WO2011108495A1

WO2011108495A1 - Pigment dispersion, negative resist composition for color filter, color filter, liquid crystal display device, and organic light-emitting display device

Info

Publication number: WO2011108495A1
Application number: PCT/JP2011/054525
Authority: WO
Inventors: 教弘小倉; 武浩小澤; 裕章瀬川
Original assignee: 大日本印刷株式会社
Priority date: 2010-03-03
Filing date: 2011-02-28
Publication date: 2011-09-09
Also published as: JP5110222B2; TW201144388A; JPWO2011108495A1; TWI443152B

Abstract

Disclosed are a negative resist composition and a pigment dispersion that are for a color filter and that can produce a coating film from which pigment agglomerates do not precipitate even after a high-temperature heating step in a color filtering step, while meeting the demands of high brightness and increased contrast. The pigment dispersion for a color filter contains C.I. pigment yellow 138, a particular imide alkylated derivative of C.I. pigment yellow 138, a pigment dispersing agent, and a solvent, and 0.1-20 masses of the aforementioned imide alkylated derivative of C.I. pigment yellow 138 are contained for every 100 masses of the aforementioned C.I. pigment yellow 138. The negative resist composition contains said pigment dispersion.

Description

Pigment dispersion, negative resist composition for color filter, color filter, liquid crystal display device and organic light emitting display device

The present invention relates to a pigment dispersion, a negative resist composition for color filters, a color filter formed using the negative resist composition, and a liquid crystal display device and an organic light emitting display device having the color filter. .

In recent years, with the development of personal computers, particularly portable personal computers, the demand for liquid crystal displays has increased. Recently, the penetration rate of home-use liquid crystal televisions is also increasing, and the market for liquid crystal displays is expanding. Furthermore, with regard to the performance of the liquid crystal display, further improvement in image quality such as improvement in contrast and color reproducibility and reduction in power consumption are strongly desired.
Under such circumstances, there is an increasing demand for higher brightness, higher contrast, and improved color reproducibility even for color filters having a function of color-displaying a liquid crystal display. Recently, particularly for television applications, there is a growing demand for higher brightness due to reduced power consumption of the backlight and the characteristics of the LED backlight.
The above-described problems are the same in organic EL displays that are expected to be widely used in the future, and higher luminance and improved color reproducibility are problems to be solved in the displays.

Here, as a general method for producing a color filter, a coating film made of a photocurable negative resist composition in which a pigment of each color is dispersed is formed on a substrate on which a light shielding portion is formed in a pattern, A method is used in which a colored layer of each color is formed into a pattern by exposure and alkali development through a photomask having a desired pattern shape.
The color filter is usually a three-color pattern of red, green, and blue formed on a transparent substrate such as glass. In order to form a red or green coloring pattern, it is difficult to obtain a desired spectral spectrum only with a red or green pigment, and therefore, a spectral spectrum is adjusted by mixing a yellow pigment.

Generally, a color filter in which a pigment is dispersed has a problem that the degree of polarization controlled by the liquid crystal is disturbed due to light scattering by the pigment. That is, since light leaks when light must be blocked (OFF state) or transmitted light attenuates when light must be transmitted (ON state), display devices in the ON state and the OFF state There is a problem that the upper luminance ratio (contrast ratio) is low. Therefore, C.I. which has been conventionally suitable for increasing the contrast. I. Pigment Yellow 150 has been used as a yellow pigment for adjusting the red color and the green color. However, C.I. I. When CI Pigment Yellow 150 was used, there was a problem that the luminance was not sufficiently high.

In order to solve the problem that the transmittance is low when a pigment is used compared to a dye, Patent Document 1 discloses C.I. I. A green resin composition using Pigment Yellow 138 is disclosed. Conventionally, however, C.I. I. When Pigment Yellow 138 was used, the contrast was low, and there was a problem that it was difficult to use particularly in television applications.
C. I. As an attempt to increase contrast using Pigment Yellow 138, Patent Document 2 discloses C.I. I. Pigment yellow 138 and C.I. I. A color paste using a sulfonic acid derivative of CI Pigment Yellow 138 is described.

On the other hand, in Patent Document 3, as a method for converting a quinophthalone crude pigment into a fine pigment form, a quinophthalone crude pigment is pulverized and the pulverized product is recrystallized in a solvent in the presence of a quinophthalone pigment derivative, or a quinophthalone crude pigment. A method of pulverizing a pigment in the presence of a quinophthalone pigment derivative and recrystallizing the pulverized product in a solvent is disclosed, and a sulfonated quinophthalone pigment or a phthalimidomethylquinophthalone pigment is disclosed as the quinophthalone pigment derivative. In Patent Document 3, when the quinophthalone pigment is produced, the quinophthalone pigment derivative is merely used as a crystallization modifier for stopping crystal growth of the crushed crude pigment, and the sulfonated quinophthalone pigment and phthalimidomethyl are used. All of the quinophthalone pigments are described as functioning.

Japanese Patent Laid-Open No. 11-256053 Japanese Patent Laid-Open No. 2002-179979 JP-T-2004-501911

The inventors of the present invention have been able to improve C.C. I. Pigment Yellow 138 has been refined, and such refinement C.I. I. It was found that by using Pigment Yellow 138, a colored layer (coating film) having high luminance and capable of achieving the demand for high contrast was obtained. However, C.I. I. With the refinement of Pigment Yellow 138, it is found that after the high temperature (230 ° C. or higher) heating step after exposure in the color filter manufacturing process, there is a problem that pigment aggregates precipitate as foreign matters on the coating film surface. It was. When such pigment aggregates are deposited on the surface of the coating film as foreign matter, the color filter cannot be used as a defective product.

The present invention has been made under such circumstances, and produces a coating film in which pigment aggregates do not precipitate even after a high-temperature heating process in a color filter process while achieving a demand for high brightness and high contrast. Pigment dispersion for color filter, negative resist composition for color filter in which precipitation of pigment aggregates is suppressed during the high-temperature heating step, and a colored layer having high brightness and high contrast can be formed, and the negative resist composition It is an object of the present invention to provide a color filter formed using the above, a liquid crystal display device and an organic light emitting display device having the color filter.

As a result of intensive studies to achieve the above object, the present inventors have found that C.I. I. Pigment Yellow 138, C.I. I. When a pigment dispersion in which a specific amount of a specific imide alkylated derivative of CI Pigment Yellow 138 is combined and dispersed is used, a pigment can be obtained even after a high-temperature heating process in a color filter process while achieving a demand for high brightness and high contrast. It has been found that a negative resist composition capable of producing a coating film in which no aggregate is deposited can be obtained.
The present invention has been completed based on such findings.

The present invention relates to C.I. I. Pigment Yellow 138 and C.I. represented by the following chemical formula (1). I. An imide alkylated derivative of CI Pigment Yellow 138, a pigment dispersant, and a solvent; I. Pigment Yellow 138 imidoalkylated derivatives are C.I. I. Provided is a pigment dispersion for a color filter containing 0.1 to 20 parts by weight with respect to 100 parts by weight of Pigment Yellow 138.

(In the chemical formula (1), R represents an alkylene group having 1 to 6 carbon atoms, X represents an arylene group, and the arylene group is a halogen atom, an arylsulfonyl group, an acyl group, or — (C═O ) —C ₆ H ₄ — (C═O) — may be substituted, and n represents the number of substitutions of the imidoalkyl group and represents an integer of 1 to 5.)

Further, the present invention relates to C.I. I. Pigment Yellow 138 and C.I. represented by the above chemical formula (1). I. Pigment Yellow 138 containing an imide alkylated derivative, a pigment dispersant, an alkali-soluble resin, a polyfunctional monomer, a photoinitiator, and a solvent. I. Pigment Yellow 138 imidoalkylated derivatives are C.I. I. Provided is a negative resist composition for a color filter, which is contained in an amount of 0.1 to 20 parts by weight with respect to 100 parts by weight of Pigment Yellow 138.

In the pigment dispersion and negative resist composition according to the present invention, C.I. I. Pigment Yellow 138 sulfonic acid derivative is C.I. I. The content of 0.1 to 20 parts by weight with respect to 100 parts by weight of Pigment Yellow 138 is preferable from the viewpoint of easily achieving high contrast.

In the pigment dispersion and negative resist composition according to the present invention, the pigment dispersant is a repeating unit (1) represented by the following general formula (I) and a repeating represented by the following general formula (II). A block copolymer having a unit (2) and a salt formed by at least part of the amino group of the repeating unit (1) and the organic acid compound and / or halogenated hydrocarbon, This is preferable because a high contrast is easily achieved.

[In Formula (I) and Formula (II), R ¹ is a hydrogen atom or a methyl group, R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and A is a carbon atom having 1 carbon atom. To 8 alkylene groups, — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —CH (R ⁶ ) —CH (R ⁷ ) — or — [(CH ₂ ) _y —O] _z — ( A divalent group represented by CH ₂ ) _y —, R ⁴ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ⁶ ) —CH A monovalent group represented by (R ⁷ ) —O] _x —R ⁸ or — [(CH ₂ ) _y —O] _z —R ⁸ . R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group, and R ⁸ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, A monovalent group represented by —CHO, —CH ₂ CHO, or —CH ₂ COOR ⁹ , wherein R ⁹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; The alkyl group, alkenyl group, aralkyl group, and aryl group each may have a substituent.
x represents an integer of 1 to 18, y represents an integer of 1 to 5, and z represents an integer of 1 to 18. m represents an integer of 3 to 200, and n represents an integer of 10 to 200. ]

In the pigment dispersion and the negative resist composition according to the present invention, in the pigment dispersant, the organic acid compound is composed of organic acids represented by the following general formula (III) and the following general formula (IV). Or the halogenated hydrocarbon is at least one selected from the group consisting of benzyl halide, allyl halide, and methyl halide. In addition, it is preferable from the standpoint that it is possible to produce a coating film in which pigment aggregates do not precipitate even after the high-temperature heating step in the color filter step while achieving the demand for high contrast.

[In the formulas (III) and (IV), R ^a and R ^{a ′} each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group. 1 represented by the group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — [(CH ₂ ) _t —O] _u —R ^e , or —O—R ^{a ″.} the valence of the group, one of R ^a and R ^{a 'comprises} a carbon atom. R ^{a ″} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e ,-[(CH ₂ ) _t —O] _u —R ^e .
R ^b is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — A monovalent group represented by [(CH ₂ ) _t —O] _u —R ^e or —O—R ^{b ′} . R ^{b ′} represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , Alternatively, it is a monovalent group represented by-[(CH ₂ ) _t -O] _u -R ^e .
R ^c and R ^d are each independently a hydrogen atom or a methyl group, and R ^e is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, —CHO, —CH ₂ CHO, —CO—CH═CH ₂ , —CO—C (CH ₃ ) ═CH ₂ or a monovalent group represented by —CH ₂ COOR ^f , and R ^f is a hydrogen atom or carbon It is an alkyl group of the number 1-5.
In R ^a , R ^{a ′} , and R ^b , each of the alkyl group, alkenyl group, aralkyl group, and aryl group may have a substituent.
s represents an integer of 1 to 18, t represents an integer of 1 to 5, and u represents an integer of 1 to 18. ]

In the pigment dispersion and negative resist composition according to the present invention, C.I. I. The average primary particle size of CI Pigment Yellow 138 is preferably 10 to 50 nm from the viewpoint of producing a high-luminance, high-contrast, high-quality liquid crystal display device and organic light-emitting display device.

Also, the negative resist composition according to the present invention is preferably used in an embodiment containing a red or green pigment.

The present invention provides a color filter comprising a colored layer formed by curing the negative resist composition for a color filter.
The present invention also provides a liquid crystal display device comprising the color filter, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.
Furthermore, the present invention provides an organic light emitting display device comprising the color filter and an organic light emitter.

According to the present invention, there is provided a pigment dispersion for a color filter capable of producing a coating film in which pigment aggregates are not deposited even after a high-temperature heating step in a color filter step while achieving a demand for high brightness and high contrast. Can be provided.
ADVANTAGE OF THE INVENTION According to this invention, precipitation of a pigment aggregate is suppressed at the time of a high temperature heating process, and the negative resist composition for color filters which can form a high-intensity and high contrast colored layer can be provided. C. of the present invention. I. By using a pigment dispersion containing Pigment Yellow 138 or a negative resist composition, a pixel portion of a color filter with high brightness, high contrast, and reduced pigment aggregate precipitation during a high-temperature heating process is realized. It is possible.
Furthermore, according to the present invention, by using the color filter, it is possible to provide a liquid crystal display device and an organic light emitting display device with high brightness and high contrast.

It is the schematic which shows an example of the color filter of this invention. It is the schematic which shows an example of the liquid crystal display device of this invention. The photograph of the heat resistance evaluation result in 260 degreeC of the pattern coating film of Example 1 of this invention is shown. The photograph of the heat resistance evaluation result in 260 degreeC of the pattern coating film of Example 2 of this invention is shown. The photograph of the heat resistance evaluation result in 260 degreeC of the pattern coating film of the comparative example 1 of this invention is shown. The photograph of the heat resistance evaluation result in 260 degreeC of the pattern coating film of the comparative example 2 of this invention is shown. It is the schematic which shows an example of the organic light emitting display apparatus of this invention.

Hereinafter, the pigment dispersion for color filter, the negative resist composition for color filter, the color filter, the liquid crystal display device and the organic light emitting display device of the present invention will be described in order.
In the present invention, light includes electromagnetic waves having wavelengths in the visible and invisible regions, and further includes radiation, and the radiation includes, for example, microwaves and electron beams. Specifically, it means an electromagnetic wave having a wavelength of 5 μm or less and an electron beam. In the present invention, (meth) acryl means either acryl or methacryl, and (meth) acrylate means either acrylate or methacrylate.

1. Color filter pigment dispersion The color filter pigment dispersion according to the present invention includes C.I. I. Pigment Yellow 138 and C.I. represented by the following chemical formula (1). I. An imide alkylated derivative of CI Pigment Yellow 138, a pigment dispersant, and a solvent; I. Pigment Yellow 138 imidoalkylated derivatives are C.I. I. It is characterized by containing 0.1 to 20 parts by weight with respect to 100 parts by weight of Pigment Yellow 138.

The pigment dispersion for color filter of the present invention is C.I. I. Pigment Yellow 138 (hereinafter may be simply referred to as “PY138”), and by combining PY138 with a specific amount of a specific imide alkylated derivative of PY138 and dispersing PY138, high brightness and high contrast can be achieved. While achieving the requirements, it becomes possible to produce a coating film in which pigment aggregates do not precipitate even after the high-temperature heating step in the color filter step.

Although it is unclear as an effect | action which exhibits the above effects by the said specific combination, it estimates as follows.
By lengthening the dispersion time in the solvent, the pigment dispersant is appropriately adsorbed on the surface of the finely exposed pigment while the PY138 is refined, and the pigment can be stabilized in the solvent. It is presumed that PY138 can be refined more uniformly. As a result, a coating film with improved contrast can be obtained.
However, after the uniformly refined PY138 is made into a coating film, when a high temperature of 230 ° C. is applied to the coating film in the heating process of the color filter process, the pigment dispersant is absorbed by the thermal movement of the pigment dispersant adsorbed on the pigment. It is presumed that the adsorption of the dispersant is weakened, the cohesive force between the finely exposed pigment surfaces is strengthened, and the pigment aggregates are precipitated.
The phenomenon of pigment aggregates precipitating on the surface of the coating film when heated at a high temperature is obtained by adding a sulfonic acid derivative of PY138 to PY138, combining the specific salt-type pigment dispersant, and refining the pigment to obtain a pigment dispersion. Also when prepared, it was noticeable.

On the other hand, in this application, by adding a specific amount of a specific imide alkylated derivative of PY138 and a pigment dispersant to PY138, the pigment surface is exposed to the finely exposed pigment surface in the dispersion step of PY138. It is estimated that not only the dispersant but also the imide alkylated derivative of PY138 is adsorbed. Even when a high temperature of 230 ° C. is applied to the coating film in the heating process of the color filter process, the imide alkylated derivative of PY138 stabilizes the pigment surface while adsorbing to the surface of PY138 by the similar skeleton part of PY138. It is presumed that a stable coating film can be formed without agglomeration of the refined pigments.
Similarly, when the sulfonic acid derivative of PY138 is used, not only the pigment dispersant but also the sulfonic acid derivative of PY138 is adsorbed on the surface of the finely exposed pigment to stabilize the pigment in the solvent. As a result, the PY138 can be more uniformly miniaturized. However, when a high temperature of 230 ° C. is applied to the coating film in the heating process, the sulfonic acid derivative of PY138 has a stronger interaction force between the sulfo group and the pigment dispersant than the adsorption power of the similar skeleton portion of PY138 to PY138. It is presumed that the pigment dispersant is likely to move away from the pigment surface during thermal movement. As a result, it is presumed that the cohesive force between the pigment surfaces exposed after being miniaturized is strengthened, and the aggregate of the pigment is precipitated.
On the other hand, since the imide alkylated derivative of PY138 as described above has a weak polarity of the imide portion, it is difficult to receive strong interaction with a pigment dispersant like a sulfo group even when a high temperature of 230 ° C. is applied to the coating film. However, it is rather presumed that a stable coating film can be formed without agglomeration of finely divided pigments in order to stabilize the pigment surface because the adsorption force with the pigment surface is relatively stronger. .

That is, in the present application, the PY138 that can increase the luminance has a pigment dispersant and an interaction with the pigment dispersant, but the interaction is not too strong. By combining and dispersing the derivatives, the exposed pigment surface can be stabilized while minimizing PY138, and even at high temperatures, the pigment surface can be maintained while stabilizing the pigment surface where the imide alkylated derivative of PY138 is finely dispersed. Therefore, it is presumed that it is possible to produce a coating film in which pigment aggregates do not precipitate even after the high-temperature heating step in the color filter step, while achieving the demand for high brightness and high contrast.

The pigment dispersion for a color filter of the present invention has at least C.I. I. Pigment Yellow 138 and the specific amount of C.I. I. It contains a specific imide alkylated derivative of Pigment Yellow 138, a pigment dispersant and a solvent as essential components, and may contain other components as necessary.
The pigment dispersion for color filters of the present invention is typically a yellow pigment dispersion, but further contains other pigments such as a red pigment and a green pigment, and is a red pigment dispersion or a green pigment dispersion. May be.
Hereinafter, each component of the pigment dispersion of the present invention will be described in detail in order.

(CI Pigment Yellow 138)
C. I. Pigment Yellow 138 has a structure represented by the following chemical formula.

C. used in the present invention. I. The average primary particle size of the pigment such as CI Pigment Yellow 138 is not particularly limited as long as it can produce a desired color when it is used as the color layer of the color filter, and varies depending on the type of pigment used. From the viewpoint of improving the contrast, it is preferably in the range of 10 to 50 nm, more preferably in the range of 10 to 30 nm. When the average primary particle size of the pigment is within the above range, the liquid crystal display device and the organic light emitting display device produced using the pigment dispersion for color filter of the present invention and the negative resist composition can be provided with high contrast and high It can be of quality.
In addition, the average particle diameter of the pigment can be obtained by a method of directly measuring the size of primary particles from an electron micrograph. Specifically, the minor axis diameter and major axis diameter of each primary particle were measured, and the average was taken as the particle diameter of the particle. Next, for 100 or more particles, the volume (weight) of each particle was obtained by approximating the obtained particle size to a rectangular parallelepiped, and the volume average particle size was obtained and used as the average particle size. The same result can be obtained regardless of whether the electron microscope is a transmission type (TEM) or a scanning type (SEM).

C. used in the present invention. I. Pigment Yellow 138 can be produced by a known method such as a recrystallization method or a solvent salt milling method. In addition, commercially available C.I. I. Pigment Yellow 138 (for example, manufactured by BASF, Paliotol Yellow K0961HD) may be used.

In the pigment dispersion for a color filter of the present invention, C.I. I. The content of Pigment Yellow 138 is not particularly limited. Usually, C.I. I. The content of the pigment containing Pigment Yellow 138 is preferably 5 to 40% by weight, more preferably 10 to 20% by weight, based on the total amount of the color filter pigment dispersion.
In the pigment dispersion for a color filter of the present invention, C.I. I. The pigment yellow 138 content is usually 100% by weight, but it may further contain other pigments. C. in the pigment. I. The content of Pigment Yellow 138 is preferably 5 to 100% by weight, more preferably 50 to 100% by weight.

(C.I. Pigment Yellow 138 Imidoalkylated Derivative)
C. used in the present invention. I. An imidoalkylated derivative of CI Pigment Yellow 138 is represented by C.I. I. It is an imide alkylated derivative of CI Pigment Yellow 138.

Such a pigment derivative is a compound having a role of adding a functional group to the pigment skeleton and adding various functions to the pigment. When a pigment derivative is added to the pigment during the dispersion of the pigment, the pigment-like skeleton of the pigment derivative is adsorbed or bonded to the pigment surface, so that the surface of the pigment has an imide alkyl group. It is thought that crystallization can be suppressed.

In the chemical formula (1), examples of the alkylene group having 1 to 6 carbon atoms of R include a linear or branched alkylene group having 1 to 6 carbon atoms, such as a methylene group, an ethylene group, a trimethylene group, a propylene group, Examples include various butylene groups. Among these, from the viewpoint of easy production, the alkylene group is preferably a methylene group.

In the chemical formula (1), X represents arylene, and examples thereof include 1,2-phenylene, 1,2-naphthylene, 2,3-naphthylene, 1,8-naphthylene, and 2,2′-biphenylene. X in the chemical formula (1) is preferably 1,2-phenylene as phthalimide and 1,8-naphthylene as naphthalimide.

In the chemical formula (1), the halogen atom that may be substituted with the arylene group of X is preferably a chlorine atom or a bromine atom.
In the chemical formula (1), the arylsulfonyl group which may be substituted on the arylene group of X includes a phenylsulfonyl group and a substituted phenylsulfonyl group such as a p-tolylsulfonyl group, a p-chlorophenylsulfonyl group, Examples thereof include p-bromophenylsulfonyl group.
In the chemical formula (1), examples of the acyl group that may be substituted with the arylene group of X include an acetyl group, a propionyl group, a butyryl group, and a benzyl group.

C. used in the present invention. I. Among them, the imide alkylated derivative of CI Pigment Yellow 138 is preferably a phthalimide alkylated derivative represented by the following chemical formula (1 ') from the viewpoint of efficiently suppressing the pigment aggregate.

(In the formula, R represents an alkylene group having 1 to 6 carbon atoms, n represents the number of substitutions of a phthalimidoalkyl group, and represents an integer of 1 to 5.)

In the phthalimidoalkylated derivative represented by the chemical formula (1 ′), the alkylene group R may be the same as the chemical formula (1), and among them, a methylene group is preferable from the viewpoint that the pigment aggregate can be efficiently suppressed. .

In addition, the number n of substitution of the specific imide alkyl group is preferably 1 to 2, and is preferably 1 from the viewpoint that the pigment aggregate can be efficiently suppressed.
C. I. When the molecular weight of the imide alkylated derivative of CI Pigment Yellow 138 is smaller, the proportion of the active ingredient per weight increases, so that the pigment aggregate can be efficiently suppressed.

C. I. Examples of the imide alkylated derivative of CI Pigment Yellow 138 include C.I. I. Pigment Yellow 138 can be produced by reacting paraformaldehyde with a specific imide such as phthalimide in sulfur trioxide or sulfuric acid. The synthesis method is described in detail in JP-T-2004-501911 and can be referred to. C. I. As the imide alkylated derivative of CI Pigment Yellow 138, one kind can be used alone, or two or more kinds can be used in combination. For example, two or more types of imide alkylated derivatives having different types of alkylene groups, types of imide alkyl groups, and various imide alkyl group substitution positions or substitution numbers may be used.

In the present invention, C.I. I. Pigment Yellow 138 imidoalkylated derivatives include C.I. I. 0.5 to 20 parts by weight is contained with respect to 100 parts by weight of Pigment Yellow 138. Among them, C.I. I. Pigment Yellow 138 imidoalkylated derivatives include C.I. I. The pigment yellow 138 is preferably contained in an amount of 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight, based on 100 parts by weight. By using such a content, it is possible to produce a coating film in which pigment aggregates do not precipitate even after the high-temperature heating step in the color filter step, while achieving the demand for high brightness and high contrast.

(Pigment dispersant)
In the present invention, as the pigment dispersant, for example, cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants can be used. Among the surfactants, polymer surfactants (polymer dispersants) as exemplified below are preferable. A pigment derivative that dissolves in a small amount in a solvent may be used as a pigment dispersant.

The pigment dispersant is appropriately selected and used in order to favorably disperse the pigment used. Specific examples include amide compounds such as nonanamide, decanamide, dodecanamide, N-dodecylhexadecanamide, N-octadecylpropioamide, N, N-dimethyldodecanamide and N, N-dihexylacetamide, diethylamine, diheptylamine, Amine compounds such as dibutylhexadecylamine, N, N, N ′, N′-tetramethylmethanamine, triethylamine, tributylamine and trioctylamine, monoethanolamine, diethanolamine, triethanolamine, N, N, N ′, N ′-(tetrahydroxyethyl) -1,2-diaminoethane, N, N, N′-tri (hydroxyethyl) -1,2-diaminoethane, N, N, N ′, N′-tetra (hydroxyethyl) Polyoxyethylene) -1,2-diaminoethane, 1 , 4-bis (2-hydroxyethyl) piperazine, 1- (2-hydroxyethyl) piperazine, and other amines having a hydroxy group, and other compounds such as nipecotamide, isonipecotamide, and nicotinamide. be able to.

Further, (co) polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters; (partial) amine salts, (partial) ammonium salts of (co) polymers of unsaturated carboxylic acid such as polyacrylic acid ( Partially) alkylamine salts; (co) polymers of hydroxyl group-containing unsaturated carboxylic acid esters such as hydroxyl group-containing polyacrylates and their modified products; polyurethanes; unsaturated polyamides; polysiloxanes; long-chain polyaminoamide phosphorus Acid salts; amides obtained by the reaction of poly (lower alkyleneimine) and free carboxyl group-containing polyester, salts thereof, and the like can be mentioned.

As the pigment dispersant used in the present invention, a polymer pigment dispersant of a block copolymer type or a graft copolymer (comb type) type in which a pigment adsorption site and a solvent affinity site are functionally separated in the molecule is C . I. From the viewpoint of pigment dispersibility of CI Pigment Yellow 138.

The pigment dispersant used in the present invention has, among other things, a repeating unit (1) represented by the following general formula (I) and a repeating unit (2) represented by the following general formula (II), Further, a block copolymer in which at least a part of the amino group of the repeating unit (1) and an organic acid compound and / or a halogenated hydrocarbon form a salt is preferable.

In the present invention, C.I. I. Pigment Yellow 138 has a specific amount of C.I. I. By combining the imide alkylated derivative of CI Pigment Yellow 138 with the pigment dispersant made of the specific salt-type block copolymer as a pigment dispersant, the contrast is particularly improved, and there is a demand for high brightness and high contrast. While achieving, it becomes possible to produce a coating film in which pigment aggregates do not precipitate even after the high-temperature heating step in the color filter step.

The pigment dispersant comprising such a specific salt-type block copolymer includes the structural unit (1) represented by the general formula (I) and the structural unit (2) represented by the general formula (II). And a salt-forming block is formed by a salt-type block copolymer in which the amino group of the structural unit (1) and the organic acid compound and / or halogenated hydrocarbon form a salt. The structural unit (1) has particularly strong adsorptivity to PY138, while the structural unit (2) has solubility in a solvent. When such a pigment dispersant is used, the dispersion time is increased in the solvent, whereby the pigment dispersant is appropriately adsorbed on the surface of the finely exposed pigment while the PY138 is refined and the solvent is dissolved in the solvent. It is presumed that the pigment can be stabilized, and PY138 can be more uniformly refined. As a result, a coating film with improved contrast can be obtained.

For PY138, which can increase the luminance, there is a salt type pigment dispersant suitable for miniaturization, and there is an interaction with the salt type pigment dispersant, but the interaction is not too strong. By combining and dispersing the derivatives of PY138 having an imide moiety, the exposed pigment surface is stabilized while minimizing PY138, and the pigment surface where the imide alkylated derivative of PY138 is finely dispersed is stabilized even at high temperatures. It is presumed that it is possible to produce a coating film that has high brightness, particularly high contrast, and that does not precipitate pigment aggregates even after the high-temperature heating step in the color filter step.

<Block copolymer>
The block copolymer has a repeating unit (1) represented by the general formula (I) and a repeating unit (2) represented by the general formula (II).
In the general formula (I), R ¹ represents a hydrogen atom or a methyl group, and R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Here, the alkyl group having 1 to 8 carbon atoms may be linear, branched or cyclic. Examples of such alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, various pentyl groups, various hexyl groups, and various octyl groups. Group, cyclopentyl group, cyclohexyl group, cyclooctyl group and the like. Among these, a methyl group and an ethyl group are preferable.
In the present invention, R ² and R ³ may be the same as or different from each other.

A represents an alkylene group having 1 to 8 carbon atoms, * — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —CH (R ⁶ ) —CH (R ⁷ ) — **, or * — [(CH ₂ ) _y —O] _z — (CH ₂ ) _y — ** is a divalent group. Here, * represents a linking site on the ester bond side, and ** represents a linking site on the amino group side. In addition, the alkylene group having 1 to 8 carbon atoms may be linear or branched, and examples thereof include a methylene group, an ethylene group, a trimethylene group, a propylene group, various butylene groups, various pentylene groups, and various types. Hexylene group and various octylene groups.
R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group.
x is an integer of 1 to 18, preferably an integer of 1 to 4, more preferably an integer of 1 to 2, and y is an integer of 1 to 5, preferably an integer of 1 to 4, more preferably 2 or 3. is there. z is an integer of 1 to 18, preferably an integer of 1 to 4, more preferably an integer of 1 to 2. In the present invention, if x, y, and z are within the above ranges, the color filter pigment dispersion of the present invention has excellent pigment dispersibility.
A is preferably an alkylene group having 1 to 8 carbon atoms, more preferably a methylene group or an ethylene group. If the carbon number is in the range of 1 to 8, the dispersibility of the pigment can be kept good.

In the general formula (II), R ⁴ represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ⁶ ) —CH (R ⁷ ) — O] _x -R ⁸ or-[(CH ₂ ) _y -O] _z -R ⁸ is shown.
The alkyl group having 1 to 18 carbon atoms may be linear, branched or cyclic, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and an isobutyl group. , Sec-butyl group, tert-butyl group, various pentyl groups, various hexyl groups, various octyl groups, various decyl groups, various dodecyl groups, various tetradecyl groups, various hexadecyl groups, various octadecyl groups, cyclopentyl groups, cyclohexyl groups, cyclohexane Examples include an octyl group, a cyclododecyl group, a bornyl group, an isobornyl group, a dicyclopentanyl group, an adamantyl group, and a lower alkyl group-substituted adamantyl group.
The alkenyl group having 2 to 18 carbon atoms may be linear, branched or cyclic. Examples of such alkenyl groups include vinyl, allyl, propenyl, various butenyl, various hexenyl, various octenyl, various decenyl, various dodecenyl, various tetradecenyl, various hexadecenyl, various octadecenyl, A cyclopentenyl group, a cyclohexenyl group, a cyclooctenyl group, etc. can be mentioned. The position of the double bond of the alkenyl group is not limited, but from the viewpoint of the reactivity of the polymer obtained, it is preferable that a double bond is present at the terminal of the alkenyl group.

Examples of the aryl group that may have a substituent include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, and a xylyl group. The aryl group preferably has 6 to 24 carbon atoms, more preferably 6 to 12 carbon atoms.
Examples of the aralkyl group which may have a substituent include a benzyl group, a phenethyl group, a naphthylmethyl group, and a biphenylmethyl group. The aralkyl group preferably has 7 to 20 carbon atoms, more preferably 7 to 14 carbon atoms.
Examples of the substituent of the aromatic ring such as an aryl group and an aralkyl group include an alkenyl group, a nitro group, and a halogen atom in addition to a linear or branched alkyl group having 1 to 4 carbon atoms.
The preferred carbon number does not include the carbon number of the substituent.

R ⁶ and R ⁷ are the same as described above, and R ⁸ is a hydrogen atom or an optionally substituted alkyl group having 1 to 18 carbon atoms, alkenyl group having 2 to 18 carbon atoms, or aralkyl group. , An aryl group, —CHO, —CH ₂ CHO, or —CH ₂ COOR ⁹ , wherein R ⁹ is a hydrogen atom or a linear, branched, or cyclic group having 1 to 5 carbon atoms It is an alkyl group.
In the monovalent group represented by R ⁸ , examples of the substituent that may be included include linear, branched or cyclic alkyl groups having 1 to 4 carbon atoms, and halogen atoms such as F, Cl, and Br. And so on.
The alkyl group, and alkenyl group having 2 to 18 carbon atoms having 1 to 18 carbon atoms of R ^8, an aralkyl group, an aryl group is as shown by the R ^4.
In the above R ⁴ , x, y and z are as described in the above A.
Moreover, R ⁴ in the repeating unit (2) represented by the general formula (II) may be the same or different.

In the present invention, as R ⁴ , it is preferable to use one having excellent solubility with a solvent described later, and specifically, it varies depending on the repeating unit constituting the block copolymer. When the solvent is an ether alcohol acetate solvent, an ether solvent, an ester solvent or the like generally used as a color filter solvent, a methyl group, an ethyl group, an n-butyl group, 2- An ethylhexyl group, a benzyl group and the like are preferable.
Here, the reason for setting R ⁴ in this way is that the repeating unit (2) containing R ⁴ has good solubility in the solvent, and the amino group of the repeating unit (1) is described later. The salt-forming site formed by the organic acid compound and / or the halogenated hydrocarbon has high adsorptivity to the pigment, thereby making the dispersibility and stability of the pigment particularly excellent. Because it can.

Further, R ⁴ is substituted with a substituent such as an alkoxy group, a hydroxyl group, a carboxyl group, an amino group, an epoxy group, an isocyanate group, or a hydrogen bond-forming group as long as it does not interfere with the dispersion performance of the block copolymer. Alternatively, after the synthesis of the block copolymer, the substituent may be added by reacting with the compound having the substituent. Moreover, after synthesizing a block copolymer having these substituents, a compound having a functional group that reacts with the substituent and a polymerizable group may be reacted to add a polymerizable group. For example, adding a polymerizable group by reacting a block copolymer having a carboxyl group with glycidyl (meth) acrylate or reacting an isocyanate group with a block copolymer having hydroxyethyl (meth) acrylate. Can do.

The ratio m / n of the unit number m of the structural unit (1) and the unit number n of the structural unit (2) used in the present invention is preferably within the range of 0.01 to 1, preferably 0.05 to More preferably, it is in the range of 0.5. When the ratio m / n is within the above range, the adsorptivity to the pigment is good, the solubility with the solvent by the structural unit (2) is not lowered, and the dispersibility and stability of the pigment are lowered. There is nothing to do.

Regarding the molecular size of the block copolymer used in the present invention, the number m of the repeating unit (1) is an integer of 3 to 200, preferably an integer of 3 to 50. The number n of the repeating units (2) is an integer of 10 to 200, preferably an integer of 20 to 100, more preferably an integer of 20 to 70. In the present invention, when m and n are within the above ranges, the solvent-soluble part and the solvent-insoluble part act effectively, and the pigment dispersion for the color filter of the present invention has excellent pigment dispersibility. Can be.
Further, the weight average molecular weight Mw of the block copolymer is preferably in the range of 500 to 20000, more preferably in the range of 1000 to 15000, and further preferably in the range of 3000 to 12000. preferable. By being within the above range, it becomes possible to achieve both wettability and dispersion stability with respect to a pigment in the initial stage of dispersion in which the pigment is uniformly dispersed.

The weight average molecular weight Mw is a value measured by GPC (gel permeation chromatography). For the measurement, HLC-8120GPC manufactured by Tosoh Corporation was used, the elution solvent was N-methylpyrrolidone to which 0.01 mol / liter of lithium bromide was added, and polystyrene standards for calibration curves were Mw377400, 210500, 96000, 50400. 206500, 10850, 5460, 2930, 1300, 580 (Easy PS-2 series manufactured by Polymer Laboratories) and Mw1090000 (manufactured by Tosoh Corporation), and TSK-GEL ALPHA-M × 2 (Tosoh Corporation) (Made by Co., Ltd.).

The bonding order of the block copolymer used in the present invention is not particularly limited as long as it has the repeating unit (1) and the repeating unit (2) and can stably disperse the pigment. However, it is preferable that the repeating unit (1) is bonded to only one end of the block copolymer. That is, the repeating unit (1) and the repeating unit (2) may be bonded in the order of the repeating unit (1) -the repeating unit (2), or the repeating unit (1) -the repeating unit. (2) -repeated unit (1) may be bonded in this order, or repeating unit (1) -repeating unit (2) may be bonded repeatedly, but in the present invention, However, those bonded in the order of the repeating unit (1) to the repeating unit (2) are preferred. The reason is that it is excellent in the adsorptivity with respect to a pigment, and also the aggregation of pigment dispersants using such a block copolymer can be effectively suppressed.

In the case where two or more types of the structural unit (1) and the structural unit (2) are included, a block copolymer in which the structural unit (1), the structural unit (2 ′), and the structural unit (2 ″) are combined in this order, A block copolymer bonded in the order of structural unit (1 ′) − structural unit (1 ″) − structural unit (2), structural unit (1 ′) − structural unit (1 ″) − structural unit (2 ′) -It may be a block copolymer bonded in the order of the structural unit (2 ").

<Organic acid compound>
An amino group contained in the structural unit (1) of the block copolymer having the structural unit (1) represented by the general formula (I) and the structural unit (2) represented by the general formula (II); Examples of the organic acid compound that forms a salt include an organic phosphoric acid compound having a structure represented by the following general formula (III) and / or an organic sulfonic acid compound having a structure represented by the above general formula (IV). It is done.

[In the formulas (III) and (IV), R ^a and R ^{a ′} each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group. 1 represented by the group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — [(CH ₂ ) _t —O] _u —R ^e , or —O—R ^{a ″.} the valence of the group, one of R ^a and R ^{a 'comprises} a carbon atom. R ^{a ″} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e ,-[(CH ₂ ) _t —O] _u —R ^e .
R ^b is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — A monovalent group represented by [(CH ₂ ) _t —O] _u —R ^e or —O—R ^{b ′} . R ^{b ′} represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , Alternatively, it is a monovalent group represented by-[(CH ₂ ) _t -O] _u -R ^e .
R ^c and R ^d are each independently a hydrogen atom or a methyl group, and R ^e is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, —CHO, —CH ₂ CHO, —CO—CH═CH ₂ , —CO—C (CH ₃ ) ═CH ₂ or a monovalent group represented by —CH ₂ COOR ^f , and R ^f is a hydrogen atom or carbon An alkyl group of 1 to 5;
In R ^a , R ^{a ′} , and R ^b , each of the alkyl group, alkenyl group, aralkyl group, and aryl group may have a substituent.
s represents an integer of 1 to 18, t represents an integer of 1 to 5, and u represents an integer of 1 to 18. ]

In the present invention, by using the organic acid compound and / or a halogenated hydrocarbon described later, the pigment dispersant can be excellent in dispersibility and stability of the pigment. Furthermore, when an organic acid compound is used, the salt-forming site has high solubility in an aqueous alkali solution at the time of alkali development, so that it can be excellent in alkali developability. As the particle size of the pigment becomes smaller, a large amount of pigment dispersant is required, which may cause problems such as a decrease in alkali developability and an increase in residue. However, organic acid compounds are used in the above salt-type pigment dispersants. In such a case, the possibility of such a problem occurring can be reduced.

In the general formula (III), R ^a and R ^{a ′} are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [ CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — [(CH ₂ ) _t —O] _u —R ^e , or —O—R ^{a ″} , R ^a and R ^a Any of ^' includes carbon atoms.

The alkyl group having 1 to 18 carbon atoms, the alkenyl group having 2 to 18 carbon atoms, the aryl group, and the aralkyl group are as described above for R ⁴ . The position of the double bond of the alkenyl group is not limited, but from the viewpoint of reactivity, it is preferable that a double bond is present at the terminal of the alkenyl group.
The alkyl group or alkenyl group may have a substituent, and examples of the substituent include halogen atoms such as F, Cl, and Br, nitro groups, and the like.
In addition, examples of the substituent of the aromatic ring such as the aryl group and the aralkyl group include straight chain and branched alkyl groups having 1 to 4 carbon atoms, alkenyl groups, nitro groups, and halogen atoms. .

R ^c and R ^d are each independently a hydrogen atom or a methyl group, and R ^e is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, or an aryl group. , —CHO, —CH ₂ CHO, —CO—CH═CH ₂ , —CO—C (CH ₃ ) ═CH ₂ or —CH ₂ COOR ^f , and R ^f is a hydrogen atom or A linear, branched, or cyclic alkyl group having 1 to 5 carbon atoms.

In the monovalent group represented by R ^e, Examples of the substituent which may have, for example, C 1-4 straight, branched or cyclic alkyl group, F, Cl, halogen atom such as Br And so on.
The alkyl group having 1 to 18 carbon atoms in the above R ^e is as shown in the above R ⁴ , and the alkenyl group, aralkyl group and aryl group having 2 to 18 carbon atoms are represented by the above R ^a and R ^{a ′.} It is as shown in.

When R ^a and / or R ^{a ′} is —O—R ^{a ″} , it is an acidic phosphate ester. R ^a ″ represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e is a monovalent group represented by — [(CH ₂ ) _t —O] _u —R ^e .
The alkyl group having 1 to 18 carbon atoms, the alkenyl group having 2 to 18 carbon atoms, the aralkyl group, and the aryl group are as described above for R ^a and R ^{a ′} . When R ^{a ″} has an aromatic ring, it may have an appropriate substituent on the aromatic ring, for example, a linear or branched alkyl group having 1 to 4 carbon atoms.

In R ^a , R ^{a ′} and R ^{a ″} , s is an integer of 1 to 18, t is an integer of 1 to 5, and u is an integer of 1 to 18. s is preferably an integer of 1 to 4, more preferably an integer of 1 to 2, and t is preferably an integer of 1 to 4, more preferably 2 or 3. u is preferably an integer of 1 to 4, more preferably an integer of 1 to 2.

In the above general formula (IV), R ^b represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) — O] _s -R ^e ,-[(CH ₂ ) _t -O] _u -R ^e , or -O-R ^{b '} is shown.
The alkyl group having 1 to 18 carbon atoms, the alkenyl group having 2 to 18 carbon atoms, the aralkyl group, and the aryl group are as described above for R ^a and R ^{a ′} .

When R ^b is —O—R ^b ′, it is an acidic sulfate ester. R ^b ′ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — [(CH ₂ ) _t —O] _u —R ^e .
In R ^b and R ^b ′, each of the alkyl group, alkenyl group, aralkyl group, and aryl group may have a substituent.
The alkyl group having 1 to 18 carbon atoms, the alkenyl group having 2 to 18 carbon atoms, the aralkyl group, the aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — [(CH ₂ ) _t —O] _u —R ^e is as defined for R ^a , R ^a and R ^{a ″} .
R ^c , R ^d, and R ^e are as described above for R ^a , R ^a, and R ^{a ″} .
In R ^b and R ^b ′, s is an integer of 1 to 18, t is an integer of 1 to 5, and u is an integer of 1 to 18. Preferred s, t, and u are the same as R ^a , R ^{a ′,} and R ^{a ″} described above.

As the organic acid compound represented by the general formula (III), R ^a and R ^{a ′} in the general formula (III) each independently have a hydrogen atom, a hydroxyl group, a methyl group, an ethyl group, or a substituent. Aryl group or aralkyl group, vinyl group, allyl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , or — [(CH ₂ ) _t —O] _u —R ^e , or a monovalent group represented by —O—R ^{a ″} , one of R ^a and R ^{a ′} contains a carbon atom, and R ^{a ″} is a methyl group, ethyl Group, aryl group or aralkyl group which may have a substituent, vinyl group, allyl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , or — [(CH ₂ ) and _{_{^{^{t -O] u -R e, R}}}} c and ^{R d} are each independently a hydrogen atom or a methyl group Ri, from the viewpoint of can be made of those ^{R e} is -CO-CH = CH ₂ or _{-CO-C (CH} 3) a = CH ₂ is excellent in pigment dispersibility.

Moreover, as an organic acid compound represented by general formula (IV), ^Rb in general formula (IV) is a methyl group, an ethyl group, the aryl group which may have a substituent, an aralkyl group, a vinyl group. , An allyl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , or — [(CH ₂ ) _t —O] _u —R ^e , or —O—R ^{b ′} And R ^{b ′} is a methyl group, an ethyl group, an aryl group or an aralkyl group optionally having a substituent, a vinyl group, an allyl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , or — [(CH ₂ ) _t —O] _u —R ^e , wherein R ^c and R ^d are each independently a hydrogen atom or a methyl group, and R ^e In which —CO—CH═CH ₂ or —CO—C (CH ₃ ) ═CH ₂ has excellent pigment dispersibility It is preferable from the point which can be made.

Of these, organic acid compound represented by the general formula (III) and general formula ^{(IV), R} a, R ^{a 'and} / or R ^a'', and / or as ^{R b} and / or R ^b' From the viewpoint of pigment dispersibility, it preferably has an aromatic ring. At least one of R ^a , R ^{a ′} and R ^{a ″} , or R ^b or R ^{b ′} may be an aryl group or an aralkyl group which may have a substituent, more specifically, a benzyl group, A phenyl group, a tolyl group, a naphthyl group, and a biphenyl group are preferable from the viewpoint of pigment dispersibility. In the general formula (III), when one of R ^a and R ^{a ′} has an aromatic ring, the other of R ^a and R ^{a ′} is preferably a hydrogen atom or a hydroxyl group.

In addition, from the viewpoint of heat resistance and chemical resistance, particularly alkali resistance, the organic acid compounds represented by the above general formula (III) and general formula (IV) include phosphorus (P), sulfur (S) and carbon. A compound in which atoms are directly bonded is preferable, and R ^a and R ^{a ′} each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl A monovalent group represented by the groups: — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — [(CH ₂ ) _t —O] _u —R ^e , R ^a and Any of R ^{a ′} preferably contains a carbon atom. R ^b is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — [(CH ₂ ) _t —O] _u —R ^e is preferably a monovalent group.

The organic acid compound represented by the general formula (III) and general formula ^{(IV), R} a, R ^{a 'and} / or R ^a'', and / or as ^{R b} and / or R ^b' Has a polymerizable group, that is, a vinyl group, an allyl group, or — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , or — [(CH ₂ ) _t —O] _u. a -R ^e, and, ^{R e} is -CO-CH = CH ₂ or _{-CO-C (CH} 3) = are preferable is CH _2, in ^{particular, R} a, R ^{a 'and} / or R ^a'', and / or, R ^b and / or R ^b' is a vinyl group, an allyl group, 2-methacryloyloxyethyl group, those which are 2-acryloyloxyethyl group.
In such a case, the above-mentioned polymerizable groups and / or the above-mentioned polymerizable groups and the color filter of the present invention are exposed during exposure when forming a colored layer using the negative resist composition for color filters of the present invention. Can be easily polymerized with an alkali-soluble resin and a polyfunctional monomer contained in the negative resist composition for use, and the pigment dispersant can be stably present in the colored layer of the color filter. To do. When a liquid crystal display device is manufactured using such a color filter, the pigment dispersant can be prevented from bleeding out to the liquid crystal layer or the like.

In addition, since the organic acid compound contains a polymerizable group, the polymerizable groups of the organic acid compound can be polymerized before being used for forming the colored layer, and as a result, the pigment dispersant has a high molecular weight. Therefore, the negative resist composition for the color filter at the unexposed portion can be made particularly excellent in alkali developability during the development for forming the colored layer.

In addition, the organic acid compound represented by the general formula (III) and the general formula (IV) can be used singly or in combination of two or more.

<Halogenated hydrocarbon>
The halogenated hydrocarbon used in the present invention is a block copolymer having the above-mentioned repeating unit (1) represented by the general formula (I) and the repeating unit (2) represented by the general formula (II). To form a salt with the amino group of the repeating unit (1).
In the present invention, by using the above-mentioned halogenated hydrocarbon, the salt-forming site produced by the pigment dispersant is excellent in adsorptivity to the pigment, so that it can exhibit high dispersibility, and at the same time, the dispersant Heat resistance and alkali resistance can be increased.

Examples of the halogenated hydrocarbon include those in which any one of a chlorine atom, a bromine atom and an iodine atom is substituted with a hydrogen atom of a saturated or unsaturated linear, branched or cyclic hydrocarbon. . Among these, a halogenated hydrocarbon in which one of the hydrogen atoms of the hydrocarbon is substituted with a halogen atom is preferable from the viewpoint of forming a salt with the pigment dispersant and improving the pigment dispersibility.
The halogenated hydrocarbon may be linear, branched or cyclic. The number of carbon atoms is preferably 1-18, and more preferably 1-7.

Among the halogenated hydrocarbons, examples of the halogenated alkyl include those having 1 to 18 carbon atoms, but are not particularly limited. Specifically, for example, methyl chloride, methyl bromide, ethyl chloride, ethyl bromide, methyl iodide, ethyl iodide, n-butyl chloride, hexyl chloride, octyl chloride, dodecyl chloride, tetradecyl chloride, hexadecyl chloride, etc. Can be mentioned. Examples of the allyl halide include allyl chloride, allyl bromide, and allyl iodide. Further, examples of the aralkyl group of the halogenated aralkyl include those having 7 to 18 carbon atoms, but are not particularly limited. Specific examples include benzyl chloride, benzyl bromide, benzyl iodide, naphthylmethyl chloride, pyridylmethyl chloride, naphthylmethyl bromide, pyridylmethyl bromide and the like.

Among these, at least one selected from the group consisting of benzyl halide, allyl halide, and methyl halide is easy to form a salt, and the formed salt-forming site has excellent adsorptivity to the pigment. This is preferable.

The content of the organic acid compound and / or halogenated hydrocarbon in the block copolymer used in the present invention is not particularly limited as long as good dispersion stability is exhibited. The amount is about 0.01 to 2.0 molar equivalents, more preferably 0.1 to 1.0 molar equivalents with respect to the tertiary amino group represented by (I). In such a case, the pigment dispersibility and the pigment dispersion stability are excellent. In addition, when using 2 or more types of the said organic acid compound and / or halogenated hydrocarbon together, content which added these should just be in the said range.

<Manufacture of pigment dispersant made of salt type block copolymer>
As a method for producing the block copolymer of the pigment dispersant, the repeating unit (1), the repeating unit (2), the amino group of the repeating unit (1), and the organic The method is not particularly limited as long as it can produce a salt formed with an acid compound and / or a halogenated hydrocarbon. In the present invention, for example, the repeating unit (1) and the repeating unit (2) are polymerized using a known polymerization means, and then dissolved or dispersed in a solvent described later, and then the organic acid is dissolved in the solvent. A pigment dispersant can be produced by adding a compound and / or halogenated hydrocarbon and stirring.

The polymerization means is not particularly limited as long as it is a means capable of polymerizing the above repeating unit (1) and repeating unit (2) in a desired number to obtain a desired molecular weight, and has a vinyl group. A method generally used for polymerization of a compound can be employed, and for example, anionic polymerization, living radical polymerization, or the like can be used. In the present invention, among them, a method in which polymerization proceeds in a living manner, such as group transfer polymerization (GTP) disclosed in “J. Am. Chem. Soc.” 105, 5706 (1983), is used. preferable. According to this method, the molecular weight, the molecular weight distribution, etc. can be easily set in a desired range, so that the dispersibility of the pigment dispersant can be made uniform.

In the pigment dispersion for a color filter of the present invention, one type of pigment dispersant may be used, or two or more types may be used in combination. The content thereof is not particularly limited as long as the pigment can be uniformly dispersed. For example, 10 to 150 parts by weight can be used with respect to 100 parts by weight of the pigment. Further, it is preferably blended at a ratio of 15 to 45 parts by weight with respect to 100 parts by weight of the pigment, particularly preferably at a ratio of 15 to 40 parts by weight. If the content of the pigment dispersant is within the above range, the pigment can be uniformly dispersed. In the present invention, the pigment used when the content other than the pigment derivative is defined includes a pigment derivative in addition to the pigment. I. Pigment Yellow 138, C.I. I. Also included are pigment yellow 138 derivatives.

(solvent)
The pigment dispersion for a color filter according to the present invention contains a solvent for dispersing the pigment. The solvent used in the pigment dispersion is not particularly limited as long as it is an organic solvent that does not react with each component in the pigment dispersion and can dissolve or disperse them.
Examples of the solvent used in the pigment dispersion of the present invention include alcohol solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol and i-propyl alcohol; cellosolv solvents such as methoxy alcohol and ethoxy alcohol; methoxyethoxyethanol, Carbitol solvents such as ethoxyethoxyethanol; ester solvents such as ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate and ethyl lactate; ketone solvents such as acetone, methyl isobutyl ketone and cyclohexanone; methoxyethyl acetate , Propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, methoxybutyl acetate, ethoxy Cellosolve acetate solvents such as til acetate and ethyl cellosolve acetate; Carbitol acetate solvents such as methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, and butyl carbitol acetate (BCA); Diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol Ether solvents such as monomethyl ether and tetrahydrofuran; aprotic amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; lactone solvents such as γ-butyrolactone; benzene, toluene and xylene , Unsaturated hydrocarbon solvents such as naphthalene; saturated hydrocarbons such as N-heptane, N-hexane and N-octane Organic solvents such as system solvents can be mentioned. Among these solvents, cellosolve acetate solvents such as methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, ethoxyethyl acetate, ethyl cellosolve acetate; Carbitol acetate solvents such as methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, butyl carbitol acetate (BCA); ether solvents such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether; methyl methoxypropionate, ethoxypropionic acid Ester solvents such as ethyl and ethyl lactate; ketone solvents such as cyclohexanone are preferred Used. Among them, as the solvent used in the present invention, propylene glycol monomethyl ether acetate (CH ₃ OCH ₂ CH (CH ₃ ) OCOCH ₃ ), propylene glycol monomethyl ether, butyl carbitol acetate (BCA), 3-methoxy-3-methyl- One or more selected from the group consisting of 1-butyl acetate, 3-methoxybutyl acetate and cyclohexanone is preferable from the viewpoint of solubility of other components and coating suitability.

These solvents may be used alone or in combination of two or more.
The pigment dispersion of the present invention is prepared using the solvent as described above usually in a proportion of 50 to 85% by weight with respect to the total amount of the pigment dispersion containing the solvent. Further, it is preferably prepared by using 60 to 85% by weight. When the amount of the solvent is too small, the viscosity increases and the pigment dispersibility tends to decrease. Moreover, when there are too many solvents, a pigment density | concentration will fall and it may be difficult to achieve the chromaticity coordinate which makes a resin composition the target after preparation.

(Other pigment derivatives)
Other pigment derivatives may be included as long as the effect of the present invention is not impaired. Other pigment derivatives suitably used in the pigment dispersion of the present invention include the following C.I. I. And a sulfonic acid derivative of CI Pigment Yellow 138.
<C. I. Pigment Yellow 138 Sulfonic Acid Derivative>
In the pigment dispersion of the present invention, C.I. I. It is preferable to further use a sulfonic acid derivative of CI Pigment Yellow 138. In this case, C.I. I. Pigment Yellow 138 can be further refined and dispersed, making it easy to achieve the demand for high brightness and high contrast. In particular, as a pigment dispersant, a pigment dispersant composed of the above-mentioned salt-type block copolymer; I. When combined with a sulfonic acid derivative of CI Pigment Yellow 138, it becomes easy to achieve the demand for particularly high brightness and high contrast.

C. I. Pigment Yellow 138 has a sulfonic acid derivative in which at least one sulfo group has the above structure. I. It has a structure bonded to CI Pigment Yellow 138 and is expressed as follows.

(In the formula, n represents the number of sulfo groups substituted and represents an integer of 1 to 5.)

The number of sulfo group substitutions is preferably 1 to 2, and 1 is particularly preferred from the viewpoint of efficiently improving pigment dispersibility.

C. I. Examples of the sulfonic acid derivative of CI Pigment Yellow 138 include C.I. I. Pigment Yellow 138 can be produced by adding it to concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, or a mixture thereof to carry out the sulfonation reaction. C. I. As the sulfonic acid derivative of Pigment Yellow 138, one kind can be used alone, or two or more kinds can be used in combination. For example, two or more sulfonic acid derivatives having different sulfo group substitution positions or substitution numbers may be used.

In the present invention, C.I. I. Pigment Yellow 138 is a sulfonic acid derivative. I. It is preferable to contain 0.1 to 20 parts by weight with respect to 100 parts by weight of Pigment Yellow 138. Among them, C.I. I. Pigment Yellow 138 is a sulfonic acid derivative. I. It is preferable to contain 0.5 to 15 parts by weight, and more preferably 1 to 10 parts by weight with respect to 100 parts by weight of Pigment Yellow 138. By using such a content, it is possible to produce a coating film in which the precipitation of pigment aggregates is suppressed even after the high-temperature heating step in the color filter process while achieving the demand for high brightness and high contrast. Become.

Examples of other pigment derivatives include metal salts and amine salts of sulfonic acid, and C.I. I. A sulfonated derivative of CI Pigment Yellow 138 may further be included. The sulfonamide group, which is an amine salt of sulfonic acid, is preferably represented by —SO ₂ NHR (where R is a monovalent organic group). Examples of R include dimethylaminopropyl group, diethylamino group, and the like. Examples thereof include a propyl group, a dibutylaminopropyl group, a benzyl group, and a phenyl group.

(Other ingredients)
If necessary, the pigment dispersion liquid of the present invention may further contain a pigment dispersion auxiliary resin and other components.
Examples of the pigment dispersion auxiliary resin include alkali-soluble resins exemplified by a resist composition described later. In some cases, the steric hindrance of the alkali-soluble resin makes it difficult for the pigment particles to come into contact with each other.
Further, the pigment dispersion of the present invention may contain other pigments as long as the effects of the present invention are not impaired. Examples of the other pigment include a red pigment or a green pigment necessary for preparing a red or green resist composition, which will be described later, and other yellow pigments. About such a pigment, the thing similar to the pigment illustrated by the resist composition mentioned later can be used.
Moreover, as long as the effect of this invention is not impaired, the other pigment dispersant may be included.
Other components include, for example, surfactants for improving wettability, silane coupling agents for improving adhesion, antifoaming agents, repellency inhibitors, antioxidants, anti-aggregation agents, and UV absorbers. Etc.

<Method for producing pigment dispersion>
The pigment dispersion of the present invention has the above-described C.I. I. Pigment yellow 138, C.I. I. A pigment dispersion is prepared by mixing an imide alkylated derivative of Pigment Yellow 138 and a pigment dispersant in a solvent and dispersing the mixture using a known disperser. Examples of the dispersing machine for performing the dispersion treatment include roll mills such as two rolls and three rolls, ball mills such as a ball mill and a vibration ball mill, bead mills such as a paint conditioner, a continuous disk type bead mill, and a continuous annular type bead mill. As a preferable dispersion condition of the bead mill, the bead diameter to be used is preferably 0.03 to 2.00 mm, more preferably 0.10 to 1.0 mm.

Specifically, preliminary dispersion is performed with 1.0 to 2.0 mm zirconia beads having a relatively large bead diameter, and the main dispersion is further performed with 0.03 to 0.1 mm zirconia beads having a relatively small bead diameter. Can be mentioned. Further, after dispersion, it is preferably filtered through a membrane filter of 0.5 to 0.1 μm.

In the present invention, the dispersion time for dispersion using a known disperser is appropriately adjusted and is not particularly limited.
In this manner, a pigment dispersion having excellent pigment particle dispersibility is obtained. The pigment dispersion is used as a preliminary preparation for preparing a negative resist composition for color filters having excellent pigment dispersibility.

2. Negative resist composition for color filter The negative resist composition for a color filter according to the present invention includes C.I. I. Pigment Yellow 138 and C.I. represented by the above chemical formula (1). I. Pigment Yellow 138 containing an imide alkylated derivative, a pigment dispersant, an alkali-soluble resin, a polyfunctional monomer, a photoinitiator, and a solvent. I. Pigment Yellow 138 imidoalkylated derivatives are C.I. I. The pigment yellow 138 is contained in an amount of 0.1 to 20 parts by mass with respect to 100 parts by mass.

The negative resist composition for a color filter according to the present invention uses PY138 as a pigment, and further combines a specific amount of a specific imide alkylated derivative of PY138 to suppress the precipitation of pigment aggregates during a high-temperature heating process. A luminance and high-contrast color filter can be formed.
The negative resist composition for color filters according to the present invention may be a yellow resist composition or a red or green resist composition.

Hereinafter, components used in such a negative resist composition for a color filter of the present invention will be described.
Among the components that can be contained in the color filter pigment dispersion according to the present invention, C.I. I. Pigment Yellow 138, C.I. represented by the above chemical formula (1) I. As the imide alkylated derivative of Pigment Yellow 138, the pigment dispersant, and the solvent, the same pigments as those described in the above-mentioned pigment dispersion can be used, and the description thereof is omitted here.

(Alkali-soluble resin)
As the alkali-soluble resin used in the negative resist composition for a color filter of the present invention, those generally used for negative resists can be used as long as they are soluble in an alkaline aqueous solution. The alkali-soluble resin is not particularly limited. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (Meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate , N-decyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicycle Pentanyl (meth) acrylate, 1-adamantyl (meth) acrylate, allyl (meth) acrylate, 2,2′-oxybis (methylene) bis-2-propenoate, styrene, γ-methylstyrene, glycidyl (meth) acrylate, 2- Selected from hydroxylethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, N-vinyl-2-pyrrolidone, N-methylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, etc. One or more, (meth) acrylic acid, dimer of acrylic acid (for example, M-5600 manufactured by Toagosei Co., Ltd.), itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, and anhydrous Copolymer comprising at least one selected from among products It can be exemplified. In addition, for example, a polymer having an ethylenically unsaturated bond introduced by adding an ethylenically unsaturated compound having a reactive functional group such as a glycidyl group or a hydroxyl group to the above copolymer can be exemplified, but the present invention is not limited thereto. Is not to be done.
Among these, a polymer having an ethylenically unsaturated bond introduced, for example, by adding an ethylenically unsaturated compound having a glycidyl group or a hydroxyl group to the copolymer is polymerized with a polyfunctional monomer described later at the time of exposure. This is particularly suitable in that the colored layer becomes more stable.

The alkali-soluble resin used in the negative resist composition for color filters of the present invention may be used singly or in combination of two or more, and the content thereof is a negative resist for color filters. The amount is usually in the range of 10 to 1000 parts by weight, preferably in the range of 20 to 500 parts by weight with respect to 100 parts by weight of the pigment contained in the composition. If the content of the alkali-soluble resin is too small, sufficient alkali developability may not be obtained, and if the content of the alkali-soluble resin is too large, the ratio of the pigment becomes relatively low and sufficient coloring is achieved. The concentration may not be obtained.

(Multifunctional monomer)
The polyfunctional monomer used in the negative resist composition for color filters of the present invention is not particularly limited as long as it can be polymerized by a photoinitiator described later, and usually contains an ethylenically unsaturated double bond. A compound having two or more compounds is used, and a polyfunctional (meth) acrylate having two or more acryloyl groups or methacryloyl groups is particularly preferable.

Examples of such polyfunctional (meth) acrylates include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, long chain aliphatic di (meth) acrylate, and neopentyl glycol di (Meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, stearic acid modified pentaerythritol di (meth) acrylate, propylene glycol di (meth) acrylate, glycerol di (meth) acrylate, triethylene glycol di (meth) Acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, dicyclopentani Di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene di (meth) acrylate, triglycerol di (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, allylated cyclohexyl di (meth) acrylate , Methoxylated cyclohexyl di (meth) acrylate, acrylated isocyanurate, bis (acryloxyneopentyl glycol) adipate, bisphenol A di (meth) acrylate, tetrabromobisphenol A di (meth) acrylate, bisphenol S di (meth) acrylate , Butanediol di (meth) acrylate, phthalic acid di (meth) acrylate, phosphoric acid di (meth) acrylate, zinc di (meth) acrylate, etc. Meth) acrylate.

Examples of trifunctional or higher polyfunctional (meth) acrylates include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, penta Erythritol tetra (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, succinic anhydride-modified pentaerythritol tetra (meth) acrylate, phosphoric acid tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, tris (methacrylic) Roxyethyl) isocyanurate, dipentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetraacrylate, alkyl-modified dipentaerythritol Tora (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, succinic anhydride-modified dipentaerythritol penta (meth) acrylate, urethane tri (Meth) acrylate, ester tri (meth) acrylate, urethane hexa (meth) acrylate, ester hexa (meth) acrylate and the like.

These polyfunctional (meth) acrylates may be used individually by 1 type, and may be used in combination of 2 or more type. In addition, when the negative resist composition for color filter of the present invention requires excellent photocurability (high sensitivity), the polyfunctional monomer has three polymerizable double bonds (trifunctional). Those having the above are preferable, and for example, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like are suitably used.
The content of the polyfunctional monomer used in the negative resist composition for color filters of the present invention is not particularly limited, but is usually about 5 to 500 parts by weight, preferably 100 parts by weight of the alkali-soluble resin. Is in the range of 20 to 300 parts by weight. If the content of the polyfunctional monomer is less than the above range, the photocuring may not sufficiently proceed and the exposed part may be eluted, and if the content of the polyfunctional monomer is more than the above range, the alkali developability is lowered. There is a risk.

(Photoinitiator)
There is no restriction | limiting in particular as a photoinitiator used in the negative resist composition for color filters of this invention, It can select and use suitably from conventionally well-known various photoinitiators. For example, aromatic ketones such as benzophenone, Michler ketone, 4,4′-bisdiethylaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2-ethylanthraquinone, phenanthrene, benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, etc. Benzoin ethers, benzoin such as methylbenzoin, ethylbenzoin, 2- (o-chlorophenyl) -4,5-phenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) Imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4,5-tria Reel imidazole dimer 2- (o-chlorophenyl) -4,5-di (m-methylphenyl) imidazole dimer, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2-trichloromethyl- 5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) ) 1,3,4-oxadiazole and other halomethyloxadiazole compounds, 2,4-bis (trichloromethyl) -6-p-methoxystyryl-S-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl-1,3-butadienyl) -S-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl Ru-S-triazine, 2- (naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- (4-ethoxy-naphth-1-yl) -4,6-bis-trichloro Halomethyl-S-triazine compounds such as methyl-S-triazine, 2- (4-butoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2,2-dimethoxy-1, 2-diphenylethane-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone, 1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -Butanone-1,1-hydroxy-cyclohexyl-phenyl ketone, benzyl, benzoylbenzoic acid, methyl benzoylbenzoate, 4-benzoyl-4'-methyldipheny Sulfide, benzylmethyl ketal, dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, 2-n-butoxyethyl-4-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, Isopropylthioxanthone, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (o-acetyloxime), 4-benzoyl-methyldiphenyl sulfide, 1-hydroxy -Cyclohexyl-phenyl ketone, 2-benzyl-2- (dimethylamino) -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2- (dimethylamino) -2-[(4-methylphenyl) Methyl] -1- [4- (4- Morpholinyl) phenyl] -1-butanone, α-dimethoxy-α-phenylacetophenone, phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2 -(4-morpholinyl) -1-propanone and the like. These photoinitiators may be used individually by 1 type, and may be used in combination of 2 or more type.

The content of the photoinitiator used in the negative resist composition for a color filter of the present invention is usually about 0.01 to 100 parts by weight, preferably 5 to 60 parts by weight with respect to 100 parts by weight of the polyfunctional monomer. Part. If this content is less than the above range, the polymerization reaction cannot be sufficiently caused, so that the hardness of the colored layer may not be sufficient. In some cases, the content of the pigment or the like in the solid content of the resist composition becomes relatively small, and a sufficient coloring density cannot be obtained.

(Other pigments)
In the present invention, C.I. I. Pigment Yellow 138 is used as an essential component. In order to obtain a red or green resist composition, a red pigment or a green pigment may be further used in the negative resist composition for color filters. Moreover, as long as the chromaticity required for the use and specification in the color filter can be achieved and the effects of the present invention are not impaired, other yellow pigments and further other pigments such as orange may be contained.

<Red pigment>
The red pigment is appropriately selected according to the use and specification in the color filter, and one or more of known inorganic pigments and organic pigments are mixed and used in order to achieve the necessary chromaticity.
Examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists), specifically, the following color index (C.I. .) Can be listed with numbers.

As red pigment, C.I. Pigment Red 1, C.I. Pigment Red 2, C.I. Pigment Red 3, C.I. Pigment Red 4, C.I. Pigment Red 5, C.I. Pigment Red 6, C.I. Pigment Red 7, C.I. Pigment Red 8, C.I. Pigment Red 9, C.I. Pigment Red 10, C.I. Pigment Red 11, C.I. Pigment Red 12, C.I. Pigment Red 14, C.I. Pigment Red 15, C.I. Pigment Red 16, C.I. Pigment Red 17, C.I. Pigment Red 18, C.I. Pigment Red 19, C.I. Pigment Red 21, C.I. Pigment Red 22, C.I. Pigment Red 23, C.I. Pigment Red 30, C.I. Pigment Red 31, C.I. Pigment Red 32, C.I. Pigment Red 37, C.I. Pigment Red 38, C.I. Pigment Red 40, C.I. Pigment Red 41, C.I. Pigment Red 42, C.I. Pigment Red 48: 1, C.I. Pigment Red 48: 2, C.I. Pigment Red 48: 3, C.I. Pigment Red 48: 4, C.I. Pigment Red 49: 1, C.I. Pigment Red 49: 2, C.I. Pigment Red 50: 1, C.I. Pigment Red 52: 1, C.I. Pigment Red 53: 1, C.I. Pigment Red 57, C.I. Pigment Red 57: 1, C.I. Pigment Red 57: 2, C.I. Pigment Red 58: 2, C.I. Pigment Red 58: 4, C.I. Pigment Red 60: 1, C.I. Pigment Red 63: 1, C.I. Pigment Red 63: 2, C.I. Pigment Red 64: 1, C.I. Pigment Red 81: 1, C.I. Pigment Red 83, C.I. Pigment Red 88, C.I. Pigment Red 90: 1, C.I. Pigment Red 97, C.I. Pigment Red 101, C.I. Pigment Red 102, C.I. Pigment Red 104, C.I. Pigment Red 105, C.I. Pigment Red 106, C.I. Pigment Red 108, C.I. Pigment Red 112, C.I. Pigment Red 113, C.I. Pigment Red 114, C.I. Pigment Red 122, C.I. Pigment Red 123, C.I. Pigment Red 144, C.I. Pigment Red 146, C.I. Pigment Red 149, C.I. Pigment Red 150, C.I. Pigment Red 151, C.I. Pigment Red 166, C.I. Pigment Red 168, C.I. Pigment Red 170, C.I. Pigment Red 171, C.I. Pigment Red 172, C.I. Pigment Red 174, C.I. Pigment Red 175, C.I. Pigment Red 176, C.I. Pigment Red 177, C.I. Pigment Red 178, C.I. Pigment Red 179, C.I. Pigment Red 180, C.I. Pigment Red 185, C.I. Pigment Red 187, C.I. Pigment Red 188, C.I. Pigment Red 190, C.I. Pigment Red 193, C.I. Pigment Red 194, C.I. Pigment Red 202, C.I. Pigment Red 206, C.I. Pigment Red 207, C.I. Pigment Red 208, C.I. Pigment Red 209, C.I. Pigment Red 215, C.I. Pigment Red 216, C.I. Pigment Red 220, C.I. Pigment Red 224, C.I. Pigment Red 226, C.I. Pigment Red 242, C.I. Pigment Red 243, C.I. Pigment Red 245, C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Red 264, C.I. And CI Pigment Red 265.

Above all, C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Red 177, and C.I. One or more selected from the group consisting of I. Pigment Red 242 is preferable from the viewpoint of improving contrast while achieving a specific tint necessary for the red colored layer of the color filter.

<Green pigment>
The green pigment is also appropriately selected depending on the use and specification in the color filter, and one or more of known inorganic pigments and organic pigments are used in combination in order to achieve the necessary chromaticity.
Examples of the green pigment include pigment green 7, pigment green 36, C.I. I. And CI Pigment Green 58. Among these, it is preferable to use Pigment Green 58 from the viewpoint of increasing brightness.

<Yellow pigment>
C. Other yellow pigments different from I. Pigment Yellow 138 include C.I. Pigment Yellow 150 and its derivative pigments, and C.I. And CI Pigment Yellow 139.
Here, C.I. I. Pigment Yellow 150 derivative pigments specifically include mono-, di-, tri- and tetraanions of azo compounds according to one of the following chemical formulas or one of their tautomeric structures that act as hosts for at least one guest compound: And metal complexes corresponding to Li, Cs, Mg, Cd, Co, Al, Cr, Sn, Pb, particularly preferably Na, K, Ca, Sr, Ba, Zn, Fe, Ni, Cu, Mn and La Can be mentioned.

[Wherein R and R ′ are independently OH, NH ₂ , NH—CN, acylamino or arylamino, and R ^a and R ^a ′ are independently —OH or —NH ₂ Is]

These derivative pigments are disclosed in JP 2001-354869, JP 2005-325350, JP 2007-25687, JP 2007-23287, JP 2007-23288, and JP 2008. It can be obtained by referring to Japanese Patent No. -24927.

<Other pigments>
In this invention, you may mix | blend other pigments other than the said pigment as needed.
Other pigments include C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 16, C.I. I. Blue pigments such as CI Pigment Blue 81; I. And violet pigments such as CI Pigment Violet 23.

(Optional additive)
The negative resist composition for a color filter of the present invention may contain various additives as necessary within a range that does not impair the object of the present invention. Examples of the additive include a polymerization terminator, a chain transfer agent, a leveling agent, a plasticizer, a surfactant, an antifoaming agent, a silane coupling agent, an ultraviolet absorber, and an adhesion promoter.
Among these, surfactants that can be used include, for example, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene Examples include glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, fatty acid-modified polyesters, and tertiary amine-modified polyurethanes. In addition, a fluorosurfactant can also be used.
Furthermore, examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, and tricresyl. Examples of the antifoaming agent and leveling agent include silicon-based, fluorine-based, and acrylic compounds.

<Combination ratio of each component in negative resist composition>
The total content of the pigments including the pigment derivative is preferably 10 to 50% by weight, more preferably 20 to 40% by weight based on the total solid content of the negative resist composition. If the amount of the pigment is too small, the transmission density when the negative resist composition is applied to a predetermined film thickness (usually 1.0 to 4.0 μm) may be insufficient. If the amount of the pigment is too large, There is a risk that the properties as a coating film such as adhesion to the substrate when the resist composition is applied and cured on the substrate, surface roughness of the cured film, coating film hardness, etc. may be insufficient, and its negative type Since the ratio of the amount of the dispersant used for dispersing the pigment in the resist composition increases, characteristics such as developability and heat resistance may be insufficient. In addition, in this invention, solid content is all things other than the solvent mentioned above, and the polyfunctional monomer etc. which are melt | dissolving in the solvent are also included.
Further, the total content of the pigment dispersant is preferably in the range of 1 to 40% by weight, particularly in the range of 5 to 30% by weight, based on the total solid content of the negative resist composition. Preferably there is. If the content is less than 1% by weight relative to the total solid content of the negative resist composition, it may be difficult to uniformly disperse the pigment, and if it exceeds 40% by weight , There is a risk of lowering curability and developability.
The total amount of the alkali-soluble resin, the polyfunctional monomer, and the photoinitiator is blended in a proportion of 15 to 89% by weight, preferably 25 to 80% by weight, based on the total solid content of the negative resist composition. Is preferred.
Further, the content of the solvent is not particularly limited as long as the colored layer can be formed with high accuracy. Usually, it is preferably in the range of 65 to 95% by weight, more preferably in the range of 75 to 88% by weight, based on the total amount of the negative resist composition containing the solvent. When the content of the solvent is within the above range, the coating property can be excellent.

(Manufacture of negative resist compositions for color filters)
As a method for producing the negative resist composition of the present invention, the pigment dispersion according to the present invention includes an alkali-soluble resin, a polyfunctional monomer, a photoinitiator, and, if necessary, a pigment of another color. Examples thereof include a method of adding and mixing the dispersion, the solvent, and various additive components used.
The negative resist composition for a color filter of the present invention is preferably used by previously producing and using a pigment dispersion because it can effectively prevent aggregation of the pigment and disperse it uniformly.
When the pigment dispersion according to the present invention is a yellow pigment dispersion, when preparing a red or green resist composition, separately in the same manner as in the method for producing the pigment dispersion according to the present invention, It is preferable to prepare and use a red pigment dispersion or a green pigment dispersion.

Next, the color filter of the present invention will be described.
[Color filter]
The color filter of the present invention is characterized by having a colored layer formed by curing the above-described negative resist composition for color filters of the present invention.
Such a color filter of the present invention will be described with reference to the drawings. FIG. 1 is a schematic sectional view showing an example of the color filter of the present invention. According to FIG. 1, the color filter 10 of the present invention has a transparent substrate 1, a light shielding part 2, and a colored layer 3.

(Colored layer)
The colored layer used in the color filter of the present invention is not particularly limited as long as it is formed by curing the negative resist composition for a color filter of the present invention described above. Depending on the type of pigment formed in the opening of the light-shielding part and contained in the negative resist composition for color filter, it is composed of a coloring pattern of three or more colors.
Further, the arrangement of the colored layers is not particularly limited, and for example, a general arrangement such as a stripe type, a mosaic type, a triangle type, or a four-pixel arrangement type can be used. Moreover, the width | variety, area, etc. of a colored layer can be set arbitrarily.
The thickness of the colored layer is appropriately controlled by adjusting the coating method, solid content concentration, viscosity, etc. of the color filter negative resist composition, but is usually preferably in the range of 1 to 5 μm.

The colored layer can be formed, for example, by the following method.
First, the above-described negative resist composition for a color filter of the present invention is applied onto a transparent substrate to be described later using an application means such as a spray coating method, a dip coating method, a bar coating method, a coal coating method, or a spin coating method. Then, a wet coating film is formed.
Next, after drying the wet coating film using a hot plate or oven, it is exposed to light through a mask having a predetermined pattern, and an alkali-soluble resin and a polyfunctional monomer are photopolymerized. And a coating film of a negative resist composition for color filters. Examples of the light source used for exposure include ultraviolet rays such as a low-pressure mercury lamp, a high-pressure mercury lamp, and a metal halide lamp, and an electron beam. The exposure amount is appropriately adjusted depending on the light source used, the thickness of the coating film, and the like.
Moreover, in order to promote a polymerization reaction after exposure, you may heat-process. The heating conditions are appropriately selected depending on the blending ratio of each component in the color filter negative resist composition to be used, the thickness of the coating film, and the like.

Next, it develops using a developing solution, a coating film is formed with a desired pattern by melt | dissolving and removing an unexposed part. As the developer, a solution in which an alkali is dissolved in water or a water-soluble solvent is usually used. An appropriate amount of a surfactant or the like may be added to the alkaline solution. Further, a general method can be adopted as the developing method.
After the development treatment, the developer is usually washed and the cured coating film of the negative resist composition is dried to form a colored layer. In addition, you may heat-process in order to fully harden a coating film after image development processing. The heating conditions are not particularly limited and are appropriately selected depending on the application of the coating film.

(Shading part)
The light shielding part in the color filter of the present invention is formed in a pattern on a transparent substrate described later, and can be the same as that used as a light shielding part in a general color filter.
The pattern shape of the light shielding portion is not particularly limited, and examples thereof include a stripe shape and a matrix shape. Examples of the light-shielding portion include those obtained by dispersing or dissolving a black pigment in a binder resin, and metal thin films such as chromium and chromium oxide. The metal thin film may be a CrO _x film (x is an arbitrary number) and a laminate of two Cr films, and a CrO _x film (x is an arbitrary number) with a reduced reflectance. , CrN _y films (y is an arbitrary number) and three layers of Cr films may be laminated.
When the light-shielding part is a material in which a black colorant is dispersed or dissolved in a binder resin, the light-shielding part can be formed by any method that can pattern the light-shielding part, and is not particularly limited. For example, a photolithography method, a printing method, an ink jet method and the like using a negative resist composition for a light shielding part can be exemplified.

In the above case, when a printing method or an inkjet method is used as a method for forming the light shielding portion, examples of the binder resin include polymethyl methacrylate resin, polyacrylate resin, polycarbonate resin, polyvinyl alcohol resin, polyvinyl pyrrolidone resin, hydroxy Examples thereof include ethyl cellulose resin, carboxymethyl cellulose resin, polyvinyl chloride resin, melamine resin, phenol resin, alkyd resin, epoxy resin, polyurethane resin, polyester resin, maleic acid resin, polyamide resin and the like.

In the above case, when a photolithography method is used as a method for forming the light shielding portion, the binder resin may be, for example, an acrylate-based, methacrylate-based, polyvinyl cinnamate-based, or cyclized rubber-based reactive material. A photosensitive resin having a vinyl group is used. In this case, a photopolymerization initiator may be added to the negative resist composition for a light shielding part containing a black colorant and a photosensitive resin, and further a sensitizer, a coating property improver, if necessary. A development improver, a crosslinking agent, a polymerization inhibitor, a plasticizer, a flame retardant, and the like may be added. In the present invention, the negative resist composition for color filters having a black pigment such as carbon black or titanium black as a pigment may be used as the negative resist composition for the light shielding part.

On the other hand, when the light shielding part is a metal thin film, the method for forming the light shielding part is not particularly limited as long as the light shielding part can be patterned, and for example, photolithography, vapor deposition using a mask. Law, printing method and the like.

The thickness of the light shielding part is set to about 0.2 to 0.4 μm in the case of a metal thin film, and about 0.5 to 2 μm in the case where a black colorant is dispersed or dissolved in a binder resin. Is set.

(Transparent substrate)
The transparent substrate in the color filter of the present invention is not particularly limited as long as it is a base material transparent to visible light, and a transparent substrate used for a general color filter can be used. Specific examples include inflexible transparent rigid materials such as quartz glass, alkali-free glass, and synthetic quartz plates, or transparent flexible materials having flexibility such as transparent resin films and optical resin plates. It is done.
The thickness of the transparent substrate is not particularly limited, but for example, a thickness of about 100 μm to 1 mm can be used according to the use of the color filter of the present invention.
The color filter of the present invention may be one in which, for example, an overcoat layer, a transparent electrode layer, an alignment film, a columnar spacer, or the like is formed in addition to the transparent substrate, the light shielding portion, and the colored layer. .

Next, the liquid crystal display device of the present invention will be described.
[Liquid Crystal Display]
The liquid crystal display device of the present invention includes the color filter of the present invention described above, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.
Such a liquid crystal display device of the present invention will be described with reference to the drawings. FIG. 2 is a schematic view showing an example of the liquid crystal display device of the present invention. As illustrated in FIG. 2, the liquid crystal display device 40 of the present invention includes a color filter 10, a counter substrate 20 having a TFT array substrate and the like, and a liquid crystal layer formed between the color filter 10 and the counter substrate 20. 30.
Note that the liquid crystal display device of the present invention is not limited to the configuration shown in FIG. 2, but can be a configuration generally known as a liquid crystal display device using a color filter.

The driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method generally used for a liquid crystal display device can be employed. Examples of such a driving method include a TN method, an IPS method, an OCB method, and an MVA method. In the present invention, any of these methods can be preferably used.
Further, the counter substrate can be appropriately selected and used depending on the driving method of the liquid crystal display device of the present invention.
Furthermore, as the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropy and mixtures thereof can be used according to the driving method of the liquid crystal display device of the present invention.

As a method for forming the liquid crystal layer, a method generally used as a method for manufacturing a liquid crystal cell can be used, and examples thereof include a vacuum injection method and a liquid crystal dropping method.
In the vacuum injection method, for example, a liquid crystal cell is prepared in advance using a color filter and a counter substrate, and the liquid crystal is heated to obtain an isotropic liquid, and the liquid crystal is applied to the liquid crystal cell using the capillary effect. The liquid crystal layer can be formed by injecting in this state and sealing with an adhesive. Thereafter, the sealed liquid crystal can be aligned by slowly cooling the liquid crystal cell to room temperature.
In the liquid crystal dropping method, for example, a sealant is applied to the periphery of the color filter, the color filter is heated to a temperature at which the liquid crystal becomes isotropic, and the liquid crystal is dropped in an isotropic liquid state using a dispenser or the like. Then, the color filter and the counter substrate are overlapped with each other under a reduced pressure, and bonded through a sealant, whereby a liquid crystal layer can be formed. Thereafter, the sealed liquid crystal can be aligned by slowly cooling the liquid crystal cell to room temperature.

Next, the organic light emitting display device of the present invention will be described.
[Organic light emitting display]
The organic light emitting display device of the present invention includes the above-described color filter of the present invention and an organic light emitter.
Such an organic light emitting display device of the present invention will be described with reference to the drawings. FIG. 7 is a schematic view illustrating an example of the organic light emitting display device of the present invention. As illustrated in FIG. 7, the organic light emitting display device 100 of the present invention includes a color filter 10 and an organic light emitter 80.
An organic protective layer 50 and an inorganic oxide film 60 may be provided between the color filter 10 and the organic light emitter 80.

As a method for laminating the organic light emitter 80, for example, the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, and the cathode 76 are sequentially formed on the upper surface of the color filter. Examples thereof include a method and a method in which an organic light emitter 80 formed on another substrate is bonded onto the inorganic oxide film 60. As the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, the cathode 76, and other configurations in the organic light emitting body 80, known structures can be appropriately used. The organic light emitting display device 100 manufactured as described above can be applied to, for example, a passive drive type organic EL display or an active drive type organic EL display.
Note that the organic light emitting display device of the present invention is not limited to the configuration shown in FIG. 7, and can generally have a known configuration as an organic light emitting display device using a color filter.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

(Production Example 1 Synthesis of pigment derivative A (monophthalimidomethylated derivative of PY138))
After adding 5.14 parts by weight of paraformaldehyde and 17.71 parts by weight of phthalimide to 338.67 parts by weight of fuming sulfuric acid of 3.6% by weight, the mixture was stirred at 50 ° C. for 30 minutes. Then C.I. I. Pigment Yellow 138 69.40 weight part was added, and it stirred at 100 degreeC for 3 hours.
The reaction solution was added to 2400 parts by weight of ice water and stirred at 60 ° C. for 30 minutes, and then the precipitate was filtered. The obtained wet cake was washed with 1 L of warm water at 60 ° C. three times. The wet cake was vacuum dried at 80 ° C. to obtain 85.31 parts by weight of a yellow product. The mass spectrometry result of the yellow product by TOF-MS was consistent with the molecular weight (Mw = 853) of the monophthalimidomethylated derivative (n = 1) of PY138 represented by the following formula.

(Production Example 2 Synthesis of pigment derivative B (mononaphthalimide methylated derivative of PY138))
After adding 5.14 g of paraformaldehyde and 23.72 g of naphthalimide to 338.67 g of 3.6 wt% fuming sulfuric acid at 25 ° C., the mixture was stirred at 50 ° C. for 30 minutes. Subsequently, 69.40 g of Pigment Yellow 138 was added, and the mixture was stirred at 100 ° C. for 3 hours.
The reaction solution was added to 2400 g of ice water and stirred at 60 ° C. for 30 minutes, and then the precipitate was filtered. The obtained wet cake was washed with 1 L of warm water at 60 ° C. three times. The wet cake was vacuum dried at 80 ° C. to obtain 85.65 g of a yellow product. The mass spectrometric result by TOF-MS of this yellow product was consistent with the molecular weight (Mw = 903) of the mononaphthalimide methylated derivative of PY138 (n = 1) represented by the following formula.

(Production Example 3 Synthesis of Binder Resin A)
A polymerization tank was charged with 130 parts by weight of diethylene glycol ethyl methyl ether (EMDG) as a solvent, heated to 110 ° C. in a nitrogen atmosphere, then 32 parts by weight of methyl methacrylate (MMA), 22 parts by weight of cyclohexyl methacrylate (CHMA). , A mixture containing 24 parts by weight of methacrylic acid (MAA), 2 parts by weight of azoisobutyronitrile (AIBN) as an initiator and 4.5 parts by weight of n-dodecyl mercaptan as a chain transfer agent over 1.5 hours. It was dripped continuously.
Thereafter, the reaction was continued while maintaining the synthesis temperature, and 0.05 parts by weight of p-methoxyphenol was added as a polymerization inhibitor 2 hours after the completion of the dropwise addition.
Next, 22 parts by weight of glycidyl methacrylate (GMA) was added while blowing air, the temperature was raised to 110 ° C., 0.2 part by weight of triethylamine was added, and an addition reaction was carried out at 110 ° C. for 15 hours, and the binder Resin A (44 wt% solid content) was obtained.
The obtained binder resin A had a weight average molecular weight of 8,500 and an acid value of 85 mgKOH / g. The weight average molecular weight was calculated by gel permeation chromatography (GPC) using polystyrene as a standard substance and THF as an eluent, and the acid value was measured according to JIS-K0070.

(Production Example 4 Preparation of Dispersant / Binder Resin Solution A)
In a 225 mL mayonnaise bottle, 75.2 parts by weight of propylene glycol monomethyl ether acetate (PGMEA), a block copolymer containing a tertiary amino group (the repeating unit (1) represented by the above general formula (I) and the above general formula) (Block copolymer having repeating unit (2) represented by (II)) (trade name: BYK-LPN6919, manufactured by Big Chemie) (amine value 135 mgKOH / g, solid content 60% by weight) 7.45 parts by weight Then, 6.82 g of binder resin A of Production Example 3 was dissolved. Add 0.53 parts by weight of phenylphosphonic acid (trade name: PPA, manufactured by Nissan Chemical Industries, Ltd.) to the mixed solution (0.3 molar equivalent to the tertiary amino group of the block copolymer) and stir at room temperature for 30 minutes. Thus, a dispersant / binder resin solution A was prepared.
At this time, the amino group of the block copolymer (BYK-LPN6919) is salt-modified by an acid / base reaction with the phosphonic acid group of PPA.

(Production Example 5 Preparation of Dispersant / Binder Resin Solution B)
In a 225 mL mayonnaise bottle, 68.51 parts by weight of PGMEA, 4.85 parts by weight of a block copolymer containing a tertiary amino group (BYK-LPN6919), and 13.30 g of binder resin A of Production Example 3 were dissolved. By adding 0.34 parts by weight of phenylphosphonic acid (PPA) (0.3 molar equivalent to the tertiary amino group of the block copolymer) to the mixed solution and stirring at room temperature for 30 minutes, a dispersant / binder resin Solution B was prepared.
At this time, the amino group of the block copolymer (BYK-LPN6919) is salt-modified by an acid / base reaction with the phosphonic acid group of PPA.

(Production Example 6 Preparation of Dispersant / Binder Resin Solution C)
In a 225 mL mayonnaise bottle, 66.88 parts by weight of PGMEA, 7.75 parts by weight of a block copolymer containing a tertiary amino group (BYK-LPN6919), and 11.82 g of binder resin A of Production Example 3 were dissolved. By adding 0.55 parts by weight of phenylphosphonic acid (PPA) (0.3 molar equivalent to the tertiary amino group of the block copolymer) to the mixed solution and stirring at room temperature for 30 minutes, a dispersant / binder resin Solution C was prepared.
At this time, the amino group of the block copolymer (BYK-LPN6919) is salt-modified by an acid / base reaction with the phosphonic acid group of PPA.

(Production Example 7 Preparation of dispersant / binder resin solution D)
In a 225 mL mayonnaise bottle, 75.11 parts by weight of PGMEA, 7.67 parts by weight of a block copolymer containing tertiary amino groups ((BYK-LPN6919)) and 6.82 g of binder resin A of Production Example 3 were dissolved. . To the mixed solution, 0.40 part by weight of benzyl bromide (manufactured by Kanto Chemical Co., Inc.) (0.2 molar equivalent with respect to the tertiary amino group of the block copolymer) was added, and the mixture was stirred at room temperature for 30 minutes. A binder resin solution D was prepared.
At this time, the amino group of the block copolymer (BYK-LPN6919) is salt-modified by a quaternization reaction with benzyl bromide.

(Production Example 8 Preparation of dispersant / binder resin solution E)
In a 225 mL mayonnaise bottle, 78.18 parts by weight of PGMEA, 5.0 parts by weight of “Ajisper PB821” (manufactured by Ajinomoto Fine Techno Co., Ltd., solid content concentration 100% by weight) as a commercially available dispersant, 6.82 g of binder resin A of Production Example 3 Was dissolved to prepare a dispersant / binder resin solution E.

(Production Example 9 Preparation of Dispersant / Binder Resin Solution F)
In a 225 mL mayonnaise bottle, 66.51 parts by weight of PGMEA, 16.67 parts by weight of “Disperbyk 161” (manufactured by Big Chemie, solid content concentration 30% by weight) as a commercially available dispersant, and 6.82 g of binder resin A of Production Example 3 were dissolved. Thus, a dispersant / binder resin solution F was prepared.

(Production Example 10: Synthesis of pigment derivative C (monosulfonic acid derivative of PY138))
Stirring 374.76 parts by weight of 11 wt% fuming sulfuric acid while cooling to 10 ° C, C.I. I. 74.96 parts by weight of Pigment Yellow 138 was added. Subsequently, it stirred at 90 degreeC for 6 hours.
The reaction solution was added to 1600 parts by weight of ice water and stirred for 15 minutes, and then the precipitate was filtered. The obtained wet cake was washed with 800 ml of water three times. The wet cake was vacuum dried at 80 ° C. to obtain 81.55 parts by weight of a yellow product. The result of gravimetric analysis of this yellow product by TOF-MS was consistent with the molecular weight (Mw = 774) of the monosulfonic acid derivative (n = 1) of PY138 represented by the following formula.

Example 1
(1) Preparation of Yellow Pigment Dispersion Liquid A for Color Filters CI Pigment Yellow 138 (PY138: average primary particle size 10 to 50 nm) as a coloring material component in 90 parts by weight of the dispersant / binder resin solution A prepared in Production Example 4 ) 9.0 parts by weight, Pigment derivative A of Production Example 1 (monophthalimide methylated derivative of PY138) 0.3 part by weight, Pigment derivative C of Production Example 10 (monosulfonic acid derivative of PY138) 0.7 part by weight The mixture was mixed and dispersed in a paint shaker (manufactured by Asada Tekko Co., Ltd.) with 2 mm zirconia beads for 1 hour and further with 0.1 mm zirconia beads for 24 hours to obtain a yellow pigment dispersion A.

(2) Preparation of yellow negative resist composition A for color filter 66.7 parts by weight of yellow pigment dispersion A obtained in (1) above and 53.3 parts by weight of binder composition A below are mixed and pressure filtered. To obtain a yellow negative resist composition A for color filters.
<Binder composition A>
Alkali-soluble resin (Binder resin A of Production Example 3, solid content 44 wt%): 4.28 parts by weight Trifunctional to tetrafunctional acrylate monomer (trade name: Aronix M305, manufactured by Toagosei Co., Ltd.): 4.39 Part by weight / photopolymerization initiator: 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name: Irgacure 907, manufactured by Ciba Specialty Chemicals) : 0.47 parts by weight. Photopolymerization initiator: 2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole (trade name: biimidazole) (Manufactured by Kurokin Kasei Co., Ltd.)): 0.94 parts by weight. Photopolymerization initiator: 2-mercaptobenzothiazole (manufactured by Tokyo Chemical Industry Co., Ltd.): 0.15 parts by weight. Photosensitizer: 2.4. Diethylthioxanthone (trade name: Kayacure DETX-S, manufactured by Nippon Kayaku Co., Ltd.): 1.57 parts by weight. Solvent: propylene glycol monomethyl ether acetate (PGMEA): 41.5 parts by weight

(Example 2)
(1) Preparation of Yellow Pigment Dispersion B for Color Filter In Example 1 (1), 9.7 parts by weight of CI Pigment Yellow 138 (PY138: average primary particle size 10 to 50 nm) as a color material component was produced. A yellow pigment dispersion B was prepared in the same manner as in Example 1 except that 0.3 part by weight of pigment derivative A (monophthalimidomethylated derivative of PY138) of Example 1 was used.
(2) Preparation of yellow negative resist composition B for color filter In Example 1 (2), yellow pigment dispersion B obtained in (1) above was used instead of yellow pigment dispersion A. In the same manner as in Example 1 (2), a yellow negative resist composition B for color filters was obtained.

(Example 3)
(1) Preparation of Yellow Pigment Dispersion C for Color Filter In Example 1, 9.0 parts by weight of CI Pigment Yellow 138 (PY138: average primary particle size 10 to 50 nm) as a coloring material component, Except for 0.3 parts by weight of pigment derivative B (mononaphthalimide methylated derivative of PY138) and 0.7 parts by weight of pigment derivative C (monosulfonic acid derivative of PY138) of Production Example 10, the same procedure as in Example 1 was performed. A yellow pigment dispersion C was prepared.
(2) Preparation of yellow negative resist composition C for color filter In Example 1 (2), yellow pigment dispersion C obtained in (1) above was used instead of yellow pigment dispersion A. In the same manner as in Example 1 (2), a yellow negative resist composition C for color filters was obtained.

(Comparative Example 1)
(1) Preparation of Yellow Pigment Dispersion D for Color Filter In Example 1, 9.3 parts by weight of CI Pigment Yellow 138 (PY138: average primary particle size 10 to 50 nm) as a coloring material component, A yellow pigment dispersion D was prepared in the same manner as in Example 1 except that 0.7 part by weight of pigment derivative C (monosulfonic acid derivative of PY138) was used.
(2) Preparation of yellow negative resist composition D for color filter In Example 1 (2), instead of yellow pigment dispersion A, yellow pigment dispersion D obtained in (1) above was used. In the same manner as in Example 1 (2), a yellow negative resist composition D for color filters was obtained.

(Comparative Example 2)
(1) Preparation of Yellow Pigment Dispersion Liquid E for Color Filter In Example 1, except that 10.0 parts by weight of CI Pigment Yellow 138 (PY138: average primary particle size 10 to 50 nm) was used as a color material component. In the same manner as in Example 1, a yellow pigment dispersion E was prepared.
(2) Preparation of yellow negative resist composition E for color filter In Example 1 (2), instead of the yellow pigment dispersion A, the yellow pigment dispersion E obtained in (1) above was used. In the same manner as in Example 1 (2), a yellow negative resist composition E for color filters was obtained.

Example 4
(1) Preparation of Yellow Pigment Dispersion Liquid F for Color Filter Same as Example 1, except that the dispersant / binder resin solution A in Example 1 was changed to the dispersant / binder resin solution D prepared in Production Example 7. Thus, a yellow pigment dispersion F was prepared.
(2) Preparation of yellow negative resist composition F for color filter In Example 1 (2), yellow pigment dispersion F obtained in (1) above was used in place of yellow pigment dispersion A. In the same manner as in Example 1 (2), a yellow negative resist composition F for color filters was obtained.

(Example 5)
(1) Preparation of Yellow Pigment Dispersion Liquid G for Color Filter Same as Example 1 except that the dispersant / binder resin solution A in Example 1 was changed to the dispersant / binder resin solution E prepared in Production Example 8. Thus, a yellow pigment dispersion G was prepared.
(2) Preparation of Yellow Negative Resist Composition G for Color Filter In Example 1 (2), instead of the yellow pigment dispersion A, the yellow pigment dispersion G obtained in (1) above was used. In the same manner as in Example 1 (2), a yellow negative resist composition G for color filters was obtained.

(Example 6)
(1) Preparation of yellow pigment dispersion H for color filter)
A yellow pigment dispersion H was prepared in the same manner as in Example 1 except that the dispersant / binder resin solution A in Example 1 was changed to the dispersant / binder resin solution F prepared in Production Example 9.
(2) Preparation of yellow negative resist composition H for color filter In Example 1 (2), instead of the yellow pigment dispersion A, the yellow pigment dispersion H obtained in (1) above was used. In the same manner as in Example 1 (2), a yellow negative resist composition H for color filters was obtained.

(Comparative Example 3)
(1) Preparation of Yellow Pigment Dispersion Liquid I for Color Filter In Example 1, the dispersant / binder resin solution A was changed to the dispersant / binder resin solution D prepared in Production Example 7, and CI. Example 1 except that 9.3 parts by weight of Pigment Yellow 138 (PY138: average primary particle size 10 to 50 nm) and 0.7 parts by weight of Pigment Derivative C of Production Example 10 (monosulfonic acid derivative of PY138) were used. Similarly, a yellow pigment dispersion I was prepared.
(2) Preparation of yellow negative resist composition I for color filter In Example 1 (2), yellow pigment dispersion I obtained in (1) above was used instead of yellow pigment dispersion A. In the same manner as in Example 1 (2), a yellow negative resist composition I for color filters was obtained.

(Comparative Example 4)
(1) Preparation of Yellow Pigment Dispersion Liquid J for Color Filter In Example 1, the dispersant / binder resin solution A was changed to the dispersant / binder resin solution E prepared in Production Example 8, and CI. Example 1 except that 9.3 parts by weight of Pigment Yellow 138 (PY138: average primary particle size 10 to 50 nm) and 0.7 parts by weight of Pigment Derivative C of Production Example 10 (monosulfonic acid derivative of PY138) were used. Similarly, a yellow pigment dispersion J was prepared.
(2) Preparation of yellow negative resist composition J for color filter In Example 1 (2), instead of yellow pigment dispersion A, the yellow pigment dispersion J obtained in (1) above was used. In the same manner as in Example 1 (2), a yellow negative resist composition J for color filters was obtained.

(Comparative Example 5)
(1) Preparation of Yellow Pigment Dispersion Liquid K for Color Filter In Example 1, the dispersant / binder resin solution A was used as the dispersant / binder resin solution F prepared in Production Example 9, and CI. Example 1 except that 9.3 parts by weight of Pigment Yellow 138 (PY138: average primary particle size 10 to 50 nm) and 0.7 parts by weight of Pigment Derivative C of Production Example 10 (monosulfonic acid derivative of PY138) were used. Similarly, a yellow pigment dispersion K was prepared.
(2) Preparation of yellow negative resist composition K for color filter In Example 1 (2), yellow pigment dispersion K obtained in (1) above was used in place of yellow pigment dispersion A. In the same manner as in Example 1 (2), a yellow negative resist composition K for color filters was obtained.

(Comparative Example 6)
(1) Preparation of Yellow Pigment Dispersion Liquid L for Color Filter To 90 parts by weight of the dispersant / binder resin solution A prepared in Production Example 4, CI Pigment Yellow 138 (PY138: average primary particle size of 10 to 10) as a color material component 50 nm) 10.0 parts by weight were mixed and dispersed in a paint shaker for 1 hour with 2 mm zirconia beads and further for 4 hours with 0.1 mm zirconia beads to prepare a yellow pigment dispersion L.
(2) Preparation of yellow negative resist composition L for color filter In Example 1 (2), instead of the yellow pigment dispersion A, the yellow pigment dispersion L obtained in (1) above was used. In the same manner as in Example 1 (2), a yellow negative resist composition L for color filters was obtained.

(Comparative Example 7)
(1) Preparation of Yellow Pigment Dispersion M for Color Filter In Comparative Example 6, CI Pigment Yellow 150 (PY150: average primary particle size of 10 to 50 nm) was used instead of CI Pigment Yellow 138 as a color material component. ) A yellow pigment dispersion M was prepared in the same manner as in Comparative Example 6 except that the amount was 10.0 parts by weight.
(2) Preparation of yellow negative resist composition M for color filter In Example 1 (2), instead of the yellow pigment dispersion A, the yellow pigment dispersion M obtained in (1) above was used. In the same manner as in Example 1 (2), a yellow negative resist composition M for color filters was obtained.

[Evaluation]
1. Pigment dispersibility The average particle diameter and viscosity of the pigment dispersion obtained in each example were measured. The average particle size was measured using a Nikkiso Co., Ltd. “Microtrac particle size distribution meter”, and the viscosity was measured using a Japan Siber Hegner Co., Ltd. “MCR301” shear when the shear rate was 60 rpm. The viscosity was measured.
The results are shown in Table 1.

2. Contrast The yellow negative resist composition for a color filter obtained from each of the examples and the comparative examples was placed on a 0.7 mm thick glass substrate ("NA35" manufactured by NH Techno Glass Co., Ltd.) using a spin coater. Applied. Then, it heat-dried for 3 minutes on an 80 degreeC hotplate. A cured film (yellow colored layer) was obtained by irradiating ultraviolet rays of 60 mJ / cm ² using an ultrahigh pressure mercury lamp. The film thickness after drying and curing was adjusted so that the target chromaticity y = 0.506. The glass plate on which the yellow colored layer was formed was post-baked in a clean oven at 240 ° C., and the contrast, chromaticity (x, y) and luminance (Y) of the obtained yellow colored substrate were measured. Contrast was measured using “Contrast measuring device CT-1B” manufactured by Aisaka Electric Co., Ltd., and chromaticity and luminance were measured using “Microspectrophotometric measuring device OSP-SP200” manufactured by Olympus Corporation.
The results are shown in Table 1.

3. Heat resistance The yellow negative resist composition for a color filter obtained from each example and comparative example was applied on a glass substrate having a thickness of 0.7 mm using a spin coater. Then, it heat-dried for 3 minutes on an 80 degreeC hotplate. This colored layer was irradiated with ultraviolet rays of 60 mJ / cm ² through a photomask using an ultrahigh pressure mercury lamp. Thereafter, the glass plate on which the colored layer was formed was shower-developed using a 0.05 wt% aqueous potassium hydroxide solution as an alkaline developer to obtain a yellow colored substrate having a pattern formed thereon.
The yellow colored substrate on which the pattern was formed was post-baked in a clean oven at 240 ° C. and 260 ° C., and it was confirmed that there was no precipitation of pigment aggregates on the pattern coating film.
(Evaluation criteria)
○: No precipitation △: Slight precipitation ×: Precipitation XX: Precipitation on the entire coating surface

The results are shown in Table 1. Also, photographs of the heat resistance evaluation results at 260 ° C. of the pattern coating films of Example 1 and Example 2, Comparative Example 1 and Comparative Example 2 are shown in FIGS. 3 to 6, respectively.

From the results in Table 1, Examples 1 to 6 of the present invention used PY150 by adding a pigment dispersant and an imide alkylated derivative of PY138 in combination with PY138, and increasing the dispersion time in the solvent. In comparison with the result of Comparative Example 7 in the case, the luminance is improved, and the contrast is improved compared with Comparative Example 6 in which PY138 is used alone and dispersed in the conventional dispersion time, and after the high temperature heating process in the color filter process. It was also found that a coating film in which pigment aggregates do not precipitate can be produced.
When the dispersion time is increased, the contrast is improved, but pigment aggregates are precipitated in the heat resistance evaluation as in Comparative Examples 1 to 5. In Examples 1 to 6 of the present invention, since an imide alkylated derivative of PY138 was used, it was possible to produce a coating film in which pigment aggregates did not precipitate on the coating film surface during high-temperature heating.

(Production Example 11 Preparation of Green Pigment Dispersion Liquid A for Color Filter)
In Comparative Example 6, the dispersant / binder resin solution A was added to 87.0 parts by weight of the dispersant / binder resin solution B prepared in Production Example 5 as CI pigment green 58 (PG58: average primary particle) as a color material component. A green pigment dispersion A was prepared in the same manner as in Comparative Example 6 except that 13.0 parts by weight (diameter: 10 to 50 nm) was used.

(Production Example 12 Preparation of Red Pigment Dispersion Liquid A for Color Filter)
In Comparative Example 6, the dispersant / binder resin solution A was added to 87.0 parts by weight of the dispersant / binder resin solution C prepared in Production Example 6 and CI Pigment Red 254 (PR254: average primary particle) as a colorant component. A red pigment dispersion A was prepared in the same manner as in Comparative Example 6 except that 13.0 parts by weight (diameter: 10 to 50 nm) was used.

Example 7 Preparation of Green Negative Resist Composition A for Color Filter
31.95 parts by weight of the yellow pigment dispersion A obtained in Example 1, 30.04 parts by weight of the green pigment dispersion A obtained in Production Example 11, 50.74 parts by weight of the binder composition A, and 4.92 parts by weight of PGMEA After mixing and pressure filtration, a green negative resist composition A for color filters was obtained.

Example 8 Preparation of Green Negative Resist Composition B for Color Filter
In Example 7, a green negative resist composition B for color filters was used in the same manner as in Example 7 except that the yellow pigment dispersion B obtained in Example 2 was used instead of the yellow pigment dispersion A. Got.

(Comparative Examples 8 and 9 Preparation of green negative resist compositions C and D for color filters)
In Example 6, a green negative type for color filter was used in the same manner as in Example 6 except that the yellow pigment dispersions D and E obtained in Comparative Examples 1 and 2 were used instead of the yellow pigment dispersion A. Resist composition B was obtained.

(Comparative Example 10 Preparation of Green Negative Resist Composition E for Color Filter)
In Example 6, a green negative resist composition E for color filters was used in the same manner as in Example 6 except that the yellow pigment dispersion L obtained in Comparative Example 6 was used instead of the yellow pigment dispersion A. Got.

(Comparative Example 11 Preparation of Green Negative Resist Composition F for Color Filter)
22.72 parts by weight of the yellow pigment dispersion M obtained in Comparative Example 7, 32.12 parts by weight of the green pigment dispersion A obtained in Production Example 11, 51.39 parts by weight of the binder composition A, and 6.43 parts by weight of PGMEA After mixing and pressure filtration, a green negative resist composition F for color filters was obtained.

(Evaluation results)
<Contrast>
The green negative resist composition for a color filter obtained in each example and comparative example was applied on a 0.7 mm thick glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.) using a spin coater. did. Then, it heat-dried for 3 minutes on an 80 degreeC hotplate. A cured film (green colored layer) was obtained by irradiating 30 mJ / cm ² of ultraviolet rays using an ultrahigh pressure mercury lamp. The film thickness after drying and curing was adjusted so that the target chromaticity y = 0.595. The glass plate on which the green colored layer was formed was post-baked in a clean oven at 240 ° C., and the contrast, chromaticity (x, y) and luminance (Y) of the obtained green colored substrate were measured. Contrast was measured using “Contrast measuring device CT-1B” manufactured by Aisaka Electric Co., Ltd., and chromaticity and luminance were measured using “Microspectrophotometric measuring device OSP-SP200” manufactured by Olympus Corporation.
The results are shown in Table 2.

<Heat resistance>
The green negative resist composition for color filter obtained in each Example and Comparative Example was applied on a 0.7 mm thick glass substrate using a spin coater. Then, it heat-dried for 3 minutes on an 80 degreeC hotplate. This colored layer was irradiated with ultraviolet rays of 30 mJ / cm ² through a photomask using an ultrahigh pressure mercury lamp. Thereafter, the glass plate on which the colored layer was formed was shower-developed using a 0.05 wt% aqueous potassium hydroxide solution as an alkaline developer to obtain a green colored substrate having a pattern formed thereon.
The green colored substrate on which the pattern was formed was post-baked in a clean oven at 240 ° C. and 260 ° C., and it was confirmed that there was no precipitation of pigment aggregates on the pattern coating film. The evaluation criteria were the same as those in Examples 1 to 6 and Comparative Examples 1 to 7.
The results are shown in Table 2.

From the results of Table 2, Examples 7 to 8 of the present invention used PY150 by adding a pigment dispersant and an imide alkylated derivative of PY138 in combination with PY138, and increasing the dispersion time in the solvent. As compared with the result of Comparative Example 11 in the case, the luminance is improved, and the contrast is improved as compared with Comparative Example 10 using PY138 alone and dispersed in the conventional dispersion time, and after the high temperature heating process in the color filter process. It was also found that a coating film in which pigment aggregates do not precipitate can be produced.
When the dispersion time is increased, the contrast is improved. However, as in Comparative Examples 8 to 9, precipitation of pigment aggregates occurs in the heat resistance evaluation. In Examples 7 to 8 of the present invention, since an imide alkylated derivative of PY138 was used, it was possible to produce a coating film in which pigment aggregates did not precipitate on the coating film surface when heated at a high temperature.

Example 9 Preparation of Red Negative Resist Composition A for Color Filter
12.41 parts by weight of the yellow pigment dispersion A obtained in Example 1, 36.15 parts by weight of the red pigment dispersion A obtained in Production Example 12, 29.42 parts by weight of the following binder composition B, 39.67 parts by weight of PGMEA After mixing and pressure filtration, a red negative resist composition A for color filters was obtained.

<Binder composition B>
Alkali-soluble resin (Binder resin A of Production Example 3, solid content 44 wt%): 4.82 parts by weight Trifunctional to tetrafunctional acrylate monomer (trade name: Aronix M305, manufactured by Toagosei Co., Ltd.): 6.18 Part by weight / photopolymerization initiator (2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name: Irgacure 907, manufactured by Ciba Specialty Chemicals Co., Ltd.)) : 0.53 parts by weight-photopolymerization initiator (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone (trade name: Irgacure 369, manufactured by Ciba Specialty Chemicals) ): 1.24 parts by weight-solvent (propylene glycol monomethyl ether acetate (PGMEA)): 29.80 parts by weight

(Comparative Example 12 Preparation of Red Negative Resist Composition B for Color Filter)
In Example 9, a red negative resist composition B for color filters was used in the same manner as in Example 9 except that the yellow pigment dispersion D obtained in Comparative Example 1 was used instead of the yellow pigment dispersion A. Got.

(Comparative Example 13 Preparation of Red Negative Resist Composition C for Color Filter)
9.31 parts by weight of the yellow pigment dispersion M obtained in Comparative Example 7, 40.58 parts by weight of the red pigment dispersion A obtained in Production Example 12, 29.42 parts by weight of the binder composition B, and 38.34 parts by weight of PGMEA After mixing and pressure filtration, a red negative resist composition C for color filters was obtained.

(Evaluation results)
<Contrast>
The red negative resist composition for color filters obtained in each Example and Comparative Example was applied on a 0.7 mm thick glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.) using a spin coater. did. Then, it heat-dried for 3 minutes on an 80 degreeC hotplate. A cured film (red colored layer) was obtained by irradiating 30 mJ / cm ² of ultraviolet rays using an ultra-high pressure mercury lamp. The film thickness after drying and curing was adjusted so that the target chromaticity x = 0.65. The glass plate on which the red colored layer was formed was post-baked in a clean oven at 240 ° C., and the contrast, chromaticity (x, y) and luminance (Y) of the resulting red colored substrate were measured. Contrast was measured using “Contrast measuring device CT-1B” manufactured by Aisaka Electric Co., Ltd., and chromaticity and luminance were measured using “Microspectrophotometric measuring device OSP-SP200” manufactured by Olympus Corporation.
The results are shown in Table 3.

<Heat resistance>
The red negative resist composition for color filters obtained in each Example and Comparative Example was applied on a 0.7 mm thick glass substrate using a spin coater. Then, it heat-dried for 3 minutes on an 80 degreeC hotplate. This colored layer was irradiated with ultraviolet rays of 30 mJ / cm ² through a photomask using an ultrahigh pressure mercury lamp. Thereafter, the glass plate on which the colored layer was formed was shower-developed using a 0.05 wt% aqueous potassium hydroxide solution as an alkaline developer to obtain a red colored substrate having a pattern formed thereon.
The red colored substrate on which the pattern was formed was post-baked in a clean oven at 240 ° C. and 260 ° C., and it was confirmed that there was no precipitation of pigment aggregates on the pattern coating film. The evaluation criteria were the same as those in Examples 1 to 6 and Comparative Examples 1 to 7.
The results are shown in Table 3.

From the results of Table 3, Example 9 of the present invention shows the case where PY150 was used by adding a pigment dispersant and an imide alkylated derivative of PY138 in combination with PY138, and increasing the dispersion time in the solvent. Compared with the result of Comparative Example 13, the brightness is improved, and compared with Comparative Example 12 which does not contain the imide alkylated derivative of PY138, a coating film in which pigment aggregates do not precipitate even after the high temperature heating process in the color filter process is produced. It became clear that it was possible.

DESCRIPTION OF SYMBOLS 1 Transparent substrate 2 Light-shielding part 3 Colored layer 10 Color filter 20 Opposite substrate 30 Liquid crystal layer 40 Liquid crystal display device

Claims

C. I. Pigment Yellow 138 and C.I. represented by the following chemical formula (1). I. An imide alkylated derivative of CI Pigment Yellow 138, a pigment dispersant, and a solvent; I. Pigment Yellow 138 imidoalkylated derivatives are C.I. I. Pigment dispersion for color filter, containing 0.1 to 20 parts by weight with respect to 100 parts by weight of Pigment Yellow 138

(In the chemical formula (1), R represents an alkylene group having 1 to 6 carbon atoms, X represents an arylene group, and the arylene group is a halogen atom, an arylsulfonyl group, an acyl group, or — (C═O ) —C 6 H 4 — (C═O) — may be substituted, and n represents the number of substitutions of the imidoalkyl group and represents an integer of 1 to 5.)
Furthermore, C.I. I. Pigment Yellow 138 sulfonic acid derivative is C.I. I. The pigment dispersion for color filter according to claim 1, which is contained in an amount of 0.1 to 20 parts by weight per 100 parts by weight of Pigment Yellow 138.
The pigment dispersant has a repeating unit (1) represented by the following general formula (I) and a repeating unit (2) represented by the following general formula (II), and further the repeating unit (1) The pigment dispersion for a color filter according to claim 1 or 2, which is a block copolymer in which at least a part of an amino group possessed by the organic acid compound and / or halogenated hydrocarbon forms a salt. liquid.

[In Formula (I) and Formula (II), R 1 is a hydrogen atom or a methyl group, R 2 and R 3 are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and A is a carbon atom having 1 carbon atom. To 8 alkylene groups, — [CH (R 6 ) —CH (R 7 ) —O] x —CH (R 6 ) —CH (R 7 ) — or — [(CH 2 ) y —O] z — ( A divalent group represented by CH 2 ) y —, R 4 is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R 6 ) —CH A monovalent group represented by (R 7 ) —O] x —R 8 or — [(CH 2 ) y —O] z —R 8 . R 6 and R 7 are each independently a hydrogen atom or a methyl group, and R 8 is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, A monovalent group represented by —CHO, —CH 2 CHO, or —CH 2 COOR 9 , wherein R 9 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; The alkyl group, alkenyl group, aralkyl group, and aryl group each may have a substituent.
x represents an integer of 1 to 18, y represents an integer of 1 to 5, and z represents an integer of 1 to 18. m represents an integer of 3 to 200, and n represents an integer of 10 to 200. ]
When the pigment dispersant is a block copolymer in which the salt is formed, the organic acid compound is selected from the group consisting of organic acids represented by the following general formula (III) and the following general formula (IV). Or at least one selected from the group consisting of benzyl halides, allyl halides, and methyl halides. Pigment dispersion for color filters.

[In the formulas (III) and (IV), R a and R a ′ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group. 1 represented by the group, — [CH (R c ) —CH (R d ) —O] s —R e , — [(CH 2 ) t —O] u —R e , or —O—R a ″. the valence of the group, one of R a and R a 'comprises a carbon atom. R a ″ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R c ) —CH (R d ) —O] s —R e ,-[(CH 2 ) t —O] u —R e .
R b is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R c ) —CH (R d ) —O] s —R e , — A monovalent group represented by [(CH 2 ) t —O] u —R e or —O—R b ′ . R b ′ represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R c ) —CH (R d ) —O] s —R e , Alternatively, it is a monovalent group represented by-[(CH 2 ) t -O] u -R e .
R c and R d are each independently a hydrogen atom or a methyl group, and R e is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, —CHO, —CH 2 CHO, —CO—CH═CH 2 , —CO—C (CH 3 ) ═CH 2 or a monovalent group represented by —CH 2 COOR f , and R f is a hydrogen atom or carbon An alkyl group of 1 to 5;
In R a , R a ′ , and R b , each of the alkyl group, alkenyl group, aralkyl group, and aryl group may have a substituent.
s represents an integer of 1 to 18, t represents an integer of 1 to 5, and u represents an integer of 1 to 18. ]
C. I. The pigment dispersion for a color filter according to any one of claims 1 to 4, wherein Pigment Yellow 138 has an average primary particle size of 10 to 50 nm.
C. I. Pigment Yellow 138 and C.I. represented by the following chemical formula (1). I. Pigment Yellow 138 containing an imide alkylated derivative, a pigment dispersant, an alkali-soluble resin, a polyfunctional monomer, a photoinitiator, and a solvent. I. Pigment Yellow 138 imidoalkylated derivatives are C.I. I. A negative resist composition for color filters, which is contained in an amount of 0.1 to 20 parts by weight per 100 parts by weight of Pigment Yellow 138.

(In the chemical formula (1), R represents an alkylene group having 1 to 6 carbon atoms, X represents an arylene group, and the arylene group is a halogen atom, an arylsulfonyl group, an acyl group, or — (C═O ) —C 6 H 4 — (C═O) — may be substituted, and n represents the number of substitutions of the imidoalkyl group and represents an integer of 1 to 5.)
The negative resist composition for a color filter according to claim 6, comprising a red or green pigment.
Furthermore, C.I. I. Pigment Yellow 138 sulfonic acid derivative is C.I. I. The negative resist composition for a color filter according to claim 6 or 7, which is contained in an amount of 0.1 to 20 parts by weight per 100 parts by weight of Pigment Yellow 138.
The pigment dispersant has a repeating unit (1) represented by the following general formula (I) and a repeating unit (2) represented by the following general formula (II), and further the repeating unit (1) The color filter according to any one of claims 6 to 8, wherein the color filter is a block copolymer in which at least a part of an amino group possessed by the organic acid compound and / or halogenated hydrocarbon forms a salt. Negative resist composition for use.

[In Formula (I) and Formula (II), R 1 is a hydrogen atom or a methyl group, R 2 and R 3 are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and A is a carbon atom having 1 carbon atom. To 8 alkylene groups, — [CH (R 6 ) —CH (R 7 ) —O] x —CH (R 6 ) —CH (R 7 ) — or — [(CH 2 ) y —O] z — ( A divalent group represented by CH 2 ) y —, R 4 is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R 6 ) —CH A monovalent group represented by (R 7 ) —O] x —R 8 or — [(CH 2 ) y —O] z —R 8 . R 6 and R 7 are each independently a hydrogen atom or a methyl group, and R 8 is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, A monovalent group represented by —CHO, —CH 2 CHO, or —CH 2 COOR 9 , wherein R 9 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; The alkyl group, alkenyl group, aralkyl group, and aryl group each may have a substituent.
x represents an integer of 1 to 18, y represents an integer of 1 to 5, and z represents an integer of 1 to 18. m represents an integer of 3 to 200, and n represents an integer of 10 to 200. ]
When the pigment dispersant is a block copolymer in which the salt is formed, the organic acid compound is selected from the group consisting of organic acids represented by the following general formula (III) and the following general formula (IV). Or the halogenated hydrocarbon is at least one selected from the group consisting of benzyl halide, allyl halide, and methyl halide. Negative resist composition for color filters.

[In the formulas (III) and (IV), R a and R a ′ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group. 1 represented by the group, — [CH (R c ) —CH (R d ) —O] s —R e , — [(CH 2 ) t —O] u —R e , or —O—R a ″. the valence of the group, one of R a and R a 'comprises a carbon atom. R a ″ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R c ) —CH (R d ) —O] s —R e ,-[(CH 2 ) t —O] u —R e .
R b is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R c ) —CH (R d ) —O] s —R e , — A monovalent group represented by [(CH 2 ) t —O] u —R e or —O—R b ′ . R b ′ represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R c ) —CH (R d ) —O] s —R e , Alternatively, it is a monovalent group represented by-[(CH 2 ) t -O] u -R e .
R c and R d are each independently a hydrogen atom or a methyl group, and R e is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, —CHO, —CH 2 CHO, —CO—CH═CH 2 , —CO—C (CH 3 ) ═CH 2 or a monovalent group represented by —CH 2 COOR f , and R f is a hydrogen atom or carbon An alkyl group of 1 to 5;
In R a , R a ′ , and R b , each of the alkyl group, alkenyl group, aralkyl group, and aryl group may have a substituent.
s represents an integer of 1 to 18, t represents an integer of 1 to 5, and u represents an integer of 1 to 18. ]
A color filter comprising a colored layer formed by curing the negative resist composition for a color filter according to any one of claims 6 to 10.
A liquid crystal display device comprising: the color filter according to claim 11; a counter substrate; and a liquid crystal layer formed between the color filter and the counter substrate.
An organic light-emitting display device comprising the color filter according to claim 11 and an organic light emitter.