JP2010083923A - Pigment dispersant, negative resist composition for color filter, color filter and liquid crystal display device - Google Patents

Abstract

【選択図】なしThe present invention provides a negative resist composition for a color filter having excellent pigment dispersibility and excellent alkali developability.
(A) A structural unit having the following formulas (I) and (II), wherein the amino group of formula (I) forms a salt with (R ⁵ ) ₂ PO ₂ H or R ⁶ SO ₃ H Color filter negative type comprising a pigment dispersant, (B) a pigment, (C) an alkali-soluble resin, (D) a polyfunctional monomer, (E) a photoinitiator, and (F) a solvent. Resist composition.

[Selection figure] None

Description

  The present invention relates to a pigment dispersant, a negative resist composition for color filters, a color filter, and a liquid crystal display device. More specifically, the present invention provides a pigment dispersant for imparting alkali solubility as well as excellent pigment dispersibility, a negative resist composition for color filters having excellent pigment dispersibility and excellent alkali developability, and the resist composition. The present invention relates to a color filter formed and a liquid crystal display device having the color filter.

  In recent years, with the development of personal computers, particularly portable personal computers, the demand for liquid crystal displays has increased. In recent years, the penetration rate of home-use liquid crystal televisions has been increasing, and the market for liquid crystal displays is expanding. Furthermore, liquid crystal displays that have become widespread in recent years tend to have larger screens, and this tendency is particularly strong for home-use liquid crystal televisions. In such a situation, it is desired to manufacture a liquid crystal display that has a lower cost and a higher quality with high productivity. In particular, in a color filter having a function of colorizing the liquid crystal display. However, such demands are increasing because of its high cost.

  Here, as a general method for producing a color filter, a coating film made of a photocurable resist composition in which a pigment of each color is dispersed is formed on a substrate on which a light shielding portion is formed in a pattern, and a desired color filter is formed. A method is used in which a colored layer of each color is formed in a pattern by exposure and alkali development through a photomask having a pattern.

  As the photocurable resist composition used for the production of such a color filter, in addition to the above-mentioned pigments of the respective colors, a pigment dispersant, an alkali-soluble resin, and a multi-component added to uniformly disperse the pigment are usually used. Those having a functional monomer, a photoinitiator, and a solvent are used. As a pigment dispersant used in such a photocurable resist composition, if the dispersibility of the pigment is insufficient when forming a colored layer of a color filter, color unevenness may occur in the colored layer. Therefore, those having excellent dispersibility are used. As the pigment dispersant having such excellent dispersibility, a pigment dispersant using an aromatic ester, an aromatic amine, and / or a graft copolymer having a quaternary ammonium group is disclosed (for example, Patent Document 1). Has been. Also disclosed is a pigment dispersion containing a graft copolymer having a monomer containing a nitrogen atom as a main chain and a macromonomer having an ethylenically unsaturated double bond at the terminal as a side chain (for example, Patent Document 2). . Also disclosed is a pigment dispersant which is a copolymer containing at least a monomer containing a nitrogen atom and a monomer having an ethylenically unsaturated double bond at the terminal and a polycaprolactone skeleton as a copolymerization component (Patent Documents). 3).

Special table 2003-517065 gazette JP 2003-26949 A JP 2000-95992 A

  In recent years, there has been an increasing demand for high contrast in liquid crystal display devices, and in order to achieve such a demand, finer pigments are required. However, even if the primary particle size of the pigment used is small, as shown in the comparative example described later, the conventional pigment dispersant has insufficient pigment dispersibility and pigment dispersion stability, and the pigment dispersion It was difficult to reduce the particle size.

In addition, the surface area of the pigment in the photocurable resist composition increases due to the finer pigment, and it is necessary to increase the amount of pigment dispersant required to uniformly disperse the pigment. ing.
However, the conventional pigment dispersant containing a quaternary ammonium base as disclosed in Patent Document 1 can ensure a uniform dispersibility of the pigment to some extent by increasing the amount of the additive added. However, there is a problem in that productivity is deteriorated, the time required for alkali development is prolonged, and a photocurable resist composition that remains unexposed on the substrate remains, resulting in a decrease in productivity and quality. Even in the pigment dispersants disclosed in Patent Documents 2 and 3, since the amount of the dispersant increases as the pigment concentration in the resist composition increases, the pigment dispersant as disclosed in Patent Document 1 In the same manner as the above, it was insufficient in that the developability was lowered.

  The present invention has been made under such circumstances, and has excellent pigment dispersion performance, a pigment dispersant capable of imparting alkali solubility, excellent pigment dispersibility, and color filter excellent in alkali developability. An object of the present invention is to provide a negative resist composition, a color filter formed using the resist composition, and a liquid crystal display device having the color filter.

As a result of intensive studies to achieve the above object, the inventors of the present invention include a pigment dispersant, a pigment, an alkali-soluble resin, a polyfunctional monomer, a photoinitiator, and a solvent, and A resist composition using an organic acid compound salt of a graft copolymer having a specific structure as the pigment dispersant is excellent in pigment dispersibility, excellent in alkali developability, and suitable for the purpose. I found it.
The present invention has been completed based on such findings.

  The present invention includes a structural unit (1) represented by the following general formula (I) and a structural unit (2) represented by the following general formula (II), and further the amino which the structural unit (1) has Provided is a pigment dispersant, which is a graft copolymer in which a group and an organic acid compound represented by the following general formula (III) and / or the following general formula (IV) form a salt.

［式（Ｉ）〜（ＩＶ）中、Ｒ^１及びＲ^１’は、それぞれ独立に水素原子又はメチル基、Ｒ^２及びＲ^４は、それぞれ独立に炭素数１〜８のアルキレン基、−［ＣＨ（Ｒ^７）−ＣＨ（Ｒ^８）−Ｏ］_ｘ−ＣＨ（Ｒ^７）−ＣＨ（Ｒ^８）−、又は−［（ＣＨ_２）_ｙ−Ｏ］_ｚ−（ＣＨ_２）_ｙ−で示される２価の基、Ｒ^３及びＲ^３’は、それぞれ独立に水素原子又は炭素数１〜８のアルキル基、Ａは、１個以上の重合性基を有する有機基である。
Ｒ^５及びＲ^５’は、それぞれ独立に水素原子、水酸基、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、ベンジル基、フェニル基、ビフェニル基、−［ＣＨ（Ｒ^９）−ＣＨ（Ｒ^１０）−Ｏ］_ａ−Ｒ^１１、−［（ＣＨ_２）_ｂ−Ｏ］_ｃ−Ｒ^１１、又は−Ｏ−Ｒ^４’’で示される１価の基であり、Ｒ^４及びＲ^４’のいずれかは炭素原子を含む。Ｒ^４’’は、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、ベンジル基、フェニル基、ビフェニル基、−［ＣＨ（Ｒ^９）−ＣＨ（Ｒ^１０）−Ｏ］_ａ−Ｒ^１１、−［（ＣＨ_２）_ｂ−Ｏ］_ｃ−Ｒ^１１で示される１価の基である。
Ｒ^６は、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、ベンジル基、フェニル基、ビフェニル基、−［ＣＨ（Ｒ^９）−ＣＨ（Ｒ^１０）−Ｏ］_ａ−Ｒ^１１、−［（ＣＨ_２）_ｂ−Ｏ］_ｃ−Ｒ^１１、又は−Ｏ−Ｒ^５’で示される１価の基である。Ｒ^５’は、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、ベンジル基、フェニル基、ビフェニル基、−［ＣＨ（Ｒ^９）−ＣＨ（Ｒ^１０）−Ｏ］_ａ−Ｒ^１１、−［（ＣＨ_２）_ｂ−Ｏ］_ｃ−Ｒ^１１で示される１価の基である。
Ｒ^７、Ｒ^８、Ｒ^９及びＲ^１０は、それぞれ独立に水素原子又はメチル基であり、Ｒ^１１は、水素原子、あるいは炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、ベンジル基、フェニル基、ビフェニル基、−ＣＨＯ、−ＣＨ_２ＣＨＯ、−ＣＯ−ＣＨ＝ＣＨ_２、−ＣＯ−Ｃ（ＣＨ_３）＝ＣＨ_２又は−ＣＨ_２ＣＯＯＲ^１２で示される１価の基であり、Ｒ^１２は水素原子又は炭素数１〜５のアルキル基である。
ｘ及びａは１〜１８の整数、ｙ及びｂは１〜５の整数、ｚ及びｃは１〜１８の整数を示す。ｍ及びｎは１〜２００の整数を示す。ｌは１〜５の整数、ｐは、５〜２００の整数を示す。］

[In the formulas (I) to (IV), R ¹ and R ^{1 ′} are each independently a hydrogen atom or a methyl group, R ² and R ⁴ are each independently an alkylene group having 1 to 8 carbon atoms, — [CH _{^{(R 7) -CH (R 8}} ) -O] x -CH (R 7) -CH (R 8) -, or _{- [(CH 2) y -O} ] z - (CH 2) y - represented by The divalent group, R ³ and R ^{3 ′} are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and A is an organic group having one or more polymerizable groups.
R ⁵ and R ^{5 ′} 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, a benzyl group, a phenyl group, a biphenyl group, or — [CH (R ⁹ ). —CH (R ¹⁰ ) —O] _a —R ¹¹ , — [(CH ₂ ) _b —O] _c —R ¹¹ , or —O—R ^{4 ″} , a monovalent group represented by R ⁴ and one of R 4 ^'comprises a carbon atom. R ^{4 ″} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a benzyl group, a phenyl group, a biphenyl group, — [CH (R ⁹ ) —CH (R ¹⁰ ) —O] _a -R ^11, _- a _{[(CH 2) b -O]} 1 monovalent group represented by c ^{-R 11.}
R ⁶ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a benzyl group, a phenyl group, a biphenyl group, — [CH (R ⁹ ) —CH (R ¹⁰ ) —O] _a —R. ¹¹ ,-[(CH ₂ ) _b —O] _c —R ¹¹ , or a monovalent group represented by —O—R ^{5 ′} . R ^{5 ′} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a benzyl group, a phenyl group, a biphenyl group, — [CH (R ⁹ ) —CH (R ¹⁰ ) —O] _a —. R ¹¹ is a monovalent group represented by — [(CH ₂ ) _b —O] _c —R ¹¹ .
R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom or a methyl group, and R ¹¹ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, A monovalent group represented by benzyl group, phenyl group, biphenyl group, —CHO, —CH ₂ CHO, —CO—CH═CH ₂ , —CO—C (CH ₃ ) ═CH ₂ or —CH ₂ COOR ^12. And R ¹² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
x and a are integers of 1 to 18, y and b are integers of 1 to 5, and z and c are integers of 1 to 18. m and n represent an integer of 1 to 200. l represents an integer of 1 to 5, and p represents an integer of 5 to 200. ]

  Moreover, this invention has (A) the structural unit (1) represented by the following general formula (I), and the structural unit (2) represented by the following general formula (II), and also the said structural unit ( (B) a pigment dispersant which is a graft copolymer in which an amino group possessed by 1) and an organic acid compound represented by the following general formula (III) and / or the following general formula (IV) form a salt; Provided is a negative resist composition for a color filter comprising a pigment, (C) an alkali-soluble resin, (D) a polyfunctional monomer, (E) a photoinitiator, and (F) a solvent.

［式（Ｉ）〜（ＩＶ）中、Ｒ^１及びＲ^１’は、それぞれ独立に水素原子又はメチル基、Ｒ^２及びＲ^４は、それぞれ独立に炭素数１〜８のアルキレン基、−［ＣＨ（Ｒ^７）−ＣＨ（Ｒ^８）−Ｏ］_ｘ−ＣＨ（Ｒ^７）−ＣＨ（Ｒ^８）、又は−［（ＣＨ_２）_ｙ−Ｏ］_ｚ−（ＣＨ_２）_ｙ−で示される２価の基、Ｒ^３及びＲ^３’は、それぞれ独立に水素原子又は炭素数１〜８のアルキル基、Ａは、１個以上の重合性基を有する有機基である。
Ｒ^５及びＲ^５’は、それぞれ独立に水素原子、水酸基、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、ベンジル基、フェニル基、ビフェニル基、−［ＣＨ（Ｒ^９）−ＣＨ（Ｒ^１０）−Ｏ］_ａ−Ｒ^１１、−［（ＣＨ_２）_ｂ−Ｏ］_ｃ−Ｒ^１１、又は−Ｏ−Ｒ^４’’で示される１価の基であり、Ｒ^４及びＲ^４’のいずれかは炭素原子を含む。Ｒ^４’’は、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、ベンジル基、フェニル基、ビフェニル基、−［ＣＨ（Ｒ^９）−ＣＨ（Ｒ^１０）−Ｏ］_ａ−Ｒ^１１、−［（ＣＨ_２）_ｂ−Ｏ］_ｃ−Ｒ^１１で示される１価の基である。
Ｒ^６は、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、ベンジル基、フェニル基、ビフェニル基、−［ＣＨ（Ｒ^９）−ＣＨ（Ｒ^１０）−Ｏ］_ａ−Ｒ^１１、−［（ＣＨ_２）_ｂ−Ｏ］_ｃ−Ｒ^１１、又は−Ｏ−Ｒ^５’で示される１価の基である。Ｒ^５’は、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、ベンジル基、フェニル基、ビフェニル基、−［ＣＨ（Ｒ^９）−ＣＨ（Ｒ^１０）−Ｏ］_ａ−Ｒ^１１、−［（ＣＨ_２）_ｂ−Ｏ］_ｃ−Ｒ^１１で示される１価の基である。
Ｒ^７、Ｒ^８、Ｒ^９及びＲ^１０は、それぞれ独立に水素原子又はメチル基であり、Ｒ^１１は、水素原子、あるいは炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、ベンジル基、フェニル基、ビフェニル基、−ＣＨＯ、−ＣＨ_２ＣＨＯ、−ＣＯ−ＣＨ＝ＣＨ_２、−ＣＯ−Ｃ（ＣＨ_３）＝ＣＨ_２又は−ＣＨ_２ＣＯＯＲ^１２で示される１価の基であり、Ｒ^１２は水素原子又は炭素数１〜５のアルキル基である。
ｘ及びａは１〜１８の整数、ｙ及びｂは１〜５の整数、ｚ及びｃは１〜１８の整数を示す。ｍ及びｎは１〜２００の整数を示す。ｌは１〜５の整数、ｐは、５〜２００の整数を示す。］

[In the formulas (I) to (IV), R ¹ and R ^{1 ′} are each independently a hydrogen atom or a methyl group, R ² and R ⁴ are each independently an alkylene group having 1 to 8 carbon atoms, — [CH _{^{(R 7) -CH (R 8}} ) -O] x -CH (R 7) -CH (R 8), or _{- [(CH 2) y -O} ] z - (CH 2) y - 2 represented by The valent group, R ³ and R ^{3 ′} are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and A is an organic group having one or more polymerizable groups.
R ⁵ and R ^{5 ′} 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, a benzyl group, a phenyl group, a biphenyl group, or — [CH (R ⁹ ). —CH (R ¹⁰ ) —O] _a —R ¹¹ , — [(CH ₂ ) _b —O] _c —R ¹¹ , or —O—R ^{4 ″} , a monovalent group represented by R ⁴ and Any of R ^{4 ′} includes a carbon atom. R ^{4 ″} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a benzyl group, a phenyl group, a biphenyl group, — [CH (R ⁹ ) —CH (R ¹⁰ ) —O] _a -R ^11, _- a _{[(CH 2) b -O]} 1 monovalent group represented by c ^{-R 11.}
R ⁶ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a benzyl group, a phenyl group, a biphenyl group, — [CH (R ⁹ ) —CH (R ¹⁰ ) —O] _a —R. ¹¹ ,-[(CH ₂ ) _b —O] _c —R ¹¹ , or a monovalent group represented by —O—R ^{5 ′} . R ^{5 ′} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a benzyl group, a phenyl group, a biphenyl group, — [CH (R ⁹ ) —CH (R ¹⁰ ) —O] _a —. R ¹¹ is a monovalent group represented by — [(CH ₂ ) _b —O] _c —R ¹¹ .
R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom or a methyl group, and R ¹¹ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, A monovalent group represented by benzyl group, phenyl group, biphenyl group, —CHO, —CH ₂ CHO, —CO—CH═CH ₂ , —CO—C (CH ₃ ) ═CH ₂ or —CH ₂ COOR ^12. And R ¹² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
x and a are integers of 1 to 18, y and b are integers of 1 to 5, and z and c are integers of 1 to 18. m and n represent an integer of 1 to 200. l represents an integer of 1 to 5, and p represents an integer of 5 to 200. ]

In the negative dispersant composition for a pigment dispersant and a color filter according to the present invention, R ⁵ and / or R ^{5 ′} in the general formula (III) and / or R ⁶ in the general formula (IV) are: Having a polymerizable group is preferable from the viewpoints of pigment dispersibility, alkali developability in the resist composition, and stability in the coating film. As such a polymerizable group, a (meth) acryloyl group, a vinyl group, or an allyl group is preferable.

  In the negative dispersant composition for a pigment dispersant and a color filter according to the present invention, A in the structural unit (2) represented by the general formula (II) includes a polyfunctional monomer residue. Furthermore, it is preferable from the point of stability in a coating film and the pattern formation property of a coating film.

  In the negative resist composition for color filters according to the present invention, the average particle size of the (B) pigment is 10 to 100 nm, so that a high-quality, high-contrast and high-quality liquid crystal display device can be produced. To preferred.

The present invention provides a color filter having a colored layer formed using the negative resist composition for a color filter.
Furthermore, the present invention provides a liquid crystal display device having the above color filter.

According to the present invention, it is possible to provide a pigment dispersant capable of imparting alkali solubility while having excellent pigment dispersion performance.
ADVANTAGE OF THE INVENTION According to this invention, while being excellent in pigment dispersibility, the negative resist composition for color filters which is excellent in alkali developability, the adhesiveness of the formed coating film, and heat resistance can be provided.
In addition, according to the present invention, by forming a colored layer using the negative resist composition for a color filter, it is possible to make the color filter excellent in alkali developability. can do. Moreover, by being excellent in alkali developability, it is possible to provide a high-quality color filter with few color filter negative resist residues at unexposed locations.
Furthermore, according to the present invention, a liquid crystal display device with high quality and excellent productivity can be provided by using the color filter.

First, the pigment dispersant of the present invention will be described.
[Pigment dispersant]
The pigment dispersant according to the present invention has a structural unit (1) represented by the following general formula (I) and a structural unit (2) represented by the following general formula (II). 1) A graft copolymer (hereinafter referred to as a salt-type graft copolymer) in which the amino group possessed by the organic acid compound represented by the following general formula (III) and / or the following general formula (IV) forms a salt. May be referred to.)

［式（Ｉ）〜（ＩＶ）中、Ｒ^１及びＲ^１’は、それぞれ独立に水素原子又はメチル基、Ｒ^２及びＲ^４は、それぞれ独立に炭素数１〜８のアルキレン基、−［ＣＨ（Ｒ^７）−ＣＨ（Ｒ^８）−Ｏ］_ｘ−ＣＨ（Ｒ^７）−ＣＨ（Ｒ^８）−、又は−［（ＣＨ_２）_ｙ−Ｏ］_ｚ−（ＣＨ_２）_ｙ−で示される２価の基、Ｒ^３及びＲ^３’は、それぞれ独立に水素原子又は炭素数１〜８のアルキル基、Ａは、１個以上の重合性基を有する有機基である。
Ｒ^５及びＲ^５’は、それぞれ独立に水素原子、水酸基、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、ベンジル基、フェニル基、ビフェニル基、−［ＣＨ（Ｒ^９）−ＣＨ（Ｒ^１０）−Ｏ］_ａ−Ｒ^１１、−［（ＣＨ_２）_ｂ−Ｏ］_ｃ−Ｒ^１１、又は−Ｏ−Ｒ^４’’で示される１価の基であり、Ｒ^４及びＲ^４’のいずれかは炭素原子を含む。Ｒ^４’’は、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、ベンジル基、フェニル基、ビフェニル基、−［ＣＨ（Ｒ^９）−ＣＨ（Ｒ^１０）−Ｏ］_ａ−Ｒ^１１、−［（ＣＨ_２）_ｂ−Ｏ］_ｃ−Ｒ^１１で示される１価の基である。
Ｒ^６は、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、ベンジル基、フェニル基、ビフェニル基、−［ＣＨ（Ｒ^９）−ＣＨ（Ｒ^１０）−Ｏ］_ａ−Ｒ^１１、−［（ＣＨ_２）_ｂ−Ｏ］_ｃ−Ｒ^１１、又は−Ｏ−Ｒ^５’で示される１価の基である。Ｒ^５’は、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、ベンジル基、フェニル基、ビフェニル基、−［ＣＨ（Ｒ^９）−ＣＨ（Ｒ^１０）−Ｏ］_ａ−Ｒ^１１、−［（ＣＨ_２）_ｂ−Ｏ］_ｃ−Ｒ^１１で示される１価の基である。
Ｒ^７、Ｒ^８、Ｒ^９及びＲ^１０は、それぞれ独立に水素原子又はメチル基であり、Ｒ^１１は、水素原子、あるいは炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、ベンジル基、フェニル基、ビフェニル基、−ＣＨＯ、−ＣＨ_２ＣＨＯ、−ＣＯ−ＣＨ＝ＣＨ_２、−ＣＯ−Ｃ（ＣＨ_３）＝ＣＨ_２又は−ＣＨ_２ＣＯＯＲ^１２で示される１価の基であり、Ｒ^１２は水素原子又は炭素数１〜５のアルキル基である。
ｘ及びａは１〜１８の整数、ｙ及びｂは１〜５の整数、ｚ及びｃは１〜１８の整数を示す。ｍ及びｎは１〜２００の整数を示す。ｌは１〜５の整数、ｐは、５〜２００の整数を示す。］

[In the formulas (I) to (IV), R ¹ and R ^{1 ′} are each independently a hydrogen atom or a methyl group, R ² and R ⁴ are each independently an alkylene group having 1 to 8 carbon atoms, — [CH _{^{(R 7) -CH (R 8}} ) -O] x -CH (R 7) -CH (R 8) -, or _{- [(CH 2) y -O} ] z - (CH 2) y - represented by The divalent group, R ³ and R ^{3 ′} are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and A is an organic group having one or more polymerizable groups.
R ⁵ and R ^{5 ′} 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, a benzyl group, a phenyl group, a biphenyl group, or — [CH (R ⁹ ). —CH (R ¹⁰ ) —O] _a —R ¹¹ , — [(CH ₂ ) _b —O] _c —R ¹¹ , or —O—R ^{4 ″} , a monovalent group represented by R ⁴ and Any of R ^{4 ′} includes a carbon atom. R ^{4 ″} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a benzyl group, a phenyl group, a biphenyl group, — [CH (R ⁹ ) —CH (R ¹⁰ ) —O] _a -R ^11, _- a _{[(CH 2) b -O]} 1 monovalent group represented by c ^{-R 11.}
R ⁶ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a benzyl group, a phenyl group, a biphenyl group, — [CH (R ⁹ ) —CH (R ¹⁰ ) —O] _a —R. ¹¹ ,-[(CH ₂ ) _b —O] _c —R ¹¹ , or a monovalent group represented by —O—R ^{5 ′} . R ^{5 ′} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a benzyl group, a phenyl group, a biphenyl group, — [CH (R ⁹ ) —CH (R ¹⁰ ) —O] _a —. R ¹¹ is a monovalent group represented by — [(CH ₂ ) _b —O] _c —R ¹¹ .
R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom or a methyl group, and R ¹¹ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, A monovalent group represented by benzyl group, phenyl group, biphenyl group, —CHO, —CH ₂ CHO, —CO—CH═CH ₂ , —CO—C (CH ₃ ) ═CH ₂ or —CH ₂ COOR ^12. And R ¹² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
x and a are integers of 1 to 18, y and b are integers of 1 to 5, and z and c are integers of 1 to 18. m and n represent an integer of 1 to 200. l represents an integer of 1 to 5, and p represents an integer of 5 to 200. ]

  According to the present invention, the pigment dispersant used has the structural unit (1) represented by the general formula (I) and the structural unit (2) represented by the general formula (II), And the amino group which the said structural unit (1) has, and the organic acid compound represented by the following general formula (III) and / or the following general formula (IV) are the salt-type block copolymers which formed the salt. The adsorbability of the structural unit (1) forming the salt-forming site to the (B) pigment is enhanced, while the polylactone chain grafted in the structural unit (2) is soluble in the (F) solvent. (F) Stabilization of the (B) pigment in the solvent can be achieved, and as a result, the dispersibility and stability of the (B) pigment can be improved.

  Moreover, by having the organic acid compound represented by the general formula (III) and / or the general formula (IV), the amino group contained in the nitrogen-containing monomer and the general formula (III) and / or the general formula ( IV) The salt-forming site formed by the organic acid compound represented by formula (IV) has high solubility in an alkaline aqueous solution at the time of alkaline development, so that it has excellent alkali developability when a negative resist composition is used. Can be. Therefore, when a color filter is produced with a negative resist composition using the pigment dispersant of the present invention, the alkali development time can be shortened and the productivity can be improved. Moreover, the negative resist composition using the pigment dispersant of the present invention is excellent in alkali developability, so that a high-quality color filter with few negative resist composition residues at unexposed portions can be obtained.

  In addition, since the pigment dispersant of the present invention is the above-described salt type block copolymer, the pigment can be favorably dispersed even when the amount of the pigment dispersant added is small. Therefore, according to the negative resist composition using the pigment dispersant of the present invention, there is also an effect that the alkali developability, heat resistance and solvent resistance are not adversely affected when a coating film is formed. For example, if the heat resistance is good, it is possible to suppress the color layer from being discolored and the luminance and contrast from being lowered after the post-baking step in the color filter manufacturing step.

  Furthermore, the pigment dispersant of the present invention has one or more polymerizable groups at the end of the polymer chain of the structural unit (2). Therefore, at the time of exposure when forming a colored layer with a negative resist composition using the pigment dispersant of the present invention, the above-mentioned polymerizable groups and / or the above-mentioned polymerizable groups and the polyfunctionality contained in the resist composition. Monomers and the like can be easily polymerized, the pigment dispersant can be stably present in the coating film, and the pigment dispersant is prevented from bleeding out. Since the pigment dispersant of the present invention has one or more polymerizable groups together with a portion having high solubility in an alkaline aqueous solution, the pattern forming ability when used as a coating film for a resist composition and the substrate This also has the effect of improving the adhesion of the material. Moreover, the heat resistance of the coating film is also improved.

<Graft copolymer>
The graft copolymer has a structural unit (1) represented by the following general formula (I) and a structural unit (2) represented by the following general formula (II).
In the general formula (I) and (II), ^{R 1} and R ^{1 'each} independently represent a hydrogen atom or a methyl group, ^{R 3} and R ^3' are each independently a hydrogen atom or 1 to carbon atoms 8 represents an alkyl group. Here, the alkyl group having 1 to 8 carbon atoms may be linear, branched or cyclic. Examples of such alkyl groups include 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, and various octyl groups. Group, cyclopentyl group, cyclohexyl group, cyclooctyl group and the like. Among these, a methyl group and an ethyl group are preferable.
In the present invention, R ³ and R ^{3 ′} may be the same or different.

R ² and R ⁴ are each independently an alkylene group having 1 to 8 carbon atoms, — [CH (R ⁷ ) —CH (R ⁸ ) —O] _x —CH (R ⁷ ) —CH (R ⁸ ) — Or a divalent group represented by [(CH ₂ ) _y —O] _z — (CH ₂ ) _y —. Here, the alkylene group having 1 to 8 carbon atoms may be linear or branched, for example, methylene group, ethylene group, trimethylene group, propylene group, various butylene groups, various pentylene groups, various kinds. A hexylene group, various octylene groups, and the like.
R ⁷ and R ⁸ 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 negative resist composition for color filter of the present invention has excellent pigment dispersibility.
As the R ² and R ^4, respectively, preferably an alkylene group having 1 to 8 carbon atoms, a methylene group and an 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. R ² and R ⁴ may be substituted with a substituent as long as the dispersion performance of the graft copolymer is not hindered. Examples of the substituent include a halogen atom.

  In the said general formula (II), l is an integer of 1-5, Preferably it is an integer of 2-5, More preferably, it is an integer of 4 or 5. Moreover, the unit number p of the structural unit of a polymer chain should just be an integer of 5-200, Although it does not specifically limit, It is preferable to exist in the range of 10-100.

  The weight average molecular weight Mw of the structural unit (2) 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.

  In the general formula (II), A is an organic group having one or more polymerizable groups. A includes a structure in which a polymerizable compound residue is bonded to a linking group selected from — (C═O) —NH—, — (C═O) — and the like. Here, the polymerizable compound residue means a portion excluding any one hydrogen or substituent of a polymerizable compound having one or more polymerizable groups.

  The molecular weight of the polymerizable compound having one or more polymerizable groups can be 1000 or less. As the polymerizable compound having at least one polymerizable group, a compound having at least one (meth) acryloyl group, vinyl group, or allyl group is preferably used. Among them, the polymerizable compound residue preferably has two or more polymerizable groups, and is preferably a residue of a compound as exemplified in the polyfunctional monomer described later.

  The method for producing a graft copolymer used in the present invention comprises a graft copolymer having the structural unit (1) represented by the general formula (I) and the structural unit (2) represented by the general formula (II). If a polymer can be manufactured, it will not be specifically limited. The graft copolymer used in the present invention is, for example, a copolymer containing at least a copolymerization component of a nitrogen-containing monomer represented by the following general formula (V) and a polymerizable oligomer represented by the following general formula (VI). The graft copolymer is formed by adding a polymerizable group to the terminal of the polylactone chain by reacting the terminal hydroxyl group of the polylactone chain with a compound having a functional group capable of reacting with the hydroxyl group and a polymerizable group. be able to.

［式（Ｖ）〜（ＶＩ）中、Ｒ^１及びＲ^１’、Ｒ^２及びＲ^４、並びに、Ｒ^３及びＲ^３’は、上記式（Ｉ）及び（ＩＩ）とで定義した通りである。］

[In the formulas (V) to (VI), R ¹ and R ^{1 ′} , R ² and R ⁴ , and R ³ and R ^{3 ′} are as defined in the above formulas (I) and (II). . ]

  The polymerizable oligomer represented by the general formula (VI) may be synthesized as appropriate or may be a commercially available product. Examples of commercially available products include caprolactone-modified hydroxyethyl methacrylate (“Plexel FM5 (trade name)”: Daicel Chemical Co., Ltd.), caprolactone-modified hydroxyethyl acrylate ("Placcel FA10L (trade name)" manufactured by Daicel Chemical Co., Ltd.) and the like are preferable.

  In order to synthesize such a polymerizable oligomer, for example, a lactone is polymerized in the presence of a terminal hydroxyl group (meth) acrylate such as hydroxyethyl (meth) acrylate, hydroxybutyl (meth) acrylate, polyethylene glycol (meth) acrylate or the like. Can be obtained.

  Examples of the functional group capable of reacting with a hydroxyl group include an isocyanate group, an epoxy group, and a carboxyl group. As the compound having a functional group capable of reacting with a hydroxyl group and a polymerizable group, it is preferable to use a compound having at least one (meth) acryloyl group, vinyl group, or allyl group together with the functional groups mentioned above. Specific examples of such a compound include glycidyl (meth) acrylate and (meth) acryloyloxyalkyl isocyanate. The compound having a functional group capable of reacting with a hydroxyl group and a polymerizable group is not particularly limited, and a compound in which a functional group capable of reacting with a hydroxyl group is substituted instead of hydrogen or a substituent of a polyfunctional monomer described later. Can be used.

  As a method for introducing a functional group capable of reacting with a hydroxyl group of a polyfunctional monomer, which will be described later, for example, using a compound having an isocyanate group, a polymerization inhibitor that suppresses polymerization of double bond groups using organotin as a catalyst. For example, a method of forming a urethane-bonding compound under the normal temperature reaction conditions added.

  Commercially available compounds having a functional group capable of reacting with a hydroxyl group and a polymerizable group include 2-methacryloyloxyethyl isocyanate (“Kalenz MOI” manufactured by Showa Denko KK), 2-acryloyloxyethyl isocyanate (“Karenz”). AOI ": Showa Denko KK), 1,1-bis (acryloyloxymethyl) ethyl isocyanate (" Karenz BEI ": Showa Denko KK) and the like.

  In the graft copolymer used in the present invention, the structural unit (1) derived from the nitrogen-containing monomer is preferably contained in a proportion of 3 to 80% by mass, more preferably 5 to 50% by mass, 10-40 mass% is further more preferable. If the content of the structural unit (1) derived from the nitrogen 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 is appropriate, and the polymerizability is high. Since the decrease in solubility with the solvent due to the oligomer can be suppressed, the adsorptivity to the pigment is improved, and the dispersibility and stability of the pigment are obtained.

  In addition, the weight 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 weight average molecular weight Mw is a value measured by GPC (gel permeation chromatography). For the measurement, HLC-8120GPC manufactured by Tosoh Corporation was used, the elution solvent was N-methylpyrrolidone to which 0.01 mol / liter of lithium bromide was added, and polystyrene standards for calibration curves were Mw377400, 210500, 96000, 50400. , 206500, 10850, 5460, 2930, 1300, 580 (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.).

<Organic acid compound>
An amino group contained in the structural unit (1) of the graft copolymer having the structural unit (1) represented by the general formula (I) and the structural unit (2) represented by the general formula (II); The organic acid compound that forms a salt is an organic phosphoric acid compound having a structure represented by the general formula (III) and / or an organic sulfonic acid compound having a structure represented by the general formula (IV).
In the present invention, by using the above-mentioned organic acid compound, the pigment dispersant can be made excellent in the dispersibility and stability of the pigment described later, and the salt-forming site is an alkali during alkali development. Since it has high solubility in an aqueous solution, it can be excellent in alkali developability.

In the general formula (III), R ⁵ and R ^{5 ′} 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, a benzyl group, a phenyl group, or a biphenyl group. , — [CH (R ⁹ ) —CH (R ¹⁰ ) —O] _a —R ¹¹ , — [(CH ₂ ) _b —O] c—R ¹¹ or —O—R ^{4 ″} , R ⁴ and Any of R ^{4 ′} contains a carbon atom. In addition, when R ⁴ and R ^{4 ′} have an aromatic ring, they 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 is as indicated by the ^{R 3} and R ^{3 '.}
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, and various octadecenyl groups. , Cyclopentenyl group, cyclohexenyl group, cyclooctenyl group and the like.

When R ⁵ and / or R ^{5 ′} is —O—R ^{5 ″} , it is an acidic phosphate ester. R ^{5 ″} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a benzyl group, a phenyl group, a biphenyl group, — [CH (R ⁹ ) —CH (R ¹⁰ ) —O]. _a —R ¹¹ or _a monovalent group represented by — [(CH ₂ ) _b —O] _c —R ¹¹ .
The alkyl group having 1 to 18 carbon atoms and the alkenyl group having 2 to 18 carbon atoms are as described above. When R ^{5 ″} 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.

R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a methyl group. R ¹¹ is a hydrogen atom or an optionally substituted alkyl group having 1 to 18 carbon atoms, alkenyl group having 2 to 18 carbon atoms, benzyl group, phenyl group, biphenyl group, —CHO, —CH ₂ CHO. , —CO—CH═CH ₂ , —CO—C (CH ₃ ) ═CH ₂ , or a monovalent group represented by —CH ₂ COOR ¹² , R ¹² is a hydrogen atom or a carbon number of 1 to 5 A linear, branched or cyclic alkyl group.
In the monovalent group represented by R ¹¹ , 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 and the alkenyl group having 2 to 18 carbon atoms in R ¹¹ are as shown in the above R ³ and R ^{3 ′} , R ⁵ and R ^{5 ′} , respectively.
In R ⁵ , R ^{5 ′} and R ^{5 ″} , a is an integer of 1 to 18, b is an integer of 1 to 5, and c is an integer of 1 to 18. a is preferably an integer of 1 to 4, more preferably an integer of 1 to 2, and b is preferably an integer of 1 to 4, more preferably 2 or 3. c is preferably an integer of 1 to 4, more preferably an integer of 1 to 2.

In the general formula (IV), R ⁶ represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a benzyl group, a phenyl group, a biphenyl group, — [CH (R ⁹ ) —CH (R _{^{10) -O] a -R 11,}} - it shows a _{[(CH 2) b -O]} c -R 11 or -O-R ^{6 '.} In addition, when R ⁶ 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 and the alkenyl group having 2 to 18 carbon atoms are as described above for R ³ and R ^{3 ′} , R ⁵ and R ^{5 ′} , respectively.
When R ⁶ is —O—R ^{6 ′} , it is an acidic sulfate. R ^{6 ′} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a benzyl group, a phenyl group, a biphenyl group, — [CH (R ⁹ ) —CH (R ¹⁰ ) —O] _a. It is a monovalent group represented by —R ¹¹ or — [(CH ₂ ) _b —O] _c —R ¹¹ .
The alkyl group having 1 to 18 carbon atoms and the alkenyl group having 2 to 18 carbon atoms are as described above for R ³ and R ^{3 ′} , R ⁵ and R ^{5 ′} , respectively. When R ^{6 ′} 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.
R ⁹ , R ¹⁰ and R ¹¹ are the same as described above.
In the above ^{R 6} and R ^{6 ',} a is 1 to 18 integer, b is an integer of from 1 to 5, c is 1 to 18 integer. Desirable a, b and c are the same as R ⁵ , R ^{5 ′} and R ^{5 ″} .

As the organic acid compounds represented by the general formula (III) and the general formula (IV), R ⁵ , R ^{5 ′} , R ^{5 ″} , R ⁶ and R ^{6 ′} are each independently a methyl group or an ethyl group. , A benzyl group, a phenyl group, a vinyl group, an allyl group, or — [CH (R ⁹ ) —CH (R ¹⁰ ) —O] _a —R ¹¹ or — [(CH ₂ ) _b —O] _c —R ¹¹ And R ¹¹ is preferably —CO—CH═CH ₂ or —CO—C (CH ₃ ) ═CH _2. Among them, those having a polymerizable group, that is, a vinyl group, an allyl group, or — [CH (R ⁹ ) —CH (R ¹⁰ ) —O] _a —R ¹¹ or — [(CH ₂ ) _b —O] _c —R ¹¹ , and R ¹¹ is —CO—CH═CH _2. Or those in which —CO—C (CH ₃ ) ═CH ₂ is preferred, and in particular, R ⁵ , R ^{5 ′} , R ^{5 ''} , R ⁶ and R ^{6 ′} are preferably each independently a vinyl group, an allyl group, a 2-methacryloyloxyethyl group, or a 2-acryloyloxyethyl group.

R ⁵ , R ^{5 ′} , R ^{5 ″} , R ⁶ and R ^{6 ′} in the organic acid compound are methyl group, ethyl group, benzyl group, phenyl group, vinyl group, allyl group, or — [CH (R ⁹ ) —CH (R ¹⁰ ) —O] _a —R ¹¹ or — [(CH ₂ ) _b —O] _c —R ¹¹ , and R ¹¹ is —CO—CH═CH ₂ or —CO—C. By being (CH ₃ ) = CH ₂ , the pigment dispersibility can be improved. R ⁵ , R ^{5 ′} , R ^{5 ″} , R ⁶ and R ^{6 ′} are a vinyl group, an allyl group, or — [CH (R ⁹ ) —CH (R ¹⁰ ) —O] _a —R ¹¹ or — [(CH ₂ ) _b —O] _c —R ¹¹ and R ¹¹ is —CO—CH═CH ₂ or —CO—C (CH ₃ ) ═CH ₂ , whereby the organic acid compound is A polymerizable group. In such a case, the above-mentioned polymerizable groups and / or the above-mentioned polymerizable groups and the negative-type resist composition for color filters are exposed during exposure when forming a colored layer using the negative-type resist composition for color filters. It is possible to easily polymerize an alkali-soluble resin, a polyfunctional monomer, and the like contained in the pigment, and the pigment dispersant can be stably present in the colored layer of the color filter. 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.

  Further, 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 is high. Since the molecular weight is increased, the negative resist composition for a color filter at an unexposed portion can be made particularly excellent in alkali developability during development for forming a colored layer.

Here, the reason why the polymerizable groups are particularly excellent in alkali developability due to polymerization is presumed as follows.
That is, all of the added pigment dispersant does not contribute to the improvement of the dispersibility of the pigment described later, but a part of the pigment dispersant is present in a free state from the pigment. In addition, since the pigment dispersant generally lowers alkali developability, if there is a large amount of the pigment dispersant in a free state, it inhibits alkali development during the development of the colored layer. become.
On the other hand, the polymerizable groups are polymerized before being used for forming the colored layer, and have a high molecular weight, so that when the colored layer is developed, free pigment dispersion is present in the negative resist composition for the color filter. The amount of the agent can be reduced. For this reason, the inhibition of alkali development by the free pigment dispersant can be reduced, and the negative resist composition for color filter in the unexposed area can be made particularly excellent in alkali developability.

  Furthermore, when the organic acid compound contains a polymerizable group, the polymerizable groups of the organic acid compound can be polymerized in the vicinity of the pigment after the pigment is dispersed. As a result, the pigment dispersant is fixed around the pigment, and the dispersibility and dispersion stability of the pigment can be improved.

  The content of the organic acid compound in the pigment dispersant of the present invention is not particularly limited as long as good dispersion stability is exhibited. Generally, the amino acid compound is contained in the structural unit (1). It is about 0.05 to 4.0 mol%, preferably 0.1 to 2.0 mol%, more preferably 0.2 to 1.0 mol%. 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.

<Production of salt-type graft copolymer>
As a method for producing a salt-type graft copolymer used as a pigment dispersant of the present invention, an amino group having the structural unit (1) and the structural unit (2) and having the structural unit (1) is used. Any method can be used as long as it can produce a salt formed with the organic acid compound represented by the general formula (III) and / or the general formula (IV). In the present invention, the graft copolymer is first obtained as described above, and then dissolved or dispersed in a solvent described later, and then the organic acid compound is added to the solvent and stirred. it can. In the above polymerization, additives generally used for polymerization such as a polymerization initiator and a chain transfer agent may be used.

Next, the negative resist composition for color filters of the present invention will be described.
[Negative resist composition for color filter]
The negative resist composition for color filter of the present invention has (A) a structural unit (1) represented by the following general formula (I) and a structural unit (2) represented by the following general formula (II). And a pigment which is a graft copolymer in which the amino group of the structural unit (1) and the organic acid compound represented by the following general formula (III) and / or the following general formula (IV) form a salt. Negative resist composition for color filters, comprising a dispersant, (B) a pigment, (C) an alkali-soluble resin, (D) a polyfunctional monomer, (E) a photoinitiator, and (F) a solvent. It is.

［式（Ｉ）〜（ＩＶ）中、Ｒ^１及びＲ^１’は、それぞれ独立に水素原子又はメチル基、Ｒ^２及びＲ^４は、それぞれ独立に炭素数１〜８のアルキレン基、−［ＣＨ（Ｒ^７）−ＣＨ（Ｒ^８）−Ｏ］_ｘ−ＣＨ（Ｒ^７）−ＣＨ（Ｒ^８）−、又は−［（ＣＨ_２）_ｙ−Ｏ］_ｚ−（ＣＨ_２）_ｙ−で示される２価の基、Ｒ^３及びＲ^３’は、それぞれ独立に水素原子又は炭素数１〜８のアルキル基、Ａは、１個以上の重合性基を有する有機基である。
Ｒ^５及びＲ^５’は、それぞれ独立に水素原子、水酸基、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、ベンジル基、フェニル基、ビフェニル基、−［ＣＨ（Ｒ^９）−ＣＨ（Ｒ^１０）−Ｏ］_ａ−Ｒ^１１、−［（ＣＨ_２）_ｂ−Ｏ］_ｃ−Ｒ^１１、又は−Ｏ−Ｒ^４’’で示される１価の基であり、Ｒ^４及びＲ^４’のいずれかは炭素原子を含む。Ｒ^４’’は、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、ベンジル基、フェニル基、ビフェニル基、−［ＣＨ（Ｒ^９）−ＣＨ（Ｒ^１０）−Ｏ］_ａ−Ｒ^１１、−［（ＣＨ_２）_ｂ−Ｏ］_ｃ−Ｒ^１１で示される１価の基である。
Ｒ^６は、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、ベンジル基、フェニル基、ビフェニル基、−［ＣＨ（Ｒ^９）−ＣＨ（Ｒ^１０）−Ｏ］_ａ−Ｒ^１１、−［（ＣＨ_２）_ｂ−Ｏ］_ｃ−Ｒ^１１、又は−Ｏ−Ｒ^５’で示される１価の基である。Ｒ^５’は、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、ベンジル基、フェニル基、ビフェニル基、−［ＣＨ（Ｒ^９）−ＣＨ（Ｒ^１０）−Ｏ］_ａ−Ｒ^１１、−［（ＣＨ_２）_ｂ−Ｏ］_ｃ−Ｒ^１１で示される１価の基である。
Ｒ^７、Ｒ^８、Ｒ^９及びＲ^１０は、それぞれ独立に水素原子又はメチル基であり、Ｒ^１１は、水素原子、あるいは炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、ベンジル基、フェニル基、ビフェニル基、−ＣＨＯ、−ＣＨ_２ＣＨＯ、−ＣＯ−ＣＨ＝ＣＨ_２、−ＣＯ−Ｃ（ＣＨ_３）＝ＣＨ_２又は−ＣＨ_２ＣＯＯＲ^１２で示される１価の基であり、Ｒ^１２は水素原子又は炭素数１〜５のアルキル基である。
ｘ及びａは１〜１８の整数、ｙ及びｂは１〜５の整数、ｚ及びｃは１〜１８の整数を示す。ｍ及びｎは１〜２００の整数を示す。ｌは１〜５の整数、ｐは、５〜２００の整数を示す。］

[In the formulas (I) to (IV), R ¹ and R ^{1 ′} are each independently a hydrogen atom or a methyl group, R ² and R ⁴ are each independently an alkylene group having 1 to 8 carbon atoms, — [CH _{^{(R 7) -CH (R 8}} ) -O] x -CH (R 7) -CH (R 8) -, or _{- [(CH 2) y -O} ] z - (CH 2) y - represented by The divalent group, R ³ and R ^{3 ′} are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and A is an organic group having one or more polymerizable groups.
R ⁵ and R ^{5 ′} 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, a benzyl group, a phenyl group, a biphenyl group, or — [CH (R ⁹ ). —CH (R ¹⁰ ) —O] _a —R ¹¹ , — [(CH ₂ ) _b —O] _c —R ¹¹ , or —O—R ^{4 ″} , a monovalent group represented by R ⁴ and Any of R ^{4 ′} includes a carbon atom. R ^{4 ″} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a benzyl group, a phenyl group, a biphenyl group, — [CH (R ⁹ ) —CH (R ¹⁰ ) —O] _a -R ^11, _- a _{[(CH 2) b -O]} 1 monovalent group represented by c ^{-R 11.}
R ⁶ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a benzyl group, a phenyl group, a biphenyl group, — [CH (R ⁹ ) —CH (R ¹⁰ ) —O] _a —R. ¹¹ ,-[(CH ₂ ) _b —O] _c —R ¹¹ , or a monovalent group represented by —O—R ^{5 ′} . R ^{5 ′} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a benzyl group, a phenyl group, a biphenyl group, — [CH (R ⁹ ) —CH (R ¹⁰ ) —O] _a —. R ¹¹ is a monovalent group represented by — [(CH ₂ ) _b —O] _c —R ¹¹ .
R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom or a methyl group, and R ¹¹ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, A monovalent group represented by benzyl group, phenyl group, biphenyl group, —CHO, —CH ₂ CHO, —CO—CH═CH ₂ , —CO—C (CH ₃ ) ═CH ₂ or —CH ₂ COOR ^{12. There, R 12} is hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
x and a are integers of 1 to 18, y and b are integers of 1 to 5, and z and c are integers of 1 to 18. m and n represent an integer of 1 to 200. l represents an integer of 1 to 5, and p represents an integer of 5 to 200. ]

The negative resist composition for a color filter of the present invention is a polymer in which the pigment dispersant used is the salt-type graft copolymer according to the present invention, so that the adsorptivity to the pigment is increased while the grafted polymer is grafted. Since the chain is soluble in the (F) solvent, the (B) pigment can be stabilized in the (F) solvent. As a result, (B) the pigment has excellent dispersibility and stability. It can be.
Moreover, since the salt formation site | part of the pigment dispersant used has high solubility with respect to the aqueous alkali solution at the time of alkali development, it can be made excellent in alkali developability. 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.

  In addition, since the negative resist composition for color filters of the present invention uses the pigment dispersant of the present invention, as described above, it adversely affects alkali developability, heat resistance and solvent resistance when a coating film is formed. It also has the effect of not giving. Furthermore, there is an effect that pattern formability and adhesion to a substrate are improved. Moreover, the heat resistance of the coating film is also improved.

Hereinafter, the constituent components contained in the negative resist composition for a color filter of the present invention will be described in order.
((A) Pigment dispersant)
Since the (A) pigment dispersant used in the negative resist composition for a color filter of the present invention is the pigment dispersant of the present invention, the description of (A) the pigment dispersant is omitted here.
In the negative resist composition for a color filter of the present invention, as the pigment dispersant as the component (A), 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 is appropriately selected according to the type of pigment used, the solid content concentration in the negative resist composition, and the like, but is usually 5 to 200 parts by mass with respect to 100 parts by mass of the pigment described later. It is a range, It is preferable that it is 10-100 mass parts, 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 dispersed uniformly, and the blending ratio of the alkali-soluble resin and the polyfunctional monomer is not relatively lowered, which is sufficient. A colored layer having hardness can be formed.

((B) Pigment)
In the negative resist composition for a color filter of the present invention, the pigment used as the component (B) is not particularly limited as long as it can produce a desired color when a colored layer of the color filter is formed. Various organic or inorganic colorants can be used alone or in admixture of two or more.
<Type of pigment>
As the organic colorant, for example, dyes, organic pigments, natural pigments, and the like can be used. Specific examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists).
Examples of such compounds include C.I. I. Pigment yellow 1, C.I. I. Pigment yellow 3, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180, C.I. I. Yellow pigments such as C.I. Pigment Yellow 185; I. Pigment red 1, C.I. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 242, C.I. I. Pigment red 254, C.I. I. Red pigments such as C.I. Pigment Red 177; I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. C.I. Blue pigments such as CI Pigment Blue 15: 6; I. Pigment Violet 23 such as Pigment Violet 23; and Pigment Green 36, C.I. I. And pigments having a color index (C.I.) number such as CI pigment green 58.

  Further, as the inorganic colorant, for example, inorganic pigments, extender pigments and the like can be used. Specific examples include titanium oxide, silica, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, Bengala (red iron oxide (III)), cadmium red, ultramarine blue, bitumen, chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, carbon black and the like can be mentioned.

<Particle particle size>
The average particle diameter of the pigment used in the present invention is not particularly limited as long as it can produce a desired color when it is used as a colored layer of a color filter, and varies depending on the type of pigment used. It is preferably in the range of ˜100 nm, and more preferably in the range of 10 to 50 nm. When the average particle diameter of the pigment is within the above range, a liquid crystal display device produced using the negative resist composition for color filters of the present invention can be made to have high contrast and high quality. In addition, with conventional pigment dispersants, as the particle size of the pigment becomes smaller, a large amount of pigment dispersant is required, which may cause problems such as reduced alkali developability and increased residue. Since the pigment dispersant used in the negative resist composition for color filters is excellent in alkali developability, it is less likely to cause such a problem. Therefore, as the average particle size of the pigment is within the above range, the smaller the conventional particle size is, the more the characteristics of the negative resist composition for color filters of the present invention can be exhibited.
In addition, the average particle diameter of the pigment can be obtained by a method of directly measuring the size of primary particles from an electron micrograph. Specifically, the minor axis diameter and major axis diameter of each primary particle were measured, and the average was taken as the particle diameter of the particle. Next, for 100 or more particles, the volume (weight) of each particle was obtained by approximating the obtained particle size to a rectangular parallelepiped, and the volume average particle size was obtained and used as the average particle size. The same result can be obtained regardless of whether the electron microscope is a transmission type (TEM) or a scanning type (SEM).

In the negative resist composition for a color filter of the present invention, the content of the pigment used as the component (B) is not particularly limited as long as a desired color can be formed when the colored layer of the color filter is used. Although it varies depending on the type of pigment used, it is preferably in the range of 20 to 100% by mass, and in the range of 30 to 80% by mass with respect to the solid content other than the pigment in the negative resist composition for color filters. More preferably, it is within. When the content of the pigment is in the above range, a negative resist composition for a color filter capable of forming a colored layer capable of forming a desired color can be obtained. Further, in the negative resist composition for a color filter, Can be uniformly dispersed.
In addition, the said solid content is all things other than the solvent mentioned above, and also contains the polyfunctional monomer etc. which are melt | dissolving in the solvent.

((C) Alkali-soluble resin)
In the negative resist composition for a color filter of the present invention, as the alkali-soluble resin used as the component (C), those generally used for negative resists can be used, and the alkali-soluble resin is soluble in an alkaline aqueous solution. There is no particular limitation, and 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) acryl And at least one selected from the group consisting of silicate, benzyl (meth) acrylate, styrene, γ-methylstyrene, N-vinyl-2-pyrrolidone, glycidyl (meth) acrylate, and the like, and (meth) acrylic acid and acrylic acid. Examples include copolymers comprising one or more selected from a monomer (for example, M-5600 manufactured by Toagosei Chemical Co., Ltd.), itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, and anhydrides thereof. it can. Further, 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-mentioned 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 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.

  In the negative resist composition for color filters of the present invention, the alkali-soluble resin used as the component (C) may be used singly or in combination of two or more. 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 negative resist composition for a filter. 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.

((D) polyfunctional monomer)
In the negative resist composition for color filters of the present invention, the polyfunctional monomer used as the component (D) is not particularly limited as long as it can be polymerized by a photoinitiator described later, and is usually ethylenic. A compound having two or more unsaturated double bonds 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, phosphoric acid tri (meth) acrylate, 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. When the photo resist (color filter) negative resist composition 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, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like are suitably used.
In the negative resist composition for a color filter of the present invention, the content of the polyfunctional monomer used as the component (D) is not particularly limited, but is 100 parts by weight of the alkali-soluble resin of the component (C). Usually, about 5 to 500 parts by mass, preferably 20 to 300 parts by mass. If the content of the polyfunctional monomer is less than the above range, the photocuring may not sufficiently proceed and the exposed part may be eluted, and if the content of the polyfunctional monomer is more than the above range, the alkali developability is lowered. There is a risk.

(Photoinitiator)
In the negative resist composition for a color filter of the present invention, the photoinitiator used as the component (E) is not particularly limited, and may be appropriately selected from various known photoinitiators. it can. 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-methoxy) Halomethyloxadiazole compounds such as styryl) -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-methoxystyrene 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 Rusulfide, 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.

  In the negative resist composition for a color filter of the present invention, the content of the photoinitiator used as the component (E) is usually 0.01 to 100 with respect to 100 parts by mass of the polyfunctional monomer of the component (D). About part by mass, preferably 5 to 60 parts by mass. 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.

((F) solvent)
In the negative resist composition for color filters of the present invention, the solvent used as the component (F) is an organic solvent that does not react with each component in the resist composition and can dissolve or disperse them. Well, not particularly limited. Specifically, alcohols such as methyl alcohol, ethyl alcohol, N-propyl alcohol, and isopropyl alcohol; ether alcohols such as methoxy alcohol, ethoxy alcohol, methoxyethoxyethanol, ethoxyethoxyethanol, and propylene glycol monomethyl ether; ethyl acetate, Esters such as butyl acetate, 3-methoxybutyl acetate, methyl methoxypropionate, ethyl ethoxypropionate and ethyl lactate; ketones such as acetone, methyl isobutyl ketone and cyclohexanone; methoxyethyl acetate, methoxypropyl acetate, methoxybutyl acetate, Ethoxyethyl acetate, ethyl cellosolve acetate, methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate Ether alcohol acetates such as tate and propylene glycol monomethyl ether acetate; ethers such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether and tetrahydrofuran; N, N-dimethylformamide, N, N-dimethylacetamide, N -Aprotic amides such as methylpyrrolidone; lactones such as γ-butyrolactone; unsaturated hydrocarbons such as benzene, toluene, xylene and naphthalene; saturated hydrocarbons such as n-heptane, n-hexane and n-octane Organic solvents such as systems.

Among these, ether alcohols such as propylene glycol monomethyl ether; ether alcohol acetates such as methoxyethyl acetate, ethoxyethyl acetate, ethyl cellosolve acetate, methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, propylene glycol monomethyl ether acetate; ethylene Ether systems such as glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and propylene glycol diethyl ether; ester systems such as 3-methoxybutyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, and ethyl lactate can be suitably used. .
Especially, as a solvent used for this invention, MBA (3-methoxybutyl acetate), PGMEA (propylene glycol monomethyl ether acetate), DMDG (diethylene glycol dimethyl ether), diethylene glycol methyl ethyl ether, PGME (propylene glycol monomethyl ether) or these Is preferable from the viewpoint of the solubility and coating suitability of the pigment dispersant.

  The content of the solvent as the component (F) in the negative resist composition for color filters of the present invention is not particularly limited as long as each component of the negative resist composition can be uniformly dissolved or dispersed. Not. In the present invention, the component excluding the solvent in the negative resist composition is preferably in the range of 5 to 40% by mass, more preferably in the range of 10 to 30% by mass. By being the said range, it can be set as the viscosity suitable for application | coating.

(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.

(Preparation of negative resist composition for color filter)
As a method for preparing a negative resist composition for a color filter of the present invention, the above-mentioned (A) pigment dispersant, (B) pigment, (C) alkali-soluble resin, (D) polyfunctional monomer, (E) The photoinitiator and various additive components used as required may be any method that can be uniformly dissolved or dispersed in the solvent (F), and is not particularly limited. It can be prepared by mixing.
As a method for preparing the negative resist composition, for example, (1) a pigment dispersion is prepared by adding the above-described pigment dispersant and pigment in a solvent and dispersing using a disperser. A method of adding and mixing an alkali-soluble resin, a polyfunctional monomer, a photoinitiator, and various additive components used as desired, and (2) the above-described pigment dispersant, pigment, and alkali in a solvent A method in which a soluble resin, a polyfunctional monomer, a photoinitiator, and various additive components used as desired are simultaneously added and mixed; and (3) the above pigment dispersant and an alkali-soluble resin in a solvent. And a method in which a polyfunctional monomer, a photoinitiator, and various additive components used as desired are added and mixed, and then a pigment is added and mixed.
Among these methods, the method (1) is preferable from the viewpoint that the aggregation of the pigment can be effectively prevented and the pigment can be uniformly dispersed. In this case, the content of the solvent in the pigment dispersion is preferably in the range of 60 to 90% by mass from the viewpoint of the dispersibility of the pigment, the pigment dispersion stability over time, the chromaticity of the obtained color filter, and the like.

In the preparation of the pigment dispersion in the above method (1), as a disperser for performing a pigment dispersion treatment, a roll mill such as a two-roll or a three-roll, a ball mill such as a ball mill or a vibration ball mill, a paint shaker, a continuous Examples thereof include a bead mill such as a 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 mm, more preferably 0.1 to 1 mm. Moreover, it is preferable to filter with a membrane filter of about 5.0 to 0.2 μm after dispersion. Thereby, the pigment dispersion liquid excellent in the dispersibility of a pigment is obtained.
Further, when the organic acid compound contained in the pigment dispersant used in the present invention has a polymerizable group, for example, after adding the pigment dispersant and the initiator in the solvent, or in the solvent The pigment dispersant may be polymerized after dispersing or dissolving the pigment dispersant, the pigment, and the initiator. In particular, it is preferable to polymerize the pigment dispersants after dispersing or dissolving the pigment dispersant, the pigment, and the initiator in a solvent. Thus, the dispersion stability of the pigment in the negative resist composition for color filters of this invention can be improved by polymerizing pigment dispersants. The polymerization can be carried out by light irradiation and / or heating using a photoinitiator and / or a thermal initiator as appropriate.

Next, the color filter of the present invention will be described.
[Color filter]
The color filter of the present invention is characterized by having a colored layer formed using the above-described negative resist composition for a color filter of the present invention.
Such a color filter of the present invention will be described with reference to the drawings. FIG. 1 is a schematic sectional view showing an example of the color filter of the present invention. According to FIG. 1, the color filter 10 of the present invention has a transparent substrate 1, a light shielding part 2, and a colored layer 3.
The color filter of the present invention has high productivity because it is excellent in alkali developability by forming a colored layer using the above-described negative resist composition for color filter of the present invention. Moreover, by being excellent in alkali developability, it is a high-quality thing with few residue of the negative resist composition for color filters in an unexposed location.

(Colored layer)
The colored layer used in the color filter of the present invention is not particularly limited as long as it is formed using the negative resist composition for color filter of the present invention described above, but is usually on a transparent substrate described later. 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 three or more colored patterns.
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, solid content concentration, viscosity, etc. 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, which will be described later, using a coating means such as a spray coating method, a dip coating method, a bar coating method, a coal coating method, or a spin coating method. Then, a wet coating film is formed.
Next, after drying the wet coating film using a hot plate or oven, it is exposed to light through a mask having a predetermined pattern, and an alkali-soluble resin and a polyfunctional monomer are photopolymerized. And a coating film of a negative resist composition for color filters. Examples of the light source used for exposure include ultraviolet rays such as a low-pressure mercury lamp, a high-pressure mercury lamp, and a metal halide lamp, and an electron beam. The exposure amount is appropriately adjusted depending on the light source used, the thickness of the coating film, and the like.
Moreover, in order to promote a polymerization reaction after exposure, you may heat-process. The heating conditions are appropriately selected depending on the blending ratio of each component in the color filter negative resist composition to be used, the thickness of the coating film, and the like.

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

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

  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 photosensitive resin 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 photosensitive resin composition for the light shielding part.

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

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

(Transparent substrate)
The transparent substrate in the color filter of the present invention is not particularly limited as long as it is a base material transparent to visible light, and a transparent substrate used for a general color filter can be used. Specific examples include inflexible transparent rigid materials such as quartz glass, alkali-free glass, and synthetic quartz plates, or transparent flexible materials having flexibility such as transparent resin films and optical resin plates. It is done.
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 has the color filter of the present invention described above.
Such a liquid crystal display device of the present invention will be described with reference to the drawings. FIG. 2 is a schematic view showing an example of the liquid crystal display device of the present invention. As illustrated in FIG. 2, the liquid crystal display device 40 of the present invention includes a color filter 10, a counter substrate 20 having a TFT array substrate and the like, and a liquid crystal layer formed between the color filter 10 and the counter substrate 20. 30.
Note that the liquid crystal display device of the present invention is not limited to the configuration shown in FIG. 2, but can be a configuration generally known as a liquid crystal display device using a color filter.

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

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

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

Production Example 1 Production of Graft Copolymer A A 500 mL round bottom four-neck separable flask equipped with a cooling tube, a dropping funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer was mixed with propylene glycol monomethyl ether acetate (PGMEA) as a solvent. 60 parts by mass, caprolactone-modified hydroxyethyl acrylate (“Placcel FA10L (trade name)” manufactured by Daicel Chemical Industries, Ltd.) 28.6 parts by mass (solid content 20% by mass), dimethylaminoethyl methacrylate (DMAEMA, Kanto Chemical ( Co., Ltd.) 5.0 parts by mass, and 0.25 parts by mass of 2-mercaptoethanol (manufactured by Kanto Chemical Co., Ltd.) as a chain transfer agent was added and stirred, and nitrogen substitution was sufficiently performed while maintaining at 90 ° C. . Subsequently, Plaxel FA10L 28.6 parts by mass (solid content 20% by mass), DMAEMA 5.0 parts by mass and 2,2′-azobisisobutyronitrile (AIBN, manufactured by Kanto Chemical Co., Ltd.) 0.2 parts by mass as a catalyst A solution in which 60 parts by mass of PGMEA was dissolved was dropped over 1 hour using a dropping funnel, and the mixture was stirred for 2 hours while maintaining at 90 ° C. Next, 0.2 part by weight of AIBN and 20 parts by weight of PGMEA were added dropwise over 30 minutes, and the mixture was stirred for 2 hours while maintaining at 90 ° C. The obtained graft copolymer solution was reprecipitated in hexane, and purified by filtration and vacuum drying. The graft copolymer A thus obtained was confirmed by GPC under the conditions of N-methylpyrrolidone, 0.01 mol / L lithium bromide added / polystyrene standard. 1)) and Plaxel FA10L-derived structural unit (structural unit (2)) have a weight ratio of 1/4, a weight average molecular weight Mw: 12338, a number average molecular weight Mn: 4705, and a molecular weight distribution Mw / Mn of 2.62. there were.

Production Example 2 Production of Terminal Polymerizable Group-Containing Graft Copolymer A Graft copolymer A 33.3 obtained in Production Example 1 was placed in a 500 mL round bottom 4-neck separable flask equipped with a nitrogen inlet and a mechanical stirrer. 90 parts by mass of PGMEA as a part by mass and a solvent were added, and the mixture was stirred at room temperature and sufficiently substituted with nitrogen. Next, 6.0 parts by mass of a bifunctional acrylate compound (1,1-bis (acryloyloxymethyl) ethyl isocyanate (“Karenz BEI” manufactured by Showa Denko KK)) and dibutyltin dilaurate as a catalyst (Kanto Chemical Co., Ltd.) )) 0.02 parts by mass and 3,5-dibutyl-4-hydroxytoluene (BHT, manufactured by Kanto Chemical Co., Ltd.) 0.03 parts by mass were added and stirred at room temperature for 24 hours. The obtained graft copolymer solution was reprecipitated in hexane, and purified by filtration and vacuum drying. When the terminal polymerizable group-containing graft copolymer A thus obtained was confirmed by GPC, the DMAEMA-derived structural unit (structural unit (1)), Plaxel FA10L-derived structural unit (structural unit (2)), The weight ratio of the structure derived from Karenz BEI was 1/4 / 0.7, the weight average molecular weight Mw: 13993, the number average molecular weight Mn: 5584, and the molecular weight distribution Mw / Mn was 2.50.

Example 1 Preparation of Pigment Dispersant Solution A (Salt-type Graft Copolymer Solution A) The terminal polymerizable group-containing graft copolymer A 3 obtained in Production Example 2 was added to 14.56 parts by mass of PGMEA in a plastic bottle. Dissolve parts by weight, and dimethacryloyloxyethyl acid phosphate (“light ester P-2M” manufactured by Kyoeisha Chemical Co., Ltd.), which is a salt-forming component, is 0.64 parts by weight (equimolar to the DMAEMA unit of the graft copolymer). The salt-type graft copolymer solution A having a solid content of 20% by mass was prepared by stirring at room temperature for 2 hours to obtain the pigment dispersant of the present invention.

Example 2 Negative resist composition A for color filter
<Preparation of pigment dispersion>
As a pigment dispersant, 6 parts by weight (solid content 1.2 parts by weight) of the pigment dispersant solution A obtained in Example 1 as a dispersion resin is added to a solvent part of propylene glycol methyl ether acetate (PGMEA). 2.71 parts by mass of methacrylic acid / methyl methacrylate / benzyl methacrylate copolymer (molar ratio: 10/30/50, weight average molecular weight: 9000, acid value: 70 mg KOH / g, active ingredient content: 44% by mass) As a green pigment, 2.16 parts by mass of Pigment Green 58 and 0.84 parts by mass of Pigment Yellow 150 were added, and 60 parts by mass of zirconia beads having a particle size of 2 mm were put into a mayonnaise bin, and a paint shaker was preliminarily crushed. Shake for 1 hour (manufactured by Asada Tekko Co., Ltd.), and then 30 parts by mass of the dispersion and zirconia with a particle size of 0.1 mm. Put a's 60 parts by weight mayonnaise bottle, for 3 hours dispersed by a paint shaker as well as the disintegration, to prepare a pigment dispersion.

<Preparation of resist composition>
In 17.5 parts by mass of the pigment dispersion obtained above (1.75 parts by mass of pigment, 0.7 parts by mass of dispersant), a methacrylic acid / methyl methacrylate / benzil methacrylate copolymer 1. 67 parts by mass, dipentaerythritol hexaacrylate as a polyfunctional monomer (0.95 parts by mass of “KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.), 2-methyl-1- [4- (methylthio) phenyl]-as a photoinitiator Add 0.43 parts by mass of 2-morpholinopropan-1-one (“IRGACURE907” manufactured by Ciba Specialty Chemicals Co., Ltd.) and 4.46 parts by mass of PGMEA as a solvent, and then mix until uniform. By filtering with a pressure filtration device having a mesh size of 0.2 μm, a negative resist composition A for color filters was obtained.

Comparative Example 1
Instead of the pigment dispersant solution A, a pigment dispersant solution B having a solid content of 20% by mass obtained by dissolving 30 parts by mass of the terminal polymerizable group-containing graft copolymer A obtained in Production Example 2 in 120 parts by mass of PGMEA A negative resist composition B for color filters was obtained in the same manner as in Example 2 except that the above was used.

Comparative Example 2
3 parts by mass of the graft copolymer A obtained in Production Example 1 was dissolved in 14.56 parts by mass of PGMEA, and dimethacryloyloxyethyl acid phosphate (Kyoeisha Chemical Co., Ltd. “Light Ester P— 2M ") was added at 0.64 parts by mass and stirred for 2 hours at room temperature, except that the pigment dispersant solution C having a solid content of 20% by mass was used instead of the pigment dispersant solution A. Similarly, a negative resist composition C for color filters was obtained.

  The color filter negative resist compositions obtained in Example 2, Comparative Example 1 and Comparative Example 2 have pigment dispersibility, alkali developability (development time and μm line & space resolution), and optical performance (contrast). evaluated.

<Evaluation of pigment dispersibility>
As an evaluation of the pigment dispersibility of the negative resist composition for color filters obtained in each example, for the pigment dispersion used in the preparation of the negative resist composition for color filters, the average of the pigment particles in the pigment dispersion The particle size and viscosity were measured. Nikkiso Co., Ltd. “Microtrac particle size distribution meter” is used for the measurement of the average particle size, and “MCR301 (model number)” manufactured by Nippon Sibel Hegner Co., Ltd. is used for the viscosity measurement. The shear rate is 60 rpm. The shear viscosity was measured. The results are shown in Table 1.

<Alkali developability evaluation>
The negative resist composition for color filter obtained in each example was applied onto a 10 mm × 10 mm glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.) with a thickness of 0.7 mm using a spin coater. Then, it was dried at 80 ° C. for 3 minutes using a hot plate to form a green colored layer having a thickness of 2.7 μm. This colored layer was irradiated with ultraviolet rays of 100 mJ / cm ² using a super high pressure mercury lamp through a photomask. Thereafter, the glass plate on which the colored layer was formed was subjected to shower development for 1 minute using a 0.05% by mass potassium hydroxide aqueous solution as an alkaline developer, and the adhesion and resolution were evaluated. At this time, the development time was measured until the colored layer was completely dissolved and the glass surface where the colored layer was formed appeared.
After the above alkali development, the substrate is further washed with ultrapure water for 60 seconds. The resolution (μm line & space resolution) of the obtained colored layer and the adhesion (minimum value of μm independent fine line width) are measured with an optical microscope. Was observed.
The results obtained are shown in Table 1.

<Optical performance evaluation>
The negative resist composition for color filter obtained in each example was applied onto a glass substrate (“NA35”, manufactured by NH Techno Glass Co., Ltd.) using a spin coater, and then applied using a hot plate. A green colored layer having a thickness of 2.7 μm was formed by drying at 3 ° C. for 3 minutes. This colored layer was irradiated with ultraviolet rays of 100 mJ / cm ² using an ultrahigh pressure mercury lamp without using a photomask. After measuring the contrast of the colored layer after ultraviolet irradiation (before baking), the glass plate on which this colored layer was formed was post-baked in a clean oven at 230 ° C., and the contrast of the obtained green color filter substrate was measured. The contrast was measured using “Contrast measuring device CT-1B” manufactured by Aisaka Electric Co., Ltd.

The following can be seen from Table 1.
In Example 2, the pigment dispersibility was good. The alkali developability was good at a development time of 14 seconds, and the resolution and adhesion were excellent. In Example 2, since the strength of the coating film increased due to the polymerization of double bonds present at the polymer terminal, it is presumed that good adhesion was obtained even if development was performed under severe conditions. It was also shown that the degree of contrast reduction due to post-baking was small and the heat resistance was good.
On the other hand, Comparative Example 1 used a pigment dispersant having a double bond at the polymer terminal but not forming a salt, so that the pigment dispersibility was poor. Since the pigment dispersibility was poor, the contrast was also poor. Further, the development time, adhesion, and resolution were all inferior to those of the examples.
In Comparative Example 2, the pigment dispersibility was good because a pigment dispersant which does not have a double bond at the polymer end but forms a salt is used. Although the development time was short and the resolution was good, the adhesion was inferior to the examples. In addition, the contrast after the UV irradiation was almost the same as the example because the pigment dispersibility was good, but the contrast decreased after the post-baking, and the heat resistance may be inferior to the example. Indicated.

  The pigment dispersant of the present invention is excellent in pigment dispersibility, has properties such as imparting alkali solubility, and can provide a color filter with good quality and a liquid crystal display device having the same. The negative resist composition for a color filter of the present invention provides a color filter having excellent properties such as excellent pigment dispersibility and excellent alkali developability, and a liquid crystal display device having the same. it can.

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.

Explanation of symbols

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

Claims (11)

It has a structural unit (1) represented by the following general formula (I) and a structural unit (2) represented by the following general formula (II), and further has an amino group that the structural unit (1) has, A pigment dispersant, which is a graft copolymer in which a salt is formed with an organic acid compound represented by the general formula (III) and / or the following general formula (IV).

[In the formulas (I) to (IV), R ¹ and R ^{1 ′} are each independently a hydrogen atom or a methyl group, R ² and R ⁴ are each independently an alkylene group having 1 to 8 carbon atoms, — [CH _{^{(R 7) -CH (R 8}} ) -O] x -CH (R 7) -CH (R 8) -, or _{- [(CH 2) y -O} ] z - (CH 2) y - represented by The divalent group, R ³ and R ^{3 ′} are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and A is an organic group having one or more polymerizable groups.
R ⁵ and R ^{5 ′} 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, a benzyl group, a phenyl group, a biphenyl group, or — [CH (R ⁹ ). _{^{-CH (R 10) -O] a}} -R 11, - [(CH 2) b -O] c -R 11, or a monovalent group represented by ^{-O-R 4 '', R} 4 and Any of R ^{4 ′} includes a carbon atom. R ^{4 ″} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a benzyl group, a phenyl group, a biphenyl group, — [CH (R ⁹ ) —CH (R ¹⁰ ) —O] _a -R ^11, _- a _{[(CH 2) b -O]} 1 monovalent group represented by c ^{-R 11.}
R ⁶ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a benzyl group, a phenyl group, a biphenyl group, — [CH (R ⁹ ) —CH (R ¹⁰ ) —O] _a —R. ¹¹ ,-[(CH ₂ ) _b —O] _c —R ¹¹ , or a monovalent group represented by —O—R ^{5 ′} . R ^{5 ′} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a benzyl group, a phenyl group, a biphenyl group, — [CH (R ⁹ ) —CH (R ¹⁰ ) —O] _a —. R ¹¹ is a monovalent group represented by — [(CH ₂ ) _b —O] _c —R ¹¹ .
R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom or a methyl group, and R ¹¹ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, A monovalent group represented by benzyl group, phenyl group, biphenyl group, —CHO, —CH ₂ CHO, —CO—CH═CH ₂ , —CO—C (CH ₃ ) ═CH ₂ or —CH ₂ COOR ^12. And R ¹² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
x and a are integers of 1 to 18, y and b are integers of 1 to 5, and z and c are integers of 1 to 18. m and n represent an integer of 1 to 200. l represents an integer of 1 to 5, and p represents an integer of 5 to 200. ] The pigment dispersant according to claim 1, wherein R ⁵ and / or R ^{5 '} in the general formula (III) and / or R ⁶ in the general formula (IV) has a polymerizable group.   The pigment dispersant according to claim 1 or 2, wherein the polymerizable group is a (meth) acryloyl group, a vinyl group, or an allyl group.   The pigment dispersant according to any one of claims 1 to 3, wherein A in the structural unit (2) represented by the general formula (II) contains a polyfunctional monomer residue. (A) An amino group having a structural unit (1) represented by the following general formula (I) and a structural unit (2) represented by the following general formula (II), and further having the structural unit (1) A pigment dispersant which is a graft copolymer in which a salt is formed with the organic acid compound represented by the following general formula (III) and / or the following general formula (IV), (B) a pigment, and (C) A negative resist composition for a color filter, comprising an alkali-soluble resin, (D) a polyfunctional monomer, (E) a photoinitiator, and (F) a solvent.

[In the formulas (I) to (IV), R ¹ and R ^{1 ′} are each independently a hydrogen atom or a methyl group, R ² and R ⁴ are each independently an alkylene group having 1 to 8 carbon atoms, — [CH _{^{(R 7) -CH (R 8}} ) -O] x -CH (R 7) -CH (R 8) -, or _{- [(CH 2) y -O} ] z - (CH 2) y - represented by divalent group, R ³ and R ^{3 'are} each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, a is an organic group having one or more polymerizable groups.
R ⁵ and R ^{5 ′} 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, a benzyl group, a phenyl group, a biphenyl group, or — [CH (R ⁹ ). —CH (R ¹⁰ ) —O] _a —R ¹¹ , — [(CH ₂ ) _b —O] _c —R ¹¹ , or —O—R ^{4 ″} , a monovalent group represented by R ⁴ and Any of R ^{4 ′} includes a carbon atom. R ^{4 ″} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a benzyl group, a phenyl group, a biphenyl group, — [CH (R ⁹ ) —CH (R ¹⁰ ) —O] _a -R ^11, _- a _{[(CH 2) b -O]} 1 monovalent group represented by c ^{-R 11.}
R ⁶ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a benzyl group, a phenyl group, a biphenyl group, — [CH (R ⁹ ) —CH (R ¹⁰ ) —O] _a —R. ¹¹ ,-[(CH ₂ ) _b —O] _c —R ¹¹ , or a monovalent group represented by —O—R ^{5 ′} . R ^{5 ′} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a benzyl group, a phenyl group, a biphenyl group, — [CH (R ⁹ ) —CH (R ¹⁰ ) —O] _a —. R ¹¹ is a monovalent group represented by — [(CH ₂ ) _b —O] _c —R ¹¹ .
R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom or a methyl group, and R ¹¹ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, A monovalent group represented by benzyl group, phenyl group, biphenyl group, —CHO, —CH ₂ CHO, —CO—CH═CH ₂ , —CO—C (CH ₃ ) ═CH ₂ or —CH ₂ COOR ^12. And R ¹² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
x and a are integers of 1 to 18, y and b are integers of 1 to 5, and z and c are integers of 1 to 18. m and n represent an integer of 1 to 200. l represents an integer of 1 to 5, and p represents an integer of 5 to 200. ] The negative type for a color filter according to claim 5, wherein R ⁵ and / or R ^{5 '} in the general formula (III) and / or R ⁶ in the general formula (IV) has a polymerizable group. Resist composition.   The negative resist composition for a color filter according to claim 5 or 6, wherein the polymerizable group is a (meth) acryloyl group, a vinyl group, or an allyl group.   The negative resist composition for a color filter according to any one of claims 5 to 7, wherein A in the structural unit (2) represented by the general formula (II) contains a polyfunctional monomer residue.   (B) The negative resist composition for color filters according to any one of claims 5 to 8, wherein the pigment has an average particle size of 10 to 100 nm.   A color filter comprising a colored layer formed using the negative resist composition for a color filter according to claim 5.   A liquid crystal display device comprising the color filter according to claim 10.

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