JP2011075629A - Pigment dispersion liquid for color filter, negative resist composition for color filter, color filter, and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a negative resist composition for a color filter, the composition excellent in pigment dispersibility as well as alkali developability. <P>SOLUTION: The negative resist composition for a color filter contains (A) a pigment dispersant, (B) a pigment, (C) an alkali-soluble resin, (D) a polyfunctional monomer, (E) a photoinitiator, and (F) a solvent, wherein the (A) pigment dispersant is a polyurethane-based grafted copolymer expressed by general formula (I), and further, is a grafted copolymer in which at least a part of tertiary amino groups of the above polyurethane grafted copolymer forms a salt with an organic acid compound. In formula (I), each of R<SP>1</SP>independently represents a 1-12C alkylene group; R<SP>2</SP>represents a polymer chain having at least one of structural units expressed by general formula (IV) or general formula (V); R<SP>3</SP>represents a divalent group selected from a group comprising an alkylene group, an arylene group and their combination; m is 2 to 200; R<SP>4</SP>represents a hydrogen atom or a methyl group; R<SP>5</SP>represents a monovalent group such as a 1-18C alkyl group and aralkyl group; l represents an integer of 1 to 5; and n' and n" each represent an integer of 5 to 200. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a pigment dispersion for color filters, a negative resist composition for color filters, a color filter, and a liquid crystal display device. More specifically, the present invention is a color filter pigment dispersion having excellent pigment dispersibility, a negative resist composition for color filters having excellent pigment dispersibility and excellent alkali developability, and formed using the resist composition. The present invention relates to a color filter 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, with regard to the performance of the liquid crystal display, further improvement in image quality such as improvement in contrast and color reproducibility and reduction in power consumption are strongly desired.
Under such circumstances, there is an increasing demand for higher brightness, higher contrast, and improved color reproducibility even in a color filter having a function of displaying liquid crystal displays in color.

  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. However, in general, a color filter in which a pigment is dispersed has a problem that the degree of polarization controlled by the liquid crystal is disturbed due to light scattering by the pigment. That is, since light leaks when light must be blocked (OFF state) or transmitted light attenuates when light must be transmitted (ON state), display devices in the ON state and the OFF state There is a problem that the upper luminance ratio (contrast ratio) is low.

  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 a pigment dispersant having such excellent dispersibility, a pigment dispersant (Patent Document 1) formed by reacting isocyanate with poly (ethylene glycol) alkyl ether, polyester or polyacrylate, and diamine is disclosed. ing. In addition, the present inventors have disclosed a pigment dispersant comprising a block copolymer in which a salt of an amino group of a polymer structural unit and a specific acidic phosphate ester is formed (Patent Document 2). .

  On the other hand, in Patent Document 3, an amphiphilic comb having a polyurethane chain skeleton having a tertiary amino group and an oligomer chain (alkyl chain, oxyethylene chain) in the side chain as a polymer dispersant for the conductive fine particle aqueous dispersion. Type polyurethane compounds are disclosed.

Special table 2003-506538 gazette JP 2008-242414 A JP 2006-274035 A

In recent years, there has been an increasing demand for higher contrast in liquid crystal display devices, and in order to achieve such a demand, finer pigments are required.
However, the conventional polyurethane type pigment dispersant as disclosed in Patent Document 1 has not been sufficient in the miniaturization of the pigment. By increasing the amount of the pigment dispersant added, it is possible to ensure a uniform dispersibility of the pigment to some extent, but this is insufficient to improve the contrast of the color filter. Furthermore, increasing the amount of the pigment dispersant added causes a decrease in alkali developability, resulting in problems such as a longer time required for alkali development and an unexposed photocurable resist composition remaining on the substrate. There has been a problem that productivity and quality are deteriorated. On the other hand, since the polymer dispersant disclosed in Patent Document 3 is an aqueous dispersion stabilizer, the pigment in an organic solvent used for a color filter cannot be dispersed in the first place.
In Patent Document 2, the present inventors have found a negative resist composition excellent in pigment dispersibility and alkali developability. However, further improvement in pigment dispersibility is desired for higher contrast. Mareta.

  The present invention has been made under such circumstances, and is capable of forming a color filter pigment dispersion excellent in pigment dispersibility, excellent in pigment dispersibility, and capable of forming a high-contrast color filter. It is an object of the present invention to provide an excellent negative resist composition for color filters, 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 present inventors have combined, as a pigment dispersant, an organic phosphate and / or organic sulfonate of a graft copolymer having a specific structure. The present inventors have found that it is possible to form a color filter having excellent pigment dispersibility and high contrast, being excellent in alkali developability, and suitable for the purpose.
The present invention has been completed based on such findings.

The present invention is a pigment dispersion for a color filter having (A) a pigment dispersant, (B) a pigment, and (F) a solvent,
The (A) pigment dispersant is a polyurethane-based graft copolymer represented by the following general formula (I), and at least a part of the tertiary amino group of the polyurethane-based graft copolymer and the following general formula: Provided is a pigment dispersion for a color filter, which is a graft copolymer in which a salt is formed with (II) and / or an organic acid compound represented by the following general formula (III).

［式（Ｉ）中、Ｒ^１はそれぞれ独立に、炭素数１〜１２のアルキレン基であり、Ｒ^２は、下記一般式（ＩＶ）又は一般式（Ｖ）で表される構成単位を少なくとも１種有するポリマー鎖である。Ｒ^３は、アルキレン基、アリーレン基及びこれらの組み合わせよりなる群から選択される２価の基である。ｍは２〜２００である。

[In Formula (I), each R ¹ independently represents an alkylene group having 1 to 12 carbon atoms, and R ² represents at least one structural unit represented by the following General Formula (IV) or General Formula (V). It is a polymer chain with seeds. R ³ is a divalent group selected from the group consisting of an alkylene group, an arylene group, and combinations thereof. m is 2 to 200.

《式（ＩＶ）及び（Ｖ）中、Ｒ^４は水素原子又はメチル基であり、Ｒ^５は炭素数１〜１８のアルキル基、アラルキル基、アリール基、シアノ基、−［ＣＨ（Ｒ^６）−ＣＨ（Ｒ^７）−Ｏ］_ｘ−Ｒ^８、−［（ＣＨ_２）_ｙ−Ｏ］_ｚ−Ｒ^８、−［ＣＯ−（ＣＨ_２）_ｙ−Ｏ］_ｚ−Ｒ^８、−ＣＯ−Ｏ−Ｒ^１０又は−Ｏ−ＣＯ−Ｒ^１１で示される１価の基である。
Ｒ^１０は、炭素数１〜１８のアルキル基、アラルキル基、アリール基、シアノ基、−［ＣＨ（Ｒ^６）−ＣＨ（Ｒ^７）−Ｏ］_ｘ−Ｒ^８、−［（ＣＨ_２）_ｙ−Ｏ］_ｚ−Ｒ^８、又は−［ＣＯ−（ＣＨ_２）_ｙ−Ｏ］_ｚ−Ｒ^８で示される１価の基である。
Ｒ^６、Ｒ^７は、それぞれ独立に水素原子又はメチル基である。
Ｒ^８は、水素原子、あるいは炭素数１〜１８のアルキル基、アラルキル基、アリール基、−ＣＨＯ、−ＣＨ_２ＣＨＯ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のアルキル基であり、Ｒ^１１は、炭素数１〜１８のアルキル基を示す。Ｒ^５に含まれる、アルキル基、アルケニル基、アラルキル基、アリール基はそれぞれ、置換基を有していてもよい。
ｘは１〜１８の整数、ｙは１〜５の整数、ｚは１〜１８の整数を示す。
ｌは１〜５の整数、ｎ’及びｎ”は５〜２００の整数を示す。》
式（ＩＩ）及び式（ＩＩＩ）中、Ｒ^ａ及びＲ^ａ’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、アラルキル基、アリール基、−［ＣＨ（Ｒ^ｃ）−ＣＨ（Ｒ^ｄ）−Ｏ］_ｓ−Ｒ^ｅ、−［（ＣＨ_２）_ｔ−Ｏ］_ｕ−Ｒ^ｅ、又は−Ｏ−Ｒ^ａ’’で示される１価の基であり、Ｒ^ａ及びＲ^ａ’のいずれかは炭素原子を含む。Ｒ^ａ’’は、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、アラルキル基、アリール基、−［ＣＨ（Ｒ^ｃ）−ＣＨ（Ｒ^ｄ）−Ｏ］_ｓ−Ｒ^ｅ、−［（ＣＨ_２）_ｔ−Ｏ］_ｕ−Ｒ^ｅで示される１価の基である。
Ｒ^ｂは、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、アラルキル基、アリール基、−［ＣＨ（Ｒ^ｃ）−ＣＨ（Ｒ^ｄ）−Ｏ］_ｓ−Ｒ^ｅ、−［（ＣＨ_２）_ｔ−Ｏ］_ｕ−Ｒ^ｅ、又は−Ｏ−Ｒ^ｂ’で示される１価の基である。Ｒ^ｂ’は、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、アラルキル基、アリール基、−［ＣＨ（Ｒ^ｃ）−ＣＨ（Ｒ^ｄ）−Ｏ］_ｓ−Ｒ^ｅ、又は−［（ＣＨ_２）_ｔ−Ｏ］_ｕ−Ｒ^ｅで示される１価の基である。
Ｒ^ｃ及びＲ^ｄは、それぞれ独立に水素原子又はメチル基であり、Ｒ^ｅ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、アラルキル基、アリール基、−ＣＨＯ、−ＣＨ_２ＣＨＯ、−ＣＯ−ＣＨ＝ＣＨ_２、−ＣＯ−Ｃ（ＣＨ_３）＝ＣＨ_２又は−ＣＨ_２ＣＯＯＲ^ｆで示される１価の基であり、Ｒ^ｆは水素原子又は炭素数１〜５のアルキル基である。
Ｒ^ａ、Ｒ^ａ’、及びＲ^ｂにおいて、アルキル基、アルケニル基、アラルキル基、アリール基はそれぞれ、置換基を有していてもよい。
ｓは１〜１８の整数、ｔは１〜５の整数、ｕは１〜１８の整数を示す。］

<< In Formula (IV) and (V), R < ⁴ > is a hydrogen atom or a methyl group, R < ⁵ > is a C1-C18 alkyl group, an aralkyl group, an aryl group, a cyano group,-[CH (R < ⁶ >). —CH (R ⁷ ) —O] _x —R ⁸ , — [(CH ₂ ) _y —O] _z —R ⁸ , — [CO— (CH ₂ ) _y —O] _z —R ⁸ , —CO—O It is a monovalent group represented by —R ¹⁰ or —O—CO—R ¹¹ .
R ¹⁰ is an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, a cyano group, — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —R ⁸ , — [(CH ₂ ) _y. It is a monovalent group represented by —O] _z —R ⁸ or — [CO— (CH ₂ ) _y —O] _z —R ⁸ .
R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group.
R ⁸ is a hydrogen atom, or a monovalent group represented by an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, —CHO, —CH ₂ CHO, or —CH ₂ COOR ¹² , and R ¹² is a hydrogen atom It is an atom or an alkyl group having 1 to 5 carbon atoms, and R ¹¹ represents an alkyl group having 1 to 18 carbon atoms. The alkyl group, alkenyl group, aralkyl group and aryl group contained in R ⁵ may each have a substituent.
x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18.
l represents an integer of 1 to 5, and n ′ and n ″ represent an integer of 5 to 200.
In formula (II) and formula (III), R ^a and R ^{a ′} are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, or an aryl group. , — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — [(CH ₂ ) _t —O] _u —R ^e , or —O—R ^{a ″} a group, one of R ^a and R ^{a 'comprises} a carbon atom. R ^{a ″} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e. ,-[(CH ₂ ) _t —O] _u —R ^e .
R ^b is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — [(CH ₂ ) _t —O] _u —R ^e or a monovalent group represented by —O—R ^{b ′} . R ^{b ′} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , or _- it is a monovalent group represented by _{[(CH 2) t -O]} u -R e.
R ^c and R ^d are each independently a hydrogen atom or a methyl group, and R ^e is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, _{-CHO, -CH 2 CHO, -CO-} CH = CH 2, a monovalent group represented by _{-CO-C (CH 3) =} CH 2 or _-CH 2 COOR ^{f, R f} is hydrogen or C It is an alkyl group of formula 1-5.
In R ^a , R ^{a ′} , and R ^b , each of the alkyl group, alkenyl group, aralkyl group, and aryl group may have a substituent.
s is an integer of 1 to 18, t is an integer of 1 to 5, and u is an integer of 1 to 18. ]

The present invention also includes (A) a pigment dispersant, (B) a pigment, (C) an alkali-soluble resin, (D) a polyfunctional monomer, (E) a photoinitiator, and (F) a solvent. Have
The (A) pigment dispersant is a polyurethane-based graft copolymer represented by the general formula (I), and at least part of the tertiary amino group of the polyurethane-based graft copolymer and the general formula Provided is a negative resist composition for color filters, characterized in that (II) and / or the organic acid compound represented by the general formula (III) is a graft copolymer in which a salt is formed.

In the pigment dispersion for color filter and the negative resist composition for color filter according to the present invention, R ^a , R ^{a ′} and / or R ^{a ″} in the general formula (II) and / or the general formula R ^b and / or R ^{b ′} in (III) is a methyl group, an ethyl group, an aryl group which may have a substituent, an aralkyl group, a vinyl group, an allyl group, or — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , or — [(CH ₂ ) _t —O] _u —R ^e , and R ^e is —CO—CH═CH ₂ or —CO—C ( CH ₃ ) ═CH ₂ is preferable from the viewpoint of pigment dispersibility and pigment dispersion stability.

  In the color filter pigment dispersion and the color filter negative resist composition according to the present invention, in the (A) pigment dispersant, the polyurethane-based graft copolymer of the general formula (I) is tertiary at the end. It is a graft copolymer obtained by polymerization of a polymer having an amino group and a diol and a diisocyanate, and the diisocyanate is a diisocyanate selected from the group consisting of an alicyclic diisocyanate, an araliphatic diisocyanate, and an aromatic diisocyanate. From the viewpoint of the heat resistance of the color filter coating film formed from the negative resist composition for color filters.

  In the pigment dispersion for color filter and the negative resist composition for color filter according to the present invention, the average particle size of the (B) pigment is 10 to 100 nm, so that a high-contrast and high-quality liquid crystal display device can be obtained. This is preferable from the viewpoint of production.

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 comprising the color filter.

ADVANTAGE OF THE INVENTION According to this invention, the pigment dispersion liquid for color filters excellent in pigment dispersibility can be provided.
ADVANTAGE OF THE INVENTION According to this invention, the negative resist composition for color filters which is excellent in pigment dispersibility and excellent in alkali developability can be provided. By using the pigment dispersion or resist composition having excellent pigment dispersibility according to the present invention, it is possible to realize a pixel portion of a color filter with high brightness and high contrast.
Further, according to the present invention, by forming a colored layer using the negative resist composition for a color filter, the color filter having excellent productivity can be obtained because it can be made 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.

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.

[Pigment dispersion for color filter, negative resist composition for color filter]
The pigment dispersion for a color filter of the present invention (hereinafter sometimes simply referred to as a pigment dispersion) contains (A) a pigment dispersant, (B) a pigment, and (F) a solvent. ) The pigment dispersant has the following properties.
Moreover, the negative resist composition for color filters of the present invention (hereinafter sometimes simply referred to as a resist composition) comprises (A) a pigment dispersant, (B) a pigment, (C) an alkali-soluble resin, And (D) a polyfunctional monomer, (E) a photoinitiator, and (F) a solvent, wherein the (A) pigment dispersant has the following properties.
Hereinafter, the constituent components will be described in order.

((A) Pigment dispersant)
In the pigment dispersion for a color filter of the present invention, the pigment dispersant used as the component (A) is a polyurethane-based graft copolymer represented by the following general formula (I), and further, the polyurethane-based graft copolymer. The graft copolymer in which at least a part of the tertiary amino group possessed by the organic phosphate compound represented by the following general formula (II) and / or the organic sulfonic acid compound represented by the following general formula (III) forms a salt. It is a polymer (hereinafter sometimes referred to as a salt-type graft copolymer).

［式（Ｉ）中、Ｒ^１はそれぞれ独立に、炭素数１〜１２のアルキレン基であり、Ｒ^２は、下記一般式（ＩＶ）又は一般式（Ｖ）で表される構成単位を少なくとも１種有するポリマー鎖である。Ｒ^３は、アルキレン基、アリーレン基及びこれらの組み合わせよりなる群から選択される２価の基である。ｍは２〜２００である。

[In Formula (I), each R ¹ independently represents an alkylene group having 1 to 12 carbon atoms, and R ² represents at least one structural unit represented by the following General Formula (IV) or General Formula (V). It is a polymer chain with seeds. R ³ is a divalent group selected from the group consisting of an alkylene group, an arylene group, and combinations thereof. m is 2 to 200.

《式（ＩＶ）及び（Ｖ）中、Ｒ^４は水素原子又はメチル基であり、Ｒ^５は炭素数１〜１８のアルキル基、アラルキル基、アリール基、シアノ基、−［ＣＨ（Ｒ^６）−ＣＨ（Ｒ^７）−Ｏ］_ｘ−Ｒ^８、−［（ＣＨ_２）_ｙ−Ｏ］_ｚ−Ｒ^８、−［ＣＯ−（ＣＨ_２）_ｙ−Ｏ］_ｚ−Ｒ^８、−ＣＯ−Ｏ−Ｒ^１０又は−Ｏ−ＣＯ−Ｒ^１１で示される１価の基である。
Ｒ^１０は、炭素数１〜１８のアルキル基、アラルキル基、アリール基、シアノ基、−［ＣＨ（Ｒ^６）−ＣＨ（Ｒ^７）−Ｏ］_ｘ−Ｒ^８、−［（ＣＨ_２）_ｙ−Ｏ］_ｚ−Ｒ^８、又は−［ＣＯ−（ＣＨ_２）_ｙ−Ｏ］_ｚ−Ｒ^８で示される１価の基である。
Ｒ^６、Ｒ^７は、それぞれ独立に水素原子又はメチル基である。
Ｒ^８は、水素原子、あるいは炭素数１〜１８のアルキル基、アラルキル基、アリール基、−ＣＨＯ、−ＣＨ_２ＣＨＯ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のアルキル基であり、Ｒ^１１は、炭素数１〜１８のアルキル基を示す。Ｒ^５に含まれる、アルキル基、アルケニル基、アラルキル基、アリール基はそれぞれ、置換基を有していてもよい。
ｘは１〜１８の整数、ｙは１〜５の整数、ｚは１〜１８の整数を示す。
ｌは１〜５の整数、ｎ’及びｎ”は５〜２００の整数を示す。》
式（ＩＩ）及び式（ＩＩＩ）中、Ｒ^ａ及びＲ^ａ’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、アラルキル基、アリール基、−［ＣＨ（Ｒ^ｃ）−ＣＨ（Ｒ^ｄ）−Ｏ］_ｓ−Ｒ^ｅ、−［（ＣＨ_２）_ｔ−Ｏ］_ｕ−Ｒ^ｅ、又は−Ｏ−Ｒ^ａ’’で示される１価の基であり、Ｒ^ａ及びＲ^ａ’のいずれかは炭素原子を含む。Ｒ^ａ’’は、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、アラルキル基、アリール基、−［ＣＨ（Ｒ^ｃ）−ＣＨ（Ｒ^ｄ）−Ｏ］_ｓ−Ｒ^ｅ、−［（ＣＨ_２）_ｔ−Ｏ］_ｕ−Ｒ^ｅで示される１価の基である。
Ｒ^ｂは、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、アラルキル基、アリール基、−［ＣＨ（Ｒ^ｃ）−ＣＨ（Ｒ^ｄ）−Ｏ］_ｓ−Ｒ^ｅ、−［（ＣＨ_２）_ｔ−Ｏ］_ｕ−Ｒ^ｅ、又は−Ｏ−Ｒ^ｂ’で示される１価の基である。Ｒ^ｂ’は、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、アラルキル基、アリール基、−［ＣＨ（Ｒ^ｃ）−ＣＨ（Ｒ^ｄ）−Ｏ］_ｓ−Ｒ^ｅ、又は−［（ＣＨ_２）_ｔ−Ｏ］_ｕ−Ｒ^ｅで示される１価の基である。
Ｒ^ｃ及びＲ^ｄは、それぞれ独立に水素原子又はメチル基であり、Ｒ^ｅ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、アラルキル基、アリール基、−ＣＨＯ、−ＣＨ_２ＣＨＯ、−ＣＯ−ＣＨ＝ＣＨ_２、−ＣＯ−Ｃ（ＣＨ_３）＝ＣＨ_２又は−ＣＨ_２ＣＯＯＲ^ｆで示される１価の基であり、Ｒ^ｆは水素原子又は炭素数１〜５のアルキル基である。
Ｒ^ａ、Ｒ^ａ’、及びＲ^ｂにおいて、アルキル基、アルケニル基、アラルキル基、アリール基はそれぞれ、置換基を有していてもよい。
ｓは１〜１８の整数、ｔは１〜５の整数、ｕは１〜１８の整数を示す。］

<< In Formula (IV) and (V), R < ⁴ > is a hydrogen atom or a methyl group, R < ⁵ > is a C1-C18 alkyl group, an aralkyl group, an aryl group, a cyano group,-[CH (R < ⁶ >). —CH (R ⁷ ) —O] _x —R ⁸ , — [(CH ₂ ) _y —O] _z —R ⁸ , — [CO— (CH ₂ ) _y —O] _z —R ⁸ , —CO—O It is a monovalent group represented by —R ¹⁰ or —O—CO—R ¹¹ .
R ¹⁰ is an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, a cyano group, — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —R ⁸ , — [(CH ₂ ) _y. It is a monovalent group represented by —O] _z —R ⁸ or — [CO— (CH ₂ ) _y —O] _z —R ⁸ .
R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group.
R ⁸ is a hydrogen atom, or a monovalent group represented by an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, —CHO, —CH ₂ CHO, or —CH ₂ COOR ¹² , and R ¹² is a hydrogen atom It is an atom or an alkyl group having 1 to 5 carbon atoms, and R ¹¹ represents an alkyl group having 1 to 18 carbon atoms. The alkyl group, alkenyl group, aralkyl group and aryl group contained in R ⁵ may each have a substituent.
x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18.
l represents an integer of 1 to 5, and n ′ and n ″ represent an integer of 5 to 200.
In formula (II) and formula (III), R ^a and R ^{a ′} are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, or an aryl group. , — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — [(CH ₂ ) _t —O] _u —R ^e , or —O—R ^{a ″} a group, one of R ^a and R ^{a 'comprises} a carbon atom. R ^{a ″} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e. ,-[(CH ₂ ) _t —O] _u —R ^e .
R ^b is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — [(CH ₂ ) _t —O] _u —R ^e or a monovalent group represented by —O—R ^{b ′} . R ^{b ′} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , or _- it is a monovalent group represented by _{[(CH 2) t -O]} u -R e.
R ^c and R ^d are each independently a hydrogen atom or a methyl group, and R ^e is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, _{-CHO, -CH 2 CHO, -CO-} CH = CH 2, a monovalent group represented by _{-CO-C (CH 3) =} CH 2 or _-CH 2 COOR ^{f, R f} is hydrogen or C It is an alkyl group of formula 1-5.
In R ^a , R ^{a ′} , and R ^b , each of the alkyl group, alkenyl group, aralkyl group, and aryl group may have a substituent.
s is an integer of 1 to 18, t is an integer of 1 to 5, and u is an integer of 1 to 18. ]

According to the present invention, the pigment dispersant used is a polyurethane-based graft copolymer represented by the above general formula (I), and at least a part of the tertiary amino group of the polyurethane-based graft copolymer. And the organic phosphoric acid compound and / or the organic sulfonic acid compound is a graft copolymer in which a salt is formed, the adsorptive power to the (B) pigment of the nitrogen-containing portion forming the salt-forming site is increased, The specific polymer chain R ² grafted with (F) is soluble in (F) solvent, so that (B) pigment can be stabilized in (F) solvent, and as a result (B ) The pigment can be excellent in dispersibility and stability.

  In addition, by having the organic phosphoric acid compound and / or the organic sulfonic acid compound, the salt forming site formed by the amino group contained in the nitrogen-containing monomer and the organic phosphoric acid compound and / or the organic sulfonic acid compound, Since it has high solubility in an aqueous alkali solution at the time of alkali development, it can be 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 polyurethane-based graft copolymer represented by the general formula (I) can be synthesized by urethane polymerization of a diol compound and a diisocyanate compound described later, an alicyclic skeleton or aromatic group is added to the main chain of the graft copolymer. By being able to easily introduce a group skeleton, it is possible to improve the heat resistance and solvent resistance of the formed coating film.

<Graft copolymer>
The polyurethane-based graft copolymer represented by the general formula (I) is a graft copolymer obtained by polymerization of a polymer having a tertiary amino group and a diol at a terminal and a diisocyanate.
A polymer having a tertiary amino group and a diol at the terminal can be obtained, for example, by reacting a dialkanolamine with a polymer having an acryloyl group at the terminal.

In the general formula (I), ^{R 1} each independently represent an alkylene group having 1 to 12 carbon atoms. Here, the alkylene group having 1 to 12 carbon atoms may be linear or branched, for example, methylene group, ethylene group, trimethylene group, propylene group, various butylene groups, various pentylene groups, various hexylene groups. And various octylene groups. Two R ¹ contained in the repeating unit may be the same or different, and R ¹ may be the same or different between the repeating units.
R ¹ is preferably an alkylene group having 1 to 6 carbon atoms, more preferably a methylene group or an ethylene group, and particularly preferably an ethylene group. If it is in a C1-C6 range, the dispersibility of a pigment can be kept favorable.

In the general formula (I), R ² is a polymer chain having at least one structural unit represented by the following general formula (IV) or general formula (V). The polymer chain 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 formulas (IV) and (V), R ⁴ is a hydrogen atom or a methyl group, R ⁵ is an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, a cyano group, — [CH (R ⁶ ) — _{^{CH (R 7) -O] x}} -R 8, - [(CH 2) y -O] z -R 8, - [CO- (CH 2) y -O] z -R 8, -CO-O- It is a monovalent group represented by R ¹⁰ or —O—CO—R ¹¹ . The alkyl group having 1 to 18 carbon atoms of R ^5, an aralkyl group, an aryl group may have a substituent.

The alkyl group having 1 to 18 carbon atoms may be linear, branched, or cyclic. For example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, various hexyl groups, various octyl groups, various decyl groups, various dodecyl groups, various tetradecyl groups, various hexadecyl groups, various octadecyl groups, cyclopentyl groups, cyclohexyl groups, cyclooctyl Group, cyclododecyl group, bornyl group, isobornyl group, dicyclopentanyl group, adamantyl group, lower alkyl group-substituted adamantyl group and the like.
As a substituent which the said C1-C18 alkyl group may have, halogen atoms, such as F, Cl, Br, etc. can be mentioned, for example.

The aralkyl group is not particularly limited, but preferably has 7 to 20 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, a naphthylmethyl group, and a biphenylmethyl group.
Although there is no restriction | limiting in particular as said aryl group, Preferably it is C6-C24, More preferably, it is 6-12, for example, a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group etc. .
Examples of the substituent of the aromatic ring such as an aryl group and an aralkyl group include an alkenyl group, a nitro group, and a halogen atom in addition to a linear or branched alkyl group having 1 to 4 carbon atoms.
The preferred carbon number does not include the carbon number of the substituent.

In R ⁵ , — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —R ⁸ , — [(CH ₂ ) _y —O] _z —R ⁸ , — [CO— (CH ₂ ) _y — ^{R 6} and ^{R 7} when _O] is a z -R ⁸ are each independently a hydrogen atom or a methyl group, ^{R 8} may have a hydrogen atom or a substituent, 1 to 18 carbon atoms An alkyl group, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, —CHO, —CH ₂ CHO, or a monovalent group represented by —CH ₂ COOR ¹² , and R ¹² is a hydrogen atom or a carbon number 1-5 linear, branched, or cyclic alkyl groups.
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.
Incidentally, in the monovalent group represented by the R ^8, as the substituent which may have, for example, linear 1 to 4 carbon atoms, branched or cyclic alkyl group, F, Cl, such as Br A halogen atom etc. can be mentioned.

When R ⁵ is a monovalent group represented by —CO—O—R ¹⁰ or —O—CO—R ¹¹ , R ¹⁰ is an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, A cyano group, — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —R ⁸ , — [(CH ₂ ) _y —O] _z —R ⁸ , or — [CO— (CH ₂ ) _y — O] _z is a monovalent group represented by —R ⁸ . In R ¹⁰ , R ⁶ , R ⁷ , R ⁸ , x, y, and z are as described above.
R ¹¹ represents an alkyl group having 1 to 18 carbon atoms.
In R ¹⁰ and R ¹¹ , the alkyl group having 1 to 18 carbon atoms, the aralkyl group, and the aryl group are as described for R ⁵ above.

In the present invention, it is preferable to use, as R ⁵ and R ¹⁰ , those having excellent solubility with the solvent (F) described later, specifically, the structure constituting the graft copolymer. Depending on the unit, etc., when using a solvent such as an ether alcohol acetate type, ether type, ester type or the like generally used as a solvent for a color filter, a methyl group, an ethyl group, an n-butyl group, A 2-ethylhexyl group, a benzyl group and the like are preferable.
Here, the reason for setting R ⁵ and R ¹⁰ in this way is that the structural unit containing R ⁵ and R ¹⁰ has good solubility in (F) solvent, while a tertiary amino group and This is because the dispersibility and stability of the pigment can be made particularly excellent because the salt-forming site formed by the organic acid compound described later has high adsorptivity to the pigment.
The polymer chain may be a homopolymer or a copolymer.

Furthermore, R ⁵ and R ¹⁰ may be substituted with a substituent such as an alkoxy group, a carboxyl group, or an epoxy group as long as the dispersion performance of the graft copolymer is not hindered. Moreover, after synthesizing a graft copolymer having these substituents, a compound having a functional group that reacts with the substituent and a polymerizable group may be reacted to add a polymerizable group. For example, a polymerizable group can be added by reacting a graft copolymer having a carboxyl group with glycidyl (meth) acrylate.

In view of the above points, the polymer chain R ² used in the present invention includes methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, and isobutyl (meth) acrylate among the above-described structural units. , N-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, isobornyl (meth) acrylate, di Those having structural units derived from cyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, styrene, α-methylstyrene, vinylcyclohexane and the like are preferred, methyl (meth) acrylate, ethyl (meth) acrylic. Over DOO, n- butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and more preferably those having a constitutional unit derived from benzyl (meth) acrylate. However, it is not limited to these.

In the formula (V), l is an integer of 1 to 5, preferably an integer of 2 to 5, more preferably an integer of 4 or 5. Further, the number of units n ′ and n ″ of the structural units contained in the polymer chain R ² may be an integer of 5 to 200, and is not particularly limited, but is preferably in the range of 5 to 100.

  The polymer having a tertiary amino group and a diol at the terminal may be used alone or in combination of two or more in the graft copolymer.

The weight average molecular weight Mw of the polymer having a tertiary amino group and a diol at the end is preferably in the range of 500 to 20000, more preferably in the range of 1000 to 10,000, and in the range of 2000 to 5000. More preferably it is. By being the said range, while being able to hold | maintain sufficient steric repulsion effect as a pigment dispersant, the reaggregation of pigments can also be suppressed by the steric repulsion effect.
If it is smaller than the above range, there is a possibility that sufficient steric repulsion effect as a pigment dispersant cannot be maintained. If it is larger than the above range, the proportion of the amino group in the graft copolymer is decreased, so that the adsorptive power to the pigment is lowered and sufficient dispersibility may not be ensured.

  A polymer having a tertiary amino group and a diol at the terminal can be obtained by reacting a dialkanolamine with a polymer having an acryloyl group at the terminal. Examples of dialkanolamines include symmetric dialkanolamines such as dimethanolamine, diethanolamine and dipropanolamine, and asymmetric dialkanolamines such as methanolethanolamine and ethanolpropanolamine. Preferably, symmetrical dialkanolamine is mentioned, More preferably, diethanolamine is mentioned.

  A polymer having an acryloyl group at the terminal can be synthesized by a living polymerization method or a radical polymerization method using a chain transfer agent. A radical polymerization method using a chain transfer agent is preferable from the viewpoint of ease of synthesis and the degree of freedom in selecting monomers. For example, a polymer having a hydroxyl group at one end is obtained by radical polymerization of a monomer in the presence of a chain transfer agent having a hydroxyl group, such as mercaptoethanol, and a hydroxyl group at one end is reacted with an acrylate having an isocyanate group. By doing so, a polymer having an acryloyl group at one end can be obtained.

On the other hand, in the general formula (I), R ³ is a divalent group selected from the group consisting of an alkylene group, an arylene group, and a combination thereof. The alkylene group may be linear, branched or cyclic. R ³ is derived from diisocyanates having two isocyanate groups, for example. Examples of the diisocyanates include the following alicyclic diisocyanates, aliphatic diisocyanates, araliphatic diisocyanates, and aromatic diisocyanates. R ³ is preferably a residue obtained by removing two isocyanate groups of the diisocyanate as described below.

Examples of the alicyclic diisocyanate include 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), 4,4′-, 2,4′- or 2,2′-dicyclohexylmethane. Diisocyanate or its mixture (H ₁₂ MDI), 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane or its mixture (hydrogenated xylylene diisocyanate, H ₆ XDI), 2,5- or 2,6- Bis (isocyanatomethyl) norbornane or a mixture thereof (NBDI), 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2, And alicyclic diisocyanates such as 6-cyclohexane diisocyanate.

  Examples of the aliphatic diisocyanate include hexamethylene diisocyanate (HDI), trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, 1,2-, 2,3- or 1,3-butylene diisocyanate, 2,4,4- Or aliphatic diisocyanates, such as 2,2,4-trimethylhexamethylene diisocyanate, may be mentioned.

  Examples of the araliphatic diisocyanate include 1,3- or 1,4-xylylene diisocyanate or a mixture thereof (XDI), 1,3- or 1,4-tetramethylxylylene diisocyanate or a mixture thereof (TMXDI), ω , Ω'-diisocyanato-1,4-diethylbenzene, and the like.

  Examples of the aromatic diisocyanate include 4,4′-, 2,4′- or 2,2′-diphenylmethane diisocyanate or a mixture thereof (MDI), 2,4- or 2,6-tolylene diisocyanate or a mixture thereof ( TDI), 3,3′-dimethoxybiphenyl-4,4′-diisocyanate, 1,5-naphthalene diisocyanate (NDI), m- or p-phenylene diisocyanate or mixtures thereof, 4,4′-diphenyl diisocyanate, 4,4 And aromatic diisocyanates such as' -diphenyl ether diisocyanate.

Among them, in the present invention, R ³ in the general formula (I) is a residue obtained by removing two isocyanate groups of diisocyanate selected from the group consisting of alicyclic diisocyanate, araliphatic diisocyanate, and aromatic diisocyanate. A diisocyanate is preferable from the viewpoint of the heat resistance of the color filter coating film, and it is further a residue obtained by removing two isocyanate groups of a diisocyanate selected from the group consisting of an araliphatic diisocyanate and an aromatic diisocyanate. preferable.
One type of R ³ may be used in the graft copolymer, but two or more types may be included.

The graft copolymer used in the present invention may contain other repeating units as long as the effects of the present invention are not impaired. For example, repeating units derived from other diols and diisocyanates may be contained.
As other diols, diols having a tertiary amino group are preferable because they can contribute to salt formation as the main chain of the graft. Examples of the diol having a tertiary amino group include N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, and N-phenyldiethanolamine.
In addition to other diols and diisocyanates, monofunctional alcohols and isocyanate compounds may be added for molecular weight adjustment, and residues of these monofunctional alcohols and isocyanate compounds may exist at the ends. .

  The content of the amino group in the graft copolymer used in the present invention is preferably in the range where the amine value of the graft copolymer is 5 mgKOH / g to 150 mgKOH / g, and more preferably 10 mgKOH / g to 100 mgKOH / g. It is preferable from the viewpoint of pigment dispersibility that it is in the range of g, more preferably in the range of 20 mgKOH / g to 70 mgKOH / g. The amine value is expressed as the number of mg of potassium hydroxide equivalent to hydrochloric acid required to neutralize the amine contained in 1 g of the sample.

Moreover, in the graft copolymer used for this invention, m is 2-200. Especially, it is preferable that m is 5-50.
In addition, the weight average molecular weight Mw of the graft copolymer is preferably in the range of 1000 to 200000, more preferably in the range of 3000 to 100000, and further in the range of 5000 to 50000. 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>
The organic acid compound that forms a salt with the tertiary amino group in the graft copolymer represented by the general formula (I) is an organic phosphoric acid compound having a structure represented by the general formula (II) and / or An organic sulfonic acid compound having a structure represented by the general formula (III).

In the present invention, by using the organic acid compound, the pigment dispersant can be made excellent in the dispersibility and stability of the pigment to be 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 (II), R ^a and R ^{a ′} are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, or — [ CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — [(CH ₂ ) _t —O] _u —R ^e , or —O—R ^{a ″} , R ^a and R ^a Any of ^' includes carbon atoms.

The alkyl group having 1 to 18 carbon atoms is as indicated by the ^{R 5.}
The alkenyl group having 2 to 18 carbon atoms may be linear, branched or cyclic. Examples of such alkenyl groups include vinyl, allyl, propenyl, various butenyl, various hexenyl, various octenyl, various decenyl, various dodecenyl, various tetradecenyl, various hexadecenyl, various octadecenyl, A cyclopentenyl group, a cyclohexenyl group, a cyclooctenyl group, etc. can be mentioned. The position of the double bond of the alkenyl group is not limited, but from the viewpoint of reactivity, it is preferable that the alkenyl group has a double bond at the terminal.
The alkyl group or alkenyl group may have a substituent, and examples of the substituent include halogen atoms such as F, Cl, and Br, nitro groups, and the like.

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

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

In the monovalent group represented by R ^e, Examples of the substituent which may have, for example, linear 1 to 4 carbon atoms, branched or cyclic alkyl group, F, Cl, halogen atom such as Br And so on.
The alkyl group having 1 to 18 carbon atoms of the above ^{R e} are as indicated by ^{R 5} described above, an alkenyl group, an aralkyl group having 2 to 18 carbon atoms, an aryl group, said ^{R a} and R ^{a '} It is as shown in.

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

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

In the general formula (III), R ^b is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —. _O] s ^-R _e, - shows a _{[(CH 2) t -O]} u -R e, or -O-R ^{b '.}
The alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group is as shown by the above ^{R a} and R ^{a '.}

When R ^b is —O—R ^b ′, it becomes an acidic sulfate. R ^b ′ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e. ,-[(CH ₂ ) _t —O] _u —R ^e .
In R ^b and R ^b ′, each of the alkyl group, alkenyl group, aralkyl group, and aryl group may have a substituent.
The alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl ^{group, - [CH (R c)} -CH (R d) -O] s -R e, - [(CH ₂ ) _t— O] _u— R ^e is as described for R ^a , R ^a and R ^{a ″} .
R ^c , R ^d, and R ^e are the same as those described for R ^a , R ^a, and R ^{a ″} .
In said ^Rb and ^Rb ', s is an integer of 1-18, t is an integer of 1-5, u is an integer of 1-18. Preferred s, t, and u are the same as R ^a , R ^{a ′,} and R ^{a ″} described above.

Examples of the organic acid compound represented by the general formula (II) and the general formula (III) include R ^a , R ^{a ′} and / or R ^{a ″} in the general formula (II), and / or the general formula. R ^b and / or R ^{b ′} in (III) are each independently a methyl group, an ethyl group, an aryl group or an aralkyl group optionally having a substituent, a vinyl group, an allyl group, or — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , or — [(CH ₂ ) _t —O] _u —R ^e , and R ^e is —CO—CH═CH ₂ or — _{CO-C (CH} 3) = ones is CH ₂ are preferred from the viewpoint that it can be excellent in pigment dispersibility. In the general formula (II), when one of R ^a and R ^{a ′} is the above organic group, the other of R ^a and R ^{a ′} is preferably a hydrogen atom or a hydroxyl group.

Among ^{them, R} a, R ^{a 'and} / or R ^a'', and / or as ^{R b} and / or R ^b' are those having an aromatic ring, i.e., may have a substituent aryl group Alternatively, an aralkyl group is preferable from the viewpoint of pigment dispersibility. More specifically, benzyl group, phenyl group, tolyl group, naphthyl group, biphenyl group and the like are preferable. In the general formula (II), when one of R ^a and R ^{a ′} has an aromatic ring, the other of R ^a and R ^{a ′} is preferably a hydrogen atom or a hydroxyl group.

From the viewpoint of heat resistance and chemical resistance, the organic acid compound represented by the above general formula (II) and general formula (III) is a carbon atom directly bonded to phosphorus (P) or sulfur (S). R ^a and R ^{a ′} are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [ CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — [(CH ₂ ) _t —O] _u —R ^e , a monovalent group represented by R ^a and R ^{a ′} Either preferably contains a carbon atom. R ^b is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e. , — [(CH ₂ ) _t —O] _u —R ^e is preferably a monovalent group.

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

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

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

  The content of the organic acid compound in the graft copolymer used in the present invention is not particularly limited as long as good dispersion stability is exhibited, and is generally represented by the general formula (I). It is about 0.05-5.0 molar equivalent with respect to a tertiary amino group, More preferably, it is 0.2-2.0 molar equivalent. In such a case, the pigment dispersibility and the pigment dispersion stability are excellent. In addition, when using together 2 or more types of the said organic acid compound, content which added these should just be in the said range.

<Production of salt-type graft copolymer>
In the present invention, the production method of the salt-type graft copolymer used as the pigment dispersant of the component (A) includes at least a tertiary amino group of the polyurethane-based graft copolymer represented by the general formula (I). There is no particular limitation as long as it is a method that can produce a salt formed by part of the organic acid compound represented by the general formula (II) and the general formula (III). In the present invention, it can be obtained, for example, by graft polymerization of a polymer having a tertiary amino group and a diol at the terminal, a diisocyanate, and, if necessary, other monomers using a known polymerization means. It is. Subsequently, a salt-type graft copolymer can be produced by adding the organic acid compound to the solvent and stirring. The polymerization may be performed in the presence of a catalyst. Examples of the catalyst include organic tin compounds (for example, tin carboxylates such as tin octylate, dibutyltin diacetate, dibutyltin dioctoate, and dibutyltin dilaurate), metal naphthenates (copper naphthenate, zinc naphthenate, naphthene). Organic metal catalysts such as cobalt acid; tertiary amines [eg, trialkylamines such as triethylamine, chain tertiary amines such as benzyldimethylamine; pyridine, methylpyridine, N, N-dimethylpiperazine, tri Cyclic tertiary amines such as ethylenediamine] and the like. These catalysts may be used alone or in combination of two or more.

  In the pigment dispersion for color filter and the negative resist composition for color filter of the present invention, as the pigment dispersant as the component (A), one type of the above salt-type graft copolymer may be used. Two or more species may be used in combination, and the content thereof is appropriately selected according to the type of pigment used, the solid content concentration in the negative resist composition, and the like. In the color filter pigment dispersion and the color filter negative resist composition of the present invention, the pigment dispersant as the component (A) is usually 5 to 200 parts by mass with respect to 100 parts by mass of the pigment described later. 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 uniformly dispersed. Further, in the resist composition, a colored layer having sufficient hardness can be formed without relatively reducing the blending ratio of the alkali-soluble resin and the polyfunctional monomer.

((B) Pigment)
In the color filter pigment dispersion and the color filter negative resist composition of the present invention, the pigment used as the component (B) may be any pigment that can produce a desired color when a colored layer of the color filter is formed. Well, not particularly limited, 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 “Pigment” 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; Pigment Green 7, 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. 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, the 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, a large amount of pigment dispersant is required as the particle size of the pigment becomes finer, which may cause problems such as reduced alkali developability and increased residue. Since the pigment dispersant used for the color filter pigment dispersion and the negative resist composition is excellent in alkali developability, it is less likely to cause such a problem. Therefore, as the average particle diameter of the pigment is in the above range, the smaller the conventional particle size is, the more characteristic the negative resist composition for color filter of the present invention has.
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 pigment dispersion for color filter of the present invention, the content of the pigment used as the component (B) is not particularly limited. Usually, the pigment content is preferably 5 to 40% by mass, more preferably 10 to 20% by mass, based on the total amount of the pigment dispersion for color filter.

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 depends 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 color filters of the present invention, as the alkali-soluble resin used as the component (C), those generally used for negative resists can be used, and those having solubility in an aqueous alkali 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 Benzyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 1-adamantyl (meth) acrylate , Allyl (meth) acrylate, 2,2′-oxybis (methylene) bis-2-propenoate, styrene, γ-methylstyrene, glycidyl (meth) acrylate, 2-hydroxylethyl (meth) acrylate, 2-dimethylaminoethyl ( At least one selected from (meth) acrylate, N-vinyl-2-pyrrolidone, N-methylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide and the like, and (meth) acrylic acid A dimer of acrylic acid (for example, M-5600 manufactured by Toagosei Co., Ltd.), itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, and one or more selected from these anhydrides The copolymer which can be illustrated can also be illustrated. 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. It is not 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 the trifunctional or higher polyfunctional (meth) acrylate 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 te La (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, succinic anhydride-modified dipentaerythritol penta (meth) acrylate, urethane tri (Meth) acrylate, ester tri (meth) acrylate, urethane hexa (meth) acrylate, ester hexa (meth) acrylate and the like.

These polyfunctional (meth) acrylates may be used individually by 1 type, and may be used in combination of 2 or more type. In addition, when the negative resist composition for color filter of the present invention requires excellent photocurability (high sensitivity), the polyfunctional monomer has three polymerizable double bonds (trifunctional). Those having the above are preferable, and 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 mass 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.

((E) 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-methoxystyryl) ) Halomethyloxadiazole compounds such as 1,3,4-oxadiazole, 2,4-bis (trichloromethyl) -6-p-methoxystyryl-S-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl-1,3-butadienyl) -S-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl Ru-S-triazine, 2- (naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- (4-ethoxy-naphth-1-yl) -4,6-bis-trichloro Halomethyl-S-triazine compounds such as methyl-S-triazine, 2- (4-butoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2,2-dimethoxy-1, 2-diphenylethane-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone, 1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -Butanone-1,1-hydroxy-cyclohexyl-phenyl ketone, benzyl, benzoylbenzoic acid, methyl benzoylbenzoate, 4-benzoyl-4'-methyldipheny Sulfide, benzylmethyl ketal, dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, 2-n-butoxyethyl-4-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, Isopropylthioxanthone, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (o-acetyloxime), 4-benzoyl-methyldiphenyl sulfide, 1-hydroxy -Cyclohexyl-phenyl ketone, 2-benzyl-2- (dimethylamino) -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2- (dimethylamino) -2-[(4-methylphenyl) Methyl] -1- [4- (4- Morpholinyl) phenyl] -1-butanone, α-dimethoxy-α-phenylacetophenone, phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2 -(4-morpholinyl) -1-propanone and the like can be mentioned. These photoinitiators may be used individually by 1 type, and may be used in combination of 2 or more type.

  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 pigment dispersion for color filters and the negative resist composition for color filters of the present invention, the solvent used as the component (F) reacts with the components in the pigment dispersion or the resist composition. The organic solvent is not particularly limited as long as it is an organic solvent capable of dissolving or dispersing them. Specifically, alcohols such as methyl alcohol, ethyl alcohol, N-propyl alcohol, isopropyl alcohol; ether alcohols such as methoxy alcohol, ethoxy alcohol, methoxyethoxyethanol, ethoxyethoxyethanol; ethyl acetate, butyl acetate, acetic acid 3 -Esters such as methoxybutyl, methyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate; ketones such as acetone, methyl isobutyl ketone, cyclohexanone; methoxyethyl acetate, methoxypropyl acetate, methoxybutyl acetate, ethoxyethyl acetate, ethyl Cellosolve acetate, methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, propylene glycol monomethyl Ether alcohol acetates such as ether acetate; ethers such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, diethylene glycol methyl ethyl ether, propylene glycol monomethyl ether, propylene glycol diethyl ether; N, N-dimethylformamide, N, N- Aprotic amides such as dimethylacetamide and N-methylpyrrolidone; lactones such as γ-butyrolactone; unsaturated hydrocarbons such as benzene, toluene, xylene and naphthalene; n-heptane, n-hexane, n-octane, etc. And organic solvents such as saturated hydrocarbons.

Among these, ether alcohol acetates such as methoxyethyl acetate, ethoxyethyl acetate, ethyl cellosolve acetate, methoxyethoxyethyl acetate and ethoxyethoxyethyl acetate; ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and propylene glycol diethyl ether; acetic acid Esters such as 3-methoxybutyl, methyl methoxypropionate, ethyl ethoxypropionate, and ethyl lactate can be suitably used.
Among them, as the solvent used in the present 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 are used. What mixed is preferable from the point of the solubility of a pigment dispersant, and the applicability | paintability.

  The content of the solvent as the component (F) in the pigment dispersion for the color filter of the present invention is not particularly limited as long as the (B) pigment can be uniformly dissolved or dispersed. The content of the solvent (F) in the pigment dispersion used for preparing the resist composition is 60 from the viewpoint of the dispersibility of the pigment, the stability of the pigment dispersion with time, the chromaticity of the resulting color filter, and the like. The range of -90 mass% is preferable.

  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 pigment dispersion for a color filter and 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 pigment dispersion for color filter)
In the pigment dispersion of the present invention, the (A) pigment dispersant, (B) pigment, and other components as necessary are mixed in the (F) solvent in any order, and a known disperser is used. It can be prepared by using and dispersing.
When the pigment dispersion of the present invention contains two or more kinds of pigments as the (B) pigment, one pigment dispersion is prepared for each one of the pigments and then mixed to prepare the pigment dispersion of the present invention. The pigment dispersion of the present invention may be obtained by dispersing two or more kinds of pigments at a time.

In the case of preparing a resist composition later, after confirming that the dispersibility by the dispersant is not inhibited, (C) an alkali-soluble resin may be added to the dispersion in advance. In this case, the pigment particles are less likely to come into contact with each other due to the steric hindrance of the alkali-soluble resin, and there may be an effect of stabilizing the dispersion or reducing the dispersant due to the dispersion stabilizing effect.
Examples of the dispersing machine for performing the dispersion treatment include roll mills such as two rolls and three rolls, ball mills such as a ball mill and a vibrating ball mill, bead mills such as a paint conditioner, a continuous disk type bead mill, and a continuous annular type bead mill. As a preferable dispersion condition of the bead mill, the bead diameter to be used is preferably 0.03 to 2.00 mm, and more preferably 0.10 to 1.0 mm.

Specifically, preliminary dispersion is performed with 2 mm zirconia beads having a relatively large bead diameter, and main dispersion is further performed with 0.1 mm zirconia beads having a relatively small bead diameter. Moreover, it is preferable to filter with a membrane filter of 0.5 to 0.1 μm after dispersion.
Thereby, the pigment dispersion liquid excellent in the dispersibility of a pigment is obtained.

(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 aforementioned (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) after preparing a pigment dispersion as described above, an alkali-soluble resin, a polyfunctional monomer, a photoinitiator, and a photoinitiator are used as desired. (2) In the solvent, the above pigment dispersant, pigment, alkali-soluble resin, polyfunctional monomer, photoinitiator, and various additions used as desired A method of simultaneously charging and mixing the components, and (3) a pigment dispersant, an alkali-soluble resin, a polyfunctional monomer, a photoinitiator, and various additive components used as desired in a solvent. And a method of adding and mixing a pigment and mixing the pigment.
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.

  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.
Since the color filter of the present invention is excellent in alkali developability by forming a colored layer using the negative resist composition for color filter of the present invention described above, it has high productivity. 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.

  Furthermore, the color filter of this invention is excellent in the heat resistance of a colored layer by forming the colored layer using the negative resist composition of this invention mentioned above. Therefore, after the post-baking process of heating at 230 ° C. for 30 minutes, for example, in the color filter manufacturing process, the colored layer is discolored and the decrease in luminance and contrast is suppressed.

(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 portion and contained in the negative resist composition for color filter, it is composed of three or more colored patterns.
Further, the arrangement of the colored layers is not particularly limited, and for example, a general arrangement such as a stripe type, a mosaic type, a triangle type, or a four-pixel arrangement type can be used. Moreover, the width | variety, area, etc. of a colored layer can be set arbitrarily.
The thickness of the colored layer is appropriately controlled by adjusting the coating method, solid content concentration, viscosity, etc. of the negative resist composition for a color filter, but is usually preferably in the range of 1 to 5 μm.

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

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

(Shading part)
The light shielding part in the color filter of the present invention is formed in a pattern on a transparent substrate described later, and can be the same as that used as a light shielding part in a general color filter.
The pattern shape of the light shielding 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 film (y is an arbitrary number) and three layers of Cr film 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. Method, printing method and the like.

  The thickness of the light shielding part is set to about 0.2 to 0.4 μm in the case of a metal thin film, and 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, and 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. The acid value was measured according to JIS-K0070.
Production Example 1 Production of one-end acryloyl group-containing oligomer 70.0 parts by mass of propylene glycol methyl ether acetate (abbreviated as PGMEA) in a reactor equipped with a cooling tube, addition funnel, nitrogen inlet, mechanical stirrer, and digital thermometer Was heated to 90 ° C. while stirring under a nitrogen stream. 1. A mixed solution of 100.0 parts by mass of methacrylic acid-n-butyl, 4.0 parts by mass of mercaptoethanol, 30 parts by mass of PGMEA, and 1.0 part by mass of α, α′-azobisisobutyronitrile (abbreviation AIBN) The solution was added dropwise over 5 hours and reacted for another 3 hours. Next, the nitrogen stream was stopped, the reaction solution was cooled to 80 ° C., 7.95 parts by weight of Karenz AOI (manufactured by Showa Denko KK), 0.125 g of dioctyltin dilaurate, and 0.1% of p-methoxyphenol. 125 parts by mass and 10 parts by mass of PGMEA were added and stirred for 3 hours to obtain a 52.2% solution of the one-end acryloyl group-containing oligomer. When the obtained one-terminal acryloyl group-containing oligomer was confirmed by GPC (gel permeation chromatography) under the conditions of N-methylpyrrolidone, 0.01 mol / L lithium bromide added / polystyrene standard, the weight average molecular weight was confirmed. (Mw) 4905, number average molecular weight (Mn) 2132, molecular weight distribution (Mw / Mn) was 2.30.

Production Example 2 Production of Single-Terminal Diol Group-Containing Oligomer A reactor equipped with a condenser, a nitrogen inlet, a mechanical stirrer, and a digital thermometer was added to 210 mass parts of the terminal acryloyl group-containing oligomer solution of Production Example 1 and 5.92 mass of diethanolamine. And 50 parts by mass of propylene glycol monomethyl ether were added and stirred at 70 ° C. for 24 hours. By distilling off the solvent by evaporation, 109 parts by mass of a one-terminal diol group-containing oligomer was obtained. The molecular weight calculated by GPC of the obtained one-end diol group-containing oligomer was weight average molecular weight (Mw) 4366, number average molecular weight (Mn) 1845, and molecular weight distribution (Mw / Mn) was 2.37.

Production Example 3 Production of Polyurethane Graft Copolymer A 108 parts by mass of one-end diol group-containing oligomer of Production Example 2 in a reactor equipped with a cooling pipe, an inlet for nitrogen, a mechanical stirrer, and a digital thermometer, 200 parts by mass of PGMEA, 9.8 parts by mass of tolylene diisocyanate and 0.10 g by mass of dioctyltin dilaurate were added and stirred at 80 ° C. for 3 hours. By evaporating the solvent by evaporation, 115 parts by mass of polyurethane graft copolymer A was obtained. The molecular weight calculated by GPC of the obtained polyurethane graft copolymer A was weight average molecular weight (Mw) 24350, number average molecular weight (Mn) 5300, and molecular weight distribution (Mw / Mn) was 4.59.

Production Example 4 Production of Salt Graft Copolymer Solution A After dissolving 20 parts by mass of the polyurethane graft copolymer A of Production Example 3 in 85.7 parts by mass of PGMEA, phenylphosphonic acid (manufactured by Nissan Chemical Co., Ltd. “ 1.42 parts by mass of PPA ") was added, and the mixture was stirred at a reaction temperature of 40 ° C for 2 hours to prepare a salt-type graft copolymer solution A having a solid content of 20% by mass. The acid value of the obtained salt-type graft copolymer solution A was 46 mgKOH / g.

Production Example 5 Production of Salt Graft Copolymer Solution B After 20 parts by mass of polyurethane graft copolymer A of Production Example 3 was dissolved in 89.6 parts by mass of PGMEA, dimethacryloyloxyethyl phosphate (Kyoeisha Chemical Co., Ltd.) 2.41 parts by mass of “Light Ester P-2M” manufactured by the company was added and stirred at a reaction temperature of 40 ° C. for 2 hours to prepare a salt-type graft copolymer solution B having a solid content of 20% by mass. The acid value of the obtained salt-type graft copolymer solution B was 33 mgKOH / g.

Production Example 6 Production of Salt-type Graft Copolymer Solution C After dissolving 20 parts by mass of polyurethane graft copolymer A of Production Example 3 in 83.9 parts by mass of PGMEA, vinylsulfonic acid (manufactured by Asahi Kasei Finechem Co., Ltd. “ 0.98 parts by mass of VSA-H ") was added, and the mixture was stirred at a reaction temperature of 40 ° C for 2 hours to prepare a salt-type graft copolymer solution C having a solid content of 20% by mass. The acid value of the obtained salt-type graft copolymer solution C was 25 mgKOH / g.

Comparative Production Example 1 Production of Graft Copolymer Solution D By dissolving 20 parts by mass of the polyurethane-based graft copolymer of Production Example 3 in 80.0 parts by mass of PGMEA, a graft copolymer solution D having a solid content of 20% by mass was obtained. Prepared. The acid value of the obtained graft copolymer solution D was 0 mgKOH / g.

Production Example 7 Preparation of Pigment Dispersion A As a pigment dispersant, 12.0 parts by mass (solid content: 2.4 parts by mass) of the salt-type graft copolymer solution A prepared in Production Example 4; I. Pigment Green 58 Pigment (“FASTOGEN Green A110” manufactured by DIC Corporation) 3.0 parts by weight, PGMEA 15 parts by weight, 2.0 mm zirconia beads 30 parts by weight are put into a mayonnaise bin, and paint shaker (Asada Tekko) And then 30 parts by weight of the dispersion and 60 parts by weight of zirconia beads having a particle size of 0.1 mm are placed in a mayonnaise bin. And pigment dispersion A was prepared.

Production Example 8 Preparation of Pigment Dispersion Liquid B In Production Example 7, except that the salt-type graft copolymer solution B prepared in Production Example 5 was made 12.0 parts by mass (solid content 2.4 parts by mass). Prepared a pigment dispersion B in the same manner as in Production Example 7.

Production Example 9 Preparation of Pigment Dispersion C In Production Example 7, except that the salt-type graft copolymer solution C prepared in Production Example 6 was 12.0 parts by mass (solid content 2.4 parts by mass). Prepared a pigment dispersion C in the same manner as in Production Example 7.

Comparative Production Example 2 Preparation of Pigment Dispersion D In Production Example 7, except that the graft copolymer solution D prepared in Comparative Production Example 1 was 12.0 parts by mass (solid content 2.4 parts by mass). Prepared a pigment dispersion D in the same manner as in Production Example 7.

Comparative Production Example 3 Preparation of Pigment Dispersion E In Production Example 7, 8.0 parts by mass of the commercially available “Disperbyk161” (manufactured by Big Chemie Japan Co., Ltd., solid content concentration 30% by mass) and the solvent PGMEA19 A pigment dispersion E was prepared in the same manner as in Production Example 7, except that the amount was changed to 0.0 part by mass.

Comparative Production Example 4 Preparation of Pigment Dispersion Liquid F In Production Example 7, the commercially available “Azisper PB822” (manufactured by Ajinomoto Fine Techno Co., Ltd., basic functional group-containing copolymer, solid content concentration 100 mass) %) Pigment dispersion F was prepared in the same manner as in Production Example 7, except that 2.4 parts by mass and the solvent was 24.6 parts by mass of PGMEA.

Example 1
To 66.67 parts by mass of the pigment dispersion A obtained in Production Example 7, as an alkali-soluble resin, a 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 40% by mass) 8.0 parts by mass, dipentaerythritol pentaacrylate as a polyfunctional monomer (“Aronix M403” manufactured by Toagosei Co., Ltd.), 2.8 parts by mass, 1.6 parts by mass of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (manufactured by Ciba Specialty Chemicals, Inc., “IRGACURE907”) as a photoinitiator, 0.4 parts by mass of 2,4-dimethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd., “KAYACURE DETX-S”), and After adding 20.53 mass parts of PGMEA as a solvent, it mixed until it became uniform, and also filtered with the pressure filtration apparatus which is mesh size 0.2micrometer, and the negative resist composition A for color filters was obtained.

Examples 2 and 3
In Example 1, negative resist compositions B and C for color filters were obtained in the same manner as in Example 1 except that pigment dispersions B and C were used instead of pigment dispersion A, respectively.

Comparative Examples 1-3
In Example 1, negative resist compositions D to F for color filters were obtained in the same manner as Example 1 except that pigment dispersions D to F were used instead of pigment dispersion A, respectively.

As described above, for the negative resist compositions for color filters obtained in Examples 1 to 3 and Comparative Examples 1 to 3, pigment dispersibility, alkali developability (development time), and optical performance (y = 0.500) x, Δx (change in x value before and after post-baking), luminance (Y), contrast) were evaluated. The results are shown in Table 1.
<Evaluation of pigment dispersibility>
As an evaluation of the pigment dispersibility of the color filter negative resist composition obtained in each example, measurement of the average particle diameter of the pigment particles in the pigment dispersion used in the preparation of the color filter negative resist composition was performed. went. For measurement of the average particle diameter, “Microtrac particle size distribution analyzer UPA-EX150” manufactured by Nikkiso Co., Ltd. was used.

<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 2.5 μm. This colored layer was irradiated with ultraviolet rays of 60 mJ / cm ² through a photomask using an ultrahigh pressure mercury lamp. Thereafter, the glass plate on which the colored layer was formed was shower-developed for 60 seconds using a 0.05% by weight aqueous potassium hydroxide solution as an alkaline developer, and the colored layer was completely dissolved to form the colored layer. The time until the glass surface of the part appeared was measured as the development time.

<Optical performance evaluation>
The negative resist composition for color filters obtained in each example was applied on 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 2.5 μm was formed by drying at 3 ° C. for 3 minutes. The colored layer was irradiated with ultraviolet rays of 60 mJ / cm ² using an ultrahigh pressure mercury lamp without using a photomask. The glass plate on which the colored layer was formed was post-baked in a clean oven at 230 ° C., and the contrast, chromaticity (x, y), and luminance (Y) of the obtained green color filter substrate were measured. Contrast is “Contrast measurement device CT-1B” manufactured by Aisaka Electric Co., Ltd., and chromaticity (x, y) and luminance (Y) are “Microspectrophotometer OSP-SP200” manufactured by Olympus Corporation. And measured.

The following can be seen from Table 1.
In the examples, the average particle diameter of the pigment particles in the pigment dispersion was in the range of 38 to 45 nm, and the pigment dispersibility was good. The optical performance was such that the contrast value was 7000 or more, the color change after post-baking was small, and the heat resistance was good. Further, the development time was in the range of 25 to 30 seconds, and the alkali developability was excellent.
On the other hand, in Comparative Example 1, the average particle diameter of the pigment particles in the pigment dispersion is as large as 520 nm, and the contrast value is significantly lower than that in the Examples. Moreover, alkali developability is also inferior compared with an Example. The pigment dispersant used in Comparative Example 1 is not modified with an organic acid compound as in Examples 1 to 3, and thus has a weak adsorption power to the pigment and does not have an acid value. It is considered that the property and alkali developability were inferior to those of the examples.
In Comparative Example 2, the average particle diameter of the pigment particles in the pigment dispersion was larger than that of the example, and the contrast value was inferior. The color change after post-baking was large compared to the examples, and the alkali developability could not be developed in 60 seconds.
In Comparative Example 3, the alkali developability was good, but the average particle diameter of the pigment particles in the pigment dispersion was larger than that of the Examples, and the contrast value and heat resistance were also inferior.

Claims (9)

A pigment dispersion for a color filter having (A) a pigment dispersant, (B) a pigment, and (F) a solvent,
The (A) pigment dispersant is a polyurethane graft copolymer represented by the following general formula (I), and at least a part of the tertiary amino group of the polyurethane graft copolymer and the following general formula: A pigment dispersion for a color filter, which is a graft copolymer in which (II) and / or an organic acid compound represented by the following general formula (III) forms a salt.

[In Formula (I), each R ¹ independently represents an alkylene group having 1 to 12 carbon atoms, and R ² represents at least one structural unit represented by the following General Formula (IV) or General Formula (V). It is a polymer chain with seeds. R ³ is a divalent group selected from the group consisting of an alkylene group, an arylene group, and combinations thereof. m is 2 to 200.

<< In Formula (IV) and (V), R < ⁴ > is a hydrogen atom or a methyl group, R < ⁵ > is a C1-C18 alkyl group, an aralkyl group, an aryl group, a cyano group,-[CH (R < ⁶ >). —CH (R ⁷ ) —O] _x —R ⁸ , — [(CH ₂ ) _y —O] _z —R ⁸ , — [CO— (CH ₂ ) _y —O] _z —R ⁸ , —CO—O It is a monovalent group represented by —R ¹⁰ or —O—CO—R ¹¹ .
R ¹⁰ is an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, a cyano group, — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —R ⁸ , — [(CH ₂ ) _y. It is a monovalent group represented by —O] _z —R ⁸ or — [CO— (CH ₂ ) _y —O] _z —R ⁸ .
R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group.
R ⁸ is a hydrogen atom, or a monovalent group represented by an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, —CHO, —CH ₂ CHO, or —CH ₂ COOR ¹² , and R ¹² is a hydrogen atom It is an atom or an alkyl group having 1 to 5 carbon atoms, and R ¹¹ represents an alkyl group having 1 to 18 carbon atoms. The alkyl group, alkenyl group, aralkyl group and aryl group contained in R ⁵ may each have a substituent.
x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18.
l represents an integer of 1 to 5, and n ′ and n ″ represent an integer of 5 to 200.
In formula (II) and formula (III), R ^a and R ^{a ′} are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, or an aryl group. , — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — [(CH ₂ ) _t —O] _u —R ^e , or —O—R ^{a ″} a group, one of R ^a and R ^{a 'comprises} a carbon atom. R ^{a ″} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e. ,-[(CH ₂ ) _t —O] _u —R ^e .
R ^b is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — [(CH ₂ ) _t —O] _u —R ^e or a monovalent group represented by —O—R ^{b ′} . R ^{b ′} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , or _- it is a monovalent group represented by _{[(CH 2) t -O]} u -R e.
R ^c and R ^d are each independently a hydrogen atom or a methyl group, and R ^e is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, _{-CHO, -CH 2 CHO, -CO-} CH = CH 2, a monovalent group represented by _{-CO-C (CH 3) =} CH 2 or _-CH 2 COOR ^{f, R f} is hydrogen or C It is an alkyl group of formula 1-5.
In R ^a , R ^{a ′} , and R ^b , each of the alkyl group, alkenyl group, aralkyl group, and aryl group may have a substituent.
s is an integer of 1 to 18, t is an integer of 1 to 5, and u is an integer of 1 to 18. ] ^R a in formula (II), R ^{a 'and} / or R ^a'', and / or is ^{R b} and / or R ^b' in formula (II), a methyl group, an ethyl group, a substituent An aryl group or an aralkyl group, a vinyl group, an allyl group, or — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , or — [(CH ₂ ) _{t -O]} a u -R ^e, and, ^{R e} is -CO-CH = CH ₂ or _{-CO-C (CH} 3) = is CH _2, the pigment dispersion for a color filter according to claim 1.   In the pigment dispersant (A), the polyurethane-based graft copolymer of the general formula (I) is a graft copolymer obtained by polymerization of a polymer having a tertiary amino group and a diol at a terminal and a diisocyanate, The pigment dispersion for a color filter according to claim 1 or 2, wherein the diisocyanate is a diisocyanate selected from the group consisting of alicyclic diisocyanates, araliphatic diisocyanates, and aromatic diisocyanates.   (B) The pigment particle dispersion for color filters according to any one of claims 1 to 3, wherein the pigment has an average particle diameter of 10 to 100 nm. Color filter negative having (A) pigment dispersant, (B) pigment, (C) alkali-soluble resin, (D) polyfunctional monomer, (E) photoinitiator, and (F) solvent. Type resist composition comprising:
The (A) pigment dispersant is a polyurethane-based graft copolymer represented by the general formula (I) according to claim 1, and a tertiary amino group of the polyurethane-based graft copolymer. A negative resist for a color filter, characterized in that it is a graft copolymer in which at least a part and the organic acid compound represented by the general formula (II) and / or the general formula (III) form a salt. Composition. R ^a , R ^{a ′} and / or R ^{a ″} in the general formula (II) and / or R ^b and / or R ^{b ′} in the general formula (III) are a methyl group, an ethyl group or a substituent. An aryl group or an aralkyl group, a vinyl group, an allyl group, or — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , or — [(CH ₂ ) _{t -O]} a u -R ^e, and, ^{R e} is -CO-CH = CH ₂ or _{-CO-C (CH} 3) = is CH _2, a negative resist composition for a color filter according to claim 5 object. In the pigment dispersant (A), the polyurethane-based graft copolymer of the general formula (I) is a graft copolymer obtained by polymerization of a polymer having a tertiary amino group and a diol at a terminal and a diisocyanate, The negative resist composition for a color filter according to claim 5 or 6, wherein the diisocyanate is a diisocyanate selected from the group consisting of alicyclic diisocyanates, araliphatic diisocyanates, and aromatic diisocyanates.   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 8.

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