboxylic acid may be either aromatic or aliphatic, but those having a relatively low acid dissociation constant pKa are preferred from the viewpoint of thickening inhibiting action. Specifically, a compound of 4.5 or less is preferable, and 4.2 or less is more preferable. Here, the acid dissociation constant pKa is a value measured at 23 ° C. using water as a solvent.
Although the detailed mechanism is unknown, this effect is hardly seen with acids other than carboxylic acids such as sulfonic acid and phosphoric acid, and conversely there are many negative aspects such as unstable viscosity. Among the carboxylic acids, monobasic acids containing one carboxyl group in the molecule are most preferred, and the effects of improving viscosity reduction, viscosity stability over time, high contrast, etc. are more prominent than polyvalent carboxylic acids. It is.

  Specific examples of such a structure of (e) carboxylic acid include lactic acid, propiolic acid, benzoic acid, or a compound in which these are substituted with a halogen atom or a phenyl group. Among them, a compound substituted with a halogen atom is preferable because the thickening suppressing effect of the composition tends to be enhanced. Particularly preferred compounds include 3-phenylpropiolic acid, 2-bromobenzoic acid, benzoic acid, and lactic acid, most preferably 3-phenylpropiolic acid.

  The content of (e) carboxylic acid is preferably 0.01 to 3.5 equivalents, more preferably 0.1 to the equivalent number of amino groups contained in the block copolymer contained in (d) the dispersant. -3 equivalents, particularly preferably 0.2-2.5 equivalents. By setting it to the above upper limit or less, it is preferable because a sufficient thickening suppressing effect can be achieved while maintaining high pixel formation. In addition, the number of equivalents of amino groups contained in the block copolymer is obtained by first obtaining the amine value (effective solid content conversion) of the block copolymer by the above-described method, and then per unit weight of the block copolymer. As the gram equivalent of the amine (that is, the value obtained from (amine value) /56.1 because KOH used for titration is 56.1 g / mol). On the other hand, what is necessary is just to determine content of carboxylic acid so that it may become the equivalent number of the range mentioned above.

(E) Since the carboxylic acid compound does not adversely affect the properties of the graft copolymer in the (d) dispersant, the flatness, dispersibility, viscosity can be obtained by using these three together with the block copolymer. A colorant dispersion and a colored curable resin composition having both excellent stability and inkjet coating stability can be obtained.
[2] Colored curable resin composition The colored curable resin composition of the present invention comprises (a) a color material, (b) a binder resin, (c) an organic solvent, (d) a dispersant, and (e) an aromatic or It contains an aliphatic carboxylic acid, and (d) the dispersant contains at least one block copolymer and graft copolymer.

Such a colored curable resin composition may be prepared by preparing a colorant dispersion liquid containing each of the above-described components in advance and adding (b) another component such as a binder resin thereto. Alternatively, the components contained in the composition may be added simultaneously or sequentially and mixed. The method for preparing the colored curable resin composition will be described in detail later.
The (a) color material, (c) organic solvent, (d) dispersant and (e) aromatic or aliphatic carboxylic acid, which are essential components of the colored curable resin composition of the present invention, are each [1] color material. Examples of the components contained in the dispersion are the same as those described above.

Hereinafter, components other than these will be described.
[2-1] (b) Binder resin
(B) The type of the binder resin is not particularly limited. For example, JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, JP-A-11-174224, Known polymer compounds described in JP-A-2000-56118, JP-A-2003-233179, JP-A-2009-52031, and the like can be used. explain.

(B-1) (A) mono (meth) acrylate having a structure represented by the following general formula (1), and (B1) epoxy group-containing (meth) acrylate or (B2) (meth) acrylic acid A (meth) acrylic copolymer obtained by reacting an ethylenically unsaturated group-containing monomer. (Hereinafter, this copolymer is simply referred to as “(b-1) copolymer”.)
(B-1) The copolymer has (A) a partial structure derived from mono (meth) acrylate having a structure represented by the following general formula (1) as an essential component.

(In the general formula (1), R ^{1 to} R ⁸ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ⁶ and R ⁷ are linked to each other to form a ring. May be.)
In the general formula (1), the ring formed by connecting R ⁶ and R ⁷ is preferably an aliphatic ring, which may be saturated or unsaturated, and has 5 to 6 carbon atoms. Is preferred.
Especially, as a structure represented by General formula (1), the structure represented by following formula (1a), (1b), or (1c) is preferable.

When the colored curable resin composition of the present invention is used for a color filter by containing a resin having these structures introduced, the heat resistance of the composition can be further improved, or the composition can be used. It is possible to increase the intensity of the formed pixel.
In addition, the mono (meth) acrylate which has a structure represented by the said General formula (1) may be used individually by 1 type, and may use 2 or more types together.

  As the mono (meth) acrylate having the structure represented by the general formula (1), various known ones can be used as long as it has the structure, and those represented by the following general formula (2) are particularly preferable. .

In formula (2), R ⁹ represents a hydrogen atom or a methyl group, and R ¹⁰ represents a structure represented by the general formula (1).
The copolymer (b-1) contains (B1) epoxy group-containing (meth) acrylate (hereinafter referred to as “(B1) epoxy group-containing (meth) acrylate”) or (B2) (meth) acrylic acid (hereinafter referred to as “(B1) epoxy group-containing (meth) acrylate”). A partial structure derived from “(B2) (meth) acrylic acid”) is an essential component.

(B1) As epoxy group-containing (meth) acrylate, for example, glycidyl (meth)
Examples include acrylate, 3,4-epoxybutyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate glycidyl ether. Of these, glycidyl (meth) acrylate is preferred. These epoxy group-containing (meth) acrylates may be used alone or in combination of two or more.

  In the copolymerization reaction between (A1) mono (meth) acrylate having the structure represented by the general formula (1) and (B1) epoxy group-containing (meth) acrylate or (B2) (meth) acrylic acid. A known solution polymerization method is applied. The solvent to be used is not particularly limited as long as it is inert to radical polymerization, and a usual amount of a commonly used organic solvent can be used.

The radical polymerization initiator used in the copolymerization reaction is not particularly limited as long as it can initiate radical polymerization, and a normal amount of a commonly used organic peroxide catalyst or azo compound catalyst is used. Can be used.
The copolymerization reaction may be carried out by dissolving the monomer and radical polymerization initiator used in the copolymerization reaction in a solvent and raising the temperature while stirring, or by adding the monomer to which the radical polymerization initiator has been added. Alternatively, the reaction may be performed dropwise in a solvent that has been heated and stirred. Further, the monomer may be added dropwise while the temperature is raised by adding a radical polymerization initiator to the solvent. The reaction conditions can be freely changed according to the target molecular weight.

As described above, (A) mono (meth) acrylate having a structure represented by the general formula (1) and (B1) epoxy group-containing (meth) acrylate or (B2) (meth) acrylic acid as essential components. The copolymer obtained by the reaction may further contain (E) a partial structure derived from another monomer.
(E) There is no restriction | limiting in particular as another monomer, What is necessary is just a compound which can be copolymerized with (A) and (B1) or (B2).

  Specifically, for example, vinyl aromatics such as styrene, styrene α-, o-, m-, p-alkyl, nitro, cyano, amide, ester derivatives; butadiene, 2,3-dimethylbutadiene, isoprene, Dienes such as chloroprene; methyl (meth) acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid-sec-butyl, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid cyclohexyl, (Meth) acrylic acid esters such as (meth) acrylic acid adamantyl, (meth) acrylic acid benzyl, (meth) acrylic acid-2-hydroxyethyl; (meth) acrylic acid amide, (meth) acrylic acid N, N- (Meth) acrylic acid amides such as dimethylamide; N-phenylmaleimide, N-cyclohexylmaleimide, etc. Mono maleimides, and the like.

Among these (E) other monomers, in order to impart excellent heat resistance, coating strength, and pigment dispersibility to the colored curable resin composition, styrene, benzyl (meth) acrylate, etc. (E1) An ethylenically unsaturated monomer having an aromatic hydrocarbon group is preferred.
When the partial structure derived from the (E1) ethylenically unsaturated monomer having an aromatic hydrocarbon group is contained in the copolymer (b-1), the content ratio is 1 to 70 mol%. Is preferable, and what is 3-50 mol% is still more preferable.

(B-1) The polystyrene-converted weight average molecular weight (Mw) of the copolymer measured by GPC is preferably from 3,000 to 100,000, particularly preferably from 5,000 to 50,000. When the molecular weight is less than 3000, the film strength may be inferior, and when it exceeds 100000, the viscosity of the resin increases, and the inkjet dischargeability of the composition using the resin tends to deteriorate. In addition, as a measure of molecular weight distribution, the ratio of weight average molecular weight (Mw) / number average molecular weight (Mn) is 2.0.
-5.0 is preferred.

Note that when forming a pixel of a color filter by an inkjet method, it is common to provide an alignment film directly without providing an overcoat layer on the pixel. Therefore, the pixel is required to have high resistance to a solvent such as N-methylpyrrolidone used for the alignment film provided in the vicinity.
From the point that a pixel excellent in chemical resistance can be obtained, and when the pixel is formed by thermosetting the composition, “(A) the above general formula among (b-1) copolymers from the thermosetting point” A (meth) acrylic polymer obtained by polymerizing a monomer containing an ethylenically unsaturated group, including a mono (meth) acrylate having a structure represented by (1) and (B1) an epoxy group-containing (meth) acrylate A “copolymer” is particularly preferred.

(B-2) A (meth) acrylic copolymer (hereinafter referred to as “(b-2) copolymer”) containing the compound represented by the following general formula (4) as an essential monomer component. ").
(B-2) A copolymer is a copolymer obtained by using the compound represented by the following general formula (4) as an essential monomer.

In the general formula (4), R ^1a and R ^2a each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
In the ether dimer represented by the general formula (4), the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ^1a and R ^2a is not particularly limited. A linear or branched alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl, 2-ethylhexyl; an aryl group such as phenyl; Cycloaliphatic hydrocarbon groups such as cyclohexyl, t-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl and 2-methyl-2-adamantyl; alkoxy such as 1-methoxyethyl and 1-ethoxyethyl An alkyl group substituted with an aryl group such as benzyl; and the like.

Among these, an acid such as methyl, ethyl, cyclohexyl, benzyl or the like, or a primary or secondary carbon substituent which is difficult to be removed by heat is preferable from the viewpoint of heat resistance. Note that R ^1a and R ^2a may be the same type of substituent or different substituents.
Specific examples of the ether dimer include compounds described in JP-A No. 2004-300203 and JP-A No. 2004-300204. Among these, dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2'-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2'- [Oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate are preferred. These ether dimers may be used alone or in combination of two or more.

(B-2) Although the ratio of the said ether dimer in a monomer component at the time of obtaining a copolymer is not restrict | limited, It is 2-60 weight% normally in all the monomer components, Preferably it is 5-55. % By weight, more preferably 5 to 50% by weight. If the amount of the ether dimer is too large, it may be difficult to obtain a low molecular weight product during polymerization, or may be easily gelled. On the other hand, if the amount is too small, the transparency, heat resistance, etc. There is a possibility that the performance of the coating film becomes insufficient.

(B-2) When the copolymer further has an acid group, when the colored curable resin composition of the present invention contains a resin (b-3) having an epoxy group, which will be described later, these epoxy groups have It is preferable because it can be cured by a crosslinking reaction in which an acid group reacts with each other to form an ester bond (hereinafter sometimes referred to as “acid-epoxy curing”). The acid group is not particularly limited, and examples thereof include a carboxyl group, a phenolic hydroxyl group, and a carboxylic anhydride group. These acid groups may be only one kind or two or more kinds.

  In order to introduce an acid group, for example, a monomer having an acid group and / or a “monomer capable of imparting an acid group after polymerization” (hereinafter also referred to as “monomer for introducing an acid group”). May be used as a monomer component. In addition, when using "monomer which can give an acid group after superposition | polymerization" as a monomer component, the process for providing an acid group as described in Unexamined-Japanese-Patent No. 2009-52031 is required after superposition | polymerization, for example It becomes.

Examples of the monomer having an acid group include monomers having a carboxyl group such as (meth) acrylic acid and itaconic acid; monomers having a phenolic hydroxyl group such as N-hydroxyphenylmaleimide; maleic anhydride and itaconic anhydride. Although the monomer etc. which have a carboxylic anhydride group are mentioned, Especially, (meth) acrylic acid is preferable among these.
Examples of the monomer capable of adding an acid group after the polymerization include monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate; monomers having an epoxy group such as glycidyl (meth) acrylate; 2-isocyanatoethyl (meta ) Monomers having an isocyanate group such as acrylate.

These monomers for introducing an acid group may be only one type or two or more types.
When the monomer for introducing an acid group is included, the content ratio is not particularly limited, but is usually 5 to 70% by weight in the total monomer components constituting the (b-2) copolymer, preferably 10 to 60% by weight. If the amount is too large, the acid value becomes too high, so that compatibility with the dispersant may deteriorate, and problems such as turbidity may occur, and the storage stability of the colored curable resin composition tends to decrease. There is.

Further, the (b-2) copolymer may have a radical polymerizable double bond or an epoxy group. Specific examples of the copolymer having these include the compounds described in JP-A-2009-52031, and the production method includes the synthesis method described in the publication.
(B-2) The monomer component for obtaining the copolymer may contain other copolymerizable monomers as required in addition to the essential monomer component.

Other copolymerizable monomers are not particularly limited, but methyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and styrene have good transparency and impair heat resistance. It is preferable in terms of difficulty. These other copolymerizable monomers may be used alone or in combination of two or more.
When the other copolymerizable monomer is included, the content is not particularly limited, but is preferably 95% by weight or less, and more preferably 85% by weight or less.

As will be described later, this (b-2) copolymer is preferably used in a dispersion treatment step together with (d) a dispersant. In that case, in particular, benzyl (meth) acrylate is used as a part of the raw material monomer. Is preferably used. The content of benzyl (meth) acrylate is usually 1 to 70% by weight, preferably 5 to 60% by weight, based on all monomer components constituting the (b-2) copolymer.

  The molecular weight of the (b-2) copolymer is not particularly limited, but the polystyrene-equivalent weight average molecular weight (Mw) measured by GPC is preferably 2,000 to 200,000, more preferably 4,000 to 100,000. When the weight average molecular weight exceeds 200,000, the viscosity may become too high to form a coating film, and when it is less than 2,000, sufficient heat resistance tends to be hardly exhibited.

In addition, (b-2) a copolymer can be manufactured by the method of Unexamined-Japanese-Patent No. 2004-300203 and Unexamined-Japanese-Patent No. 2004-300204, for example.
(B-3) Resin having an epoxy group (b-3) A resin having an epoxy group (hereinafter sometimes referred to as “(b-3) resin”) has an epoxy group in the resin. Although the structure is not particularly limited, among them, preferred are alicyclic polyether compounds having an epoxy group in the side chain, polyglycidyl ether compounds, polyglycidyl ester compounds, polyglycidyl amine compounds having an epoxy group (meth). A polymer obtained by combining one kind of acrylate alone or two or more kinds, or other monomer in the (meth) acrylate structural unit having an epoxy group is usually 10 to 70 mol%, preferably 15 to 60 mol%. Examples of the polymer include.

Specific examples of the resin containing an epoxy group include the following compounds.
(B-3-1) An alicyclic polyether compound having an epoxy group in the side chain
Examples of the alicyclic polyether compound having an epoxy group in the side chain include 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol, Examples include polycyclohexyl ether having an epoxy group in the side chain. As a commercial item of such a compound, EHPE3150 (made by Daicel Chemical Industries Ltd.) etc. are mentioned, for example.

(B-3-2) Polyglycidyl ether compound
Examples of the polyglycidyl ether compound include diglycidyl ether type epoxy of polyethylene glycol, triglycidyl ether type epoxy of glycerol, triglycidyl ether type epoxy of trimethylolpropane, tetraglycidyl ether type epoxy of pentaerythritol, hexaglycidyl ether of sorbitol Type epoxy, bis (4-hydroxyphenyl) diglycidyl ether type epoxy, bis (3,5-dimethyl-4-hydroxyphenyl) diglycidyl ether type epoxy, bisphenol F diglycidyl ether type epoxy, bisphenol A di Glycidyl ether type epoxy, tetramethylbisphenol A diglycidyl ether type epoxy, ethylene oxide added bisphenol A jig Cisyl ether type epoxy, dihydroxyoxyfluorene type epoxy, dihydroxyalkyleneoxyl fluorene type epoxy, bisphenol A / aldehyde novolak type epoxy, phenol novolac type epoxy, cresol novolac type epoxy, and bisphenol S epoxy resin as polyglycidyl ether resin Phenol novolac epoxy resins, cresol novolac epoxy resins, trisphenol epoxy resins, phenol and dicyclopentadiene polymerized epoxy resins, phenol and naphthalene polymerized epoxy resins, and the like.

These (poly) glycidyl ether compounds may be those obtained by reacting the remaining hydroxyl group with an acid anhydride or dibasic acid to introduce a carboxyl group.
(B-3-3) Polyglycidyl ester compound
Examples of the polyglycidyl ester compound include a diglycidyl ester type epoxy of hexahydrophthalic acid, a diglycidyl ester type epoxy of phthalic acid, and the like.

(B-3-4) Polyglycidylamine compound
Examples of the polyglycidylamine compound include diglycidylamine type epoxy of bis (4-aminophenyl) methane, triglycidylamine type epoxy of isocyanuric acid, and the like.
(B-3-5) Other monomers
Other examples include glycidyl (meth) acrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, (meth) acrylic acid-3,4- (Meth) having an epoxy group such as epoxybutyl, (meth) acrylic acid-4,5-epoxypentyl, (meth) acrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl A polymer containing one acrylate alone or a combination of two or more, or a (meth) acrylate structural unit having an epoxy group usually contains 10 to 70 mol%, preferably 15 to 60 mol% of another comonomer. The polymer made into is mentioned. Among these, as the copolymer, for example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylate-2-ethylhexyl, (meth) acrylic Esters of (meth) acrylic acid such as phenyl acid, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, and styrene And vinyl aromatic compounds such as α-methylstyrene, p-methylstyrene, and vinylnaphthalene. A preferred (meth) acrylate having an epoxy group is glycidyl (meth) acrylate. Preferred copolymers include dicyclopentanyl (meth) acrylate and α-styrene.

In addition, the epoxy group used in the (b-3) resin is usually a 1,2-epoxy group, but for the purpose of improving stability over time or imparting flexibility, a 1,3-epoxy group (oxetane) 4,3-epoxycyclohexyl groups can also be used.
In addition, in the resin (b-3) according to the present invention, those that do not contain an aromatic ring or those that are unsubstituted or contain a phenyl group having a substituent at the p (para) position suppresses discoloration due to heat treatment. Therefore, it is preferable.

Among (b-3) resins, (b-3-1) or (b-3-2) is preferable, and those not containing an aromatic ring are particularly preferable.
The colored curable resin composition of the present invention may be photocurable, thermosetting, or cured by both actions. In the case of forming, a thermosetting colored curable resin composition is used because it does not require a photopolymerization initiator capable of lowering luminance and can increase productivity by omitting the photocuring process. It is preferable.

In the case of curing using a thermosetting action, among the binder resins described as the (b-1) copolymer, “(A) mono (meta) having a structure represented by the general formula (1)” The (meth) acrylic copolymer obtained by polymerizing an acrylate and an ethylenically unsaturated group-containing monomer containing (B1) an epoxy group-containing (meth) acrylate ”and the (b-3) resin are used in combination. It is preferable.

When used together, the proportion of (b-3) resin is usually 0.5% by weight or more, preferably 1% by weight or more, and usually 50% by weight or less in the total solid content in the curable resin composition of the present invention. , Preferably 40% by weight or less, more preferably 35% by weight or less. (B-3) If the ratio of the resin is too small, the chemical resistance improving effect may be insufficient, and if it is too large, the storage stability may be insufficient.

  (B-3) The weight average molecular weight (Mw) of the resin is usually 300 or more, preferably 500 or more, and usually 100,000 or less, preferably 50,000 or less. If the molecular weight is too small, the film strength tends to be inferior, and if it is too large, the liquid properties as a coating solution may be non-Newtonian. The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) is preferably 2.0 or more and 5.0 or less.

  In the colored curable resin composition of the present invention, the content of the (b) binder resin is usually 10% by weight or more, preferably 20% by weight or more, and usually 80% by weight or less, preferably in the total solid content. Is 70% by weight or less. (B) If the content of the binder resin is less than this range, the film becomes brittle, the adhesion to the substrate may be reduced, and heat resistance and luminance may be reduced. On the other hand, when the amount is larger than this range, the coloring power may be insufficient or it may be difficult to adjust the film thickness to an appropriate thickness.

  Further, by using a part of the above-described (b) binder resin together with the above-mentioned (d) dispersant in a dispersion treatment step described later, a high-density color pixel having excellent adhesion to the substrate can be formed. Therefore, it is preferable. At this time, the binder resin (b) used in combination is preferably used in an amount of about 5 to 200% by weight, more preferably about 10 to 100% by weight, based on the color material (a).

As described above, as the binder resin used in combination in the dispersion treatment step, the above-described various resins can be used. In particular, the (b-2) copolymer is preferable.
(D) The acid value of the binder resin used in the dispersion treatment step together with the dispersant is preferably 10 mgKOH / g or more, more preferably 30 mgKOH / g or more, most preferably 150 mgKOH / g or more, and 500 mgKOH / g or less. Preferably, 300 mgKOH / g or less is more preferable, and 200 mgKOH / g or more is most preferable. In addition, from the viewpoint of the storage stability of the composition, it is preferable that the acid value is low.

  When used in the dispersion treatment step together with (d) the dispersant, the polystyrene-equivalent weight average molecular weight measured by GPC of the binder resin used in combination is preferably 1000 or more, more preferably 1500 or more, most preferably 2000 or more, Moreover, 200000 or less are preferable, 50000 or less are more preferable, and 30000 or less are the most preferable. If the molecular weight is too large, the viscosity of the resin increases, and the inkjet dischargeability of the composition may deteriorate. If the molecular weight is too small, the dispersion stability may decrease.

[2-2] Surfactant
The colored curable resin composition of the present invention may contain a surfactant as long as the effects of the present invention are not impaired. Various types of surfactants such as anionic, cationic, nonionic, and amphoteric surfactants are used as surfactants, but they may adversely affect various properties such as voltage holding ratio and compatibility with organic solvents. Nonionic surfactants are preferred at low points.

  Especially, it is preferable to contain the compound represented by the following general formula (XI).

(In the above formula, the substituent A ¹¹ represents a fluorinated alkyl group having 1 to 5 carbon atoms, and n ¹¹ represents an integer of 2 to 100.)
In the compound represented by the general formula (XI), the substituent A ¹¹ represents a fluorinated alkyl group having 1 to 5 carbon atoms, preferably 1 to 4 carbon atoms. When the number of carbon atoms is 6 or more, the substituent portion becomes too bulky, and the orientation to the interface may be impaired.

Of these, a perfluoroalkyl group in which all of the hydrogen atoms are substituted with fluorine atoms is preferred. Further, the number of fluorine-substituted carbon atoms is preferably 1 to 3, and more preferably 1 or 2. When four or more carbon atoms are fluorine-substituted, they may show harmful effects accumulated in the human body.
Specific examples of such substituent A ¹¹ include —CF ₃ , —CF ₂ CF ₃ , —CF ₂ C ₂ F ₅ , and among them, —CF ₃ or —CF ₂ CF ₃ is particularly preferable.

^{N 11} in the general formula (XI) represents an integer of 2 to 100, preferably an integer of 5-30. When n ¹¹ is more than 100, the molecular weight becomes too large, there is concern that solubility will be impaired. On the other hand, when n ¹¹ is less than 2, the molecular weight becomes too small, and the stability in the solution may be impaired.
Of the compounds represented by the general formula (XI), more preferable compounds are, for example, the following compounds.

Moreover, the compound represented by general formula (XI) is marketed, for example, P made by OMNOVA
F-636, PF-656, PF-6320, PF-6520 (all are trade names), etc. can be used.
From the viewpoint of spreading in the pixel bank, the colored curable resin composition preferably has a small contact angle with the transparent substrate of the color filter described later, for example, the colored curable resin composition of the present invention. In this case, the contact angle with respect to the glass (clean glass) surface is preferably less than 5 degrees. In terms of easily achieving such a contact angle, for example, (ii), (iii) and (iv) are particularly preferable among the above four compounds.

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

The surfactant may contain a surfactant other than the compound represented by the general formula (XI) as long as the effects of the present invention are not impaired. In this case, it is preferable to use in the form of replacing a part of the content of the compound represented by the general formula (XI).
In addition, when using together the compound represented with the said general formula (XI), and other surfactant, various things can be used, but it has a bad influence on various characteristics, such as a voltage holding rate and the compatibility with an organic solvent. It is preferable to use a nonionic surfactant because it is less likely to affect.

[2-3] Other ingredients
The colored curable resin composition of the present invention may contain a monomer in addition to the above components. Examples of the monomer type, amount used, and preferable ones include monomers described in JP-A-2009-52031. Further, it may contain a photopolymerization initiation system and / or a thermal polymerization initiation system. As a kind, usage-amount, and preferable thing of a photoinitiation system and / or a thermal-polymerization initiation system, the thing as described in Unexamined-Japanese-Patent No. 2009-52031 is mentioned, for example.

The colored curable resin composition of the present invention may further contain a dispersion aid, a plasticizer, a thermal polymerization inhibitor, a storage stabilizer, a surface protective agent, an adhesion improver, a development improver, and the like.
The dispersing aid is used for (a) improving the dispersibility of the coloring material, improving the dispersion stability, and the like. For example, azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindo Examples thereof include derivatives such as linone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, and dioxazine pigments.

  Examples of the substituent of these pigment derivatives include a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a phthalimidomethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, and an amide group. These substituents may be directly bonded to the pigment skeleton, or may be bonded via an alkyl group, an aryl group, a heterocyclic group or the like. Of the substituents, a sulfonamide group, a quaternary salt thereof, and a sulfonic acid group are preferable, and a sulfonic acid group is more preferable. A plurality of these substituents may be substituted on one pigment skeleton, or a mixture of compounds having different numbers of substitutions.

Specific examples of pigment derivatives include sulfonic acid derivatives of azo pigments, sulfonic acid derivatives of phthalocyanine pigments, sulfonic acid derivatives of quinophthalone pigments, sulfonic acid derivatives of anthraquinone pigments, sulfonic acid derivatives of quinacridone pigments, diketo Examples include sulfonic acid derivatives of pyrrolopyrrole pigments and sulfonic acid derivatives of dioxazine pigments. Of these, sulfonic acid derivatives of Pigment Yellow 138, Pigment Yellow 139 are preferred.
Sulfonic acid derivative of Pigment Red 254, sulfonic acid derivative of Pigment Red 255, sulfonic acid derivative of Pigment Red 264, sulfonic acid derivative of Pigment Red 272, sulfonic acid derivative of Pigment Red 209, sulfone of Pigment Orange 71 An acid derivative, a sulfonic acid derivative of Pigment Violet 23, and more preferably a sulfonic acid derivative of Pigment Yellow 138 and a sulfonic acid derivative of Pigment Red 254.

  In the colored curable resin composition of the present invention, the content ratio of these dispersion aids is usually 0.1% by weight or more, usually 30% by weight or less, based on the color material component (a). Preferably it is 200 weight% or less, More preferably, it is 10 weight% or less, Most preferably, it is 5 weight% or less. This is because if the addition amount is small, the effect may not be exhibited. Conversely, if the addition amount is too large, the dispersibility and dispersion stability may be deteriorated.

The colored curable resin composition of the present invention may contain a thermal polymerization inhibitor. Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6- Examples include t-butyl-p-cresol, β-naphthol and the like. The content of these thermal polymerization inhibitors is preferably in the range of 3% by weight or less based on the total solid content.
[3] Preparation method of colored curable resin composition
Next, a method for preparing the colored curable resin composition of the present invention will be described.

  The colored curable resin composition of the present invention may be prepared by preparing a colorant dispersion liquid containing each of the above-described components in advance and adding (b) another component such as a binder resin thereto. Alternatively, the components contained in the composition may be added simultaneously or sequentially and mixed. As the colorant dispersion, (d) a dispersant containing both a block copolymer and a graft copolymer may be prepared and used, or a dispersant containing a block copolymer and a graft copolymer may be used. A plurality of colorant dispersions such as those containing a polymer may be prepared and mixed at a desired ratio for use.

In view of the fact that components such as binder resins and monomers having a property of being cured by heat and light, or polymerization initiators are difficult to change due to heat generated in the dispersion treatment step, the colorant dispersion prepared in advance may be A method of blending the components is preferred. Hereinafter, the method for preparing the colored curable resin composition of the present invention will be described using this method as an example.
First, (a) the color material, (c) the organic solvent, and (d) the dispersant are weighed in predetermined amounts, and (a) the color material is dispersed to obtain a color material dispersion (dispersion processing step). In this dispersion treatment step, a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like can be used. By performing this dispersion treatment, the color material is made into fine particles, so that the coating characteristics of the colored curable resin composition are improved and the transmittance of the product color filter substrate and the like is improved.

When dispersing the color material, it is preferable to use (b) a part of the binder resin and a dispersion aid as appropriate. Further, (e) an aromatic or aliphatic carboxylic acid is preferably contained in this dispersion treatment step.
When the dispersion treatment is performed using a sand grinder, it is preferable to use glass beads or zirconia beads having a diameter of 0.1 to several mm. The temperature during the dispersion treatment is usually set to 0 ° C. or higher, preferably room temperature or higher, and usually 100 ° C. or lower, preferably 80 ° C. or lower. The dispersion time needs to be appropriately adjusted because the appropriate time varies depending on the composition of the colorant dispersion, the size of the sand grinder apparatus, and the like.

In addition to the colorant dispersion obtained by the above dispersion treatment, (b) a binder resin (the remainder of what was added in the dispersion treatment step), (c) an organic solvent, and in some cases, an optional monomer, photopolymerization A colored curable resin composition is obtained by mixing an initiator system and / or a thermal polymerization initiator system and other components to obtain a uniform dispersion solution. In addition, since fine dust may be mixed in each of the dispersion treatment step and the mixing step, it is preferable to filter the obtained color material dispersion with a filter or the like.

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

[4-1] Color filter The colored curable resin composition of the present invention is particularly suitable for forming a pixel of a color filter by an inkjet method. In manufacturing a color filter by the ink jet method, first, a partition pattern (black matrix) is provided on a substrate, and ink for pixel formation is directly applied in the pattern to produce a color filter. Since ink droplets can be drawn at a desired position, high productivity and cost reduction of the color filter can be achieved.

  Since the black matrix (BM) of the color filter formed by the inkjet method not only functions as a light shielding function that has been conventionally required, but also functions as a partition wall to prevent color mixing of RGB ink that has been driven into the pixel. The film thickness is larger than that of a conventional color filter by photolithography (usually a film thickness of 1.5 μm or more, preferably about 1.8 to 2.5 μm, more preferably about 2.0 to 2.3 μm). It is the thickness.) Further, in order to prevent color mixing of RGB ink, liquid repellent treatment is often applied to the upper surface of the black matrix.

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

  Next, in a substantially rectangular recessed area surrounded by the resin BM pattern, the colored curable resin composition of the present invention is used to draw with an ink jet apparatus, and the composition is dried, photocured and / or thermally cured. A color filter is obtained by completely curing and forming pixels. As the colored curable resin composition for pixel formation, three colors of R (red), G (green), and B (blue) are often used, but are not limited thereto.

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

For drying the coating film of the colored curable resin composition, heat drying such as a hot plate, IR oven, convection oven or the like can be used. Preferred drying conditions are 40 to 150 ° C., and drying time is 10 seconds to 60 minutes. It is a range. Further, reduced pressure (vacuum) drying can be used, and preferable drying conditions are 0.1 to 1 Torr, and drying time is in the range of 10 seconds to 60 minutes. Furthermore, both can be used together and can also be performed sequentially or simultaneously.

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

[4-2] Liquid crystal display device
Next, the liquid crystal display device (panel) of the present invention will be described.
The liquid crystal display device of the present invention is manufactured, for example, as follows using the above-described color filter of the present invention.
First, an alignment film is formed on the color filter, a spacer is disposed on the alignment film, and then a liquid crystal cell is formed by bonding to the counter substrate. Next, liquid crystal is injected into the formed liquid crystal cell and connected to the counter electrode to complete.

The alignment film is preferably a resin film such as polyimide. For the formation of the alignment film, a gravure printing method or a flexographic printing method is usually employed, and the thickness of the alignment film is usually 10 to 100 nm. After the alignment film is cured by thermal baking, it is surface-treated by ultraviolet (UV) irradiation or a rubbing cloth to be processed into a surface state in which the tilt of the liquid crystal can be adjusted.
A spacer having a size corresponding to a gap (gap) with the counter substrate is used, and a spacer of 2 to 8 μm is usually preferable. A photo spacer (PS) of a transparent resin film is formed on the color filter substrate by a photolithography method, and this can be used instead of the spacer. As the counter substrate, an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly preferable.

The gap for bonding to the counter substrate varies depending on the use of the liquid crystal display device, but is usually selected in the range of 2 to 8 μm. After bonding to the counter substrate, portions other than the liquid crystal injection port are sealed with a sealing material such as an epoxy resin. The sealing material is cured by UV irradiation and / or heating, and the periphery of the liquid crystal cell is sealed.
The liquid crystal cell whose periphery is sealed is cut into panel units, then the pressure is reduced in the vacuum chamber, the liquid crystal injection port is immersed in the liquid crystal, and then the liquid crystal is injected into the liquid crystal cell by leaking in the chamber. To do. The degree of vacuum in the liquid crystal cell is usually 1 × 10 ⁻² to 1 × 10 ⁻⁷ Pa, preferably 1 × 10 ⁻³ to 1 × 10 ⁻⁶ Pa. Moreover, it is preferable to heat a liquid crystal cell at the time of pressure reduction, and heating temperature is 30-100 degreeC normally, Preferably it is 50-90 degreeC. The warming holding at the time of depressurization is usually in the range of 10 to 60 minutes, and then immersed in the liquid crystal. In the liquid crystal cell into which the liquid crystal is injected, a liquid crystal display device (panel) is completed by sealing the liquid crystal injection port by curing the UV curable resin.

The type of the liquid crystal is not particularly limited, and is a conventionally known liquid crystal such as an aromatic, aliphatic, or polycyclic compound, and may be any of a lyotropic liquid crystal, a thermotropic liquid crystal, and the like. As the thermotropic liquid crystal, nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal and the like are known, but any of these may be used.
[4-3] Organic EL Display When an organic EL display is produced using the color filter of the present invention, for example, as shown in FIG. 3, a pattern formed from a colored resin composition on a transparent support substrate 10 ( That is, a color filter in which a pixel black and a resin black matrix (not shown) provided between adjacent pixels 20 are formed is produced, and the organic protective layer 30 and the inorganic oxide film 40 are formed on the color filter. The organic EL element 100 can be manufactured by stacking the organic light-emitting body 500 through the substrate. Note that at least one of the pixels 20 is manufactured using the colored resin composition of the present invention. 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. A method described in, for example, “Organic EL Display” (Om, Aug. 20, 2004 Luminescence, Shizushi Tokito, Chiba Adachi, Hideyuki Murata) using the organic EL element 100 thus manufactured, etc. Thus, an organic EL display can be produced.

  The color filter of the present invention can be applied to both passive drive type organic EL displays and active drive type organic EL displays.

EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to a following example, unless the summary is exceeded.
(Example)
<Synthesis Example 1: Synthesis of Binder Resin 1>
Prepare a separable flask with a cooling tube as a reaction tank, charge 400 parts by weight of propylene glycol monomethyl ether acetate, purge with nitrogen, and heat in an oil bath while stirring to raise the temperature of the reaction tank to 90 ° C. did.

  Meanwhile, 10 parts by weight of dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, 15 parts by weight of methacrylic acid, 20 parts by weight of methyl methacrylate, 55 parts by weight of benzyl methacrylate, t- 2.6 parts by weight of butyl peroxy-2-ethylhexanoate and 40 parts by weight of propylene glycol monomethyl ether acetate are charged, 5.7 parts by weight of n-dodecyl mercaptan and 27 parts by weight of propylene glycol monomethyl ether acetate are added to the chain transfer agent tank. After the temperature of the reaction vessel was stabilized at 90 ° C., dropping was started from the monomer tank and the chain transfer agent tank to initiate polymerization.

While maintaining the temperature at 90 ° C., dropping was carried out over 135 minutes each, and 60 minutes after the dropping was finished, the temperature was raised and the reaction vessel was brought to 110 ° C. After maintaining at 110 ° C. for 3 hours, the mixture was cooled to room temperature to obtain a polymer solution having a weight average molecular weight of 6000 and an acid value of 100 mgKOH / g.
<Synthesis Example 2: Synthesis of Binder Resin 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.

To this, 95.1 parts by weight of glycidyl methacrylate and 72.6 parts by weight of a monoacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were added dropwise, and 2.2'-azobis-2-methylbutyronitrile was further added. 10.2 parts by weight were added dropwise over 3 hours and further stirred at 90 ° C. for 2 hours to obtain a resin solution having a weight average molecular weight Mw of about 4200.
<Synthesis Example 3: Synthesis of Graft Copolymer Type Dispersant>
50 parts by weight of polyethyleneimine having a weight average molecular weight of about 5000, 40 parts by weight of polycaprolactone (pentamer), and 6 parts by weight of stearic acid are mixed with 300 parts by weight of propylene glycol monomethyl ether acetate, and nitrogen is added at 150 ° C. for 3 hours. The mixture was stirred under an atmosphere to obtain a graft copolymer (A). The resulting graft copolymer (A) had an amine value of 54 mgKOH / g and an acid value of 10 mgKOH / g.

<Example 1>
(Preparation of colorant dispersion 1)
As a pigment ((a) color material), C.I. I. Pigment Blue 15: 6 29.4 g, C.I. I. 3.3 g of Pigment Violet 23, (d) As a dispersant, 12.5 g of a block copolymer, BYK-LPN6919, a polymer dispersant manufactured by Big Chemie, in terms of solid content, and (e) 3-carboxylic acid as 3-carboxylic acid 3.9 g of phenylpropiolic acid (manufactured by Tokyo Chemical Industry Co., Ltd., pKa = 2.45) (that is, 1 equivalent to the number of amino group equivalents of the block copolymer), (b) Synthesis Example 1 as a binder resin 10.9 g of the resin (binder resin 1) obtained in (1) in terms of solid content and (c) 240.0 g of diethylene glycol mono-n-butyl ether acetate as an organic solvent were mixed and homogenized with stirring. Subsequently, using a stirring and rotating type circulation dispersion device, the dispersion treatment is performed for 1 hour with zirconia beads having a particle diameter of 0.5 mm, and then the dispersion treatment is further performed for 5 hours with zirconia beads having a diameter of 0.1 mm. did.

(Preparation of colorant dispersion 2)
As a pigment ((a) color material), C.I. I. Pigment Blue 15: 6 (hereinafter sometimes referred to as “P.B.15: 6”) 28.9 g, C.I. I. 3.2 g of Pigment Violet 23 (hereinafter sometimes referred to as “P.V.23”), and (d) a polymer dispersant “PB880” manufactured by Ajinomoto Fine Techno Co., Ltd., which is a graft copolymer. 21.4 g in terms of solid content, (b) 6.4 g in terms of solid content (binder resin 1) obtained in Synthesis Example 1 as a binder resin, and (c) diethylene glycol mono-n-butyl ether acetate as an organic solvent 240 0.0 g was mixed and stirred uniformly. Subsequently, the mixture was dispersed for 1 hour with zirconia beads having a particle diameter of 0.5 mm using a stirring and rotating type dispersion apparatus, and further dispersed for 4 hours with zirconia beads having a diameter of 0.1 mm to prepare a colorant dispersion 2. .

(Preparation of colored curable resin composition)
The obtained color material dispersions 1 and 2 were mixed at a weight ratio of 1: 0.75.
Separately, diethylene glycol mono-n-butyl ether acetate was added and mixed so that the solid content of the resin obtained in Synthesis Example 2 (binder resin 2) was 21.6% by weight to prepare a clear base.

While stirring the previously mixed color material dispersion (mixed dispersion), the above clear base is dropped so that the pigment concentration ratio in the total solid content of the colored curable resin composition is 20% by weight. After mixing, the mixture was filtered through a 5 μm membrane filter to obtain a uniform colored curable resin composition.
(Evaluation of coloring material dispersion and colored curable resin composition)
The color material dispersions 1 and 2 were mixed in the above-described ratio, and the viscosity stability of the obtained color material dispersion (mixed dispersion) was measured by the method described later.

Moreover, about the obtained colored curable resin composition, (DELTA) T-B and the contrast value were measured in accordance with the evaluation method mentioned later. The results are shown in Table 1.
<Example 2>
(E) Colorant dispersion 1 in Example 1 except that the carboxylic acid was changed to benzoic acid and the content was changed to 3.3 g (1 equivalent to the number of equivalents of amino groups of the block copolymer). A color material dispersion was prepared in the same manner as described above (color material dispersion 1 ′). Further, a colorant dispersion was prepared in the same manner as the colorant dispersion 2 in Example 1 except that the graft copolymer was changed to the graft copolymer (A) obtained in Synthesis Example 3 (colorant) Dispersion 2 ′). A colored curable resin composition was prepared and evaluated in the same manner as in Example 1 except that these colorant dispersions 1 ′ and 2 ′ were used. The results are shown in Table 1.

<Comparative Example 1>
(E) A color material dispersion was prepared in the same manner as the color material dispersion 1 in Example 1 except that no carboxylic acid was used (color material dispersion 1 ″). This color material dispersion 1 ″ was used. Except for the above, a colored curable resin composition was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1. Note that ΔT-B was not measured because the composition had a high viscosity immediately after preparation and could not be applied by the ink jet method.

<Example 3>
As a pigment ((a) color material), C.I. I. 1.07 g of Pigment Red 177 (hereinafter sometimes referred to as “PR.177”), (d) As a dispersant, a polymer dispersant “BYK-LPN6919” manufactured by Big Chemie, which is a block copolymer, is used. 0.11 g in terms of solid content, 0.40 g of the graft copolymer (A) obtained in Synthesis Example 3, (e) 0.03 g of benzoic acid as the carboxylic acid, (c) diethylene glycol mono-n- as the organic solvent 6.40 g of butyl ether acetate was mixed and dispersed with zirconia beads having a particle diameter of 0.5 mm for 6 hours using a paint shaker to prepare a colorant dispersion 3 to evaluate the viscosity stability. The results are shown in Table 2.

<Comparative example 2>
A color material dispersion was prepared in the same manner as the color material dispersion 3 in Example 3 except that the graft copolymer was not used (color material dispersion 3 ′). Viscosity stability was evaluated in the same manner as in Example 3 except that this colorant dispersion 3 ′ was used. The results are shown in Table 2.
<Comparative Example 3>
A color material dispersion was prepared in the same manner as the color material dispersion 3 in Example 3 except that no block copolymer and carboxylic acid were used (color material dispersion 3 ″). This color material dispersion 3 ″. Viscosity stability was evaluated in the same manner as in Example 3 except that was used. The results are shown in Table 2.

<Example 4>
Pigment Y (1.07 g) as pigment ((a) colorant), (d) 0.21 g as a dispersant, block copolymer, BYK-LPN6919, a polymer dispersant manufactured by BYK-Chemie , 0.27 g of graft copolymer (A), (e) 0.06 g of benzoic acid as carboxylic acid, (c) 6.40 g of diethylene glycol mono-n-butyl ether acetate as an organic solvent, and particles using a paint shaker Dispersion treatment was carried out with zirconia beads having a diameter of 0.5 mm for 6 hours to prepare a colorant dispersion liquid 4, and the viscosity stability was evaluated. The results are shown in Table 2.

<Comparative example 4>
A color material dispersion was prepared in the same manner as the color material dispersion 4 in Example 4 except that the graft copolymer was not used (color material dispersion 4 ′). Viscosity stability was evaluated in the same manner as in Example 4 except that this colorant dispersion 4 ′ was used. The results are shown in Table 2.
<Comparative Example 5>
A color material dispersion was prepared in the same manner as the color material dispersion 4 in Example 4 except that the block copolymer and carboxylic acid were not used (color material dispersion 4 ″). Viscosity stability was evaluated in the same manner as in Example 4 except that it was used. The results are shown in Table 2.

In addition, the detail of the commercially available material used in the Example and the comparative example is as follows.
[High molecular dispersant "BYK-LPN6919" manufactured by Big Chemie]
A methacrylic AB block copolymer having a tertiary amino group. The weight average molecular weight Mw is 9000, the amine value is 121 mgKOH / g, the acid value is almost 0 mgKOH / g, and the “repeating unit having an amino group in the side chain” in the B block has the structure represented by the following formula (i): Yes, the ratio of the repeating unit represented by the following formula (ii) contained in the A block to the total repeating units is 11 mol%.

[Ajinomoto Fine Techno Co., Ltd. Polymer Dispersant "Ajisper PB-880"]
A polymer dispersant comprising a polyallylamine derivative having the following partial structures (a), (b) and (c). The amine value is 17 mgKOH / g, and the acid value is 14 mgKOH / g.

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

Amine value [mgKOH / g] = (561 × V) / (W × S)
(W: Dispersant sample weighed [g], V: Titration amount at the end of titration [mL], S: Dispersant sample solid content concentration [wt%].)
<Evaluation method>
The “viscosity stability”, “ΔT-B” and “contrast value” in Tables 1 and 2 were measured by the following methods.

(Viscosity stability: initial viscosity and viscosity after 1 week)
In each of the above Examples and Comparative Examples, the viscosity was measured for each of the mixed dispersion liquid that was allowed to stand for 24 hours and the mixed dispersion liquid that was allowed to stand for one week in a thermostatic bath at 23 ° C. after preparation. For measurement, a viscometer “DV-IIIULTRA” manufactured by BROOKFIELD was used, and 150 S ⁻ at 23 ° C.
The value at ¹ was measured.

(Pixel flatness: ΔT-B)
Asahi Glass Co., Ltd. alkali-free glass substrate (AN635) 10 cm square 0.7 mm thick, a curable resin composition for black matrix (BM) is applied, line width 20 μm, opening width 220 μm × 700 μm, thickness 2. A 0 μm BM pattern was formed.
Next, the surface of the BM is made liquid-repellent by fluorine plasma treatment on the glass substrate provided with the BM pattern, and then an amount equivalent to 550 pL is applied to the central portion of each pixel bank formed by the BM pattern by the inkjet method. The colored curable resin composition 1 was applied. The application range was 10 cm square.

Thereafter, drying under reduced pressure was performed at 50 Pa for 5 minutes, and further, thermosetting treatment was performed under conditions of 100 ° C. for 10 minutes using a hot plate and 240 ° C. for 40 minutes using an oven to form pixels.
The cross-sectional shape of the obtained pixel (the view of the pixel as viewed from above is shown in FIG. 1) in the cross section (schematic diagram is shown in FIG. 2) was measured with a laser microscope. Specifically, the difference (ΔT−B) between the maximum film thickness and the minimum film thickness in the above-mentioned cross section is calculated for the pixels after heat curing (average film thickness 2.0 μm), and this is calculated as the flatness. An evaluation index was used. The calculation results are shown in Table-1.

A smaller value of ΔT-B indicates that the shape is flatter, and if it is 1.0 or less, it is considered that the flatness is sufficient.
(Contrast value)
First, on the same glass substrate as used in “(Pixel flatness: ΔT-B)”, the colored curable resin composition obtained in each of Examples and Comparative Examples was spin-coated, dried, A coating film having a thickness of 2 μm was provided. The glass substrate provided with this coating film is hereinafter referred to as a “colored plate”.

  FIGS. 5A and 5B are schematic diagrams for explaining a method of measuring the chromaticity of the parallel transmitted light and the orthogonal transmitted light of the colored plate. First, as shown in FIG. 5 (a), the polarizing plates 3 and 5 are overlapped on both sides of the colored plate, and the polarizing axes of the polarizing plates 3 and 5 are parallel to each other. Luminance Lp of light transmitted through the other polarizing plate 3 by applying light 6 from the backlight 7 (luminance of parallel transmitted light) is 2 ° using a color luminance meter “BM-5A” 32 manufactured by Topcon Technohouse. Measured under visual field conditions.

Next, as shown in FIG. 5B, in the state where the polarization axes of the polarizing plates 3 and 5 are orthogonal to each other, the light 6 of the backlight 7 is applied from one polarizing plate 5 side, and the other polarizing plate 3 The luminance Lc of the light transmitted through (the luminance of the orthogonal transmitted light) was measured with the color luminance meter 2 in the same manner as the above Lp.
The backlight 7 has an emission spectrum as shown in FIG. This spectrum was measured and calculated using a Konica Minolta spectral radiance meter CS-1000A and a filter “ND filter ND4” manufactured by Kenko in order to control the amount of light and facilitate the measurement.

The polarizing plates 3 and 5 have the spectral characteristics shown in FIG.
The contrast value of the pixel in the coloring plate is calculated from the luminance Lp of the parallel transmitted light and the luminance Lc of the orthogonal transmitted light using the formula Lp / Lc, and the contrast value when the composition obtained in Example 1 is used. The contrast value in Example 2 and Comparative Example 1 is shown as a relative value. The results are shown in Table-1.

According to the present invention, in the color material dispersion and the colored curable resin composition, it is possible to achieve both pixel (coating film) flatness and color material dispersibility, further suppress an increase in viscosity, and improve viscosity stability over time. Can be improved.
As a result, it is possible to provide a colored curable resin composition having good viscosity stability and high contrast, which is suitable for the production of an ink-jet color filter. By using the composition, pixel flatness is improved. A good color filter can be obtained. Further, since such a color filter can be manufactured with high quality yield, a liquid crystal display device can be provided in a large amount at a low cost.

2 Color luminance meter 3, 5 Polarizing plate 4 Colored plate 6 Light 7 Backlight 10 Transparent support substrate
20 pixels
30 Organic protective layer
40 Inorganic oxide film
50 transparent anode
51 Hole injection layer
52 Hole transport layer
53 Light emitting layer
54 Electron injection layer
55 Cathode
100 Organic EL device
500 Organic light emitter

Claims (26)

(A) a coloring material, (c) an organic solvent, (d) a dispersant, and (e) an aromatic or aliphatic carboxylic acid,
(D) A colorant dispersion, wherein the dispersant contains a block copolymer and a graft copolymer.   The colorant dispersion according to claim 1, wherein the block copolymer contained in the (d) dispersant includes a (meth) acrylic block copolymer containing a nitrogen atom.   The colorant dispersion according to claim 2, wherein the amine value of the (meth) acrylic block copolymer containing a nitrogen atom is 80 to 150 mgKOH / g in terms of effective solid content.   The (meth) acrylic block copolymer containing a nitrogen atom comprises (d1) a B-block having an amino group in the side chain and an A-block having no amino group in the side chain. The colorant dispersion according to claim 2 or 3, comprising a block copolymer and / or an ABA block copolymer.   The colorant dispersion according to any one of claims 1 to 4, wherein the graft copolymer contained in the dispersant (d) includes a graft copolymer containing a nitrogen atom. The colorant dispersion according to claim 5, wherein the graft copolymer containing a nitrogen atom contains (d2) a polyallylamine derivative represented by the following general formula (VII).
(In the formula, R ⁷¹ is a group represented by —NHCOR ⁷² or —NH ₃ ⁺ OCOR ⁷² —, and X ⁷ and Y ⁷ are each independently a hydrogen atom, a polymerization initiator residue, or a chain transfer catalyst residue. N ⁷ represents an integer of 2 to 1000, wherein R ⁷² is a carboxyl from any of a polyester having a free carboxylic acid, a polyamide having a free carboxylic acid, or a polyester amide having a free carboxylic acid. Represents a residue excluding a group, provided that at least one of n ⁷ R ⁷¹ represents a group represented by —NHCOR ^72. ) The graft copolymer containing the nitrogen atom has (d3) at least one of a repeating unit represented by the following general formula (II) and a repeating unit represented by the formula (III): The colorant dispersion according to claim 5 or 6, comprising
(In the general formula (II), R ⁵¹ represents an alkylene group having 1 to 5 carbon atoms, and A represents a hydrogen atom or any one of the following formulas (IV) to (VI).)
(In the general formula ^{(III), R 51} and A have the same meanings as ^{R 51} and A in the general formula (II).)
(In the general formula (IV), W ₁ represents a linear or branched alkylene group having 2 to 10 carbon atoms, and p represents an integer of 1 to 20).
(In the general formula (V), Y ₁ represents a divalent linking group, W ₂ represents an alkylene group having 2 to 10 carbon atoms, and Y ₂ represents a hydrogen atom or —CO—R ⁵² (where R ⁵² represents Represents an alkyl group having 1 to 10 carbon atoms.) Q represents an integer of 1 to 20, and preferably an integer of 5 to 10.
(In the general formula (VI), W ₃ represents an alkyl group having 1 to 50 carbon atoms or a hydroxyalkyl group having 1 to 50 carbon atoms having 1 to 5 hydroxyl groups.)   The colorant dispersion according to any one of claims 1 to 7, wherein the dissociation constant pKa of the (e) aromatic or aliphatic carboxylic acid is 4.5 or less. Content of said (e) aromatic or aliphatic carboxylic acid is 0.01-3.5 equivalent with respect to the equivalent number of the amino group contained in the block copolymer in said (d) dispersing agent, Claims Item 9. The colorant dispersion according to any one of Items 2 to 8.   The colorant dispersion according to any one of claims 1 to 9, wherein the content of the block copolymer and the graft copolymer in the (d) dispersant is 5/95 to 95/5 by weight ratio. liquid.   11. The colorant dispersion according to claim 1, wherein the organic solvent (c) contains a solvent having a boiling point of 180 ° C. or higher (boiling point under a pressure of 1013.15 [hPa]). .   A colored curable resin composition comprising the colorant dispersion according to any one of claims 1 to 11, and (b) a binder resin. (A) a coloring material, (b) a binder resin, (c) an organic solvent, (d) a dispersant and (e) an aromatic or aliphatic carboxylic acid,
(D) A colored curable resin composition, wherein the dispersant contains a block copolymer and a graft copolymer.   The colored curable resin composition according to claim 13, wherein the block copolymer contained in the (d) dispersant contains a (meth) acrylic block copolymer containing a nitrogen atom.   The colored curable resin composition according to claim 14, wherein the amine value of the (meth) acrylic block copolymer containing a nitrogen atom is 80 to 150 mgKOH / g in terms of effective solid content.   The (meth) acrylic block copolymer containing a nitrogen atom comprises (d1) a B-block having an amino group in the side chain and an A-block having no amino group in the side chain. The colored curable resin composition according to claim 14 or 15, comprising a block copolymer and / or an ABA block copolymer.   The colored curable resin composition according to any one of claims 13 to 16, wherein the graft copolymer contained in the dispersant (d) includes a graft copolymer containing a nitrogen atom. The colored curable resin composition according to claim 17, wherein the graft copolymer containing a nitrogen atom comprises (d2) a polyallylamine-based derivative represented by the following general formula (VII).
(In the formula, R ⁷¹ is a group represented by —NHCOR ⁷² or —NH ₃ ⁺ OCOR ⁷² —, and X ⁷ and Y ⁷ are each independently a hydrogen atom, a polymerization initiator residue, or a chain transfer catalyst residue. N ⁷ represents an integer of 2 to 1000, wherein R ⁷² is a carboxyl from any of a polyester having a free carboxylic acid, a polyamide having a free carboxylic acid, or a polyester amide having a free carboxylic acid. Represents a residue excluding a group, provided that at least one of n ⁷ R ⁷¹ represents a group represented by —NHCOR ^72. ) The graft copolymer containing the nitrogen atom has (d3) at least one of a repeating unit represented by the following general formula (II) and a repeating unit represented by the formula (III): The colored curable resin composition according to claim 17 or 18, comprising:
(In the general formula (II), R ⁵¹ represents an alkylene group having 1 to 5 carbon atoms, and A represents a hydrogen atom or any one of the following formulas (IV) to (VI).)
(In the general formula ^{(III), R 51} and A have the same meanings as ^{R 51} and A in the general formula (II).)
(In the general formula (IV), W ₁ represents a linear or branched alkylene group having 2 to 10 carbon atoms, and p represents an integer of 1 to 20).
(In the general formula (V), Y ₁ represents a divalent linking group, W ₂ represents an alkylene group having 2 to 10 carbon atoms, and Y ₂ represents a hydrogen atom or —CO—R ⁵² (where R ⁵² represents Represents an alkyl group having 1 to 10 carbon atoms.) Q represents an integer of 1 to 20, and preferably an integer of 5 to 10.
(In the general formula (VI), W ₃ represents an alkyl group having 1 to 50 carbon atoms or a hydroxyalkyl group having 1 to 50 carbon atoms having 1 to 5 hydroxyl groups.)   The colored curable resin composition according to any one of claims 13 to 19, wherein the dissociation constant pKa of the (e) aromatic or aliphatic carboxylic acid is 4.5 or less.   Content of said (e) aromatic or aliphatic carboxylic acid is 0.01-3.5 equivalent with respect to the equivalent number of the amino group contained in the block copolymer in said (d) dispersing agent, Claims Item 21. The colored curable resin composition according to any one of Items 4 to 20.   The colored curable property according to any one of claims 13 to 21, wherein the content of the block copolymer and the graft copolymer in the (d) dispersant is 5/95 to 95/5 by weight ratio. Resin composition.   The colored curable resin according to any one of claims 13 to 22, wherein the organic solvent (c) contains a solvent having a boiling point of 180 ° C or higher (a boiling point under a pressure of 1013.15 [hPa]). Composition.   The color filter which has a pixel formed using the colored curable resin composition as described in any one of Claims 12 thru | or 23.   A liquid crystal display device comprising the color filter according to claim 24.   An organic EL display having the color filter according to claim 24.