JP5942365B2 - Color filter pigment dispersion, color filter negative resist composition and method for producing the same, color filter, liquid crystal display device, and organic light emitting display device - Google Patents

Description

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

In recent years, flat panel displays have been rapidly spread due to the price drop of liquid crystal panels and the influence of the start of digital terrestrial broadcasting. Among flat panel displays currently in practical use, liquid crystal displays are widely used in mobile terminals such as mobile phones, portable game machines, and tablet PCs in addition to monitors for televisions and personal computers. The situation is expanding.
Under such circumstances, there is an increasing demand for higher brightness, higher contrast, and improved color reproducibility even in a color filter having a function of displaying liquid crystal displays in color. In particular, recently, there is an increasing demand for higher brightness of the color filter due to reduced power consumption of the backlight and the characteristics of the LED backlight.
The above-mentioned problem is the same in an organic EL display that is expected to be widely used in the future, and high luminance and improvement in color reproducibility are problems to be solved in the display.

  Here, as a general method for producing a color filter, on a substrate on which a light shielding portion is formed in a pattern, a coating film made of a photocurable negative resist composition in which pigments of respective colors are dispersed is formed, 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 has a pattern of three colors 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.

  In general, 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 it was difficult to use particularly for television.
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. However, the method of Patent Document 2 has not reached a level sufficient to obtain the high contrast required for recent liquid crystal displays.

  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. 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 JP 2002-179799 A Special table 2004-501911 gazette

  The present inventors have improved C.D. 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, a new problem arises in that pigment aggregates precipitate as foreign matter on the coating film surface after the high-temperature (230 ° C. or higher) heating step after exposure in the color filter manufacturing process. I understood it. C. I. Such a problem of Pigment Yellow 138 has not been known. When the aggregate of the pigment is deposited on the surface of the coating film like a foreign substance, the color filter cannot be used as a defective product. In addition, C.I. I. Even if high contrast is achieved by miniaturization of Pigment Yellow 138, the contrast retention after the high-temperature heating process is lowered.

  The present invention has been made under such circumstances, and achieves a coating film in which pigment aggregates do not precipitate even after a high-temperature heating process in a color filter manufacturing process while achieving a demand for high brightness and high contrast. A color filter pigment dispersion that can be produced, a negative resist for a color filter that is capable of forming a colored layer with high brightness and high contrast while suppressing the precipitation of pigment aggregates during a high-temperature heating step, and having excellent developability It is an object of the present invention to provide a composition, a method for producing the same, a color filter formed using the negative resist composition, 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. A specific amount of a specific imide alkylated derivative of CI Pigment Yellow 138 is combined in a specific amount and dispersed in the presence of a specific graft copolymer in which at least a part of the amino group of the polymer structural unit and an organic acid compound form a salt. By using the pigment dispersion thus prepared, it is possible to produce a coating film in which pigment aggregates do not precipitate even after the high-temperature heating process in the color filter manufacturing process, while achieving the demand for high brightness and high contrast. It was found that a negative resist composition having excellent properties 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. Pigment Yellow 138, an imide alkylated derivative, a pigment dispersant, and a solvent. The pigment dispersant includes a monomer having an ethylenically unsaturated double bond and an amino group, a polymer chain, and ethylene at its terminal. A graft copolymer containing, as a copolymerization component, a macromonomer containing a group having an ethylenically unsaturated double bond, and at least an amino group derived from a monomer having an ethylenically unsaturated double bond and an amino group Graft copolymer in which a part and an organic acid compound form a salt {provided that the polymer chain of the macromonomer is — [CH (R ⁱ ) —CH (R ⁱⁱ ) —O] _x —R ⁱⁱⁱ , or _{- [(CH 2) y -O} ] z -R iii ( wherein ^{R i} and R ⁱⁱ are each independently a hydrogen atom or a methyl group, R ⁱⁱⁱ represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, Alkenyl prime 2-18, aralkyl group, aryl group, _-CHO, -CH 2 CHO, or a monovalent group represented by _-CH 2 COOR ^iv, R ^iv is a hydrogen atom or a carbon number from 1 to 5 Except that x is an integer from 1 to 18, y is an integer from 1 to 5, and z is an integer from 1 to 18. } , And the C.I. 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 mass with respect to 100 parts by mass 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 imide alkyl group and represents an integer of 1 to 5.)

The present invention also provides C.I. I. Pigment Yellow 138 and C.I. represented by the 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, wherein the pigment dispersant is an ethylenically unsaturated double bond And a monomer having an amino group and a macromonomer having a polymer chain and a group having an ethylenically unsaturated double bond at its terminal as a copolymerization component, and further comprising an ethylenically unsaturated group Graft copolymer in which at least a part of an amino group derived from a monomer having a double bond and an amino group and an organic acid compound form a salt {provided that the polymer chain of the macromonomer is — [CH (R ^{i ) -CH (R ii) -O]} x -R iii, or _{- [(CH 2) y -O} ] z -R iii ( wherein ^{R i} and R ⁱⁱ are each independently a hydrogen atom or a methyl group, ⁱⁱⁱ represents a hydrogen atom or 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, or monovalent represented by _-CH 2 COOR ^iv R ^iv is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18.) Except the case. } , And the C.I. 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 mass with respect to 100 parts by mass of Pigment Yellow 138.

The present invention also provides a pigment dispersant comprising a monomer having an ethylenically unsaturated double bond and an amino group, and a macromonomer containing a polymer chain and a group having an ethylenically unsaturated double bond at its terminal. A graft copolymer contained as a polymerization component, wherein the organic acid compound forms a salt with at least a part of an amino group derived from a monomer having an ethylenically unsaturated double bond and an amino group. {However, the polymer chain of the macromonomer is — [CH (R ⁱ ) —CH (R ⁱⁱ ) —O] _x —R ⁱⁱⁱ , or — [(CH ₂ ) _y —O] _z —R ⁱⁱⁱ (here R ⁱ and R ⁱⁱ each independently represent a hydrogen atom or a methyl group, R ⁱⁱⁱ represents a hydrogen atom, or 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, or a monovalent group represented by _-CH 2 COOR ^iv, R ^iv is hydrogen or a carbon number of 1 to 5 alkyl groups .x 1 to 18 integer, y is 1 An integer of 5 and z represents an integer of 1 to 18.). } Preparing steps,
In the presence of the pigment dispersant in a solvent, C.I. I. Pigment Yellow 138 and C.I. represented by the chemical formula (1). I. Preparing a pigment dispersion by dispersing an imide alkylated derivative of CI Pigment Yellow 138;
Provided is a method for producing a negative resist composition for a color filter, comprising a step of mixing the pigment dispersion, an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator.

Furthermore, the present invention provides a pigment dispersant comprising a monomer having an ethylenically unsaturated double bond and an amino group, and a macromonomer containing a polymer chain and a group having an ethylenically unsaturated double bond at its terminal. A graft copolymer contained as a polymerization component, wherein the organic acid compound forms a salt with at least a part of an amino group derived from a monomer having an ethylenically unsaturated double bond and an amino group. {However, the polymer chain of the macromonomer is — [CH (R ⁱ ) —CH (R ⁱⁱ ) —O] _x —R ⁱⁱⁱ , or — [(CH ₂ ) _y —O] _z —R ⁱⁱⁱ (here R ⁱ and R ⁱⁱ each independently represent a hydrogen atom or a methyl group, R ⁱⁱⁱ represents a hydrogen atom, or 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, or a monovalent group represented by _-CH 2 COOR ^iv, R ^iv is hydrogen or a carbon number of 1 to 5 alkyl groups .x 1 to 18 integer, y is 1 An integer of 5 and z represents an integer of 1 to 18.). } Preparing steps,
In the presence of the pigment dispersant in a solvent, C.I. I. Pigment yellow 138 is dispersed to prepare a pigment dispersion;
The pigment dispersion and C.I. represented by the chemical formula (1). I. Provided is a method for producing a negative resist composition for a color filter, which comprises a step of mixing an imide alkylated derivative of CI Pigment Yellow 138, an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator.

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

  In the pigment dispersion for color filter according to the present invention, the negative resist composition for color filter according to the present invention, and the production method thereof, in the pigment dispersant, the ethylenically unsaturated double bond and the amino group are It is preferable that the monomer to be contained is a monomer represented by the following general formula (I) from the viewpoint of achieving high brightness and high contrast requirements and being excellent in pigment dispersibility and alkali developability.

(In formula (I), R ¹ represents a hydrogen atom or a methyl group, R ² and R ³ each independently represents a hydrogen atom, or an optionally substituted cyclic or chain hydrocarbon group, or R 1 ² and R ³ combine with each other to form a cyclic structure, Q represents a divalent linking group.

  In the pigment dispersion according to the present invention, the negative resist composition for a color filter according to the present invention, and the production method thereof, the organic acid compound is represented by the following general formula (II) and / or the following general formula (III): It is preferable that it is expressed in terms of achieving high brightness and high contrast, and being excellent in pigment dispersibility and alkali developability.

(In Formula (II) and 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, or an aryl group. A monovalent group represented by a 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 ′} each contain ^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 , a monovalent group represented by — [(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 , — [(CH ₂ ) _t —O] _u —R ^e or a monovalent group represented by —O—R ^{b ′} . 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 , or _- 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, a monovalent group represented by _{-CO-C (CH 3) =} CH 2 or _-CH 2 COOR ^{f, R f} is hydrogen or C It is an alkyl group of formula 1-5. In R ^a , R ^{a ′} , R ^b , R ^e and R ^f , each of the alkyl group, alkenyl group, aralkyl group and aryl group may have a substituent.
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. )

  In the pigment dispersion according to the present invention, the negative resist composition for a color filter according to the present invention, and the production method thereof, the polymer chain of the macromonomer is represented by the following general formula (IV) or general formula (V). It is preferable to have at least one structural unit represented from the viewpoints of achieving high brightness and high contrast requirements and being excellent in pigment dispersibility and alkali developability.

(Formula (IV) and wherein (V), ^{R 4} is a hydrogen atom or a methyl group, ^{R 5} is an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, a cyano group, - [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —R ⁸ , — [(CH ₂ ) _y —O] _z —R ⁸ , — [CO— (CH ₂ ) _y —O] _z —R ⁸ , —CO It is a monovalent group represented by —O—R ⁹ or —O—CO—R ^10. R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group.
R ⁸ is a hydrogen atom or a monovalent group represented by an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, —CHO, —CH ₂ CHO, or —CH ₂ COOR ¹¹ , and R ⁹ is C1-C18 alkyl group, aralkyl group, aryl group, cyano group, — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —R ⁸ , — [(CH ₂ ) _y —O] _z It is a monovalent group represented by —R ⁸ or — [CO— (CH ₂ ) _y —O] _z —R ⁸ . R ¹⁰ is an alkyl group having 1 to 18 carbon atoms, and R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
m represents an integer of 1 to 5, and l and l ′ represent an integer of 5 to 200. x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18. )

The present invention, curing a transparent substrate, and at least comprising a color filter and a colored layer provided on the transparent substrate, at least one of a color filter for a negative resist composition according to the present invention of the colored layer There is provided a color filter characterized by having a colored layer formed.

The present invention also provides a liquid crystal display device comprising the color filter according to the present invention, 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 according to the present invention and an organic light emitter.

  According to the present invention, a pigment dispersion for a color filter capable of producing a coating film in which pigment aggregates do not precipitate even after a high-temperature heating step in a color filter manufacturing process while achieving a demand for high brightness and high contrast. In addition, the precipitation of pigment aggregates is suppressed during the high-temperature heating step, and a color layer having a high luminance and a high contrast can be formed, and the color filter negative resist composition having excellent developability, and a method for producing the same, and the negative type A color filter formed using a resist composition, a liquid crystal display device and an organic light emitting display device having the color filter can be provided.

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. It is the schematic which shows an example of the organic light emitting display apparatus of this invention. It is a schematic diagram which shows an example of the preferable structure of the graft copolymer used for this invention. The photograph of the heat resistance evaluation result in 260 degreeC of the coating film of Example 1 of this invention is shown. The photograph of the heat resistance evaluation result in 260 degreeC of the coating film of Example 2 of this invention is shown. The photograph of the heat resistance evaluation result in 260 degreeC of the coating film of the comparative example 1 is shown. The photograph of the heat resistance evaluation result in 260 degreeC of the coating film of the comparative example 2 is shown.

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. Pigment Yellow 138, an imide alkylated derivative, a pigment dispersant, and a solvent. The pigment dispersant includes a monomer having an ethylenically unsaturated double bond and an amino group, a polymer chain, and ethylene at its terminal. A graft copolymer containing, as a copolymerization component, a macromonomer containing a group having an ethylenically unsaturated double bond, and at least an amino group derived from a monomer having an ethylenically unsaturated double bond and an amino group A graft copolymer in which a part and an organic acid compound form a salt (hereinafter sometimes simply referred to as a salt-type graft copolymer); I. Pigment Yellow 138 imidoalkylated derivatives are C.I. I. The pigment dispersant is 0.1 to 20 parts by mass with respect to 100 parts by mass of CI 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 imide alkyl group and represents an integer of 1 to 5.)

  According to the present invention, C.I. I. Pigment Yellow 138 (hereinafter sometimes referred to as PY138) and the specific C.I. I. By using a combination of the imide alkylated derivative of Pigment Yellow 138 and the above-mentioned specific salt-type graft copolymer, the pigment dispersibility and dispersion stability are excellent, while achieving the demand for high brightness and high contrast, It is possible to obtain a pigment dispersion capable of producing a coating film in which pigment aggregates do not precipitate even after the high-temperature heating process in the color filter manufacturing process.

Although it is unclear as an effect | action which exhibits the above effects by the said specific combination, it estimates as follows.
By extending the dispersion time in the solvent, the above-mentioned specific pigment dispersant is appropriately adsorbed on the exposed pigment surface by refining PY138 to the primary particle size or less, and the pigment in the solvent. It is estimated that the PY138 can be more uniformly refined. 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 high temperature heating process of the color filter manufacturing process, the thermal motion of the pigment dispersant adsorbed on the pigment It is presumed that the adsorption of the pigment dispersant is weakened by this, the cohesive force between the finely exposed pigment surfaces is strengthened, and the pigment aggregate is precipitated.
The phenomenon that pigment aggregates precipitate on the surface of the coating film when heated at a high temperature is that a sulfonic acid derivative of PY138 is added to PY138, and the above-mentioned specific salt-type pigment dispersant is combined to refine the pigment to prepare a pigment dispersion. Also when prepared, it was noticeable.

On the other hand, in the present application, by combining PY138 with a specific amount of a specific imide alkylated derivative of PY138 and a specific salt-type graft copolymer used as a pigment dispersant, the PY138 is refined in the dispersion step. It is estimated that not only the salt-type graft copolymer but also an imide alkylated derivative of PY138 is adsorbed on the exposed pigment surface. Even when a high temperature of 230 ° C. is applied to the coating film in the high temperature heating process of the color filter manufacturing 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. Therefore, 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. . For the purpose of recrystallizing the crude pigment of Patent Document 3, sulfonic acid derivatives and imide alkylated derivatives are used in the same manner.

  In this application, PY138, which can increase the brightness, interacts with a specific salt-type graft copolymer, and the salt-type graft copolymer, but the interaction is not too strong. By combining and dispersing the derivative of PY138 having a part, the exposed pigment surface is stabilized while refining PY138, and the surface of the pigment in which 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 in which pigment aggregates do not precipitate even after a high-temperature heating process in the color filter manufacturing process 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 CI Pigment Yellow 138, the specific 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 pigments such as CI Pigment Yellow 138 is not particularly limited as long as it can produce a desired color when used as a colored layer of a color filter, and varies depending on the type of pigment used. From the viewpoint of improving contrast, the thickness is preferably within the range of 10 to 70 nm, and more preferably within the range of 10 to 50 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 manufactured using the pigment dispersion for color filter of the present invention and the negative resist composition can be produced 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, with respect to 100 or more particles, the volume (mass) 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 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 mass, more preferably 8 to 20% by mass, based on the total amount of the pigment dispersion for color filter.
In the pigment dispersion for a color filter of the present invention, C.I. I. The pigment yellow 138 content is usually 100% by mass, but may further contain other pigments. C. in the pigment. I. The content of Pigment Yellow 138 is preferably 5 to 100% by mass, and more preferably 30 to 100% by mass.

(C.I. Pigment Yellow 138 Imidoalkylated Derivative)
C. used in the present invention. I. An imidoalkylated derivative of CI Pigment Yellow 138 is a C.I. I. It is an imide alkylated derivative of CI 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 imide alkyl group and represents an integer of 1 to 5.)

  Such a pigment derivative is a compound having a role of imparting a functional group to the pigment skeleton and adding various functions to the pigment. When the pigment derivative is added to the pigment, the pigment-like skeleton of the pigment derivative is adsorbed or bonded to the pigment surface, whereby the pigment surface has an imide alkyl group. Thereby, it is considered that aggregation of pigments can be suppressed even after the high-temperature heating process in the color filter manufacturing process.

  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. As X in the chemical formula (1), 1,2-phenylene serving as phthalimide and 1,8-naphthylene serving as naphthalimide are preferable.

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 with 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 a 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 that pigment aggregates can be efficiently suppressed.

(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 1 is particularly preferable 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 mass 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. In addition, about a synthesis method, it describes in detail in Japanese translations of PCT publication No. 2004-501911, and can refer this. In concentrated sulfuric acid, C.I. I. By reacting Pigment Yellow 138 with a hydroxyalkyl cyclic imide such as hydroxyalkylphthalimide, R is any C.I. I. An imidoalkylated derivative of CI Pigment Yellow 138 can be prepared. The synthesis method is described in Japanese Patent Application No. 2011-101554 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 mass is contained with respect to 100 parts by mass of Pigment Yellow 138. Among them, C.I. I. Pigment Yellow 138 imidoalkylated derivatives include C.I. I. It is preferable to contain 0.1-10 mass parts with respect to 100 mass parts of pigment yellow 138, and also 1-5 mass parts. 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 manufacturing process, while achieving the demand for high brightness and high contrast.

(Pigment dispersant)
The pigment dispersant used in the present invention is a copolymer of a monomer having an ethylenically unsaturated double bond and an amino group and a macromonomer having a polymer chain and a group having an ethylenically unsaturated double bond at its terminal. A graft copolymer contained as a component, further comprising at least a part of an amino group derived from a monomer having an ethylenically unsaturated double bond and an amino group, and an organic acid compound forming a salt. is there.

  According to the present invention, since the pigment dispersant used is the above-mentioned salt-type graft copolymer, the salt-forming site is strongly adsorbed to the pigment, while the grafted polymer chain is dissolved in the solvent. Have sex. When the above pigment dispersant is used, it is possible to achieve stabilization in a solvent even for pigments that have previously had poor pigment dispersibility and pigment dispersion stability, and excellent pigment dispersibility and dispersion stability. It can be.

  In addition, by having an organic acid compound, the salt-forming site formed by the amino group contained in the monomer and the organic acid compound has high solubility in an alkaline aqueous solution during alkali development. It can be made excellent. Therefore, when a color filter is produced using the negative resist composition for a color filter of the present invention, the alkali development time can be shortened and the productivity can be improved. Moreover, by being excellent in alkali developability, it is possible to obtain a high-quality color filter with little residue of the negative resist composition for color filter in an unexposed area.

<Graft copolymer>
The graft copolymer contains a monomer having an ethylenically unsaturated double bond and an amino group, and a macromonomer containing a polymer chain and a group having an ethylenically unsaturated double bond at the terminal as copolymerization components. To do.

  The monomer having an ethylenically unsaturated double bond and an amino group is not particularly limited. Among these, those represented by the following general formula (I) are preferable from the viewpoint of pigment dispersibility.

(In formula (I), R ¹ represents a hydrogen atom or a methyl group, R ² and R ³ each independently represents a hydrogen atom, or an optionally substituted cyclic or chain hydrocarbon group, or R 1 ² and R ³ combine with each other to form a cyclic structure, Q represents a divalent linking group.

The cyclic or chain hydrocarbon group in R ² and R ³ is not particularly limited. Among them, an alkyl group having 1 to 8 carbon atoms is preferable, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, Examples include various hexyl groups, various octyl groups, cyclopentyl groups, cyclohexyl groups, and cyclooctyl groups. Among these, a methyl group and an ethyl group are preferable.
R ² and R ³ may be the same as or different from each other.

Examples of the cyclic structure formed by combining R ² and R ³ with each other include a 5- to 7-membered nitrogen-containing heterocyclic monocycle or a condensed ring formed by condensing two of these. The nitrogen-containing heterocycle preferably has no aromaticity, more preferably a saturated ring. Specifically, the structure of the following formula is mentioned, for example.

Examples of the divalent linking group Q include, for example, an alkylene group having 1 to 8 carbon atoms, an arylene group, a -CONH-A- group, and a -COO-A- group (provided that A is a group having 1 to 8 carbon atoms). An alkylene group, — [CH (R ¹² ) —CH (R ¹³ ) —O] _x —CH (R ¹² ) —CH (R ¹³ ) — or — [(CH ₂ ) _y —O] _z — (CH ₂ ) _Y is a divalent group represented by-, R ¹² and R ¹³ are each independently a hydrogen atom or a methyl group, x is an integer of 1 to 18, y is an integer of 1 to 5, z is 1 to 1. An integer of 18) and the like, and a -COO-A- group is preferable.

Here, the alkylene group having 1 to 8 carbon atoms may be linear or branched. For example, a methylene group, an ethylene group, a trimethylene group, a propylene group, various butylene groups, various pentylene groups, various types. A hexylene group, various octylene groups, and the like. Examples of the arylene group include a phenylene group.
R ¹² and R ¹³ 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 1-18, preferably an integer of 1-4, more preferably an integer of 1-2. In the present invention, when x, y, and z are in the above ranges, the pigment dispersion and color filter negative resist composition of the present invention have excellent pigment dispersibility.
As this A, a C1-C8 alkylene group is preferable, and a methylene group and ethylene group are more preferable. If the carbon number is in the range of 1 to 8, the dispersibility of the pigment can be kept good.

  As the monomer represented by the general formula (I), a monomer represented by the following general formula (I ′) is preferably used.

(In General Formula (I ′), 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 each independently a carbon atom having 1 to 1 carbon atoms. 8 alkylene group, — [CH (R ¹² ) —CH (R ¹³ ) —O] _x —CH (R ¹² ) —CH (R ¹³ ) — or — [(CH ₂ ) _y —O] _z — (CH _{2) y} - is a divalent group represented by ^{.R 12} and ^{R 13} are each independently a hydrogen atom or a methyl group .x 1 to 18 integer, y is an integer of from 1 to 5, z is Represents an integer of 1 to 18.)

In the general formula (I ′), R ^{1 to} R ³ and A can be the same as those described in the general formula (I).

The macromonomer used in the present invention is composed of a polymer chain and a group having an ethylenically unsaturated double bond at its terminal. The group having an ethylenically unsaturated double bond is preferably contained only at one end of the polymer chain (hereinafter sometimes referred to as “one end”). Further, the macromonomer may be substituted with a substituent as long as it does not interfere with the dispersion performance of the graft copolymer, and examples of the substituent include a halogen atom.
Preferred examples of the group having an ethylenically unsaturated double bond include a (meth) acryloyl group, a vinyl group, and an allyl group. Among them, a (meth) acryloyl group and a vinyl group are preferable, and a (meth) acryloyl group is particularly preferable. preferable.

  The polymer chain of the macromonomer preferably has at least one structural unit represented by the following general formula (IV) or general formula (V).

(Formula (IV) and wherein (V), ^{R 4} is a hydrogen atom or a methyl group, ^{R 5} is an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, a cyano group, - [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —R ⁸ , — [(CH ₂ ) _y —O] _z —R ⁸ , — [CO— (CH ₂ ) _y —O] _z —R ⁸ , —CO It is a monovalent group represented by —O—R ⁹ or —O—CO—R ^10. R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group.
R ⁸ is a hydrogen atom, or a monovalent group represented by 1 to 18 alkyl group, aralkyl group, aryl group, —CHO, —CH ₂ CHO, or —CH ₂ COOR ¹¹ , and R ⁹ is the number of carbon atoms. 1-18 alkyl groups, aralkyl groups, aryl groups, cyano groups, — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —R ⁸ , — [(CH ₂ ) _y —O] _z —R ⁸ or a monovalent group represented by — [CO— (CH ₂ ) _y —O] _z —R ⁸ . R ¹⁰ is an alkyl group having 1 to 18 carbon atoms, and R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
m represents an integer of 1 to 5, and l and l ′ represent an integer of 5 to 200. x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18. )

The alkyl group having 1 to 18 carbon atoms in R ⁵ may be linear, branched or cyclic, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 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 , Cyclooctyl group, cyclododecyl group, bornyl group, isobornyl group, dicyclopentanyl group, adamantyl group, lower alkyl group-substituted adamantyl group and the like.

Examples of the aryl group in R ⁵ include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, and a xylyl group. 6-24 are preferable and, as for carbon number of an aryl group, 6-12 are more preferable.
Examples of the aralkyl group in R ⁵ include a benzyl group, a phenethyl group, a naphthylmethyl group, and a biphenylmethyl group. 7-20 are preferable and, as for carbon number of an aralkyl group, 7-14 are more preferable.
When R ⁵ has an aromatic ring, it may further have a substituent on the aromatic ring. Examples of the substituent include linear and branched alkyl having 1 to 4 carbon atoms. In addition to groups, alkenyl groups, nitro groups, halogen atoms and the like can be mentioned.

R ⁹ is an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, a cyano group, — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —R ⁸ , — [(CH ₂ ) _y. It is a monovalent group represented by —O] _z —R ⁸ or — [CO— (CH ₂ ) _y —O] _z —R ⁸ . The alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group is as shown by the above R ^5.

R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group, and R ⁸ is a hydrogen atom or an optionally substituted alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, A monovalent group represented by —CHO, —CH ₂ CHO, or —CH ₂ COOR ¹¹ . R ¹¹ is a hydrogen atom or a linear, branched, or cyclic alkyl group having 1 to 5 carbon atoms, and R ¹⁰ is an alkyl group having 1 to 18 carbon atoms.
In the monovalent group represented by R ⁸ , the substituent that may be included is, for example, a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms, a halogen atom such as F, Cl, or Br. And so on.
The alkyl group having 1 to 18 carbon atoms, the aralkyl group, and the aryl group in R ¹⁰ and R ⁸ are as described above for R ⁵ .
In the above R ⁵ and R ⁹ , x, y and z are as described in the formula (I).

In the present invention, as R ⁵ and R ⁹ , it is preferable to use those having excellent solubility in the solvent described later, and specifically, depending on the structural unit constituting the graft copolymer, etc. However, when the solvent is an ether alcohol acetate type, ether type, ester type or the like generally used as a solvent for a color filter, a methyl group, an ethyl group, or an n-butyl group is used. , 2-ethylhexyl group, benzyl group and the like are preferable.
Here, the reason for setting R ⁵ and R ⁹ in this manner is that the structural unit containing R ⁵ and R ⁹ has solubility in the solvent, and the amino group of the monomer and the organic group described later. This is because the dispersibility and stability of the pigment can be made particularly excellent because the salt-forming site formed by the acid compound has high adsorptivity to the pigment.

Furthermore, R ^{5 and} R ⁹ are substituents such as an alkoxy group, a hydroxyl group, a carboxyl group, an amino group, an epoxy group, an isocyanate group, and a hydrogen bond-forming group as long as they do not interfere with the dispersion performance of the graft copolymer. It may be substituted by. Moreover, after synthesizing a graft 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 graft copolymer having a carboxyl group with glycidyl (meth) acrylate, or reacting a graft copolymer having an isocyanate group with hydroxyethyl (meth) acrylate. Can do.

  The polymer chain of the macromonomer used in the resist composition of the present invention preferably has a glass transition temperature of 30 ° C. or higher, and more preferably 50 ° C. or higher. When the glass transition temperature of the polymer chain of the macromonomer used in the present invention is 30 ° C. or higher, the heat resistance and solvent resistance of the colored layer formed using the pigment dispersion or resist composition of the present invention are high. improves. When the heat resistance is improved, it is possible to suppress the color layer from being discolored and the luminance and contrast from being lowered after a post-baking step of heating at 230 ° C. for 30 minutes in the color filter manufacturing process. In addition, when the solvent resistance is improved, it is possible to suppress the problem that the colored layer surface becomes rough due to N-methylpyrrolidone used when forming a polyimide film, for example, as a liquid crystal alignment film in the color filter manufacturing process. become.

The glass transition temperature (Tg) of the polymer chain of the macromonomer in the present invention can be calculated by the following formula.
1 / Tg = Σ (Xi / Tgi)
Here, it is assumed that n monomer components from i = 1 to n are copolymerized in the polymer. Xi is the mass fraction of the i-th monomer (ΣXi = 1), and Tgi is the glass transition temperature (absolute temperature) of the homopolymer of the i-th monomer. However, Σ is the sum from i = 1 to n. The homopolymer glass transition temperature value (Tgi) of each monomer may adopt the value of Polymer Handbook (3rd Edition) (by J. Brandrup, EH Immergut (Wiley-Interscience, 1989)). it can.

  In consideration of the above points, the polymer chain of the macromonomer used in the present invention includes methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, cyclohexyl metallate, benzyl, among the above-described structural units. 1 selected from the group consisting of (meth) acrylate, phenyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, styrene, α-methylstyrene, and vinylcyclohexane The total amount of structural units derived from more than one monomer is preferably 30% by mass or more of the entire macromonomer polymer chain, more preferably 50% by mass or more. Methyl methacrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, and / or isobornyl (meth) is more preferable that contains structural units derived from acrylate. However, it is not limited to these.

The polymer chain of the macromonomer may be a homopolymer or a copolymer.
For example, even if the homopolymer is a structural unit having a glass transition temperature of less than 30 ° C., it is included as a copolymer component of the polymer chain, and the calculated Tg of the entire polymer chain represented by the above formula is 30 ° C. When it becomes the above, it can use suitably as a macromonomer of the resist composition of this invention.

Furthermore, the macromonomer used for a graft copolymer may be used individually by 1 type, but may be used in mixture of 2 or more types.
When two or more kinds of macromonomers are used as a mixture, the macromonomer having a polymer chain having a glass transition temperature of 30 ° C. or higher is used so as to be 30% by mass or more, further 50% by mass or more of the entire macromonomer. It is preferable.

  m is an integer of 1 to 5, preferably an integer of 2 to 5, more preferably an integer of 4 or 5. Moreover, the unit numbers 1 and 1 'of the structural unit of a macromonomer should just be an integer of 5-200, Although it does not specifically limit, It is preferable to exist in the range of 5-100.

  The mass average molecular weight Mw of the macromonomer is preferably in the range of 500 to 20000, and more preferably in the range of 1000 to 10,000. By being the said range, while being able to hold | maintain sufficient steric repulsion effect as a pigment dispersant, the increase in the adsorption time to the pigment by a steric effect can also be suppressed.

  Such a macromonomer may be appropriately synthesized or may be a commercially available product. Examples of commercially available products include one-end methacryloylated polymethyl methacrylate oligomer (mass average molecular weight: 6000, “AA-6 (product Name) ": manufactured by Toagosei Chemical Co., Ltd.), one-end methacryloylated poly-n-butyl acrylate oligomer (mass average molecular weight: 6000," AB-6 (trade name) "manufactured by Toagosei Chemical Co., Ltd.), Single-end methacryloylated polystyrene oligomer (mass average molecular weight: 6000, “AS-6 (trade name)” manufactured by Toagosei Chemical Co., Ltd.), caprolactone-modified hydroxyethyl methacrylate (“Placcel FM5 (trade name)”: Daicel Chemical ( Co., Ltd.), caprolactone-modified hydroxyethyl acrylate ("Placcel FA10L ( Name) ": manufactured by Daicel Chemical Industries Co., Ltd.), and the like.

  In order to synthesize such a macromonomer, a living polymerization method and a radical polymerization method using a chain transfer agent are well known. The radical polymerization method is easier to use because it has a greater degree of freedom in monomer selection. For example, an oligomer having a carboxyl group at one end can be obtained by radical polymerization of a monomer in the presence of a chain transfer agent having a carboxyl group such as mercaptopropionic acid. When glycidyl methacrylate is added to this oligomer, an oligomer having a methacryloyl group at one end, that is, a macromonomer is obtained.

  In the graft copolymer used in the present invention, the repeating unit derived from the monomer having an ethylenically unsaturated double bond and an amino group is preferably contained in a proportion of 3 to 80% by mass. -50 mass% is more preferable, and 10-40 mass% is further more preferable. If the content of the repeating unit derived from the monomer in the graft copolymer is within the above range, the ratio of the salt forming site formed by the amino group in the graft copolymer becomes appropriate, and the macromonomer side chain causes a solvent. Therefore, the adsorptivity to the pigment is improved, and the dispersibility and stability of the pigment can be obtained.

  Further, the mass average molecular weight Mw of the graft copolymer is preferably in the range of 1000 to 100,000, more preferably in the range of 3000 to 50000, and further in the range of 5000 to 30000. preferable. By being the said range, a pigment can be disperse | distributed uniformly.

  The mass 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 the polystyrene standard for calibration curve was Mw377400, 210500, 96000, 50400. , 206500, 10850, 5460, 2930, 1300, 580 (Easi 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 graft copolymer used in the present invention has the above-mentioned monomer having an amino group and a macromonomer as copolymer components, and further, a salt formed by the amino group and the organic acid compound of the monomer. There is a structure as shown in FIG. In FIG. 4, in the graft copolymer, a monomer unit 51 having an amino group forms a main chain by a polymerization reaction, and a polymerizable group site (group site having an ethylenically unsaturated double bond) of the macromonomer in the polymerization reaction. ) 52 is simultaneously polymerized with the nitrogen-containing monomer, and the macromonomer is connected to the group site having the ethylenically unsaturated double bond to form a side chain as the polymer chain 53, and the organic acid compound 54 is an amino group. A salt formed with the amino group of the monomer unit 51 having

<Organic acid compound>
The organic acid compound used in the present invention is not particularly limited as long as it forms a salt with the amino group of the monomer having an amino group described above.
In the present invention, by using the organic acid compound, the pigment dispersant can be made excellent in the dispersibility and stability of the pigment, and the salt-forming site can be used with respect to the alkaline aqueous solution during alkali development. In addition, since it has high solubility, it can be excellent in alkali developability.

  Among them, the organic acid compound is preferably a compound represented by the following general formula (II) and / or the following general formula (III).

(In Formula (II) and 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, or an aryl group. A monovalent group represented by a 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 ′} each contain ^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 , a monovalent group represented by — [(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 , — [(CH ₂ ) _t —O] _u —R ^e or a monovalent group represented by —O—R ^{b ′} . 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 , or _- 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, a monovalent group represented by _{-CO-C (CH 3) =} CH 2 or _-CH 2 COOR ^{f, R f} is hydrogen or C It is an alkyl group of formula 1-5. In R ^a , R ^{a ′} , R ^b , R ^e and R ^f , each of the alkyl group, alkenyl group, aralkyl group and aryl group may have a substituent.
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. )

In the general formula (II), 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, or — [ CH (R ^c ) —CH (R ^d ) —O] _a —R ^e , — [(CH ₂ ) _b —O] c—R ^e or —O—R ^{a ″} , and R ^a and R ^{a ′} One of them contains a carbon atom, and when R ^a and R ^{a ′} have an aromatic ring, an appropriate substituent on the aromatic ring, for example, a linear or branched alkyl having 1 to 4 carbon atoms. It may have a group or the like.
The alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group is as shown by the R ^5.

  The alkenyl group having 2 to 18 carbon atoms may be linear, branched or cyclic. Examples of such alkenyl groups include vinyl groups, allyl groups, propenyl groups, various butenyl groups, various hexenyl groups, various octenyl groups, various decenyl groups, various dodecenyl groups, various tetradecenyl groups, various hexadecenyl groups, various octadecenyl groups, 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 there is a double bond at the terminal of the alkenyl group.

When R ^a and / or R ^{a ′} is —O—R ^{a ″} , it is an acidic phosphate ester. The 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, a monovalent group represented by — [CH (R ^c ) —CH (R ^d ) —O] _a —R ^e , or — [(CH ₂ ) _b —O] _c —R ^e is there.
The alkyl group having 1 to 18 carbon atoms, the aralkyl group, and the aryl group are as described above for R ⁵ , and the alkenyl group having 2 to 18 carbon atoms are as described above for R ^a and R ^{a ′.} It is. In addition, when R ^{a ″} has an aromatic ring, it may have an appropriate substituent on the aromatic ring, such as a linear or branched alkyl group having 1 to 4 carbon atoms.

R ^c and R ^d each independently represent a hydrogen atom or a methyl group. R ^e is a hydrogen atom or an optionally substituted alkyl group having 1 to 18 carbon atoms, alkenyl group having 2 to 18 carbon atoms, aralkyl group, aryl group, —CHO, —CH ₂ CHO, —CO It is a monovalent group represented by —CH═CH ₂ , —CO—C (CH ₃ ) ═CH ₂ , or —CH ₂ COOR ^f , and R ^f is a hydrogen atom or a straight chain having 1 to 5 carbon atoms. A branched or cyclic alkyl group.
In the monovalent group represented by R ^e, Examples of the substituent which may have, for example, linear 1 to 4 carbon atoms, 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 ⁵ , and the alkenyl group having 2 to 18 carbon atoms is as shown in the above R ^a and R ^{a ′.} .
In R ^a , R ^{a ′} and R ^{a ″} , s is an integer of 1 to 18, t is an integer of 1 to 5, u is an integer of 1 to 18. s is preferably an integer of 1 to 4, Preferably, it is an integer of 1-2, t is preferably an integer of 1-4, more preferably 2 or 3. u is preferably an integer of 1-4, more preferably an integer of 1-2. is there.

In the general formula (III), 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] a ^-R _e, - it shows a _{[(CH 2) b -O]} c -R e , or -O-R ^{b '.} In addition, when ^Rb 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.
The alkyl group having 1 to 18 carbon atoms, the aralkyl group, and the aryl group are as described above for R ⁵ , and the alkenyl group having 2 to 18 carbon atoms are as described above for R ^a and R ^{a ′.} It is.
When R ^b is —O—R ^b ′, it becomes an acidic sulfate. 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. Or a monovalent group represented by — [(CH ₂ ) _t —O] _u —R ^e .
The alkyl group having 1 to 18 carbon atoms, the aralkyl group, and the aryl group are as described above for R ⁵ , and the alkenyl group having 2 to 18 carbon atoms are as described above for R ^a and R ^{a ′.} It is. When R ^b ′ 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.
The above R ^c , R ^d and R ^e are the same as described above.
In said ^Rb and ^Rb ', s is an integer of 1-18, t is an integer of 1-5, u is an integer of 1-18. Preferred s, t, and u are the same as R ^a , R ^{a ′,} and R ^{a ″} above.

As the organic acid compound represented by the general formula (II), R ^a and R ^{a ′} in the general formula (II) 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 represents a hydrogen atom or a methyl group R ^e is preferable because it can be assumed that -CO-CH = CH ₂ or _{-CO-C (CH} 3) = one is CH ₂ and excellent pigment dispersibility.

In addition, as the organic acid compound represented by the general formula (III), R ^b in the general formula (III) may be a methyl group, an ethyl group, an aryl group which may have a substituent, an aralkyl group, or 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 ′} 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 is excellent in pigment dispersibility It is preferable because it can be used.

Of these, organic acid compound represented by the above general formula (II) and general formula ^{(III), 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 ′} , an aryl group or 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 (II), 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, organic acid compounds represented by the above general formula (II) and general formula (III) include carbon (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 a group, — [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.
From the viewpoint of pigment dispersibility, heat resistance, chemical resistance, and alkali resistance, a compound in which an aryl group is directly bonded to phosphorus (P) or sulfur (S) is particularly preferable, and R ^a and R ^a It is preferable that either R ^′ or R ^b is an aryl group which may have a substituent.

The organic acid compound represented by the above general formula (II) and general formula ^{(III), 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. It is preferable that -R ^e and R ^e is -CO-CH = CH ₂ or -CO-C (CH ₃ ) = CH ₂ , especially R ^a , R ^{a ′} and / or R ^{a ′. '} And / or R ^b and / or R ^b' are preferably vinyl, allyl, 2-methacryloyloxyethyl, or 2-acryloyloxyethyl.
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.

  The content of the organic acid compound in the salt-type graft copolymer used in the present invention is not particularly limited as long as good dispersion stability is exhibited, and is generally included in a monomer-derived constituent unit. It is about 0.1-2.0 molar equivalent with respect to an amino group, Preferably it is 0.2-1.5 molar equivalent, More preferably, it is 0.3-1.0 molar equivalent. In such a case, the pigment dispersibility and the pigment dispersion stability are excellent. In addition, when using together 2 or more types of the said organic acid compound, content which added these should just be in the said range.

In the pigment dispersion of the present invention and the negative resist composition for color filters, as described above, as the pigment dispersant, a monomer having an ethylenically unsaturated double bond and an amino group, a polymer chain and its terminal A graft copolymer containing, as a copolymerization component, a macromonomer composed of a group having an ethylenically unsaturated double bond, and the amino group of the nitrogen-containing monomer and an organic acid compound form a salt. A salt-type graft copolymer is used.
By using such a salt-type graft copolymer as a pigment dispersant, the color filter pigment dispersion of the present invention and the color filter negative resist composition have excellent pigment dispersion stability. be able to.

<Production of salt-type graft copolymer>
In the present invention, a method for producing a salt-type graft copolymer used as a pigment dispersant includes a macromolecule comprising the above-mentioned monomer having an amino group, a polymer chain and a group having an ethylenically unsaturated double bond at its terminal. The method is not particularly limited as long as it is a method that can produce a salt containing a monomer and an amino group of a nitrogen-containing monomer and an organic acid compound. In the present invention, for example, the monomer, the macromonomer, and, if necessary, other monomers can be graft-polymerized using a known polymerization means. Next, the salt-type graft copolymer can be produced by adding the organic acid compound to the solvent and stirring. In the above polymerization, additives generally used for polymerization such as a polymerization initiator and a chain transfer agent may be used.

In the pigment dispersion for a color filter and the negative resist composition for a color filter of the present invention, as the pigment dispersant, one type of the above-mentioned salt type graft copolymer may be used, or two or more types may be used in combination. The content may be appropriately selected according to the type of pigment used, the solid content concentration in the negative resist composition, and the like. In the pigment dispersion for a color filter and the negative resist composition for a color filter of the present invention, the pigment dispersant is usually in the range of 5 to 200 parts by mass with respect to 100 parts by mass of the pigment. It is preferable that it is a mass part, and it is more preferable that it is 20-80 mass parts. If the content of the salt-type graft copolymer is within the above range, the pigment can be uniformly dispersed. Further, in the resist composition, a colored layer having sufficient hardness can be formed without relatively reducing the blending ratio of the alkali-soluble resin and the polyfunctional monomer.
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. Also included are phthalimidoalkylated derivatives of CI Pigment Yellow 138.

(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 by using the solvent as described above usually at a ratio of 50 to 85% by mass with respect to the total amount of the pigment dispersion containing the solvent. Furthermore, it is preferable to prepare by using it in a proportion of 60 to 85% by mass. 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 salt-type block copolymer, and C.I. 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 substituted sulfo groups is preferably 1 to 2, and 1 is particularly preferable from the viewpoint that the pigment dispersibility can be improved efficiently.

  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 that 0.1-20 mass parts is contained with respect to 100 mass parts of pigment yellow 138. Among them, C.I. I. Pigment Yellow 138 is a sulfonic acid derivative. I. It is preferable to contain 0.5-15 mass parts with respect to 100 mass parts of pigment yellow 138, and also 1-10 mass parts. 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 process in the color filter manufacturing 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. As the sulfonamide group which is an amine salt of sulfonic acid, those represented by —SO ₂ NHR (where R is a monovalent organic group) are preferable. Examples of R include, for example, a dimethylaminopropyl group, diethylamino 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.
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 vibrating 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, and more preferably 0.05 to 1.0 mm.

  Specifically, pre-dispersion may be performed with 1.0 to 2.0 mm zirconia beads having a relatively large bead diameter, and the main dispersion may be performed with 0.03 to 0.1 mm zirconia beads having a relatively small bead diameter. Can be mentioned. Moreover, it is preferable to filter with a 0.1-5.0 micrometers membrane filter after dispersion | distribution.

In the present invention, the dispersion time for dispersion using a known disperser is appropriately adjusted and is not particularly limited.
In this way, 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 a color filter 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, wherein the pigment dispersant is an ethylenically unsaturated double bond And a monomer having an amino group and a macromonomer having a polymer chain and a group having an ethylenically unsaturated double bond at its terminal as a copolymerization component, and further comprising an ethylenically unsaturated group A graft copolymer in which at least a part of an amino group derived from a monomer having a double bond and an amino group and an organic acid compound form a salt; I. Pigment Yellow 138 imidoalkylated derivatives are C.I. I. It is characterized by containing 0.1 to 20 parts by mass with respect to 100 parts by mass of CI Pigment Yellow 138.

The negative resist composition for a color filter according to the present invention uses PY138 as a pigment, further combines a specific amount of a specific imide alkylated derivative of PY138, and further uses the specific pigment dispersant to perform a high-temperature heating step. Sometimes precipitation of pigment aggregates is suppressed, and a colored layer with high luminance and high contrast can be formed, and the developability is excellent.
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 included in the color filter pigment dispersion according to the present invention, C.I. I. Pigment Yellow 138, C.I. represented by Chemical Formula (1) above. 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. Although it does not specifically limit as alkali-soluble resin, 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 Chemical Co., Ltd.), itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, 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. It is usually in the range of 10 to 1000 parts by mass, preferably in the range of 20 to 500 parts by mass with respect to 100 parts by mass 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, dicyclopentanyl (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, Bifunctional (butanediol di (meth) acrylate, phthalic acid di (meth) acrylate, phosphoric acid di (meth) acrylate, zinc di (meth) acrylate) Data) acrylate and the like.

  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, tri (meth) acrylate phosphate, tris (acryloxyethyl) isocyanurate, tris (methacrylic) Roxyethyl) isocyanurate, dipentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetraacrylate, alkyl-modified dipentaerythritol La (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, for example, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, succinic acid modified products of pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipenta A succinic acid modified product of erythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like are preferably 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 mass, preferably 100 parts by mass of the alkali-soluble resin. Is in the range of 20 to 300 parts by mass. If the content of the polyfunctional monomer is less than the above range, the photocuring may not proceed sufficiently, and the exposed part may be eluted. 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) ) Halomethyloxadiazole compounds such as 1,3,4-oxadiazole, 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 can be mentioned. 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 mass, preferably 5 to 60 parts by mass with respect to 100 parts by mass 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 depending on 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.

  Examples of red pigments include 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.

  Among them, 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 according to the use and specifications 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 green pigments 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 the following chemical formula 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 ^g and R ^g ′ are independently OH, NH ₂ , NH—CN, acylamino or arylamino, and R ^h and R ^h ′ are independently —OH or — NH ₂ )

  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 the present invention, if necessary, other pigments other than the above pigments may be blended.
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 mass, more preferably 20 to 40% by mass, based on the total solid content of the negative resist composition. If the amount of the pigment is too small, there is a possibility that the transmission density when the negative resist composition is applied to a predetermined film thickness (usually 1.0 to 3.0 μm) may not be sufficient. 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 contained.
Further, the total content of the pigment dispersant is preferably in the range of 1 to 40% by mass, particularly in the range of 5 to 30% by mass, based on the total solid content of the negative resist composition. Preferably there is. If the content is less than 1% by mass relative to the total solid content of the negative resist composition, it may be difficult to uniformly disperse the pigment. If the content exceeds 40% by mass, , There is a risk of lowering curability and developability.
The total amount of the alkali-soluble resin, polyfunctional monomer, and photoinitiator is 15 to 89% by mass, preferably 25 to 80% by mass, 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 accurately formed. Usually, it is preferably in the range of 65 to 95% by mass, particularly preferably in the range of 75 to 88% by mass, 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)
The first method for producing the negative resist composition of the present invention comprises a monomer having an ethylenically unsaturated double bond and an amino group as a pigment dispersant, a polymer chain, and an ethylenically unsaturated double bond at its terminal. A graft copolymer containing as a copolymerization component a macromonomer containing a group having an organic group, and at least a part of an amino group derived from a monomer having an ethylenically unsaturated double bond and an amino group, and an organic acid compound A step of preparing a graft copolymer in which a salt is formed;
In the presence of the pigment dispersant in a solvent, C.I. I. Pigment Yellow 138 and C.I. represented by the above chemical formula (1). I. Preparing a pigment dispersion by dispersing an imide alkylated derivative of CI Pigment Yellow 138;
A step of mixing the pigment dispersion, an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator.
In addition, the second production method of the negative resist composition of the present invention comprises, as a pigment dispersant, a monomer having an ethylenically unsaturated double bond and an amino group, a polymer chain and an ethylenically unsaturated diester at the terminal. A graft copolymer containing, as a copolymerization component, a macromonomer containing a group having a heavy bond, and at least a part of an amino group derived from a monomer having an ethylenically unsaturated double bond and an amino group, and organic Preparing a graft copolymer in which an acid compound forms a salt;
In the presence of the pigment dispersant in a solvent, C.I. I. Pigment yellow 138 is dispersed to prepare a pigment dispersion;
The pigment dispersion and C.I. represented by the chemical formula (1). I. And a step of mixing an imide alkylated derivative of CI Pigment Yellow 138, an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator.

According to the method for producing a negative resist composition for a color filter of the present invention, since a pigment dispersion is produced and used in advance, the aggregation of the pigment can be effectively prevented and dispersed uniformly.
When preparing the red or green resist composition when the pigment dispersion according to the present invention is a yellow pigment dispersion, 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.

Further, according to the second production method, the imide alkylated derivative of a specific pigment capable of suppressing the precipitation of the pigment aggregate is not added at the time of pigment treatment or when the pigment is dispersed, Independently added to the color filter resin composition, the pigment dispersibility and dispersion stability are improved and high contrast is achieved while suppressing the precipitation of pigment aggregates after the high-temperature heating process of the color filter manufacturing process. Thus, a resin composition that achieves the requirement for conversion can be obtained.
In this case, since the imide alkylated derivative of the pigment is not added until the step of preparing the pigment dispersion, that is, the pigment treatment for preparing the pigment composition or the time of dispersing the pigment, the pigment dispersion Sometimes, the dispersibility and stability of the pigment can be improved by selecting an appropriate pigment dispersant or pigment derivative without weakening the polarity of the pigment surface.
Next, after preparing the finely divided pigment dispersion, when the imide alkylated derivative of the pigment is added, when the adsorption of the pigment dispersant is weakened by thermal motion in the high-temperature heating process, the pigment surface is relatively It is presumed that imide alkylated derivatives of pigments with strong adsorptive power may instead stabilize the pigment surface. As a result, it is possible to maintain the surface of the pigment in which the imide alkylated derivative of the pigment is finely dispersed, even at high temperatures, while maintaining the demand for higher contrast than in the past, while producing a color filter. 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 addition, in the said manufacturing method, since the process of preparing the said specific graft copolymer as a pigment dispersant and the process of preparing a pigment dispersion liquid may be the same as the above-mentioned, description here is abbreviate | omitted.

  In the second production method, the pigment dispersion and the C.I. I. The method of mixing the imide alkylated derivative of Pigment Yellow 138 is not particularly limited. For example, the binder component and the imide alkylated derivative may be mixed and blended in advance. Among them, it is preferable to have a step of preparing a pigment derivative solution in which the imide alkylated derivative is dissolved or dispersed in a solvent, and the pigment derivative solution prepared in the step is mixed with a pigment dispersion or a binder component. .

As a solvent for preparing the pigment derivative solution, the solubility (25 ° C.) of the imide alkylated derivative of the pigment is preferably 1 g / L or more, and more preferably 3 g / L or more.
On the other hand, the solvent for preparing the pigment derivative solution is preferably compatible with the solvent used for preparing the pigment dispersion, and the solvent for preparing the pigment derivative solution prepares the pigment dispersion. Therefore, the solubility (25 ° C.) of the solvent used for this purpose is preferably 100 g / L or more, and more preferably 500 g / L or more.

The method for dissolving or dispersing the imide alkylated derivative of the pigment in the solvent is not particularly limited. When the solubility in the solvent is high, it may be dissolved by mixing or heat treatment. On the other hand, when the solubility in the solvent is low, the pigment is dispersed by a pigment dispersion method using a pigment dispersant, other pigment derivatives, a pigment dispersion auxiliary resin, or the like as described in the step of preparing the pigment dispersion. It is preferable to dissolve or disperse the imide alkylated derivative in a solvent.

The pigment dispersion and, optionally, C.I. I. In the step of mixing an imide alkylated derivative of Pigment Yellow 138, an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator, at least the prepared pigment dispersion, and optionally the prepared pigment derivative. The solution and the binder component are mixed, but a solvent and, if necessary, other components may be further added and mixed.
The mixing method is not particularly limited.

Next, the color filter of the present invention will be described.
[Color filter]
The color filter of the present invention has a colored layer formed by curing the negative resist composition for a color filter of the present invention described above.
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.
In addition, 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, the solid content concentration, the viscosity, and the like of the negative resist composition for a color filter, 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 condition is appropriately selected depending on the blending ratio of each component in the negative resist composition for color filter 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 part 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. Method, 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 0.5 to 3.0 μm in the case where the black colorant is dispersed or dissolved in the binder resin. Set by degree.

(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.
Although the thickness of the said transparent substrate is not specifically limited, According to the use of the color filter of this invention, the thing of about 100 micrometers-1 mm can be used, for example.
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 drive 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 according to 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 reduced pressure, and are adhered 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.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.

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

(Production Example 2 Synthesis of yellow pigment imidoalkylated derivative B (PY138 tetrachlorophthalimidomethyl derivative))
After adding 5.14 parts by mass of paraformaldehyde and 34.27 parts by mass of 3,4,5,6-tetrachlorophthalimide to 338.67 parts by mass of fuming sulfuric acid of 3.6% by mass at 25 ° C., 30% at 50 ° C. Stir for minutes. Subsequently, 69.40 parts by mass of Pigment Yellow 138 was added and stirred at 100 ° C. for 3 hours. The reaction solution was added to 2400 parts by mass of ice water and stirred at 60 ° C. for 30 minutes, and then the precipitate was filtered. The obtained wet cake was washed three times with 1 L of hot water at 60 ° C. three times, vacuum-dried and pulverized, whereby one tetrachloronaphthalimide methyl group was substituted on Pigment Yellow 138, and represented by the following formula (n = 1). A yellow pigment imidoalkylated derivative B was obtained. The molecular weight of the target product was confirmed by TOF-MS.

(Production Example 3 Synthesis of yellow pigment imide alkylated derivative C (PY138 naphthalimidomethyl derivative))
After adding 5.14 parts by mass of paraformaldehyde and 23.72 parts by mass of naphthalimide to 338.67 parts by mass of 3.6% by mass of fuming sulfuric acid, the mixture was stirred at 50 ° C. for 30 minutes. Subsequently, 69.40 parts by mass of Pigment Yellow 138 was added and stirred at 100 ° C. for 3 hours. The reaction solution was added to 2400 parts by mass of ice water and stirred at 60 ° C. for 30 minutes, and then the precipitate was filtered. The obtained wet cake was washed 3 times with 1 L of warm water at 60 ° C. three times, vacuum dried, and pulverized, whereby one yellow naphthalimide group was substituted for Pigment Yellow 138, represented by the following formula (n = 1) Pigment imide alkylated derivative C was obtained. The molecular weight of the target product was confirmed by TOF-MS.

(Production Example 4 Synthesis of yellow pigment sulfonic acid derivative A (PY138 sulfonic acid derivative))
374.76 parts by mass of 11% by mass fuming sulfuric acid was stirred while being cooled to 10 ° C., and 74.96 parts by mass of Pigment Yellow 138 was added. Subsequently, it stirred at 90 degreeC for 6 hours. The reaction solution was added to 1600 parts by mass 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. and pulverized to obtain a yellow pigment sulfonic acid derivative A represented by the following formula (n = 1) in which one sulfonic acid group was substituted on Pigment Yellow 138. The molecular weight of the target product was confirmed by TOF-MS.

(Production Example 5 Synthesis of Binder Resin A)
A reactor equipped with a condenser, addition funnel, nitrogen inlet, mechanical stirrer, and digital thermometer was charged with 130 parts by mass of diethylene glycol ethyl methyl ether (EMDG) as a solvent, and the temperature was raised to 110 ° C. in a nitrogen atmosphere. Thereafter, 32 parts by mass of methyl methacrylate (MMA), 22 parts by mass of cyclohexyl methacrylate (CHMA), 24 parts by mass of methacrylic acid (MAA), 2 parts by mass of α, α′-azobisisobutyronitrile (AIBN) as an initiator And a mixture containing 4.5 parts by mass of n-dodecyl mercaptan as a chain transfer agent were continuously added dropwise over 1.5 hours.
Thereafter, the reaction was continued while maintaining the synthesis temperature, and 0.05 parts by mass of p-methoxyphenol was added as a polymerization inhibitor 2 hours after the completion of the dropping.
Next, 22 parts by mass of glycidyl methacrylate (GMA) was added while blowing air, the temperature was raised to 110 ° C., 0.2 parts by mass of triethylamine was added, and an addition reaction was carried out at 110 ° C. for 15 hours to obtain a binder. Resin A (solid content: 44% by mass) was obtained.
The obtained binder resin A had a mass average molecular weight of 8,500 and an acid value of 85 mgKOH / g. The mass 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 6 Synthesis of Macromonomer MM-1)
A reactor equipped with a condenser, addition funnel, nitrogen inlet, mechanical stirrer, and digital thermometer was charged with 80.0 parts by mass of propylene glycol monomethyl ether acetate (abbreviated as PGMEA), and the temperature was maintained while stirring under a nitrogen stream. Warmed to 90 ° C. Methyl methacrylate 50.0 parts by mass, methacrylate-n-butyl 30.0 parts by mass, benzyl methacrylate 20.0 parts by mass, mercaptoethanol 4.0 parts by mass, PGMEA 30 parts by mass, α, α'-azobisiso A mixed solution of 1.0 part by mass of butyronitrile (abbreviation AIBN) was added dropwise over 1.5 hours, and the reaction was further continued for 3 hours. Next, the nitrogen stream was stopped, the reaction solution was cooled to 80 ° C., 8.74 parts by mass of Karenz MOI (manufactured by Showa Denko KK), 0.125 g of dibutyltin dilaurate, and 0.15 g of p-methoxyphenol. 125 mass parts and 10 mass parts of PGMEA were added and it stirred for 3 hours, and the 49.5 mass% solution of macromonomer MM-1 was obtained. When the obtained macromonomer MM-1 was confirmed by GPC (gel permeation chromatography) under the conditions of N-methylpyrrolidone, 0.01 mol / L lithium bromide added / polystyrene standard, the mass average molecular weight (Mw 4010, number average molecular weight (Mn) 1910, molecular weight distribution (Mw / Mn) was 2.10. Tg calculated by the calculation of the macromonomer MM-1 is 64 ° C.

(Production Example 7 Synthesis of Macromonomer MM-2)
A reactor equipped with a condenser, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer was charged with 80.0 parts by mass of PGMEA and heated to 90 ° C. while stirring under a nitrogen stream. A mixed solution of 100.0 parts by mass of methyl methacrylate, 4.0 parts by mass of mercaptoethanol, 30 parts by mass of PGMEA, and 1.0 part by mass of AIBN was added dropwise over 1.5 hours, and the reaction was further performed for 3 hours. Next, the nitrogen stream was stopped, the reaction solution was cooled to 80 ° C., and Karenz MOI 8.74 parts by mass, dibutyltin dilaurate 0.125 g, p-methoxyphenol 0.125 parts by mass, and PGMEA 10 parts by mass, In addition, by stirring for 3 hours, a 49.8% by mass solution of macromonomer MM-2 was obtained. When the obtained macromonomer MM-2 was confirmed by GPC (gel permeation chromatography) under the conditions of N-methylpyrrolidone, 0.01 mol / L lithium bromide added / polystyrene standard, the mass average molecular weight (Mw 4130, number average molecular weight (Mn) 1940, molecular weight distribution (Mw / Mn) was 2.13. Tg calculated by calculation of the macromonomer MM-2 is 105 ° C.

(Production Example 8 Synthesis of Graft Copolymer GP-1)
A reactor equipped with a condenser, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer was charged with 85.0 parts by mass of PGMEA and heated to 85 ° C. while stirring under a nitrogen stream. 67.34 parts by mass of the macromonomer MM-1 solution of Production Example 6 (33.33 parts by mass of effective solid content), 16.67 parts by mass of 2- (dimethylamino) ethyl methacrylate (abbreviation DMA), n-dodecyl mercaptan 1 A mixed solution of 24 parts by mass, 20.0 parts by mass of PGMEA, and 0.5 parts by mass of AIBN was dropped over 1.5 hours, and after stirring for 3 hours, a mixed solution of AIBN 0.10 parts by mass and PGMEA 10.0 parts by mass Was added dropwise over 10 minutes, and further aged at the same temperature for 1 hour to obtain a 26.0% by mass solution of graft copolymer GP-1. As a result of GPC measurement, the obtained graft copolymer GP-1 had a mass average molecular weight (Mw) of 12420, a number average molecular weight (Mn) of 4980, and a molecular weight distribution (Mw / Mn) of 2.49. The amine value was 118 mgKOH / g.

(Production Example 9 Synthesis of Graft Copolymer GP-2)
A reactor equipped with a condenser, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer was charged with 85.0 parts by mass of PGMEA and heated to 85 ° C. while stirring under a nitrogen stream. 66.93 parts by mass of macromonomer MM-2 solution of Production Example 7 (effective solid content 33.33 parts by mass), DMA 16.67 parts by mass, n-dodecyl mercaptan 1.24 parts by mass, PGMEA 20.0 parts by mass, AIBN 0. After 5 parts by mass of the mixed solution was added dropwise over 1.5 hours and heated and stirred for 3 hours, a mixed solution of AIBN 0.10 parts by mass and PGMEA 10.0 parts by mass was added dropwise over 10 minutes. By aging for a time, a 26.2 mass% solution of graft copolymer GP-2 was obtained. As a result of GPC measurement, the obtained graft copolymer GP-2 had a mass average molecular weight (Mw) of 11320, a number average molecular weight (Mn) of 4460, and a molecular weight distribution (Mw / Mn) of 2.54. The amine value was 120 mgKOH / g.

(Production Example 10 Synthesis of Graft Copolymer GP-3)
A reactor equipped with a condenser, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer was charged with 85.0 parts by mass of PGMEA and heated to 85 ° C. while stirring under a nitrogen stream. 44.89 parts by mass of macromonomer MM-1 solution of Production Example 6 (22.22 parts by mass of effective solid content), 15.87 parts by mass of Plaxel FA-10L (Tg = -60 ° C.) (hydroxyethyl manufactured by Daicel Chemical Industries, Ltd.) 70% solution of caprolactone to acrylate 70% solution effective solid content 11.11 parts by mass), DMA 16.67 parts by mass, n-dodecyl mercaptan 1.24 parts by mass, PGMEA 30.0 parts by mass, AIBN 0.5 parts by mass After dripping over 1.5 hours and heating and stirring for 3 hours, a mixed solution of AIBN 0.10 parts by mass and PGMEA 10.0 parts by mass was added dropwise over 10 minutes, and further aging at the same temperature for 1 hour, A 26.8 mass% solution of copolymer GP-3 was obtained. As a result of GPC measurement, the obtained graft copolymer GP-3 had a mass average molecular weight (Mw) of 12810, a number average molecular weight (Mn) of 4980, and a molecular weight distribution (Mw / Mn) of 2.57. The amine value was 121 mgKOH / g.

(Production Example 11 Preparation of Dispersant Solution A)
In a 225 mL mayonnaise bottle, 31.25 parts by mass of PGMEA and 65.88 parts by mass of the graft copolymer GP-1 solution of Production Example 8 (17.13 parts by mass of effective solid content) were dissolved, respectively, and phenylphosphonic acid (trade name) : PPA, manufactured by Nissan Chemical Co., Ltd.) 2.87 parts by mass (0.5 molar equivalent to the tertiary amino group of the graft copolymer GP-1) was added, and the mixture was stirred at room temperature for 30 minutes, thereby dispersing agent solution A. (20% solid content) was prepared. The acid value of the resulting dispersant solution A was 101 mgKOH / g.
At this time, the amino group of the graft copolymer GP-1 is salt-formed by an acid / base reaction with the phosphonic acid group of PPA.

(Production Example 12 Preparation of Dispersant Solution B)
In a 225 mL mayonnaise bottle, 30.53 parts by mass of PGMEA and 66.85 parts by mass of the graft copolymer GP-1 solution of Production Example 8 (effective solid content of 17.38 parts by mass) were dissolved, respectively, and phenylphosphinic acid (Tokyo Kasei) 2.62 parts by mass (0.5 molar equivalent based on the tertiary amino group of the graft copolymer GP-1) was added, and the mixture was stirred at room temperature for 30 minutes, whereby the dispersant solution B (solid content 20%) ) Was prepared. The acid value of Dispersant Solution B obtained was 52 mgKOH / g.
At this time, the amino group of the graft copolymer GP-1 is salt-formed by an acid / base reaction with the phosphinic acid group of phenylphosphinic acid.

(Production Example 13 Preparation of Dispersant Solution C)
In a 225 mL mayonnaise bottle, 31.75 parts by mass of PGMEA and 65.38 parts by mass of the graft copolymer GP-2 solution of Production Example 9 (effective solid content of 17.13 parts by mass) were dissolved, respectively, and phenylphosphonic acid (trade name) : PPA, manufactured by Nissan Chemical Co., Ltd.) 2.87 parts by mass (0.5 molar equivalent based on the tertiary amino group of the graft copolymer GP-2) is added, and the mixture is stirred at room temperature for 30 minutes, thereby dispersing agent solution C. (20% solid content) was prepared. The acid value of Dispersant Solution C obtained was 99 mgKOH / g.
At this time, the amino group of the graft copolymer GP-2 is salt-formed by an acid / base reaction with the phosphonic acid group of PPA.

(Production Example 14 Preparation of Dispersant Solution D)
In a 225 mL mayonnaise bottle, 33.21 parts by mass of PGMEA and 63.92 parts by mass of the graft copolymer GP-3 solution of Production Example 10 (17.13 parts by mass of effective solid content) were dissolved, and 2.87 parts by mass of PPA ( Dispersant solution D (solid content 20%) was prepared by adding 0.5 molar equivalent) to the tertiary amino group of graft copolymer GP-3 and stirring at room temperature for 30 minutes. The acid value of the resulting dispersant solution D was 100 mgKOH / g.
At this time, the amino group of the graft copolymer GP-3 is salt-formed by an acid / base reaction with the phosphonic acid group of PPA.

(Production Example 15 Preparation of Dispersant Solution E)
In a 200 mL flask equipped with a condenser, 29.82 parts by mass of PGMEA and 67.81 parts by mass of the graft copolymer GP-1 solution of Production Example 8 (effective solid content of 17.63 parts by mass) were dissolved, respectively. (Kanto Chemical Co., Inc.) 2.37 parts by mass (0.5 molar equivalent to the tertiary amino group of the graft copolymer) was added, and the mixture was reacted at 80 ° C. for 6 hours. %) Was prepared. The acid value of the obtained dispersant solution E was 0 mgKOH / g.
At this time, the amino group of the graft copolymer GP-1 is salt-formed by a quaternization reaction with benzyl chloride.

Example 1
(1) Preparation of PY138 pigment dispersion A 25.0 parts by mass of the dispersant solution A prepared in Production Example 11, 6.82 parts by mass of binder resin A of Production Example 5, 58.18 parts by mass of PGMEA, and C.I as a coloring material component 9.2 parts by mass of Pigment Yellow 138 (PY138: average primary particle size 10 to 40 nm), 0.3 parts by mass of yellow pigment imide alkylated derivative A (PY138 phthalimidomethyl derivative) of Production Example 1, yellow pigment of Production Example 4 0.5 parts by mass of sulfonic acid derivative A (PY138 sulfonic acid derivative) is mixed, and pre-dispersed with a paint shaker (manufactured by Asada Tekko) for 1 hour with 2 mm zirconia beads and further with 0.1 mm zirconia beads as main dispersion. Dispersion with time gave PY138 pigment dispersion A.

(2) Preparation of Yellow Negative Resist Composition A for Color Filter 53.33 parts by mass of PY138 pigment dispersion A obtained in (1) above, 42.67 parts by mass of the following binder composition A, 4.000 parts by mass of PGMEA, interface 0.04 parts by mass of activator R08MH (manufactured by DIC) and 0.4 parts by mass of silane coupling agent KBM503 (manufactured by Shin-Etsu Silicone) are added and mixed, and pressure filtration is performed to obtain a yellow negative resist composition A for color filters. Got.
<Binder composition A (solid content 15%)>
Alkali-soluble resin (Binder resin A of Production Example 5, solid content 44% by mass): 8.18 parts by mass 3-4 functional acrylate monomer (trade name: Aronix M305, manufactured by Toagosei Co., Ltd.): 8.4 parts by mass Photopolymerization initiator: 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name: Irgacure 907, manufactured by BASF)): 0.82 parts by mass Polymerization initiator: 2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole (trade name: biimidazole, manufactured by Kurokin Kasei Co., Ltd.) : 1.64 parts by mass. Photopolymerization initiator: 2-mercaptobenzothiazole (manufactured by Tokyo Chemical Industry Co., Ltd.): 0.26 parts by mass. Photosensitizer: 2,4 diethylthioxanthone (trade name: Kayacure DETX-S, Japan. (Made by Kayaku Co., Ltd.): 0.28 Mass parts / Solvent: Propylene glycol monomethyl ether acetate (PGMEA): 80.42 parts by mass

(Example 2)
(1) Preparation of PY138 Pigment Dispersion B In Example 1 (1), 9.7 parts by mass of CI Pigment Yellow 138 as a colorant component, Yellow Pigment Imide Alkylated Derivative A (PY138 Phthalimide Methyl) of Production Example 1 Derivative) PY138 pigment dispersion B was prepared in the same manner as in Example 1 (1) except that the yellow pigment sulfonic acid derivative A of Production Example 4 was not used as 0.3 part by mass.

(2) Preparation of yellow negative resist composition B for color filter In Example 1 (2), PY138 pigment dispersion B obtained in (1) above was used instead of PY138 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 PY138 Pigment Dispersion C In Example 1 (1), except that Dispersant Solution A prepared in Production Example 12 was used instead of Dispersant Solution A in Production Example 11, Example 2 was used. PY138 pigment dispersion C was prepared in the same manner as 1 (1).

(2) Preparation of Yellow Negative Resist Composition C for Color Filter In Example 1 (2), PY138 pigment dispersion C obtained in (1) above was used instead of PY138 pigment dispersion A. In the same manner as in Example 1 (2), a yellow negative resist composition C for color filters was obtained.

Example 4
(1) Preparation of PY138 Pigment Dispersion D In Example 1 (1), 9.2 parts by mass of CI Pigment Yellow 138 as a colorant component, Yellow Pigment Imide Alkylated Derivative B (PY138 Tetrachloro of Production Example 2) PY138 pigment dispersion in the same manner as in Example 1 (1) except that 0.3 parts by mass of phthalimidomethyl derivative) and 0.5 parts by mass of yellow pigment sulfonic acid derivative A (PY138 sulfonic acid derivative) of Production Example 4 were used. Liquid D was prepared.

(2) Preparation of yellow negative resist composition D for color filter In Example 1 (2), PY138 pigment dispersion D obtained in (1) above was used instead of PY138 pigment dispersion A. In the same manner as in Example 1 (2), a yellow negative resist composition D for color filters was obtained.

(Example 5)
(1) Preparation of PY138 Pigment Dispersion E In Example 1 (1), 9.2 parts by mass of CI Pigment Yellow 138 as a colorant component, Yellow Pigment Imidalkylated Derivative C of Production Example 3 (PY138 Naphthalimide) PY138 pigment dispersion in the same manner as in Example 1 (1) except that 0.3 part by weight of methyl derivative) and 0.5 part by weight of yellow pigment sulfonic acid derivative A (PY138 sulfonic acid derivative) of Production Example 4 were used. E was prepared.

(2) Preparation of yellow negative resist composition E for color filter In Example 1 (2), PY138 pigment dispersion E obtained in (1) above was used instead of PY138 pigment dispersion A. In the same manner as in Example 1 (2), a yellow negative resist composition E for color filters was obtained.

(Example 6)
(1) Preparation of PY138 Pigment Dispersion F F Example 1 (1), except that Dispersant Solution A prepared in Production Example 13 was used instead of Dispersant Solution A in Production Example 11, except that the amount was 25.0 parts by mass. PY138 pigment dispersion F was prepared in the same manner as 1 (1).

(2) Preparation of yellow negative resist composition F for color filter In Example 1 (2), PY138 pigment dispersion F obtained in (1) above was used instead of PY138 pigment dispersion A. Then, a yellow negative resist composition F for color filters was obtained in the same manner as in Example 1 (2).

(Example 7)
(1) Preparation of PY138 pigment dispersion G Example 1 (1), except that the dispersant solution D prepared in Production Example 14 was replaced by 25.0 parts by mass instead of the dispersant solution A in Production Example 11. PY138 pigment dispersion G was prepared in the same manner as 1 (1).

(2) Preparation of yellow negative resist composition G for color filter In Example 1 (2), PY138 pigment dispersion G obtained in (1) above was used instead of PY138 pigment dispersion A. In the same manner as in Example 1 (2), a yellow negative resist composition G for color filters was obtained.

(Comparative Example 1)
(1) Preparation of PY138 Pigment Dispersion Liquid H In Example 1 (1), 9.5 parts by mass of CI Pigment Yellow 138 as a colorant component, Yellow Pigment Sulfonate Derivative A (PY138 Sulfonate Derivative) of Production Example 4 ) PY138 pigment dispersion H was prepared in the same manner as in Example 1 (1) except that the yellow pigment imide alkylated derivative was not used as 0.5 part by mass.

(2) Preparation of yellow negative resist composition H for color filter Except that PY138 pigment dispersion H obtained in (1) above was used instead of PY138 pigment dispersion A in Example 1 (2). In the same manner as in Example 1 (2), a yellow negative resist composition H for color filters was obtained.

(Comparative Example 2)
(1) Preparation of PY138 Pigment Dispersion I In Example 1 (1), yellow pigment imide alkylated derivative and yellow pigment sulfonic acid derivative were used as 10.0 parts by mass of CI Pigment Yellow 138 as a color material component. A PY138 pigment dispersion I was prepared in the same manner as in Example 1 (1) except that there was not.

(2) Preparation of yellow negative resist composition I for color filter In Example 1 (2), instead of PY138 pigment dispersion A, PY138 pigment dispersion I obtained in (1) above was used. In the same manner as in Example 1 (2), a yellow negative resist composition I for color filters was obtained.

(Comparative Example 3)
(1) Preparation of PY138 Pigment Dispersion Liquid J In Example 1 (1), 10.0 parts by mass of CI Pigment Yellow 138 was used as a color material component, and a yellow pigment imide alkylated derivative and a yellow pigment sulfonic acid derivative were used. First, PY138 pigment dispersion J was prepared in the same manner as in Example 1 (1) except that the dispersion time was 4 hours.

(2) Preparation of Yellow Negative Resist Composition J for Color Filter In Example 1 (2), instead of PY138 pigment dispersion A, PY138 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 4)
(1) Preparation of PY138 Pigment Dispersion Liquid K In Example 1 (1), 9.5 parts by mass of CI Pigment Yellow 138 as a color material component, Yellow Pigment Sulfonate Derivative A (PY138 Sulfonate Derivative) of Production Example 4 ) Implementation was performed except that 0.5 parts by mass and 19.23 parts by mass of the graft copolymer GP-1 prepared in Production Example 8 instead of the dispersant solution A of Production Example 11 and 63.95 parts by mass of PGMEA were used. PY138 pigment dispersion K was prepared in the same manner as in Example 1 (1).

(2) Preparation of Yellow Negative Resist Composition K for Color Filter In Example 1 (2), PY138 pigment dispersion K obtained in (1) above was used instead of PY138 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 5)
(1) Preparation of PY138 Pigment Dispersion L In Example 1 (1), 9.5 parts by mass of CI Pigment Yellow 138 as a color material component, Yellow Pigment Sulfonate Derivative A (PY138 Sulfonate Derivative) of Production Example 4 ) PY138 pigment dispersion in the same manner as in Example 1 (1) except that 0.5 part by mass and the dispersant solution E25 prepared in Production Example 15 instead of Dispersant Solution A in Production Example 11 were used. Liquid L was prepared.

(2) Preparation of Yellow Negative Resist Composition L for Color Filter In Example 1 (2), PY138 pigment dispersion L obtained in (1) above was used instead of PY138 pigment dispersion A. In the same manner as in Example 1 (2), a yellow negative resist composition L for color filters was obtained.

(Comparative Example 6)
(1) Preparation of PY138 Pigment Dispersion M In Example 1 (1), 9.5 parts by mass of CI Pigment Yellow 138 as a color material component, Yellow Pigment Sulfonate Derivative A (PY138 Sulfonate Derivative) of Production Example 4 ) 0.5 parts by mass, and instead of the dispersant solution A in Production Example 11, 5.00 parts by mass, PGMEA 78.18, commercially available dispersant “Ajisper PB821” (manufactured by Ajinomoto Fine Techno Co., Ltd., solid content concentration 100% by mass) A PY138 pigment dispersion M was prepared in the same manner as in Example 1 (1) except that the amount was changed to parts by mass.

(2) Preparation of yellow negative resist composition M for color filter In Example 1 (2), instead of PY138 pigment dispersion A, PY138 pigment dispersion M obtained in (1) above was used. Then, a yellow negative resist composition M for color filters was obtained in the same manner as in Example 1 (2).

(Comparative Example 7)
(1) Preparation of PY138 Pigment Dispersion N In Example 1 (1), 9.5 parts by mass of CI Pigment Yellow 138 as a color material component, Yellow Pigment Sulfonate Derivative A (PY138 Sulfonate Derivative) of Production Example 4 ) 0.5 parts by mass, Dispersant solution A was a commercially available dispersant “BYK-LPN6919” (by Big Chemie, solid content concentration 60% by mass), 8.33 parts by mass, and PGMEA was 74.85 parts by mass. Prepared PY138 pigment dispersion N in the same manner as in Example 1 (1).

(2) Preparation of yellow negative resist composition N for color filter In Example 1 (2), PY138 pigment dispersion N obtained in (1) above was used instead of PY138 pigment dispersion A. In the same manner as in Example 1 (2), a yellow negative resist composition N for color filters was obtained.

(Example 8)
(1) Preparation of PY138 phthalimidomethyl derivative dispersion A 3.00 parts by mass of yellow pigment imide alkylated derivative A (PY138 phthalimidomethyl derivative) of Production Example 1, “Disperbyk2000” (manufactured by BYK Chemie, solid content concentration) 40 mass%) 6.00 mass parts, 72.08 mass parts of PGMEA, and 18.92 mass parts of propylene glycol monomethyl ether were mixed and pre-dispersed with a paint shaker (manufactured by Asada Tekko Co., Ltd.) with 2 mm zirconia beads for 1 hour. Further, this dispersion was dispersed with 0.1 mm zirconia beads for 3 hours to obtain PY138 phthalimidomethyl derivative dispersion liquid A.

(2) Preparation of yellow negative resist composition O for color filter To 97 parts by mass of PY138 pigment dispersion H obtained in Comparative Example 1 (1), PY138 phthalimidomethyl derivative dispersion A obtained in (1) above PY138 pigment dispersion O was prepared by adding and mixing 10 parts by mass.
Yellow negative type for color filter is obtained by mixing 57.07 parts by mass of PY138 pigment dispersion O obtained above, 42.67 parts by mass of binder composition A and 0.26 parts by mass of PGMEA, and performing pressure filtration. Resist composition O was obtained.

(Evaluation)
<Pigment dispersion stability>
As an evaluation of the pigment dispersion stability, the PY138 pigment dispersion obtained in each Example and Comparative Example was allowed to stand at 40 ° C. for 1 week, and the average particle size of the pigment particles in the pigment dispersion before and after the standing was determined. The shear viscosity was measured. To measure the average particle size, use “Nanotrack particle size distribution meter UPA-EX150” manufactured by Nikkiso Co., Ltd., and to measure the viscosity, use the “Rheometer MCR301” manufactured by Anton Paar, and measure the shear viscosity when the shear rate is 60 rpm. It was measured.
The results are shown in Table 1.

<Optical performance (chromaticity, brightness, contrast)>
The yellow negative resist composition for color filter obtained in each Example and Comparative Example was applied on a 0.7 mm-thick glass substrate ("OA-10G" manufactured by Nippon Electric Glass Co., Ltd.) using a spin coater. did. 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 30 mJ / cm ² using an ultrahigh pressure mercury lamp. The film thickness after drying and curing was adjusted so that the target chromaticity x = 0.420. The glass plate on which the colored layer was formed was post-baked in a clean oven at 230 ° C. for 30 minutes, and the contrast, chromaticity (x, y) and luminance (Y) before and after post-baking of the obtained 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 “Microspectral light measuring device OSP-SP200” manufactured by Olympus Corporation.
The results are shown in Table 2.

<Solvent resistance>
The yellow colored substrate obtained by the above (optical performance) evaluation was immersed in N-methylpyrrolidone (NMP) at room temperature for 30 minutes, washed with pure water, and then the color difference (ΔEab) before and after the NMP immersion was measured. The results are shown in Table 2.

<Alkali developability>
The yellow negative resist composition for color filters obtained in 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 30 mJ / cm ² through a photomask using an ultrahigh pressure mercury lamp. Thereafter, the glass plate on which the colored layer has been formed is shower-developed using a 0.05% by weight aqueous potassium hydroxide solution as an alkaline developer, and the time until the glass surface where the colored layer is formed appears is developed. Measured as time. The results are shown in Table 2.

<Heat resistance>
The yellow colored substrate obtained by the above (alkali developability) evaluation was post-baked for 30 minutes 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 results are shown in Table 2. As examples, photographs of the heat resistance evaluation results at 260 ° C. of Example 1, Example 2, Comparative Example 1, and Comparative Example 2 are shown in FIGS.
(Evaluation criteria)
○: No precipitation ×: Precipitation on the coating surface XX: Precipitation on the entire coating surface

<Alkali resistance>
The yellow negative resist composition for color filters obtained in 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 30 mJ / cm ² using a super high pressure mercury lamp through a photomask on which a stripe pattern having a line and space of 80 μm was drawn. Thereafter, the glass plate on which the colored layer was formed was shower-developed for 60 seconds using a 0.05% by weight aqueous potassium hydroxide solution as an alkaline developer, and further washed with ultrapure water for 60 seconds. Post-baked in a clean oven for 30 minutes. If development was not possible in 60 seconds, shower development was performed until development was possible.
The obtained glass substrate on which the colored pattern was formed was immersed in a 5.0% by mass aqueous sodium hydroxide solution maintained at 40 ° C., and the time until the colored pattern peeled from the glass substrate was measured.
The results are shown in Table 2.

(Production Example 16 Preparation of PY150 pigment dispersion)
26.00 parts by mass of dispersant solution A prepared in Production Example 11, 11.82 parts by mass of binder resin A in Production Example 5, 49.18 parts by mass of PGMEA, and CI Pigment Yellow 150 (PY150: average primary particle as a coloring material component) 13.0 parts by mass) (with a diameter of 10 to 50 nm) was mixed, and dispersed with a paint shaker (manufactured by Asada Tekko Co., Ltd.) as a pre-dispersion for 1 hour with 2 mm zirconia beads, and further dispersed with 0.1 mm zirconia beads for 4 hours, and PY150 A pigment dispersion was obtained.

(Production Example 17 Preparation of PG58 pigment dispersion)
22.75 parts by mass of the dispersant solution A prepared in Production Example 11, 10.34 parts by mass of Binder Resin A in Production Example 5, 53.91 parts by mass of PGMEA, and CI Pigment Green 58 (PG58: average primary particle as a coloring material component) 13.0 parts by mass) (with a diameter of 10 to 50 nm) was mixed, and dispersed with a paint shaker (manufactured by Asada Tekko Co., Ltd.) as a pre-dispersion for 1 hour with 2 mm zirconia beads and further dispersed with 0.1 mm zirconia beads for 4 hours as PG58. A pigment dispersion was obtained.

(Production Example 18 Preparation of PR254 pigment dispersion)
20.00 parts by mass of the dispersant solution A prepared in Production Example 11, 9.09 parts by mass of binder resin A in Production Example 5, 60.91 parts by mass of PGMEA, and CI Pigment Red 254 (PR254: average primary particle as a colorant component) 10.0 parts by mass (diameter: 10 to 50 nm) were mixed, and dispersed in a paint shaker (manufactured by Asada Tekko Co., Ltd.) as a preliminary dispersion with 2 mm zirconia beads for 1 hour and further as a main dispersion with 0.1 mm zirconia beads for 4 hours, and PR254 A pigment dispersion was obtained.

(Production Example 19 Preparation of PY139 pigment dispersion)
Dispersant solution A prepared in Production Example 11 (20.00 parts by mass), binder resin A (Production Example 5) 5.45 parts by mass, PGMEA 66.55 parts by mass, CI Pigment Yellow 139 (PY139: average primary particle as a colorant component) 8.0 parts by mass (diameter: 10 to 50 nm) was mixed, and dispersed with a paint shaker (manufactured by Asada Tekko Co., Ltd.) as a pre-dispersion for 1 hour with 2 mm zirconia beads, and further dispersed with 0.1 mm zirconia beads for 16 hours, and PY139 A pigment dispersion was obtained.

Example 9 Preparation of Green Negative Resist Composition A for Color Filter
28.69 parts by mass of PY138 pigment dispersion A obtained in Example 1, 26.97 parts by mass of PG58 pigment dispersion obtained in Production Example 17, 39.17 parts by mass of the binder composition A, 5.17 parts by mass of PGMEA, Surfactant R08MH (manufactured by DIC) 0.04 parts by mass and silane coupling agent KBM503 (manufactured by Shin-Etsu Silicone) 0.4 parts by mass are added and mixed, followed by pressure filtration, and a green negative resist composition for color filters. A was obtained.

Example 10 Preparation of Green Negative Resist Composition B for Color Filter
In Example 9, a green negative resist composition B for color filters was used in the same manner as in Example 9 except that the PY138 pigment dispersion B obtained in Example 2 was used instead of the PY138 pigment dispersion A. Got.

(Comparative Examples 8 to 10 Preparation of green negative resist compositions C to E for color filters)
In Example 9, instead of PY138 pigment dispersion A, a green negative type for color filter was used in the same manner as in Example 9 except that PY138 pigment dispersions H to J obtained in Comparative Examples 1 to 3 were used. Resist compositions C to E were obtained.

(Comparative Example 11 Preparation of Green Negative Resist Composition F for Color Filter)
15.69 parts by mass of the PY150 pigment dispersion obtained in Production Example 16, 33.35 parts by mass of the PG58 pigment dispersion obtained in Production Example 17, 39.72 parts by mass of the binder composition A, 11.24 parts by mass of PGMEA, Surfactant R08MH (manufactured by DIC) 0.04 parts by mass and silane coupling agent KBM503 (manufactured by Shin-Etsu Silicone) 0.4 parts by mass are added and mixed, followed by pressure filtration, and a green negative resist composition for color filters. F was obtained.

(Evaluation results)
<Optical performance (chromaticity, brightness, contrast)>
Except for using the green negative resist compositions for color filters obtained in Examples 9 to 10 and Comparative Examples 8 to 11, the film thickness after drying and curing was adjusted to the target chromaticity y = 0.590. The chromaticity, luminance and contrast were evaluated in the same manner as in Examples 1 to 8 and Comparative Examples 1 to 7.
The results are shown in Table 3.

<Heat resistance>
Using the green negative resist compositions for color filters obtained in Examples 9 to 10 and Comparative Examples 8 to 11, heat resistance was evaluated in the same manner as in Examples 1 to 8 and Comparative Examples 1 to 7. It was.
The results are shown in Table 3.

Example 11 Preparation of Red Negative Resist Composition A for Color Filter
10.55 parts by mass of PY138 pigment dispersion A obtained in Example 1, 42.21 parts by mass of PR254 pigment dispersion obtained in Production Example 18, 18.76 parts by mass of the following binder composition B, 28.48 parts by mass of PGMEA, Surfactant R08MH (manufactured by DIC) 0.04 parts by mass and silane coupling agent KBM503 (manufactured by Shin-Etsu Silicone) 0.4 parts by mass are added and mixed, filtered under pressure, and a red negative resist composition for color filters. A was obtained.

<Binder composition B (solid content 40%)>
Alkali-soluble resin (Binder resin A of Production Example 5, solid content 44% by mass): 23.18 parts by mass 3 to 4 functional acrylate monomer (trade name: Aronix M305, manufactured by Toagosei Co., Ltd.): 23.80 Mass parts / photopolymerization initiator (2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name: Irgacure 907, manufactured by Ciba Specialty Chemicals)) : 1.80 parts by mass-photopolymerization initiator (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone (trade name Irgacure 369, manufactured by Ciba Specialty Chemicals) ): 4.2 parts by mass / solvent (PGMEA): 47.02 parts by mass

(Comparative Example 12 Preparation of Red Negative Resist Composition B for Color Filter)
In Example 11, a red negative resist composition B for color filters was used in the same manner as in Example 11 except that the PY138 pigment dispersion H obtained in Comparative Example 1 was used instead of the PY138 pigment dispersion A. Got.

(Comparative Example 13 Preparation of Red Negative Resist Composition C for Color Filter)
PY150 pigment dispersion obtained in Production Example 16 6.09 parts by mass, PR254 pigment dispersion obtained in Production Example 18 44.84 parts by mass, the following binder composition B 18.76 parts by mass, PGMEA 30.31 parts by mass, Surfactant R08MH (manufactured by DIC) 0.04 parts by mass and silane coupling agent KBM503 (manufactured by Shin-Etsu Silicone) 0.4 parts by mass are added and mixed, filtered under pressure, and a red negative resist composition for color filters. C was obtained.

Example 12 Preparation of Yellow Negative Resist Composition P for Color Filter
37.46 parts by mass of PY138 pigment dispersion A obtained in Example 1, 8.26 parts by mass of PY139 pigment dispersion obtained in Production Example 19, 22.67 parts by mass of the binder composition B, 31.61 parts by mass of PGMEA, Surfactant R08MH (manufactured by DIC) 0.04 parts by mass and silane coupling agent KBM503 (manufactured by Shin-Etsu Silicone) 0.4 parts by mass are added and mixed and subjected to pressure filtration to provide a yellow negative resist composition for color filters. P was obtained.

(Comparative Example 14 Preparation of Yellow Negative Resist Composition Q for Color Filter)
In Example 12, a yellow negative resist composition Q for color filters was used in the same manner as in Example 12 except that the PY138 pigment dispersion H obtained in Comparative Example 1 was used instead of the PY138 pigment dispersion A. Got.

(Comparative Example 15 Preparation of Yellow Negative Resist Composition R for Color Filter)
30.51 parts by mass of PY150 pigment dispersion obtained in Production Example 16, 5.51 parts by mass of PY139 pigment dispersion obtained in Production Example 19, 22.67 parts by mass of the following binder composition B, 41.31 parts by mass of PGMEA, Surfactant R08MH (manufactured by DIC) 0.04 parts by mass and silane coupling agent KBM503 (manufactured by Shin-Etsu Silicone) 0.4 parts by mass are added and mixed and subjected to pressure filtration to provide a yellow negative resist composition for color filters. R was obtained.

<Optical performance (chromaticity, brightness, contrast)>
Using the red and yellow negative resist compositions for color filters obtained in Examples 11 to 12 and Comparative Examples 12 to 15, the film thickness after dry curing is the target chromaticity is red: x = 0.650, yellow : Chromaticity, luminance, and contrast were evaluated in the same manner as in Examples 1 to 8 and Comparative Examples 1 to 7 except that x was adjusted to 0.445. The results are shown in Tables 4-5.

<Heat resistance>
Using the red and yellow negative resist compositions for color filters obtained in Examples 11-12 and Comparative Examples 12-15, the heat resistance was evaluated in the same manner as in Examples 1-8 and Comparative Examples 1-7. Went. The results are shown in Tables 4-5.

[Summary of results]
C. I. Pigment yellow 138, C.I. I. The yellow pigment dispersions of Examples 1 to 8 using a combination of the imide alkylated derivative of Pigment Yellow 138 and the specific salt-type graft copolymer had good dispersibility and dispersion stability. In addition, the negative resist compositions of Examples 1 to 8 using the pigment dispersion suppressed the precipitation of pigment aggregates during the high-temperature heating process, had high contrast retention after the high-temperature heating process, high brightness, A high-contrast colored layer could be formed, and a colored layer excellent in developability could be formed. The colored layer was further excellent in solvent resistance and alkali resistance.
Furthermore, C.I. I. The negative resist compositions of Examples 1 and 3 to 7 using a combination of Pigment Yellow 138 sulfonic acid derivatives are C.I. I. Compared to Example 2 in which no sulfonic acid derivative of Pigment Yellow 138 was used, the contrast was higher.
Further, among the examples, C.I. I. C.I. Pigment Yellow 138 pigment dispersion I. C.I. is not coexisting with the imide alkylated derivative of CI Pigment Yellow 138; I. It was revealed that Example 8, in which an imide alkylated derivative of Pigment Yellow 138 was added later, further improved the contrast.

C. I. In the negative resist compositions of Comparative Examples 1 and 2 and Comparative Examples 4 to 7 in which no imide alkylated derivative of Pigment Yellow 138 was used, pigment aggregates were precipitated, and the contrast after post-baking deteriorated. In particular, it was found that when a commercially available dispersant was used, the contrast deteriorated after post-baking. When the dispersion time is as short as in the conventional case as in Comparative Example 3, C.I. I. Even if the imide alkylated derivative of CI Pigment Yellow 138 was not used, the pigment aggregate did not precipitate, but the contrast was low due to the short dispersion time.
The pigment dispersion of Comparative Example 4 using a graft copolymer not salted with an organic acid compound as a dispersant had poor dispersibility and dispersion stability. Moreover, the negative resist composition of Comparative Example 4 using the pigment dispersion had poor developability and alkali resistance, and low contrast.
The negative resist composition of Comparative Example 5 using a graft copolymer quaternary ammonium salified with benzyl chloride as a dispersant had poor developability.
Further, the negative resist compositions of Comparative Examples 6 and 7 using a commercially available dispersant that did not form a salt with the organic acid compound were particularly poor in alkali resistance.
C. I. Pigment yellow 138, C.I. I. The yellow pigment dispersion using a combination of the imide alkylated derivative of Pigment Yellow 138 and the specific salt-type graft copolymer was a case where another pigment was further used as in Examples 9-12. However, it was found that the brightness and contrast were high and the heat resistance was excellent.

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 51 Monomer unit which has an amino group 52 Polymerizable part of macromonomer 53 Polymer chain by macromonomer 54 Organic acid compound

Claims (16)

C. I. Pigment Yellow 138 and C.I. represented by the following chemical formula (1). I. Pigment Yellow 138, an imide alkylated derivative, a pigment dispersant, and a solvent. The pigment dispersant includes a monomer having an ethylenically unsaturated double bond and an amino group, a polymer chain, and ethylene at its terminal. A graft copolymer containing, as a copolymerization component, a macromonomer containing a group having an ethylenically unsaturated double bond, and at least an amino group derived from a monomer having an ethylenically unsaturated double bond and an amino group Graft copolymer in which a part and an organic acid compound form a salt {provided that the polymer chain of the macromonomer is — [CH (R ⁱ ) —CH (R ⁱⁱ ) —O] _x —R ⁱⁱⁱ , or _{- [(CH 2) y -O} ] z -R iii ( wherein ^{R i} and R ⁱⁱ are each independently a hydrogen atom or a methyl group, R ⁱⁱⁱ represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, Alkenyl prime 2-18, aralkyl group, aryl group, _-CHO, -CH 2 CHO, or a monovalent group represented by _-CH 2 COOR ^iv, R ^iv is a hydrogen atom or a carbon number from 1 to 5 Except that x is an integer from 1 to 18, y is an integer from 1 to 5, and z is an integer from 1 to 18. }, And the C.I. I. Pigment Yellow 138 imidoalkylated derivatives are C.I. I. A pigment dispersion for a color filter, which is contained in an amount of 0.1 to 20 parts by mass with respect to 100 parts by mass 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 imide alkyl 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 a color filter according to claim 1, which is contained in an amount of 0.1 to 20 parts by mass with respect to 100 parts by mass of Pigment Yellow 138. The pigment dispersion for color filters according to claim 1 or 2, wherein in the pigment dispersant, the monomer having an ethylenically unsaturated double bond and an amino group is represented by the following general formula (I).
(In formula (I), R ¹ represents a hydrogen atom or a methyl group, R ² and R ³ each independently represents a hydrogen atom, or an optionally substituted cyclic or chain hydrocarbon group, or R 1 ² and R ³ combine with each other to form a cyclic structure, Q represents a divalent linking group. The pigment dispersion for a color filter according to any one of claims 1 to 3, wherein in the pigment dispersant, the organic acid compound is represented by the following general formula (II) and / or the following general formula (III). liquid.
(In Formula (II) and 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, or 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 ″.} R ^a and R ^{a ′} each contain ^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, and 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 , — [(CH ₂ ) _t —O] _u —R ^e or a monovalent group represented by —O—R ^{b ′} . 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 , or _- 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, a monovalent group represented by _{-CO-C (CH 3) =} CH 2 or _-CH 2 COOR ^{f, R f} is hydrogen or C It is an alkyl group of formula 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 is an integer of 1 to 18, t is an integer of 1 to 5, and u is an integer of 1 to 18. ) 5. The pigment dispersant according to claim 1, wherein the polymer chain of the macromonomer has at least one structural unit represented by the following general formula (IV) or general formula (V). The pigment dispersion for color filters according to one item.
(Formula (IV) and wherein (V), ^{R 4} is a hydrogen atom or a methyl group, ^{R 5} is an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, a cyano group, - [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —R ⁸ , — [(CH ₂ ) _y —O] _z —R ⁸ , — [CO— (CH ₂ ) _y —O] _z —R ⁸ , —CO It is a monovalent group represented by —O—R ⁹ or —O—CO—R ^10. R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group.
R ⁸ is a hydrogen atom or a monovalent group represented by an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, —CHO, —CH ₂ CHO, or —CH ₂ COOR ¹¹ , and R ⁹ is C1-C18 alkyl group, aralkyl group, aryl group, cyano group, — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —R ⁸ , — [(CH ₂ ) _y —O] _z It is a monovalent group represented by —R ⁸ or — [CO— (CH ₂ ) _y —O] _z —R ⁸ . R ¹⁰ is an alkyl group having 1 to 18 carbon atoms, and R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
m represents an integer of 1 to 5, and l and l ′ represent an integer of 5 to 200. x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18. ) 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, wherein the pigment dispersant is an ethylenically unsaturated double bond And a monomer having an amino group and a macromonomer having a polymer chain and a group having an ethylenically unsaturated double bond at its terminal as a copolymerization component, and further comprising an ethylenically unsaturated group Graft copolymer in which at least a part of an amino group derived from a monomer having a double bond and an amino group and an organic acid compound form a salt {provided that the polymer chain of the macromonomer is — [CH (R ^{i ) -CH (R ii) -O]} x -R iii, or _{- [(CH 2) y -O} ] z -R iii ( wherein ^{R i} and R ⁱⁱ are each independently a hydrogen atom or a methyl group, ⁱⁱⁱ represents a hydrogen atom or 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, or monovalent represented by _-CH 2 COOR ^iv R ^iv is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18.) Except the case. }, And the C.I. 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 mass with respect to 100 parts by mass 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 imide alkyl 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 mass with respect to 100 parts by mass of Pigment Yellow 138. 9. The color filter according to claim 6, wherein in the pigment dispersant, the monomer having the ethylenically unsaturated double bond and the amino group is represented by the following general formula (I). Negative resist composition.
(In formula (I), R ¹ represents a hydrogen atom or a methyl group, R ² and R ³ each independently represents a hydrogen atom, or an optionally substituted cyclic or chain hydrocarbon group, or R 1 ² and R ³ combine with each other to form a cyclic structure, Q represents a divalent linking group. The negative type for color filters according to any one of claims 6 to 9, wherein, in the pigment dispersant, the organic acid compound is represented by the following general formula (II) and / or the following general formula (III). Resist composition.
(In Formula (II) and 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, or 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 ″.} R ^a and R ^{a ′} each contain ^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, and 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 , — [(CH ₂ ) _t —O] _u —R ^e or a monovalent group represented by —O—R ^{b ′} . 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 , or _- 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, a monovalent group represented by _{-CO-C (CH 3) =} CH 2 or _-CH 2 COOR ^{f, R f} is hydrogen or C It is an alkyl group of formula 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 is an integer of 1 to 18, t is an integer of 1 to 5, and u is an integer of 1 to 18. ) 11. The pigment dispersant according to claim 6, wherein the polymer chain of the macromonomer has at least one structural unit represented by the following general formula (IV) or general formula (V). The negative resist composition for a color filter according to one item.
(Formula (IV) and wherein (V), ^{R 4} is a hydrogen atom or a methyl group, ^{R 5} is an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, a cyano group, - [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —R ⁸ , — [(CH ₂ ) _y —O] _z —R ⁸ , — [CO— (CH ₂ ) _y —O] _z —R ⁸ , —CO It is a monovalent group represented by —O—R ⁹ or —O—CO—R ^10. R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group.
R ⁸ is a hydrogen atom or a monovalent group represented by an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, —CHO, —CH ₂ CHO, or —CH ₂ COOR ¹¹ , and R ⁹ is C1-C18 alkyl group, aralkyl group, aryl group, cyano group, — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —R ⁸ , — [(CH ₂ ) _y —O] _z It is a monovalent group represented by —R ⁸ or — [CO— (CH ₂ ) _y —O] _z —R ⁸ . R ¹⁰ is an alkyl group having 1 to 18 carbon atoms, and R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
m represents an integer of 1 to 5, and l and l ′ represent an integer of 5 to 200. x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18. ) Graft containing, as a pigment dispersant, a monomer having an ethylenically unsaturated double bond and an amino group, and a macromonomer containing a polymer chain and a group having an ethylenically unsaturated double bond at its terminal as a copolymerization component A graft copolymer in which at least a part of an amino group derived from a monomer having an ethylenically unsaturated double bond and an amino group and an organic acid compound form a salt {provided that the macromonomer Wherein the polymer chain is — [CH (R ⁱ ) —CH (R ⁱⁱ ) —O] _x —R ⁱⁱⁱ , or — [(CH ₂ ) _y —O] _z —R ⁱⁱⁱ (where R ⁱ and R ⁱⁱ each independently represent a hydrogen atom or a methyl group, R ⁱⁱⁱ represents a hydrogen atom or 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 Or a monovalent group represented by _-CH 2 COOR ^iv, R ^iv is hydrogen or .x 1 to 18 integer alkyl group having 1 to 5 carbon, y is an integer from 1 to 5, z represents an integer of 1 to 18). } Preparing steps,
In the presence of the pigment dispersant in a solvent, C.I. I. Pigment Yellow 138 and C.I. represented by the following chemical formula (1). I. Preparing a pigment dispersion by dispersing an imide alkylated derivative of CI Pigment Yellow 138;
The manufacturing method of the negative resist composition for color filters which has the process of mixing the said pigment dispersion liquid, alkali-soluble resin, a polyfunctional monomer, and a photoinitiator.
(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 imide alkyl group and represents an integer of 1 to 5.) Graft containing, as a pigment dispersant, a monomer having an ethylenically unsaturated double bond and an amino group, and a macromonomer containing a polymer chain and a group having an ethylenically unsaturated double bond at its terminal as a copolymerization component A graft copolymer in which at least a part of an amino group derived from a monomer having an ethylenically unsaturated double bond and an amino group and an organic acid compound form a salt {provided that the macromonomer Wherein the polymer chain is — [CH (R ⁱ ) —CH (R ⁱⁱ ) —O] _x —R ⁱⁱⁱ , or — [(CH ₂ ) _y —O] _z —R ⁱⁱⁱ (where R ⁱ and R ⁱⁱ each independently represent a hydrogen atom or a methyl group, R ⁱⁱⁱ represents a hydrogen atom or 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 Or a monovalent group represented by _-CH 2 COOR ^iv, R ^iv is hydrogen or .x 1 to 18 integer alkyl group having 1 to 5 carbon, y is an integer from 1 to 5, z represents an integer of 1 to 18). } Preparing steps,
In the presence of the pigment dispersant in a solvent, C.I. I. Pigment yellow 138 is dispersed to prepare a pigment dispersion;
The pigment dispersion and C.I. represented by the following chemical formula (1). I. The manufacturing method of the negative resist composition for color filters which has the process of mixing the imide alkylation derivative of pigment yellow 138, alkali-soluble resin, a polyfunctional monomer, and a photoinitiator.
(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 imide alkyl group and represents an integer of 1 to 5.) A color filter negative resist according to any one of claims 6 to 11, wherein the color filter comprises at least a transparent substrate and a colored layer provided on the transparent substrate, and at least one of the colored layers is a color filter negative resist. a color filter characterized by having a colored layer of the composition was cured composed is formed.   15. A liquid crystal display device comprising: the color filter according to claim 14; 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 14 and an organic light emitter.