JP2012128012A - Red pigment dispersion liquid for color filter, red photosensitive resin composition for color filter, color filter and liquid crystal display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a red pigment dispersion liquid for a color filter and a red photosensitive resin composition for a color filter suppressing aggregation and crystallization of pigments even after a high temperature heating process in a color filter process, and particularly, achieving high luminance and high contrast.SOLUTION: The red pigment dispersion liquid for a color filter contains (A) a red pigment having a diphenyl diketopyrrolopyrrole skeleton, (B) an asymmetric diketopyrrolopyrrole derivative, (C) a sulfonated derivative of at least one kind of yellow pigment selected from the group consisting of C.I.Pigment Yellow 138, 139, 150, 215 and their derivative pigments, (D) a pigment dispersant which is a block copolymer containing a tertiary amine salt or a quaternary ammonium salt, and (E) a solvent. The red photosensitive resin composition for a color filter contains the pigment dispersion liquid.

Description

  The present invention relates to a pigment dispersion, a red photosensitive resin composition for a color filter using the pigment dispersion, a color filter formed using the photosensitive resin composition, and a liquid crystal display device having the color filter. Is.

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, the color filter used in the liquid crystal display device generally defines a transparent substrate, a colored layer formed on the transparent substrate, which is composed of colored patterns of three primary colors of red, green, and blue, and each colored pattern. As described above, the light shielding portion is formed on the transparent substrate.
As a method for forming such a colored layer, a pigment dispersion method, a dyeing method, an electrodeposition method, a printing method, and the like are known. Among these, from the viewpoint of spectral characteristics, durability, pattern shape, accuracy, etc., a pigment dispersion method having excellent characteristics on average is most widely adopted.

  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.

In recent years, there has been a growing demand for higher luminance of color filters for television applications due to reduced power consumption of backlights and LED backlight characteristics.
Currently, as a LED for a backlight, a three-color LED has a small cost merit, so a pseudo white LED (a combination of a blue LED and a yellow phosphor (B-) is formed by applying a phosphor on the surface of a blue LED. YAG) or a combination of a blue LED, a red phosphor and a green phosphor (B-RG)). When such a white LED backlight is used, since the red light emission intensity is weak compared to the blue light emission intensity, the brightness of the red color layer is lowered, and thus the red color layer is required to have high brightness. ing.

  In order to realize a high contrast of the color filter, it has been studied to refine the pigment contained in the colored layer. As an attempt to refine the pigment, a pigment blend in which a pigment and a pigment derivative having a structure similar to the pigment are combined is used. For the red colored layer, attempts have been made to combine diketopyrrolopyrrole pigments with a diketopyrrolopyrrole pigment derivative having a diketopyrrolopyrrole pigment derivative into which a substituent such as sulfonamide is introduced (for example, a pigment dispersant) (for example, Patent Document 1). However, when the diketopyrrolopyrrole pigment derivative as described above is combined with the diketopyrrolopyrrole pigment, the pigment can be finely dispersed. However, the diketopyrrolopyrrole pigment derivative as described above is affected by the electron withdrawing group. Red colored layer using a combination of diketopyrrolopyrrole pigment derivatives as described above, which often has a blue side color (becomes absorbed to a longer wavelength) than the diketopyrrolopyrrole pigment to be mixed. Has a problem of lowering the luminance because a compound having absorption at the transmission wavelength of the diketopyrrolopyrrole pigment is added. According to the demand for higher brightness for the red colored layer as described above, pigment derivatives that lower brightness cannot be used. Furthermore, although the above-mentioned pigment derivatives can finely disperse the diketopyrrolopyrrole pigment, there is a problem that crystals are precipitated during baking of the photosensitive resin composition produced using the dispersion. .

  In order to solve the problem that crystals are precipitated during baking, Patent Document 2 discloses a diketopyrrolopyrrole pigment produced by cyclization reaction of at least two kinds of benzonitrile compounds and succinic acid diesters. And a diketopyrrolopyrrole pigment composition (particles) in which an asymmetrical diketopyrrolopyrrole derivative is mixed. Although it is described that the dye derivative used when forming the diketopyrrolopyrrole pigment composition (particles) may be used for improving the hue, the hue is different from the saturation and brightness. There is no idea of improving the luminance without changing the hue as much as possible. In addition, in the technique specifically described in Patent Document 2, a red benzoisoindole derivative is used as a pigment derivative, resulting in insufficient brightness and pigment dispersion when a pigment dispersion is prepared. The improvement of the property was also insufficient.

Further, in Patent Document 3, for the purpose of having excellent dispersion stability and contrast and preventing crystal precipitation of diketopyrrolopyrrole pigments even by heat treatment, diketopyrrolopyrrole pigments, acidic groups and Disclosed is a pigment dispersion composition in which a pigment derivative having at least one group selected from basic groups and a diaryl diketopyrrolopyrrole having at least one substituent are mixed. However, the technique disclosed in Patent Document 3 has a problem that the luminance is insufficient.
As described above, in the conventional technique, crystal precipitation at the time of baking, low luminance, dispersion stability, and low contrast have been problems.

JP 2001-214085 A International Publication No. 2009/081930 Pamphlet JP 2009-149707 A

  The present invention has been made under such circumstances, and is a color filter that can suppress aggregation and crystal precipitation of the pigment even after the high-temperature heating step in the color filter step, and can achieve particularly high brightness and high contrast. It is an object of the present invention to provide a red pigment dispersion for color, a red photosensitive resin composition for a color filter, a color filter formed using the photosensitive resin composition, and a liquid crystal display device having the color filter. .

As a result of intensive research to achieve the above object, the present inventors have determined that a red pigment having a diphenyl diketopyrrolopyrrole skeleton in the presence of a sulfonated derivative of a specific yellow pigment and a specific pigment dispersant. When dispersed in a solvent and further containing a specific asymmetric diketopyrrolopyrrole derivative, aggregation and crystal precipitation of the pigment are suppressed even after the high-temperature heating step in the color filter step, and particularly high brightness and high contrast. The present inventors have found that a pigment dispersion and a photosensitive resin composition that can meet the demands for the production of a resin are obtained.
The present invention has been completed based on such findings.

  The red pigment dispersion for a color filter according to the present invention includes (A) a red pigment having a diphenyl diketopyrrolopyrrole skeleton, (B) an asymmetric diketopyrrolopyrrole derivative represented by the following general formula (1), (C) C.I. I. A block comprising a sulfonated derivative of one or more yellow pigments selected from the group consisting of CI Pigment Yellow 138, 139, 150, 215, and derivative pigments thereof; and (D) a salt of a tertiary amine or a quaternary ammonium salt It contains a pigment dispersant which is a copolymer, and (E) a solvent.

（一般式（１）中、Ｐｃは、置換基を有していても良く、ヘテロ原子を含んでいても良い多環式化合物基を表す。Ｘは、ハロゲン原子、ベンジル基、フェニル基、及び炭素数１〜１０の直鎖又は分枝のアルキル基よりなる群から選択される置換基であり、ｎは０〜５の整数を表す。ｎが２以上の場合、複数のＸは同一であっても異なっていても良い。）
また、本発明に係るカラーフィルタ用赤色顔料分散液は、前記（Ｅ）溶媒中、（Ｂ）下記一般式（１）で表される非対称型ジケトピロロピロール誘導体と前記（Ｃ）黄色顔料のスルホン化誘導体と前記（Ｄ）顔料分散剤との存在下で、前記（Ａ）ジフェニルジケトピロロピロール骨格を持つ赤色顔料を分散させて得られたものであることが好ましい。

(In general formula (1), Pc represents a polycyclic compound group which may have a substituent and may contain a hetero atom. X represents a halogen atom, a benzyl group, a phenyl group, and And a substituent selected from the group consisting of linear or branched alkyl groups having 1 to 10 carbon atoms, and n represents an integer of 0 to 5. When n is 2 or more, a plurality of Xs are the same. Or different.)
The red pigment dispersion for color filters according to the present invention comprises (B) an asymmetric diketopyrrolopyrrole derivative represented by the following general formula (1) and (C) a yellow pigment in the solvent (E). It is preferably obtained by dispersing the red pigment having the (A) diphenyl diketopyrrolopyrrole skeleton in the presence of the sulfonated derivative and the (D) pigment dispersant.

  Moreover, the red photosensitive resin composition for color filters which concerns on this invention contains the red pigment dispersion liquid for color filters which concerns on the said invention, and the (F) photosensitive binder component, It is characterized by the above-mentioned.

  In the red pigment dispersion for a color filter and the red photosensitive resin composition for a color filter according to the present invention, the pigment dispersant is a repeating unit (1) represented by the following general formula (I): And a repeating unit (2) represented by the general formula (II), and at least a part of the amino group of the repeating unit (1) forms a salt with an organic acid compound and / or a halogenated hydrocarbon. The block copolymer can achieve high brightness and high contrast by improving dispersibility and dispersion stability of a red pigment having a diphenyl diketopyrrolopyrrole skeleton while achieving particularly high brightness. It is preferable from the point.

［式（Ｉ）及び式（ＩＩ）中、Ｒ^１は、水素原子又はメチル基、Ｒ^２及びＲ^３は、それぞれ独立に水素原子又は炭素数１〜８のアルキル基、Ａは、炭素数１〜８のアルキレン基、−[ＣＨ（Ｒ^６）−ＣＨ（Ｒ^７）−Ｏ]_ｘ−ＣＨ（Ｒ^６）−ＣＨ（Ｒ^７）−又は−[（ＣＨ_２）_ｙ−Ｏ]_ｚ−（ＣＨ_２）_ｙ−で示される２価の基、Ｒ^４は、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、アラルキル基、アリール基、−[ＣＨ（Ｒ^６）−ＣＨ（Ｒ^７）−Ｏ]_ｘ−Ｒ^８又は−[（ＣＨ_２）_ｙ−Ｏ]_ｚ−Ｒ^８で示される１価の基である。Ｒ^６及びＲ^７は、それぞれ独立に水素原子又はメチル基であり、Ｒ^８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、又は−ＣＨ_２ＣＯＯＲ^９で示される１価の基であり、Ｒ^９は水素原子又は炭素数が１〜５のアルキル基である。上記アルキル基、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良い。
ｘは１〜１８の整数、ｙは１〜５の整数、ｚは１〜１８の整数を示す。ｍは３〜２００の整数、ｎは１０〜２００の整数を示す。］

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

  In the red pigment dispersion for a color filter and the red photosensitive resin composition for a color filter according to the present invention, the (B) asymmetric diketopyrrolopyrrole derivative is an asymmetric represented by the following general formula (2). The type diketopyrrolopyrrole derivative is preferred from the standpoint of heat resistance such as suppression of crystal precipitation at the time of baking and reduction in contrast, and the point of not significantly changing the phase difference of the main pigment.

（一般式（２）中、Ａｒ^１〜Ａｒ^５は、それぞれ独立に、水素原子、ハロゲン原子、又は有機基であり、それらが結合して環状構造を形成していても良く、ヘテロ原子の結合を含んでいても良い。但し、Ａｒ^１〜Ａｒ^５の少なくとも１つが置換基を有していても良いアリール基又は置換基を有していても良いヘテロアリール基であるか、及び／又は、Ａｒ^１〜Ａｒ^５の少なくとも２つが結合して環状構造を形成しているものである。Ｘ及びｎは、一般式（１）と同じである。）

(In the general formula (2), Ar ^{1 to} Ar ⁵ are each independently a hydrogen atom, a halogen atom, or an organic group, which may be bonded to form a cyclic structure. Provided that at least one of Ar ^{1 to} Ar ⁵ is an aryl group which may have a substituent or a heteroaryl group which may have a substituent, and / or (At least two of Ar ^{1 to} Ar ⁵ are bonded to form a cyclic structure. X and n are the same as those in the general formula (1).)

  In the red pigment dispersion for color filter and the red photosensitive resin composition for color filter according to the present invention, the sulfonated derivative of the yellow pigment is C.I. I. Pigment Yellow 138 is a sulfonated derivative that achieves high brightness while improving the dispersibility and dispersion stability of red pigments having a diphenyl diketopyrrolopyrrole skeleton, and demands high brightness and high contrast. Is preferable from the point that can be achieved.

  In the red pigment dispersion for color filter and the red photosensitive resin composition for color filter according to the present invention, at least a part of the amino group of the repeating unit (1) and the organic acid compound formed a salt. It is a block copolymer, and it is particularly high that the organic acid compound is at least one selected from the group consisting of organic acids represented by the following general formula (III) and the following general formula (IV). While achieving brightness, the dispersibility and dispersion stability of a red pigment having a diphenyl diketopyrrolopyrrole skeleton is improved, which is preferable from the standpoint of achieving high brightness and high contrast requirements.

［式（ＩＩＩ）及び式（ＩＶ）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 (III) and Formula (IV), R ^a and R ^{a ′} are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, or an aryl group. 1 represented by the group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — [(CH ₂ ) _t —O] _u —R ^e , or —O—R ^{a ″.} the valence of the group, one of R ^a and R ^{a 'comprises} a carbon atom. R ^{a ″} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e. ,-[(CH ₂ ) _t —O] _u —R ^e .
R ^b is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — [(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. ]

  In the red pigment dispersion for color filter and the red photosensitive resin composition for color filter according to the present invention, the red pigment having the (A) diphenyl diketopyrrolopyrrole skeleton is C.I. I. Pigment red 254 or C.I. I. Pigment Red 255 is preferable.

The present invention also provides a color filter having a colored layer formed by curing the red photosensitive resin composition for a color filter.
Furthermore, the present invention provides a liquid crystal display device comprising the color filter, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.

According to the present invention, pigment pigment aggregation and crystal precipitation are suppressed even after a high-temperature heating step in a color filter step, and particularly a red pigment dispersion for color filters capable of achieving high brightness and high contrast, and for color filters. A red photosensitive resin composition can be provided. By using the pigment dispersion of the present invention and the photosensitive resin composition, the red color of the color filter with particularly high brightness and high contrast, in which the aggregation and crystal precipitation of the pigment is suppressed even after the high temperature heating step in the color filter step. A pixel portion can be realized.
Furthermore, according to the present invention, a liquid crystal display device with high brightness and high contrast 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.

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

1. Red pigment dispersion for color filter The red pigment dispersion for a color filter according to the present invention includes (A) a red pigment having a diphenyl diketopyrrolopyrrole skeleton, and (B) an asymmetric type represented by the following general formula (1). Diketopyrrolopyrrole derivatives and (C) C.I. I. A block comprising a sulfonated derivative of one or more yellow pigments selected from the group consisting of CI Pigment Yellow 138, 139, 150, 215, and derivative pigments thereof; and (D) a salt of a tertiary amine or a quaternary ammonium salt It contains a pigment dispersant which is a copolymer, and (E) a solvent.

（一般式（１）中、Ｐｃは、置換基を有していても良く、ヘテロ原子を含んでいても良い多環式化合物基を表す。Ｘは、ハロゲン原子、ベンジル基、フェニル基、及び炭素数１〜１０の直鎖又は分枝のアルキル基よりなる群から選択される置換基であり、ｎは０〜５の整数を表す。ｎが２以上の場合、複数のＸは同一であっても異なっていても良い。）

(In general formula (1), Pc represents a polycyclic compound group which may have a substituent and may contain a hetero atom. X represents a halogen atom, a benzyl group, a phenyl group, and And a substituent selected from the group consisting of linear or branched alkyl groups having 1 to 10 carbon atoms, and n represents an integer of 0 to 5. When n is 2 or more, a plurality of Xs are the same. Or different.)

The red pigment dispersion for a color filter of the present invention is a sulfonation of at least (B) the asymmetric diketopyrrolopyrrole derivative represented by the general formula (1) and (C) the yellow pigment in the solvent (E). It is preferable to be obtained by dispersing the red pigment having the (A) diphenyl diketopyrrolopyrrole skeleton in the presence of the derivative and the (D) pigment dispersant.
When dispersing a red pigment having a diphenyl diketopyrrolopyrrole skeleton in a solvent, a pigment dispersion which is a block copolymer containing a sulfonated derivative of the specific yellow pigment and a salt of a tertiary amine or a quaternary ammonium salt Dispersion in the presence of a pigment dispersant combined with an agent improves the dispersibility and dispersion stability of a red pigment having a diphenyl diketopyrrolopyrrole skeleton, while achieving particularly high brightness, with high brightness. In addition, a pigment dispersion and a photosensitive resin composition that can achieve the demand for high contrast can be obtained.
Furthermore, by combining specific asymmetrical diketopyrrolopyrrole derivatives, pigment aggregation and crystallization are suppressed even after the high-temperature heating process in the color filter process without causing a large color change while maintaining high brightness. The effect of improving the contrast without greatly changing the phase difference can be obtained.

Although it is unclear as an effect | action which exhibits the above effects by the said specific combination, it estimates as follows.
According to the present invention, when a red pigment having a diphenyl diketopyrrolopyrrole skeleton is dispersed in a solvent, the sulfonated derivative of the specific yellow pigment is used. The sulfonated derivative of the specific yellow pigment has a high affinity with a red pigment having a diphenyl diketopyrrolopyrrole skeleton, and adsorbs to the surface of the red pigment to make the surface of the red pigment acidic, thereby diphenyl diketopyrrolopyrrole. It acts as an intermediary with the pigment dispersant to increase the affinity with the pigment dispersant rather than the red pigment itself having a skeleton. In addition, the sulfonated derivative of the yellow pigment is different from the sulfonated derivative of the red pigment, because the original color is yellow with a low coloring power, so the wavelength is shorter than the transmission wavelength of the red pigment having a diphenyl diketopyrrolopyrrole skeleton. By transmitting to the side, the brightness of the red pigment dispersion is maintained high without greatly changing the color of the red pigment. In particular, the red pigment having a diphenyl diketopyrrolopyrrole skeleton is C.I. I. Pigment red 254, C.I. I. Great effect when using Pigment Red 255.

According to the invention, the pigment dispersant used in combination with the sulfonated derivative of the specific yellow pigment is a salt-type block copolymer containing a tertiary amine salt or a quaternary ammonium salt. In the block type block copolymer, the block of the structural unit having a salt forming site has a strong adsorptivity to a sulfonated derivative of a pigment and particularly a yellow pigment adsorbed on the pigment surface, while having no salt forming site. The block containing the unit is soluble in the solvent.
When such a pigment dispersant and a sulfonated derivative of a yellow pigment are used in combination, C.I. I. Pigment Red 254 and the like can be refined, and the sulfonated derivative of the yellow pigment and the pigment dispersant can be appropriately adsorbed on the finely exposed pigment surface to stabilize the pigment in the solvent. It is presumed that a red pigment having a diketopyrrolopyrrole skeleton can be more uniformly refined. As a result, a coating film with improved contrast can be obtained.

Further, according to the present invention, a diketopyrrolopyrrole skeleton is used in combination with an asymmetrical diketopyrrolopyrrole derivative in which one is substituted with a polycyclic compound group containing one phenyl group and the other with two or more rings. . Such an asymmetric type diketopyrrolopyrrole derivative has a high affinity with a red pigment having a diphenyl diketopyrrolopyrrole skeleton, but a polycyclic compound group containing two or more rings is bulky and easily forms a twisted structure. Therefore, by adsorbing on the surface of the red pigment, it has an effect of suppressing aggregation of the red pigment having a diphenyl diketopyrrolopyrrole skeleton.
Since the asymmetric diketopyrrolopyrrole derivative does not have a highly polar substituent and has low solubility in a solvent, when used alone, the dispersibility of a red pigment having a diphenyl diketopyrrolopyrrole skeleton may be reduced. When combined with a sulfonated derivative of a diketopyrrolopyrrole skeleton or a sulfonated derivative of a red pigment of another skeleton, the luminance may decrease.
In the present invention, the synergistic effect of combining the specific yellow pigment derivative and the asymmetrical diketopyrrolopyrrole with a red pigment having a diphenyl diketopyrrolopyrrole skeleton, brightness and contrast without causing a large color change. The heat resistance can be increased without any trade-off relationship.

The red pigment dispersion for color filters of the present invention comprises at least (A) a red pigment having a diphenyl diketopyrrolopyrrole skeleton, (B) the specific asymmetric diketopyrrolopyrrole derivative, and (C) C.I. I. A block comprising a sulfonated derivative of one or more yellow pigments selected from the group consisting of CI Pigment Yellow 138, 139, 150, 215, and derivative pigments thereof; and (D) a salt of a tertiary amine or a quaternary ammonium salt It contains a pigment dispersant, which is a copolymer, and (E) a solvent, and may contain other components as necessary.
Hereinafter, each component of the red pigment dispersion of the present invention will be described in detail.

((A) Red pigment having diphenyl diketopyrrolopyrrole skeleton)
A red pigment having a diphenyl diketopyrrolopyrrole skeleton has a structure represented by the following chemical formula.

（Ｘはそれぞれ独立に、ハロゲン原子又は水素原子を示す。）
上記式中のＸにおけるハロゲン原子としては、Ｃｌ、Ｂｒなどが挙げられる。

(X each independently represents a halogen atom or a hydrogen atom.)
Examples of the halogen atom for X in the above formula include Cl and Br.

The average primary particle size of the red pigment having a diphenyl diketopyrrolopyrrole skeleton used in the present invention is not particularly limited as long as it can produce a desired color when used as a color layer of a color filter. Although it varies depending on the type of pigment used, it is preferably in the range of 10 to 70 nm, and more preferably in the range of 10 to 50 nm. When the average primary particle diameter of the pigment is in the above range, the liquid crystal display device manufactured using the red pigment dispersion for the color filter and the photosensitive resin composition of the present invention has high contrast and high quality. can do. In addition, with conventional pigment dispersants, as the particle size of the pigment becomes smaller, a large amount of pigment dispersant is required, which may cause problems such as reduced alkali developability and increased residue. Since the pigment dispersant used in the red pigment dispersion for color filters and the photosensitive resin composition is excellent in alkali developability if a salt is formed using an organic acid compound, such a problem is less likely to occur. 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 color filter photosensitive resin composition 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).

The average dispersed particle size of the pigment in the pigment dispersion varies depending on the type of pigment used, but is preferably in the range of 10 to 70 nm, and more preferably in the range of 10 to 50 nm.
The average dispersed particle size of the pigment in the pigment dispersion is a dispersed particle size of pigment particles dispersed in a dispersion medium containing at least a solvent, and is measured by a laser light scattering particle size distribution meter. For particle size measurement with a laser light scattering particle size distribution meter, the pigment dispersion is appropriately diluted to a concentration that can be measured with a laser light scattering particle size distribution meter (for example, 1000 times, etc.) It can be measured at 23 ° C. by a dynamic light scattering method using a laser light scattering particle size distribution meter (for example, Nanotrack particle size distribution measuring device UPA-EX150 manufactured by Nikkiso Co., Ltd.). The average dispersed particle size here is a volume average particle size.

  The red pigment having a diphenyl diketopyrrolopyrrole skeleton used in the present invention can be produced by a known method such as a recrystallization method or a solvent salt milling method. A red pigment having a diphenyl diketopyrrolopyrrole skeleton is C.I. I. In the case of Pigment Red 254, commercially available C.I. I. Pigment Red 254 (for example, BASF Japan Irgafore Red B-CF) may be used after milling.

  In the red pigment dispersion for a color filter of the present invention, the content of the red pigment having a diphenyl diketopyrrolopyrrole skeleton may be appropriately adjusted and is not particularly limited. Usually, the content of the pigment containing a red pigment having a diphenyl diketopyrrolopyrrole skeleton is in the range of 5 to 40% by weight, more preferably 10 to 20% by weight, based on the total amount of the red pigment dispersion for the color filter. Is preferred.

((B) Asymmetric diketopyrrolopyrrole derivative)
The diketopyrrolopyrrole derivative used in the present invention is an asymmetric diketopyrrolopyrrole derivative represented by the following general formula (1). The diketopyrrolopyrrole derivative used in the present invention has one phenyl group of a red pigment having a diphenyl diketopyrrolopyrrole skeleton as a polycyclic compound group, so that it is compared with a phthalimidomethylated diketopyrrolopyrrole derivative. Great effect on heat resistance. Further, by appropriately selecting a polycyclic compound group, it is possible to improve heat resistance without greatly changing the phase difference as compared with a phthalimidomethylated diketopyrrolopyrrole derivative. The asymmetric type means that two substituents substituted on the diketopyrrolopyrrole skeleton are different.

（一般式（１）中、Ｐｃは、置換基を有していても良く、ヘテロ原子を含んでいても良い多環式化合物基を表す。Ｘは、ハロゲン原子、ベンジル基、フェニル基、及び炭素数１〜１０の直鎖又は分枝のアルキル基よりなる群から選択される置換基であり、ｎは０〜５の整数を表す。ｎが２以上の場合、複数のＸは同一であっても異なっていても良い。）

(In general formula (1), Pc represents a polycyclic compound group which may have a substituent and may contain a hetero atom. X represents a halogen atom, a benzyl group, a phenyl group, and And a substituent selected from the group consisting of linear or branched alkyl groups having 1 to 10 carbon atoms, and n represents an integer of 0 to 5. When n is 2 or more, a plurality of Xs are the same. Or different.)

X substituted by the phenyl group in General formula (1) is a substituent selected from the group which consists of a halogen atom, a benzyl group, a phenyl group, and a C1-C10 linear or branched alkyl group. . In the case of the specific substituent X, the effect of the present invention is not significantly hindered.
The phenyl group preferably has no substituent (n = 0). When there is no substituent such as chlorine in the phenyl group, the steric hindrance on the side that acts on the red pigment having the diphenyl diketopyrrolopyrrole skeleton is small, and more on the surface of the primary particle of the red pigment having the diphenyl diketopyrrolopyrrole skeleton. Since it can be hydrogen-bonded or adsorbed, it has a great effect on improving heat resistance.
X having a substituent X is preferably a halogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms from the viewpoint of small steric hindrance and prevention of adsorption to the pigment. Examples of the halogen atom include Cl and Br. Examples of the linear or branched alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

  The polycyclic compound group in Pc of the general formula (1) refers to the remaining atomic group obtained by removing one hydrogen atom from a polycyclic compound containing two or more ring structures. The polycyclic compound here includes not only a condensed polycyclic compound in which two or more rings are condensed, but also a non-condensed polycyclic compound in which ring structures are connected to each other directly or via a connecting group. Examples of the ring structure include aromatic hydrocarbons, aromatic heterocyclic compounds, non-aromatic heterocyclic compounds, and aliphatic cyclic hydrocarbons. Among these, aromatic hydrocarbons, aromatic heterocyclic compounds, and non-aromatic heterocyclic compounds are preferable from the viewpoint of causing rigid steric hindrance.

  Benzene is mentioned as a monocyclic structure of the aromatic hydrocarbon. Examples of the monocyclic structure of the aromatic heterocyclic compound include furan, thiophene, and pyrrole. Non-aromatic heterocyclic compounds include structures such as cyclic ethers, lactones, cyclic imines, and lactams, such as oxetane, tetrahydrofuran (THF), tetrahydropyran (THP), butyrolactone, and ethyleneimine. It is done. Examples of the aliphatic cyclic hydrocarbon include cyclopentane, cyclohexane, cycloheptane, and the like.

  Examples of the condensed polycyclic compound include condensed ring hydrocarbons such as naphthalene, indene, azulene, fluorene, phenalene, phenanthrene, anthracene, pyrene, chrysene and naphthacene, and condensed heterocyclic compounds such as benzofuran and isobenzofuran. The condensed polycyclic compound also includes a structure in which a part of a condensed ring hydrocarbon or a condensed heterocyclic compound is hydrogenated.

  As the polycyclic compound in Pc, a condensed polycyclic compound is used, or monocyclic structures, condensed polycyclic compounds, or a monocyclic structure and a condensed polycyclic compound are directly bonded or linked. Polycyclic compounds linked together are used.

  Examples of the linking group include a hydrocarbon group, ether bond, thioether bond, carbonyl bond, thiocarbonyl bond, ester bond, thioester bond, amide bond, urethane bond, carbonate bond, sulfonyl bond, and combinations thereof. It is done.

  Specific examples of the polycyclic compound in which the monocyclic structures in Pc, the condensed polycyclic compounds, or the monocyclic structure and the condensed polycyclic compound are mutually connected by a direct bond or a linking group include: Biphenyl, 1-phenyl-2,5-dimethylpyrrole, bipyridyl and the like can be mentioned.

  Among these, it is preferable to use a condensed polycyclic compound, or a monocyclic structure or a polycyclic compound in which a monocyclic structure and a condensed polycyclic compound are connected to each other by a direct bond. In the case of polycyclic compounds connected to each other by a linking group, the linking group site is easy to move, and a ring bonded during heating may move, which may cause a decrease in heat resistance. On the other hand, in the case of a polycyclic compound in which a condensed polycyclic compound is used, or between monocyclic structures or a monocyclic structure and a condensed polycyclic compound are connected to each other by a direct bond, This is because the ring structure is strongly fixed at a stable position by mutual hydrogen atoms and steric hindrance, and thus has a merit that it is rigid and hardly moves even when heated, and the effect of improving heat resistance is further enhanced.

  The polycyclic compound in Pc may have a substituent, and examples of the substituent include the same substituent as X which may be bonded to a phenyl group.

  The polycyclic compound in Pc preferably has 4 to 20 carbon atoms, and more preferably 5 to 18 carbon atoms, and the balance between the adsorptivity of the pigment to the diketopyrrolopyrrole skeleton and the heat resistance effect. , And from the viewpoint of solubility and affinity in a solvent.

  The asymmetrical diketopyrrolopyrrole derivative used in the present invention has a balance between the adsorptive and heat-resistant effects of the pigment on the diketopyrrolopyrrole skeleton, and has solubility in the solvent, affinity, and diphenyl diketopyrrolopyrrole skeleton. Since it has almost the same color as the red pigment, and there is little color change and luminance decrease due to addition, among them, it is preferable to have a structure in which an aromatic hydrocarbon is directly bonded to the diketopyrrolopyrrole skeleton. An asymmetric diketopyrrolopyrrole derivative represented by the formula (2) is preferable.

（一般式（２）中、Ａｒ^１〜Ａｒ^５は、それぞれ独立に、水素原子、ハロゲン原子、又は有機基であり、それらが結合して環状構造を形成していても良く、ヘテロ原子の結合を含んでいても良い。但し、Ａｒ^１〜Ａｒ^５の少なくとも１つが置換基を有していても良いアリール基又は置換基を有していても良いヘテロアリール基であるか、及び／又は、Ａｒ^１〜Ａｒ^５の少なくとも２つが結合して環状構造を形成しているものである。Ｘ及びｎは、一般式（１）と同じである。）

(In the general formula (2), Ar ^{1 to} Ar ⁵ are each independently a hydrogen atom, a halogen atom, or an organic group, which may be bonded to form a cyclic structure. Provided that at least one of Ar ^{1 to} Ar ⁵ is an aryl group which may have a substituent or a heteroaryl group which may have a substituent, and / or (At least two of Ar ^{1 to} Ar ⁵ are bonded to form a cyclic structure. X and n are the same as those in the general formula (1).)

In Ar ^{1 to} Ar ⁵ in the general formula (2), at least two of Ar ^{1 to} Ar ⁵ are bonded to form a cyclic structure, and / or at least one of Ar ^{1 to} Ar ⁵ has a substituent. It is an aryl group which may have or a heteroaryl group which may have a substituent. As if it at least two of Ar ¹ to Ar ⁵ to form a ring structure by ^bonding, described by combining at least two Ar 1 to Ar ^5, together with the benzene ring to which Ar 1 to Ar ⁵ are attached The case where the condensed polycyclic compound is formed. In addition, examples of the aryl group when at least one is an aryl group or a heteroaryl group include the above-described aromatic hydrocarbons, and examples of the heteroaryl group include the above-described aromatic heterocyclic compounds and non-aromatic heterocyclic rings. And formula compounds. Moreover, as a substituent which the said aryl group or heteroaryl group may have, a halogen atom, a benzyl group, or a C1-C10 linear or branched alkyl group is mentioned.

  Examples of the (B) asymmetric diketopyrrolopyrrole derivative used in the present invention include, but are not limited to, the following structures.

The (B) asymmetric diketopyrrolopyrrole derivative used in the present invention is, for example,
It can be produced by reacting a specific pyrrolinone with benzonitrile. This synthetic method is described in detail in European Patent Application Publication No. 0184982, and can be referred to. As an asymmetric type diketopyrrolopyrrole derivative, it can be used individually by 1 type or in mixture of 2 or more types.

Red pigments having a diphenyl diketopyrrolopyrrole skeleton, particularly those that have been refined, are prone to hydrogen bonding and crystal growth in the stacking direction due to heating, and crystal growth in the hydrogen bonding direction is particularly prominent. This crystal growth reduces the contrast.
On the other hand, an increase in the phase difference during heating occurs because the crystal growth in the hydrogen bonding direction or the crystal growth in the stacking direction, which cannot be completely suppressed by visual observation, occurs at the nano level, and is ordered in the cured film. Guessed. Therefore, if the crystal growth can be suppressed more strongly, it is considered that the phase difference increase due to heating does not occur.
In order to suppress the crystal precipitation more strongly, the red pigment having the adjacent diphenyl diketopyrrolopyrrole skeleton, which causes crystal growth, should not be contacted or bonded due to the steric hindrance of the asymmetric diketopyrrolopyrrole derivative. It is considered that the degree of heat resistance changes depending on the direction and size of the steric hindrance. In the present invention, by substituting a polycyclic compound group for the diketopyrrolopyrrole derivative, it becomes possible to suppress the contact and hydrogen bond formation of the red pigment molecule having an adjacent diphenyl diketopyrrolopyrrole skeleton, A decrease in contrast and an increase in phase difference during heating can be suppressed. In particular, the addition of an asymmetric diketopyrrolopyrrole derivative having rigid steric hindrance can suppress an increase in phase difference during heating. Spatial conformation can be optimized by performing classical mechanics calculation (MM3 calculation) and semi-empirical molecular orbital method (PM6 calculation) using Fujitsu SCIGRESS (manufactured by Fujitsu Limited). it can. As a result of the simulation, the steric hindrance, that is, the asymmetric type in which the maximum value is 10 degrees or more among dihedral angles between the central two pyrrole ring planes and the plane formed by the ring included in the polycyclic compound group. The diketopyrrolopyrrole derivative was found to be particularly effective. For example, when the polycyclic compound group is a biphenyl group, the dihedral angle with the plane formed by the second bonded phenyl group is the maximum value, not the phenyl group directly bonded to the pyrrole ring plane. Take.

  In the present invention, the asymmetric diketopyrrolopyrrole derivative is preferably contained in an amount of 0.5 to 25 parts by weight with respect to 100 parts by weight of the red pigment having the diphenyl diketopyrrolopyrrole skeleton. Among these, the asymmetrical diketopyrrolopyrrole derivative should be contained in an amount of 0.5 to 20 parts by weight, and further 0.5 to 15 parts by weight, with respect to 100 parts by weight of the red pigment having the diphenyl diketopyrrolopyrrole skeleton. Is preferred. By using in such a content, aggregation and crystal precipitation of the pigment are suppressed even after the high-temperature heating step in the color filter step, and particularly high brightness and high contrast can be achieved.

((C) Sulfonated derivative of yellow pigment)
Examples of yellow pigments that can be used in the pigment dispersion of the present invention to derive sulfonated derivatives of yellow pigments include C.I. I. Pigment Yellow 138, 139, 150, 185, 215, and one or more yellow pigments selected from the group consisting of these derivative pigments. These pigments are preferable because they have high luminance and high affinity with red pigments having a diphenyl diketopyrrolopyrrole skeleton.
Here, C.I. I. Pigment Yellow 150 derivative pigments specifically include mono-, di-, tri- and tetraanions of azo compounds according to the following chemical formula or one of their tautomeric structures that act as hosts for at least one guest compound And metal complexes corresponding to Li, Cs, Mg, Cd, Co, Al, Cr, Sn, Pb, particularly preferably Na, K, Ca, Sr, Ba, Zn, Fe, Ni, Cu, Mn and La Can be mentioned.

［上記化学式中、ＲおよびＲ’は、独立して、ＯＨ、ＮＨ_２、ＮＨ−ＣＮ、アシルアミノまたはアリールアミノであり、そしてＲ^ａおよびＲ^ａ’は、独立して、−ＯＨまたは−ＮＨ_２である］

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

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

  In the present invention, examples of yellow pigments for derivatizing sulfonated derivatives of yellow pigments include C.I. I. Pigment Yellow 138, 139 is used in addition to C.I. I. Pigment Yellow 138 has particularly high brightness, high affinity with a red pigment having a diphenyl diketopyrrolopyrrole skeleton, and high brightness and high contrast without changing the hue. preferable.

The sulfonated derivative of the yellow pigment has a structure in which at least one sulfonic acid group (—SO ₃ H) or a sulfonamide group is bonded to the specific yellow pigment, and a part of the sulfonic acid group. Alternatively, all of them may be salted with amine, ammonium hydroxide, chloride, bromide or the like, metal or the like to form a sulfonate.

As the sulfonamide group which is an amide compound of a sulfonic acid group, sulfonamide groups represented by the following chemical formulas (A) to (C) are preferable.
Chemical Formula (A): —SO ₂ NH— (CH ₂ ) _m —NR′R ″
Formula _{(B): -SO 2 NH- (} CH 2) m -COOH
Formula _{(C): -SO 2 NH- (} CH 2) m -SO 3 H
In the chemical formula (A), R ′ and R ″ each independently represent a hydrogen atom, an optionally substituted saturated or unsaturated aliphatic hydrocarbon group or aromatic hydrocarbon group having 1 to 20 carbon atoms, or It represents a heterocyclic ring which may further contain nitrogen, oxygen or sulfur atoms together with the adjacent nitrogen atom.
In chemical formulas (A) to (C), m is each independently an integer of 1 to 6.

Representative of the amine component (— (CH ₂ ) _m —NR′R ″) introduced as a substituent represented by —SO ₂ NH— (CH ₂ ) _m —NR′R ″ in the chemical formula (A) Examples include piperidinomethyl, dimethylaminoethyl, diethylaminoethyl, dimethylaminopropyl, diethylaminopropyl, dibutylaminopropyl, piperidinoethyl, pipecolinoethyl, morpholinoethyl, piperidinopropyl, pipecolinopropyl, diethylaminohexyl, diethylaminoethoxypropyl, diethylaminobutyl, Examples include dimethylaminoamyl, NN-methyl-lauryl-aminopropyl, 2-ethylhexylaminoethyl, stearylaminoethyl, oleylaminoethyl and the like.

Furthermore, it seems that p-dimethylaminoethylsulfamoylphenyl, p-diethylaminoethylsulfamoylphenyl, p-dimethylaminopropylsulfamoylphenyl, p-diethylaminoethylcarbamoylphenyl and the like are bonded to the —SO ₂ NH— group. It may be a sulfonamido group.

When there is a sulfonic acid group that does not form a salt, the pigment adsorbing power of the dispersant is improved by interaction with a tertiary amine site of a block copolymer type pigment dispersant described later and salt formation or ions. This is preferable.
The sulfonated derivative of the yellow pigment may be further substituted with other functional groups such as a phthalimidomethyl group in addition to the sulfonic acid group, sulfonamide group, and sulfonate.

  As the sulfonamide group, those having 5 or less carbon atoms are preferable.

The number of substitutions in one molecule of the yellow pigment of the sulfonic acid group (—SO ₃ H) or sulfonamide group is preferably 1 to 3, more preferably 1 to 2, and more preferably 1. From the viewpoint of steric hindrance and affinity with a dispersant.

  Examples of the sulfonated derivative of the yellow pigment preferably used in the present invention include C.I. I. Pigment Yellow 138 has the following structure in which at least a sulfonic acid group, a sulfonamide group, and a sulfonate are bonded.

（式（３）において、Ｑは、スルホン酸基、−ＳＯ_２ＮＨ−（ＣＨ_２）_ｍ−ＮＲ’Ｒ”、−ＳＯ_２ＮＨ−（ＣＨ_２）_ｍ−ＣＯＯＨ、−ＳＯ_２ＮＨ−（ＣＨ_２）_ｍ−ＳＯ_３Ｈ、及びスルホン酸塩よりなる群から選択される１種であり、Ｒ’及びＲ”はそれぞれ独立に、水素原子、炭素数１〜２０の置換されていても良い飽和若しくは不飽和の脂肪族炭化水素基若しくは芳香族炭化水素基、又は、隣接する窒素原子と共に更に窒素、酸素、若しくは硫黄原子を含んでいても良い複素環を形成したものを表し、ｍはそれぞれ独立に、１〜６の整数である。ｎは置換基数を示し、１〜４の整数を表す。）

In (Equation (3), Q is a sulfonic acid _{group, -SO 2 NH- (CH 2)} m -NR'R ", - SO 2 NH- (CH 2) m -COOH, -SO 2 NH- (CH ₂ ) _m— SO ₃ H, and one selected from the group consisting of sulfonates, wherein R ′ and R ″ are each independently a hydrogen atom, an optionally substituted saturated group having 1 to 20 carbon atoms. Or an unsaturated aliphatic hydrocarbon group or an aromatic hydrocarbon group, or a heterocyclic ring which may contain a nitrogen, oxygen or sulfur atom together with an adjacent nitrogen atom, and each m is independently And n represents an integer of 1 to 6. n represents the number of substituents and represents an integer of 1 to 4.)

The substituents are preferably used, sulfonic acid _{group, -SO 2 NHC 2 H 4 COOH} , -SO 2 - N (CH 3) 2 (C 18 H 37) 2 +, -SO 2 NHC 3 H 6 N ( C ₂ H ₅ ) _{2 and the} like.

  In the formula (3), the number of substituents n is preferably 1 to 2, and is preferably 1 from the viewpoint of easily forming a salt with the tertiary amine moiety of the pigment dispersant.

  A sulfonated derivative of a yellow pigment can be produced, for example, by introducing a yellow pigment into concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, or a mixture thereof to perform a sulfonation reaction. After the sulfonation reaction, the reaction solution is diluted with a large amount of water or is preferably neutralized with an aqueous amine solution when producing an amine salt. The resulting suspension is filtered and then washed with an aqueous washing solution. And dry. By appropriately selecting the amine of the aqueous amine solution to be used, the amine salt of sulfonic acid can be appropriately introduced as designed. Further, when producing the sulfonic acid amide, thionyl chloride is allowed to act on the sulfonated product of the yellow pigment obtained by the above-mentioned method to form a sulfonic acid chloride, and then mixed with an amine so that the sulfonated amide is appropriately designed. Can be introduced.

  When sulfonation is performed by the above method, the amount of sulfonic acid groups or sulfonamide groups introduced per molecule can be controlled by adjusting the reaction solution concentration, reaction temperature, reaction time, and the like.

  As the sulfonated derivative of the yellow pigment, one kind can be used alone, or two or more kinds can be used in combination. For example, two or more kinds of sulfonated derivatives having different types, substitution positions, or substitution numbers of sulfonic acid groups and / or sulfonamide groups may be used.

  In the present invention, the sulfonated derivative of the yellow pigment is preferably contained in an amount of 1 to 25 parts by weight with respect to 100 parts by weight of the red pigment having the diphenyl diketopyrrolopyrrole skeleton. Among them, the sulfonated derivative of the yellow pigment is preferably contained in an amount of 1 to 15 parts by weight, and more preferably 3 to 10 parts by weight with respect to 100 parts by weight of the red pigment having the diphenyl diketopyrrolopyrrole skeleton. By using it in such a content, it becomes possible to produce a coating film that achieves the demand for high brightness and high contrast without greatly changing the hue.

Further, the ratio of the content of the sulfonated derivative of the yellow pigment and the asymmetric type diketopyrrolopyrrole derivative is 20: 1 to 20:40, particularly 20: 1 to 20:30. It is preferable because the aggregation and crystal precipitation of the pigment are suppressed even after the high-temperature heating step in the color filter step without largely changing, and particularly high brightness and high contrast can be achieved.
When the sulfonated derivative of the yellow pigment and the asymmetric type diketopyrrolopyrrole derivative are used in combination, the synergistic effect thereof can suppress a change in hue when the red pigment derivative is used alone, and the luminance can be improved. In addition, the heat resistance is improved, and crystal precipitation of a red pigment having a diphenyl diketopyrrolopyrrole skeleton at the time of baking can be suppressed.

((D) Pigment dispersant)
The pigment dispersant used in the present invention is a block copolymer containing a tertiary amine salt or a quaternary ammonium salt. In such a block copolymer, a block portion containing a tertiary amine salt or a quaternary ammonium salt is adsorbed on a sulfonated derivative of a pigment and a yellow pigment, and contains a tertiary amine salt or a quaternary ammonium salt. Since the non-blocking portion has solubility in the solvent, the dispersibility of the pigment can be improved. In particular, in the present invention, a yellow pigment derivative having a sulfonic acid group and / or a sulfonamide group and a pigment dispersant comprising a salt-type block copolymer are used in combination, so that a red pigment having a diphenyl diketopyrrolopyrrole skeleton Miniaturization can be realized and contrast can be improved.
By using a pigment dispersant made of a block copolymer, the size of the pigment adsorbing part and the solvent-soluble part can be designed smaller than when a graft polymer type pigment dispersant is used. Get higher. Furthermore, heat resistance is also relatively high, and deterioration of heat resistance due to the pigment dispersant can be suppressed.

Examples of the tertiary amine salt include a salt formed at a tertiary amine moiety such as dimethylaminoethyl acrylate, which is a unit forming a block copolymer, with an acid such as a phosphoric acid compound or a sulfonic acid compound. In addition, examples of the quaternary ammonium salt include a quaternary ammonium salt such as dimethylaminoethyl acrylate, which is a unit that forms a block copolymer, at a tertiary amine moiety by an allyl halide and / or an aralkyl halide. It is done.
The block portion containing a tertiary amine salt or a quaternary ammonium salt may contain an amine that does not form a salt.

  The amount of the tertiary amine salt or quaternary ammonium salt contained in the copolymer is preferably 1 to 50% in terms of the number of repeating units with respect to the total number of repeating units of the block copolymer. It is preferable that it is 1 to 20%.

  Examples of the main chain structure of the polymer include (meth) acrylic resins and styrene resins. Among these, a (meth) acrylic resin is preferable in that it easily synthesizes a block copolymer.

  The weight average molecular weight Mw of the block copolymer containing a tertiary amine salt or a quaternary ammonium salt used in the present invention is preferably in the range of 500 to 20000, and preferably in the range of 1000 to 15000. More preferably, it is still more preferably in the range of 3000-12000. By being within the above range, it becomes possible to achieve both wettability and dispersion stability with respect to a pigment in the initial stage of dispersion in which the pigment is uniformly dispersed. Here, the weight average molecular weight can be determined as a standard polystyrene equivalent value by gel permeation chromatography (GPC).

  A commercially available product may be used as the pigment dispersant made of a block copolymer containing a tertiary amine salt or a quaternary ammonium salt, such as DISPERBYK-2000 manufactured by Big Chemie. You may use what made the tertiary amine part the salt and the thing made the quaternary ammonium salt using the LPN-6919 made from Big Chemie.

  Among them, the pigment dispersant used in the present invention has a repeating unit (1) represented by the following general formula (I) and a repeating unit (2) represented by the following general formula (II), It is a block copolymer in which at least a part of the amino group of the repeating unit (1) and an organic acid compound and / or a halogenated hydrocarbon form a salt. Hereinafter, the salt type block copolymer having the specific repeating unit will be described in detail.

［式（Ｉ）及び式（ＩＩ）中、Ｒ^１は、水素原子又はメチル基、Ｒ^２及びＲ^３は、それぞれ独立に水素原子又は炭素数１〜８のアルキル基、Ａは、炭素数１〜８のアルキレン基、−[ＣＨ（Ｒ^６）−ＣＨ（Ｒ^７）−Ｏ]_ｘ−ＣＨ（Ｒ^６）−ＣＨ（Ｒ^７）−又は−[（ＣＨ_２）_ｙ−Ｏ]_ｚ−（ＣＨ_２）_ｙ−で示される２価の基、Ｒ^４は、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、アラルキル基、アリール基、−[ＣＨ（Ｒ^６）−ＣＨ（Ｒ^７）−Ｏ]_ｘ−Ｒ^８又は−[（ＣＨ_２）_ｙ−Ｏ]_ｚ−Ｒ^８で示される１価の基である。Ｒ^６及びＲ^７は、それぞれ独立に水素原子又はメチル基であり、Ｒ^８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、又は−ＣＨ_２ＣＯＯＲ^９で示される１価の基であり、Ｒ^９は水素原子又は炭素数が１〜５のアルキル基である。上記アルキル基、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良い。
ｘは１〜１８の整数、ｙは１〜５の整数、ｚは１〜１８の整数を示す。ｍは３〜２００の整数、ｎは１０〜２００の整数を示す。］

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

<Block copolymer>
The block copolymer has a repeating unit (1) represented by the general formula (I) and a repeating unit (2) represented by the general formula (II).
In the said general formula (I), R < ¹ > shows a hydrogen atom or a methyl group, R < ² > and R < ³ > show a hydrogen atom or a C1-C8 alkyl group each independently. Here, the alkyl group having 1 to 8 carbon atoms may be linear, branched or cyclic. Examples of such alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, various pentyl groups, various hexyl groups, and various octyl groups. Group, cyclopentyl group, cyclohexyl group, cyclooctyl group and the like. Among these, a methyl group and an ethyl group are preferable.
In the present invention, R ² and R ³ may be the same as or different from each other.

A is an alkylene group having 1 to 8 carbon atoms, * — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —CH (R ⁶ ) —CH (R ⁷ ) — **, or * — _{[(CH 2) y -O]} z - (CH 2) y - is a divalent group represented by **. Here, * represents a linking site on the ester bond side, and ** represents a linking site on the amino group side. The alkylene group having 1 to 8 carbon atoms may be linear or branched. For example, a methylene group, an ethylene group, a trimethylene group, a propylene group, various butylene groups, various pentylene groups, various kinds. Hexylene group and various octylene groups.
R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group.
x is an integer of 1 to 18, preferably an integer of 1 to 4, more preferably an integer of 1 to 2, and y is an integer of 1 to 5, preferably an integer of 1 to 4, more preferably 2 or 3. is there. z is an integer of 1-18, preferably an integer of 1-4, more preferably an integer of 1-2. In the present invention, if x, y, and z are within the above ranges, the red pigment dispersion for color filter of the present invention has excellent pigment dispersibility.
As said A, a C1-C8 alkylene group is preferable and a methylene group and ethylene group are more preferable. If the carbon number is in the range of 1 to 8, the dispersibility of the pigment can be kept good.

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

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

In the present invention, as R ⁴ , it is preferable to use those having excellent solubility in the solvent described later, and specifically, it varies depending on the repeating units constituting the block copolymer. When the solvent is tetrahydrofuran, toluene or the like, it is preferable to use a methyl group, an ethyl group, a benzyl group or the like, and the solvent is an ether alcohol acetate generally used as a solvent for a color filter. In the case of using a solvent such as a system, ether, or ester, a methyl group, an ethyl group, an n-butyl group, a 2-ethylhexyl group, a benzyl group, or the like is preferable. Moreover, when the said solvent is a thing with lower polarity, such as pentane and hexane, it is preferable to use a pentyl group, a hexyl group, a heptyl group, etc.
Here, the reason for setting R ⁴ in this way is that the repeating unit (2) containing R ⁴ has solubility in the solvent, and the amino group of the repeating unit (1) and an organic acid described later Because the salt-forming site formed by the compound and / or halogenated hydrocarbon has high adsorptivity to the pigment, the dispersibility and stability of the pigment can be made particularly excellent. is there.

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

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

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

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

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

  In the case where two or more structural units (1) and structural units (2) are included, a block copolymer in which the structural units (1), the structural units (2 ′), and the structural units (2 ″) are combined in this order, A block copolymer bonded in the order of structural unit (1 ')-structural unit (1 ")-structural unit (2), or structural unit (1')-structural unit (1")-structural unit (2 ') -The block copolymer etc. which couple | bonded in order of the structural unit (2 ") may be sufficient.

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

［式（ＩＩＩ）及び式（ＩＶ）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 (III) and Formula (IV), R ^a and R ^{a ′} are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, or an aryl group. 1 represented by the group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — [(CH ₂ ) _t —O] _u —R ^e , or —O—R ^{a ″.} the valence of the group, one of R ^a and R ^{a 'comprises} a carbon atom. R ^{a ″} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e. ,-[(CH ₂ ) _t —O] _u —R ^e .
R ^b is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — [(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. ]

  In the present invention, by using the organic acid compound and / or the halogenated hydrocarbon described later, the pigment dispersant can be made excellent in pigment dispersibility and stability. Furthermore, when an organic acid compound is used, the salt-forming site has high solubility in an alkaline aqueous solution at the time of alkali development, so that a photosensitive resin composition excellent in alkali developability can be obtained. .

In the general formula (III), R ^a and R ^{a ′} are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, 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, the alkenyl group having 2 to 18 carbon atoms, the aryl group, and the aralkyl group are as described for R ⁴ . The position of the double bond of the alkenyl group is not limited, but from the viewpoint of reactivity, it is preferable that 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.
In addition, examples of the substituent of the aromatic ring such as the aryl group and the aralkyl group include alkenyl groups, nitro groups, and halogen atoms in addition to linear or branched alkyl groups having 1 to 4 carbon atoms. .

R ^c and R ^d are each independently a hydrogen atom or a methyl group, and R ^e is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, or an aryl group. , —CHO, —CH ₂ CHO, —CO—CH═CH ₂ , —CO—C (CH ₃ ) ═CH ₂ or —CH ₂ COOR ^f , and R ^f is a hydrogen atom or 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 in the R ^e is as shown in the above R ⁴ , and the alkenyl group, aralkyl group and aryl group having 2 to 18 carbon atoms are the same as the above R ^a and R ^{a ′.} It is as shown in.

When R ^a and / or R ^{a ′} is —O—R ^{a ″} , it is an acidic phosphate ester. R ^a ″ 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, for example, a linear or branched alkyl group having 1 to 4 carbon atoms.

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

In the general formula (IV), 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 an alkyl group, an alkenyl group, an aralkyl group, and an 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 above for R ^a , R ^a and R ^{a ″} .
R ^c , R ^d, and R ^e are as described for R ^a , R ^{a ′,} and R ^{a ″} .
In the above R ^b and R ^b ′, s is an integer of 1 to 18, t is an integer of 1 to 5, and u is an integer of 1 to 18. Preferred s, t, and u are the same as R ^a , R ^{a ′} and R ^{a ″} described above.

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

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

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

From the viewpoint of heat resistance and chemical resistance, the organic acid compound represented by the above general formula (III) and general formula (IV) has 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.

The organic acid compound represented by the general formula (III) and general formula ^{(IV), R} a, R ^{a 'and} / or R ^a'', and / or as ^{R b} and / or R ^b' Has a polymerizable group, that is, a vinyl group, an allyl group, or — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , or — [(CH ₂ ) _t —O] _u. It is preferable that -R ^e and R ^e is -CO-CH = CH ₂ or -CO-C (CH ₃ ) = CH ₂ , especially R ^a , R ^{a ′} and / or R ^{a ′. '} And / or R ^b and / or R ^b' are preferably vinyl, allyl, 2-methacryloyloxyethyl, or 2-acryloyloxyethyl.
In such a case, the above-mentioned polymerizable groups and / or the above-mentioned polymerizable groups and the color filter of the present invention are exposed during exposure when forming a colored layer using the photosensitive resin composition for a color filter of the present invention. Can be easily polymerized with an alkali-soluble resin, a polyfunctional monomer, and the like contained in the photosensitive resin composition, 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 photosensitive resin composition for a color filter at an unexposed portion can be made particularly excellent in alkali developability during development for forming a colored layer.

  In addition, the organic acid compound represented by the said general formula (III) and general formula (IV) can be used individually by 1 type or in combination of 2 or more types.

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

Examples of the halogenated hydrocarbon include those in which any one of a chlorine atom, a bromine atom and an iodine atom is substituted with a hydrogen atom of a saturated or unsaturated linear, branched or cyclic hydrocarbon. . Among these, allyl halide and / or aralkyl halide is preferable from the viewpoint of enhancing pigment dispersibility.
In addition, the halogenated hydrocarbon preferably has 1 to 30 carbon atoms, more preferably 1 to 25, and still more preferably 1 to 18.

  Among the halogenated hydrocarbons, examples of the halogenated alkyl include those having 1 to 18 carbon atoms, but are not particularly limited. Specifically, for example, methyl chloride, methyl bromide, ethyl chloride, ethyl bromide, methyl iodide, ethyl iodide, n-butyl chloride, hexyl chloride, octyl chloride, dodecyl chloride, tetradecyl chloride, hexadecyl chloride, etc. Can be mentioned. Examples of the allyl halide include allyl chloride, allyl bromide, and allyl iodide. Further, examples of the aralkyl group of the halogenated aralkyl include those having 7 to 18 carbon atoms, but are not particularly limited. Specific examples include benzyl chloride, benzyl bromide, benzyl iodide, naphthylmethyl chloride, pyridylmethyl chloride, naphthylmethyl bromide, pyridylmethyl bromide and the like. Examples of the aryl halide include those having 6 to 18 carbon atoms, but are not particularly limited. Specifically, benzene chloride etc. are mentioned, for example.

  Among them, it is at least one selected from the group consisting of allyl chloride, allyl bromide, allyl iodide, benzyl chloride, benzyl bromide, and benzyl iodide to facilitate the salt formation reaction and the generated salt. The formation site is preferable from the viewpoint of excellent adsorptivity to the pigment.

  The content of the organic acid compound and / or halogenated hydrocarbon in the block copolymer used in the present invention is not particularly limited as long as good dispersion stability is exhibited. 0.05-1.0 molar equivalent is preferable with respect to the tertiary amino group represented by (I). Furthermore, the organic acid compound and / or halogenated hydrocarbon is contained from the viewpoint of excellent pigment adsorption power, solubility in a solvent, interaction with a sulfonated derivative of a yellow pigment, pigment dispersibility and pigment dispersion stability. The amount is preferably 0.2 to 0.8 molar equivalent relative to the tertiary amino group. In addition, when using 2 or more types of the said organic acid compound and / or halogenated hydrocarbon together, content which added these should just be in the said range.

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

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

  In the red pigment dispersion for a color filter of the present invention, as the pigment dispersant, one type of the block copolymer may be used, or two or more types may be used in combination. Further, the content is not particularly limited as long as the pigment can be uniformly dispersed. For example, the content can be 10 to 150 parts by weight with respect to 100 parts by weight of the pigment. Furthermore, it is preferable to mix | blend in the ratio of 15-45 weight part with respect to 100 weight part of pigments, and it is preferable to mix | blend especially in the ratio of 15-40 weight part. If the content of the salt-type graft copolymer is within the above range, the pigment can be uniformly dispersed. In the present invention, the pigment used when the content other than the pigment derivative is defined includes a pigment derivative in addition to the pigment, for example, a sulfonated derivative of the yellow pigment.

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

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

(Other pigments)
Examples of the red pigment having a diphenyl diketopyrrolopyrrole skeleton of the pigment dispersion of the present invention include C.I. Pigment Red 254, C.I. I. Pigment Red 255 is preferably used, but the pigment dispersion may further contain other pigments as long as the effects of the present invention are not impaired. Other pigments include, for example, other red pigments and yellow pigments from the viewpoint of achieving a specific color necessary for the red colored layer of the color filter as described in the red photosensitive resin composition described later. . However, when dispersing a red pigment having a diphenyl diketopyrrolopyrrole skeleton, a pigment dispersant which is a block copolymer containing a sulfonated derivative of the above specific yellow pigment and a salt of a tertiary amine or a quaternary ammonium salt Is preferably present. That is, the red pigment dispersion according to the present invention is suitably used as a red pigment dispersion that is separately mixed with a yellow pigment dispersion when preparing a red photosensitive resin composition.

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

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

(Other ingredients)
The pigment dispersion of the present invention may further contain a pigment dispersion auxiliary resin, other pigment derivatives, and other components as necessary.
As pigment dispersion auxiliary resin, the alkali-soluble resin illustrated with the photosensitive resin composition mentioned later is mentioned, for example. In some cases, the steric hindrance of the alkali-soluble resin makes it difficult for the pigment particles to come into contact with each other.
Moreover, as long as the effect of this invention is not impaired, the other pigment dispersant may be included.
Other components include, for example, surfactants for improving wettability, silane coupling agents for improving adhesion, antifoaming agents, repellency inhibitors, antioxidants, anti-aggregation agents, and UV absorbers. Etc.

<Method for producing pigment dispersion>
The method for producing a pigment dispersion of the present invention comprises the step (A) of diphenyl diketo in the solvent (E) in the presence of at least the sulfonated derivative of the (C) yellow pigment and the (D) pigment dispersant. It is preferable to have a step of dispersing a red pigment having a pyrrolopyrrole skeleton. Presence of the sulfonated derivative of the (C) yellow pigment, the (D) pigment dispersant, and the (B) asymmetric diketopyrrolopyrrole derivative represented by the following general formula (1) in the solvent (E) It is preferable to have the process of disperse | distributing the red pigment which has the said (A) diphenyl diketopyrrolopyrrole frame | skeleton below.
In the dispersion process, as a disperser for performing dispersion treatment, a roll mill such as a two-roll or a three-roll, a ball mill such as a ball mill or a vibration ball mill, a paint conditioner, a continuous disk type bead mill, a bead mill such as a continuous annular type bead mill, or the like. Can be mentioned. 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.

In the present invention, the dispersion time for dispersion using a known disperser is appropriately adjusted and is not particularly limited. For example, when a paint shaker is used so that the average dispersed particle diameter of the pigment is about 15 to 50 nm. Is preferably 5 to 50 hours from the viewpoint of realizing high contrast by refining the pigment.
In this way, a pigment dispersion having excellent pigment particle dispersibility is obtained. The pigment dispersion is used as a preliminary preparation for preparing a red photosensitive resin composition for a color filter having excellent pigment dispersibility.

2. Red photosensitive resin composition for color filter The red photosensitive resin composition for color filter according to the present invention contains at least the red pigment dispersion for color filter according to the present invention and (F) a photosensitive binder component. It is characterized by that.

Since the red photosensitive resin composition for a color filter according to the present invention contains the pigment dispersion according to the present invention, the aggregation and crystal precipitation of the pigment are suppressed even after the high-temperature heating process in the color filter process, and particularly high brightness. In addition, a color filter that achieves high contrast can be formed.
Hereinafter, the component used for such a red photosensitive resin composition for color filters of this invention is demonstrated.
In addition, about the component which can be contained in the red pigment dispersion liquid for color filters which concerns on the said invention, since the thing similar to what was demonstrated in the location of the said pigment dispersion liquid can be used, other pigments and other pigments can be used. Except for the dispersant, the description here is omitted.

(Other pigments)
The red photosensitive resin composition for a color filter of the present invention can achieve chromaticity required for use and specifications in a color filter, and other yellow pigments, oranges and the like as long as the effects of the present invention are not impaired. Other pigments may be contained.
As other pigments contained in the red photosensitive resin composition for color filters, the inclusion of a yellow pigment improves the contrast while achieving the specific color required for the red colored layer of the color filter. preferable.

  Examples of yellow pigments include C.I. Pigment Yellow 150 or a derivative pigment thereof, C.I. Pigment Yellow 138 and C.I. It is preferably at least one selected from the group consisting of I. Pigment Yellow 139. C. As the derivative pigment of I. Pigment Yellow 150, the same pigments as described in the above (C) sulfonated derivative of yellow pigment can be used.

((F) photosensitive binder component)
In the present invention, from the point of imparting sufficient strength, durability and adhesion to the coating film, after forming a pattern on the substrate by coating or transfer, the coating film can be cured by a polymerization reaction. A binder component is used. In addition to the photosensitive binder component described below, a thermosetting binder component that can be polymerized and cured by heating such as an epoxy resin may be further used. In preparing the resin composition according to the present invention using the pigment dispersion according to the present invention having excellent pigment dispersibility, it is necessary to appropriately select a binder component so as not to inhibit the excellent pigment dispersibility. is there.

The photosensitive binder component contains a photo-curable resin that can be polymerized and cured by light such as ultraviolet rays and electron beams, and the exposed portion is cured and the unexposed portion is dissolved and removed to dissolve and remove the uncoated portion. Negative-type photosensitive binder components that can be prepared.
In the red photosensitive resin composition for a color filter according to the present invention, a negative photosensitive binder component is preferable in that a pattern can be easily formed using an existing process by a photolithography method.

  A negative photosensitive binder component containing a photocurable resin that can be polymerized and cured by light such as ultraviolet rays and electron beams includes (i) an alkali-soluble resin, (ii) a polyfunctional monomer, and (iii) a photopolymerization initiator. And a sensitizer and the like.

(I) Alkali-soluble resin The alkali-soluble resin in the present invention has a carboxyl group in the side chain, acts as a binder resin, and is preferably soluble in an alkali developer, particularly preferably used in pattern formation. As long as there is, it can be selected and used as appropriate.
A preferable alkali-soluble resin in the present invention is a resin having a carboxyl group, and specific examples thereof include an acrylic copolymer having a carboxyl group and an epoxy (meth) acrylate resin having a carboxyl group. Among these, particularly preferred are those having a carboxyl group in the side chain and further having a photopolymerizable functional group such as an ethylenically unsaturated group in the side chain. This is because the film strength of the cured film formed by containing the photopolymerizable functional group is improved. These acrylic copolymers and epoxy acrylate resins may be used as a mixture of two or more.

The acrylic copolymer having a carboxyl group is obtained by copolymerizing a carboxyl group-containing ethylenically unsaturated monomer and an ethylenically unsaturated monomer.
The acrylic copolymer having a carboxyl group may further contain a structural unit having an aromatic carbocyclic ring. The aromatic carbocycle functions as a component that imparts coating properties to the photosensitive resin composition.
The acrylic copolymer having a carboxyl group may further contain a structural unit having an ester group. The structural unit having an ester group not only functions as a component that suppresses alkali solubility of the photosensitive resin composition, but also functions as a component that improves the solubility in a solvent and further the solvent resolubility.

Examples of the acrylic copolymer having a carboxyl group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec- Butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) Acrylate, n-decyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, disi Lopentanyl (meth) acrylate, 1-adamantyl (meth) acrylate, allyl (meth) acrylate, 2,2′-oxybis (methylene) bis-2-propenoate, styrene, γ-methylstyrene, glycidyl (meth) acrylate, 2- Selected from hydroxylethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, N-vinyl-2-pyrrolidone, N-methylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, etc. One or more, (meth) acrylic acid, dimer of acrylic acid (for example, M-5600 manufactured by Toagosei Chemical Co., Ltd.), itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, anhydrous Copolymer consisting of one or more selected from among objects The can be exemplified. In addition, for example, a polymer having an ethylenically unsaturated bond introduced by adding an ethylenically unsaturated compound having a reactive functional group such as a glycidyl group or a hydroxyl group to the above copolymer can be exemplified, but the present invention is not limited thereto. Is not to be done.
Among these, a polymer having an ethylenically unsaturated bond introduced, for example, by adding an ethylenically unsaturated compound having a glycidyl group or a hydroxyl group to the copolymer is polymerized with a polyfunctional monomer described later at the time of exposure. This is particularly suitable in that the colored layer becomes more stable.

  The copolymerization ratio of the carboxyl group-containing ethylenically unsaturated monomer in the carboxyl group-containing copolymer is usually 5 to 50% by weight, preferably 10 to 40% by weight. In this case, when the copolymerization ratio of the carboxyl group-containing ethylenically unsaturated monomer is less than 5% by weight, the solubility of the resulting coating film in an alkaline developer is lowered, and pattern formation becomes difficult. On the other hand, when the copolymerization ratio exceeds 50% by weight, there is a tendency that the formed pattern is easily detached from the substrate or the pattern surface is roughened during development with an alkali developer.

  The preferred molecular weight of the carboxyl group-containing copolymer is preferably in the range of 1,000 to 500,000, more preferably 3,000 to 200,000. If it is less than 1,000, the binder function after curing is remarkably lowered, and if it exceeds 500,000, pattern formation may be difficult during development with an alkaline developer.

Although it does not specifically limit as an epoxy (meth) acrylate resin which has a carboxyl group, The epoxy (meth) obtained by making the reaction material of an epoxy compound and unsaturated group containing monocarboxylic acid react with an acid anhydride. Acrylate compounds are suitable.
Although it does not specifically limit as an epoxy compound, A bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol S type epoxy compound, a phenol novolac type epoxy compound, a cresol novolak type epoxy compound, an aliphatic epoxy compound, or Examples thereof include epoxy compounds such as bisphenolfluorene type epoxy compounds. These may be used alone or in combination of two or more.

  Examples of the unsaturated group-containing monocarboxylic acid include (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, (meth) acryloyloxyethyl hexahydrophthalic acid, (Meth) acrylic acid dimer, β-furfurylacrylic acid, β-styrylacrylic acid, cinnamic acid, crotonic acid, α-cyanocinnamic acid and the like. These unsaturated group-containing monocarboxylic acids may be used alone or in combination of two or more.

Acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendo Dibasic acid anhydrides such as methylenetetrahydrophthalic acid, chlorendic anhydride, methyltetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, biphenyl Aromatic polycarboxylic anhydrides such as ether tetracarboxylic acid, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, endobicyclo- [2 , 2,1] -Hept-5-ene-2,3-dica Polycarboxylic anhydride derivatives such as carbon anhydride, and the like. These may be used alone or in combination of two or more.
The molecular weight of the epoxy (meth) acrylate compound having a carboxyl group thus obtained is not particularly limited, but is preferably 1000 to 40000, more preferably 2000 to 5000.

(Ii) Polyfunctional monomer Examples of the polyfunctional monomer in the present invention include di (meth) acrylates of alkylene glycol such as ethylene glycol and propylene glycol; di (meth) acrylate of polyalkylene glycol such as polyethylene glycol and polypropylene glycol. ) Acrylates; poly (meth) acrylates of polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, etc. and their dicarboxylic acid modified products; polyesters, epoxy resins, urethane resins, alkyd resins , Oligo (meth) acrylates such as silicone resins and spirane resins; both terminal hydroxypoly-1,3-butadiene, both terminal hydroxypolyisoprene, both terminal hydroxypolycaprolactone, etc. Examples thereof include di (meth) acrylates of terminal hydroxylated polymers; tris (2- (meth) acryloyloxyethyl) phosphate and the like.

  Of these polyfunctional monomers, poly (meth) acrylates of polyhydric alcohols having three or more valences and their dicarboxylic acid-modified products are preferable. Specifically, trimethylolpropane tri (meth) acrylate, pentaerythritol tris. Succinic acid modified product of (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) ) Acrylate is preferred. The said polyfunctional monomer can be used individually or in mixture of 2 or more types.

  The usage-amount of the polyfunctional monomer in this invention is 5-500 weight part normally with respect to 100 weight part of alkali-soluble resin, Preferably it is 20-300 weight part. 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's a possibility that.

(Iii) Photopolymerization initiator and sensitizer The negative photosensitive binder component is usually blended with a photopolymerization initiator having activity with respect to the wavelength of the light source used. The photopolymerization initiator is appropriately selected in consideration of the difference in the reaction format of the polymer having photopolymerization and the photopolymerization monomer (for example, radical polymerization and cationic polymerization) and the kind of each material, and is not particularly limited.

  Examples of photopolymerization initiators are compounds that generate free radicals by the energy of ultraviolet rays, and include biimidazole compounds, benzoin compounds, acetophenone compounds, benzophenone compounds, α-diketone compounds, and polynuclear quinone compounds. , Xanthone compounds, thioxanthone compounds, triazine compounds, ketal compounds, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds, thiuram compounds, fluoroamine compounds, oxime ester compounds Compound etc. are mentioned. These can be used alone or in combination.

  The content of the photoinitiator used in the red photosensitive resin composition for a color filter of the present invention is usually about 0.01 to 100 parts by weight, preferably 5 to 60 parts per 100 parts by weight of the polyfunctional monomer. Parts by weight. If the content is less than the above range, the polymerization reaction cannot be sufficiently caused, so that the colored layer may not have sufficient hardness. In some cases, the content of the pigment or the like in the solid content of the conductive resin composition is relatively reduced, and a sufficient coloring density cannot be obtained.

  Moreover, in this invention, 1 or more types chosen from the group of a sensitizer and a hardening accelerator can also be further used together with the said photoinitiator as needed. Specific examples of the sensitizer include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, ethyl-4- Dimethylaminobenzoate, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone Etc. Specific examples of the curing accelerator include 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto-4, Examples include chain transfer agents such as 6-dimethylaminopyridine, 1-phenyl-5-mercapto-1H-tetrazole, and 3-mercapto-4-methyl-4H-1,2,4-triazole.

(Other pigment dispersants)
In the photosensitive resin composition, from the viewpoint of adjusting the chromaticity of the colored layer, other pigments such as a yellow pigment can be further used as the pigment. In order to disperse the other pigment, the pigment dispersant used in the pigment dispersion according to the present invention may be used. Alternatively, the pigment dispersant may be dispersed using another pigment dispersant. Other pigment dispersants may be included in the product.
Other pigment dispersants are not particularly limited, and for example, cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants can be used. Among the surfactants, polymer surfactants (polymer dispersants) as exemplified below are preferable. A pigment derivative that dissolves in a small amount in a solvent may be used as a pigment dispersant.

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

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

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

<Combination ratio of each component in the photosensitive resin composition>
The total pigment content is preferably 10 to 40% by weight, more preferably 15 to 35% by weight, based on the total solid content of the photosensitive resin composition. If the amount of the pigment is too small, the transmission density when the photosensitive resin composition is applied to a predetermined film thickness (usually 1.0 to 4.0 μm) may not be sufficient. If the amount of the pigment is too large, the photosensitive property may be insufficient. There is a possibility that the properties as a coating film such as adhesion to the substrate when the resin composition is applied and cured on the substrate, surface roughness of the cured film, and coating film hardness may be insufficient, and its photosensitivity. Since the ratio of the amount of the dispersant used for dispersing the pigment in the resin composition increases, characteristics such as developability and heat resistance may be insufficient. In addition, in this invention, solid content is all things other than the solvent mentioned above, and the polyfunctional monomer etc. which are melt | dissolving in the solvent are also contained.
Further, the total content of the pigment dispersant is preferably in the range of 1 to 60% by weight, more preferably in the range of 5 to 50% by weight, based on the total solid content of the photosensitive resin composition. Preferably there is. If the content is less than 1% by weight relative to the total solid content of the photosensitive resin composition, it may be difficult to uniformly disperse the pigment. If the content exceeds 60% by weight, , There is a risk of lowering curability and developability.
The total amount of the alkali-soluble resin, the polyfunctional monomer, and the photoinitiator is blended in a proportion of 15 to 95% by weight, preferably 25 to 80% by weight, based on the total solid content of the photosensitive resin composition. Is preferred.
Further, the content of the solvent is not particularly limited as long as the colored layer can be accurately formed. Usually, it is preferably in the range of 65 to 95% by weight, more preferably in the range of 75 to 88% by weight, based on the total amount of the photosensitive resin composition containing the solvent. When the content of the solvent is within the above range, the coating property can be excellent.

(Production of red photosensitive resin composition for color filter)
The method for producing a red photosensitive resin composition for a color filter of the present invention includes the step (E) in the presence of at least the sulfonated derivative of the (C) yellow pigment and the (D) pigment dispersant in the solvent. (A) a step of preparing a red pigment dispersion by dispersing a red pigment having a diphenyl diketopyrrolopyrrole skeleton;
A step of mixing the red pigment dispersion and a photosensitive binder component;

In order to achieve a specific color required for the red colored layer of the color filter, if necessary, when using another pigment different from the pigment contained in the red pigment dispersion according to the present invention as necessary. Separately, it is preferable to prepare another pigment dispersion in advance in the same manner as in the method for producing a pigment dispersion according to the present invention.
In this case, the method for producing the photosensitive resin composition of the present invention includes the pigment dispersion according to the present invention, another pigment dispersion, a photosensitive binder component, and if necessary, a solvent and various additions. Examples of the method include adding and mixing the components.
The red photosensitive resin composition for a color filter of the present invention is preferable in that a pigment dispersion is produced and used in advance, so that aggregation of pigment can be effectively prevented and dispersed uniformly.

Next, the color filter of the present invention will be described.
[Color filter]
The color filter of the present invention is a color filter comprising at least a transparent substrate and a colored layer provided on the transparent substrate, wherein at least one of the colored layers is the above-described red photosensitive resin for a color filter of the present invention. It has a colored layer formed by curing the composition.
Such a color filter of the present invention will be described with reference to the drawings. FIG. 1 is a schematic sectional view showing an example of the color filter of the present invention. According to FIG. 1, the color filter 10 of the present invention has a transparent substrate 1, a light shielding part 2, and a colored layer 3.

(Colored layer)
The colored layer used in the color filter of the present invention is not particularly limited as long as it is formed using the above-described red photosensitive resin composition for a color filter of the present invention, but is usually on a transparent substrate described later. Depending on the type of pigment contained in the red photosensitive resin composition for a color filter, it is composed of three or more colored patterns.
In addition, the arrangement of the colored layers is not particularly limited, and for example, a general arrangement such as a stripe type, a mosaic type, a triangle type, or a four-pixel arrangement type can be used. Moreover, the width | variety, area, etc. of a colored layer can be set arbitrarily.
Although the thickness of the said colored layer is suitably controlled by adjusting the coating method, the solid content density | concentration of a photosensitive resin composition for color filters, a viscosity, etc., it is preferable normally that it is the range of 1-5 micrometers.

The colored layer can be formed, for example, by the following method.
First, the above-described red photosensitive resin composition for a color filter of the present invention is applied onto a transparent substrate described later using a coating means such as a spray coating method, a dip coating method, a bar coating method, a coal coating method, or a spin coating method. Apply to form a wet coating.
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 red photosensitive resin composition for a color filter. 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 red photosensitive resin composition for a 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 photosensitive resin 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 pigment such as carbon black or titanium black as a pigment and a photosensitive resin. Sensitizers, coatability improvers, development improvers, crosslinking agents, polymerization inhibitors, plasticizers, flame retardants and the like may be added.

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

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

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

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

(Synthesis Example 1 Synthesis of Asymmetric Diketopyrrolopyrrole Derivative 1)
(1) Synthesis of 3-ethoxycarbonyl-2-phenyl-2-pyrrolin-5-one 21.2 parts of benzoylethyl acetate, 13.5 parts of ethyl chloroacetate and 18.2 parts of powdered potassium carbonate in 60 parts of acetone At reflux for 16 hours. The reaction solution was filtered and washed with hexane. The filtrate was concentrated to obtain a crude product of the following formula (a).

  The obtained crude product of the above formula (a) 29.5 parts and ammonium acetate 78.5 parts were refluxed in 90 parts of glacial acetic acid for 2 hours. The mixture was poured into ice water and the precipitated crude product was separated by filtration. Recrystallization from ethanol and water gave 3-ethoxycarbonyl-2-phenyl-2-pyrrolin-5-one of the following formula (b). The molecular weight of the target product was confirmed by TOF-MS.

(2) Synthesis of Asymmetrical Diketopyrrolopyrrole Derivative 1 5.16 parts of sodium was added to 370 parts of tert-amyl alcohol dehydrated with molecular sieves and stirred at 100 ° C. to synthesize alkoxide. 13.7 parts of 4-cyanobiphenyl was added into the alcoholate, and 17.7 parts of the 3-ethoxycarbonyl-2-phenyl-2-pyrrolin-5-one synthesized above was gradually added to the alcoholate solution heated to 100 ° C. added. Then, it stirred at 90 degreeC for 3 hours. After cooling to room temperature, the reaction solution was added to a mixed solution of 57.0 parts of methanol, 57.0 parts of water and 14.5 parts of acetic acid. The precipitate was filtered and washed with methanol. The wet cake was vacuum dried at 80 ° C. to obtain a product of the following formula (c). The molecular weight of the target product was confirmed by TOF-MS.

(Synthesis Example 2 Synthesis of Asymmetric Type Diketopyrrolopyrrole Derivative 2)
5.16 parts of sodium was added to 370 parts of tert-amyl alcohol dehydrated with molecular sieves and stirred at 100 ° C. to synthesize alkoxide. 15.6 parts of 9-cyanoanthracene was added into the alcoholate, and 17.7 parts of 3-ethoxycarbonyl-2-phenyl-2-pyrrolin-5-one was gradually added to the alcoholate solution heated to 100 ° C. Then, it stirred at 90 degreeC for 3 hours. After cooling to room temperature, the reaction solution was added to a mixed solution of 57.0 parts of methanol, 57.0 parts of water and 14.5 parts of acetic acid. The precipitate was filtered and washed with methanol. The wet cake was vacuum dried at 80 ° C. to obtain a product of the following formula (d). The molecular weight of the target product was confirmed by TOF-MS.

(Synthesis Example 3 Synthesis of Asymmetric Type Diketopyrrolopyrrole Derivative 3)
5.16 parts of sodium was added to 370 parts of tert-amyl alcohol dehydrated with molecular sieves and stirred at 100 ° C. to synthesize alkoxide. 12.2 parts of 5-cyanophthalide was added to the alcoholate, and 17.7 parts of 3-ethoxycarbonyl-2-phenyl-2-pyrrolin-5-one was gradually added to the alcoholate solution heated to 100 ° C. Then, it stirred at 90 degreeC for 3 hours. After cooling to room temperature, the reaction solution was added to a mixed solution of 57.0 parts of methanol, 57.0 parts of water and 14.5 parts of acetic acid. The precipitate was filtered and washed with methanol. The wet cake was vacuum dried at 80 ° C. to obtain a product of the following formula (e). The molecular weight of the target product was confirmed by TOF-MS.

(Synthesis Example 4 Synthesis of Asymmetric Type Diketopyrrolopyrrole Derivative 4)
5.16 parts of sodium was added to 370 parts of tert-amyl alcohol dehydrated with molecular sieves and stirred at 100 ° C. to synthesize alkoxide. 15.07 parts of 1- (4-cyanophenyl) -2,5-dimethylpyrrole was added into the alcoholate, and 3-ethoxycarbonyl-2-phenyl-2-pyrrolin-5-one was added to the alcoholate solution heated to 100 ° C. 17.7 parts were gradually added. Then, it stirred at 90 degreeC for 3 hours. After cooling to room temperature, the reaction solution was added to a mixed solution of 57.0 parts of methanol, 57.0 parts of water and 14.5 parts of acetic acid. The precipitate was filtered and washed with methanol. The wet cake was vacuum dried at 80 ° C. to obtain a product of the following formula (f). The molecular weight of the target product was confirmed by TOF-MS.

(Synthesis Example 5 Synthesis of Asymmetric Type Diketopyrrolopyrrole Derivative 5)
5.16 parts of sodium was added to 370 parts of tert-amyl alcohol dehydrated with molecular sieves and stirred at 100 ° C. to synthesize alkoxide. 16.3 parts of 1-cyano-4- (trans-4-ethylcyclohexyl) benzene was added into the alcoholate and 3-ethoxycarbonyl-2-phenyl-2-pyrrolin-5-one was added to the alcoholate solution heated to 100 ° C. 17.7 parts were gradually added. Then, it stirred at 90 degreeC for 3 hours. After cooling to room temperature, the reaction solution was added to a mixed solution of 57.0 parts of methanol, 57.0 parts of water and 14.5 parts of acetic acid. The precipitate was filtered and washed with methanol. The wet cake was vacuum dried at 80 ° C. to obtain a product of the following formula (g). The molecular weight of the target product was confirmed by TOF-MS.

Synthesis Example 6 Synthesis of Asymmetric Diketopyrrolopyrrole Comparative Derivative 1
5.16 parts of sodium was added to 370 parts of tert-amyl alcohol dehydrated with molecular sieves and stirred at 100 ° C. to synthesize alkoxide. 10.6 parts of 4-chlorobenzonitrile was added into the alcoholate, and 17.7 parts of 3-ethoxycarbonyl-2-phenyl-2-pyrrolin-5-one was gradually added to the alcoholate solution heated to 100 ° C. Then, it stirred at 90 degreeC for 3 hours. After cooling to room temperature, the reaction solution was added to a mixed solution of 57.0 parts of methanol, 57.0 parts of water and 14.5 parts of acetic acid. The precipitate was filtered and washed with methanol. The wet cake was vacuum dried at 80 ° C. to obtain a product of the following formula (h). The molecular weight of the target product was confirmed by TOF-MS.

Synthesis Example 7 Synthesis of Asymmetric Diketopyrrolopyrrole Comparative Derivative 2
5.16 parts of sodium was added to 370 parts of tert-amyl alcohol dehydrated with molecular sieves and stirred at 100 ° C. to synthesize alkoxide. 12. 12. Part of 4-tert-butylbenzonitrile was added into the alcoholate, and 3-ethoxycarbonyl-2-phenyl-2-pyrrolin-5-one synthesized in Synthesis Example 1 in an alcoholate solution heated to 100 ° C. 7 parts were gradually added. Then, it stirred at 90 degreeC for 3 hours. After cooling to room temperature, the reaction solution was added to a mixed solution of 57.0 parts of methanol, 57.0 parts of water and 14.5 parts of acetic acid. The precipitate was filtered and washed with methanol. The wet cake was vacuum dried at 80 ° C. to obtain a product of the following formula (i). The molecular weight of the target product was confirmed by TOF-MS.

[Evaluation of spatial conformation]
The spatial conformation of the asymmetric diketopyrrolopyrrole derivatives obtained in Synthesis Examples 1 to 7 was evaluated. Spatial conformation is evaluated by using Fujitsu SCIGRESS (manufactured by Fujitsu Limited), and by performing classical mechanics calculation (MM3 calculation) and semiempirical molecular orbital method (PM6 calculation). It was.
Steric hindrance in Pc of asymmetrical diketopyrrolopyrrole of Synthesis Examples 1-5, that is, the maximum value of dihedral angles between the diketopyrrolopyrrole ring plane and the plane formed by the ring contained in the polycyclic compound group Was found to be at an angle of 10 degrees or more. On the other hand, it was found that the plane formed by the chlorophenyl group of the asymmetric diketopyrrolopyrrole of Synthesis Example 6 was at an angle of 0 degrees with respect to the plane of the diketopyrrolopyrrole. In addition, the plane formed by the t-butylphenyl group of the asymmetrical diketopyrrolopyrrole of Synthesis Example 7 is 0 degree with respect to the plane of the diketopyrrolopyrrole, but one of the terminal methyl groups is diketopyrrolopyrrole. It was found to have an angle of 50 degrees to the plane.

(Synthesis Example 8 Synthesis of Yellow Pigment Sulfonated Derivative 1)
374.76 g of 11 wt% fuming sulfuric acid was stirred while being cooled to 10 ° C., and 74.96 g of Pigment Yellow 138 was added. Subsequently, it stirred at 90 degreeC for 6 hours.
The reaction solution was added to 1600 g of ice water and stirred for 15 minutes, and then the precipitate was filtered. The obtained wet cake was washed with 800 ml of water three times. The wet cake was vacuum dried at 80 ° C. to obtain a yellow product. The molecular weight of the target product was confirmed by TOF-MS.

(Synthesis Example 9 Synthesis of Red Pigment Sulfonated Derivative 1)
Stirring while cooling 300.0 g of 20% fuming sulfuric acid to 10 ° C., C.I. I. 30.0 g of Pigment Red 254 was added. Subsequently, it stirred at 63 degreeC for 6 hours.
The reaction solution was added to 3000 g of ice water and stirred for 15 minutes, and then the precipitate was filtered. The obtained wet cake was washed with 2000 ml of water and filtered. Vacuum drying at 80 ° C. gave a red product. The molecular weight of the target product was confirmed by TOF-MS.

(Production Example 1 Preparation of Dispersant Solution a)
In a 100 mL round bottom flask, 20.1 parts by weight of propylene glycol monomethyl ether acetate (PGMEA), pigment dispersant (trade name: BYK-LPN6919, manufactured by Big Chemie) (weight average molecular weight 7800, amine number 130, solid content 60 (Weight%) 1.45 parts by weight, phenylphosphonic acid (trade name: PPA, manufactured by Nissan Chemical Co., Ltd.) 0.1 parts by weight, and a block copolymer type dispersion in which a partial salt is formed by ultrasonic treatment for 15 minutes. Dispersant solution a which is an agent was obtained.
The pigment dispersant (trade name: BYK-LPN6919, manufactured by Big Chemie) is composed of a repeating unit (1) represented by the above general formula (I) and a repeating unit represented by the above general formula (II) ( 2). Furthermore, in Production Example 1, the amino group of the block copolymer (BYK-LPN6919) is salt-formed by an acid / base reaction with the phosphonic acid group of PPA.

Example 1
(1) Preparation of red pigment dispersion for color filter Red pigment refined pigment having a diphenyl diketopyrrolopyrrole skeleton (CI Pigment Red 254 (PR254: average primary particle size 15 to 50 nm) 3.51 parts by weight 21.6 parts by weight of the dispersant solution a prepared in Production Example 1 and an alkali-soluble resin with respect to 0.195 parts by weight of the yellow pigment sulfonated derivative 1 and 0.195 parts by weight of the asymmetric diketopyrrolopyrrole derivative 1 (Styrene / benzyl methacrylate / acrylic acid / 2-hydroxymethyl acrylate copolymer (molar ratio 30/40/10/20, acid value: 70 mg KOH / g, molecular weight 6000, solid content 44.1% by weight propylene glycol monomethyl ether 4.4 parts by weight mixed with acetate) 1 hour, and dispersed for 10 hours at 0.1mm zirconia beads Niabizu to give a red pigment dispersion A having a pigment concentration of 13%. Incidentally, the packing ratio of the beads in the vessel during dispersion was 50%.

(2) Preparation of red photosensitive resin composition for color filter To 4.06 parts by weight of the red pigment dispersion A obtained above, 2.22 parts by weight of the following binder composition and 3.72 parts by weight of propylene glycol monomethyl ether acetate , Surfactant R08MH (manufactured by DIC) 0.01 part by weight and silane coupling agent KBM503 (manufactured by Shin-Etsu Silicone) 0.05 part by weight are added and mixed, and pressure filtration is performed. A photosensitive resin composition was obtained.

<Binder composition>
Alkali-soluble resin (styrene / benzyl methacrylate / acrylic acid / 2-hydroxymethyl acrylate copolymer (molar ratio 30/40/10/20, acid value: 70 mg KOH / g, molecular weight 6000)): 11.0 parts by weight Tetrafunctional acrylate monomer (trade name: Aronix M450, manufactured by Toagosei Co., Ltd.): 8.2 parts by weight / photopolymerization initiator (2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropane -1-one (trade name: Irgacure 907, manufactured by Ciba Specialty Chemicals Co., Ltd.): 1.0 part by weight-photopolymerization initiator (2-benzyl-2-dimethylamino-1- (4-morpholino) Phenyl) -1-butanone (trade name Irgacure 369, manufactured by Ciba Specialty Chemicals): 2.4 parts by weight / photosensitization (4,4'-bis (dimethylamino) benzophenone): 0.7 parts by weight Solvent (propylene glycol monomethyl ether acetate): 43.2 parts by weight

(Example 2)
(1) Preparation of red pigment dispersion for color filter In Example 1, in place of the asymmetric diketopyrrolopyrrole derivative 1, the asymmetric diketopyrrolopyrrole derivative 2 was used in the same manner as in Example 1, A red pigment dispersion B for color filters was obtained.
(2) Preparation of red photosensitive resin composition for color filter In Example 1, in place of the red pigment dispersion liquid A for color filter, the above procedure was performed except that the red pigment dispersion liquid B for color filter obtained above was used. In the same manner as in Example 1, the red photosensitive resin composition for color filter of Example 2 was obtained.

(Example 3)
(1) Preparation of Red Pigment Dispersion for Color Filter In Example 1, the same procedure as in Example 1 was used except that the asymmetric diketopyrrolopyrrole derivative 3 was used instead of the asymmetric diketopyrrolopyrrole derivative 1. A red pigment dispersion C for color filters was obtained.
(2) Preparation of red photosensitive resin composition for color filter In Example 1, instead of the red pigment dispersion liquid A for color filters, the above procedure was carried out except that the red pigment dispersion liquid C for color filters obtained above was used. In the same manner as in Example 1, the red photosensitive resin composition for color filter of Example 3 was obtained.

Example 4
(1) Preparation of red pigment dispersion for color filter In Example 1, in place of the asymmetric diketopyrrolopyrrole derivative 1, the asymmetric diketopyrrolopyrrole derivative 4 was used in the same manner as in Example 1, A red pigment dispersion D for color filters was obtained.
(2) Preparation of red photosensitive resin composition for color filter In Example 1, in place of the red pigment dispersion liquid A for color filter, the red pigment dispersion liquid D for color filter obtained above was used instead of the above. In the same manner as in Example 1, the red photosensitive resin composition for color filter of Example 4 was obtained.

(Example 5)
(1) Preparation of red pigment dispersion for color filter In Example 1, the asymmetric diketopyrrolopyrrole derivative 5 was used in place of the asymmetrical diketopyrrolopyrrole derivative 1, and a red pigment having a diphenyl diketopyrrolopyrrole skeleton was used. A red pigment dispersion E for a color filter was prepared in the same manner as in Example 1 except that 3.9 parts by weight of CI pigment red 254 (PR254: average primary particle size 15 to 50 nm) was changed to 3.9 parts by weight. Obtained.
(2) Preparation of red photosensitive resin composition for color filter In Example 1, instead of the red pigment dispersion liquid A for color filter, the red pigment dispersion E for color filter obtained above was used. In the same manner as in Example 1, a red photosensitive resin composition for a color filter of Example 5 was obtained.

(Comparative Example 1)
(1) Preparation of Red Pigment Dispersion for Color Filter In Example 1, without using the yellow pigment sulfonated derivative 1 and the asymmetric diketopyrrolopyrrole derivative, a red pigment refined pigment having a diphenyl diketopyrrolopyrrole skeleton (Red pigment dispersion F for color filters was obtained in the same manner as in Example 1 except that CI Pigment Red 254 (PR254: average primary particle size 15 to 50 nm) was changed to 3.9 parts by weight.
(2) Preparation of red photosensitive resin composition for color filter In Example 1, in place of the red pigment dispersion liquid A for color filter, the red pigment dispersion liquid F for color filter obtained above was used in place of the above. In the same manner as in Example 1, a red photosensitive resin composition for color filter of Comparative Example 1 was obtained.

(Comparative Example 2)
(1) Preparation of red pigment dispersion for color filter In Example 1, a yellow pigment sulfonated derivative 1 was used without using an asymmetric diketopyrrolopyrrole derivative, and a red pigment having a diphenyl diketopyrrolopyrrole skeleton was used. A red pigment dispersion G for color filters was obtained in the same manner as in Example 1 except that the fine pigment (CI Pigment Red 254 (PR254: average primary particle size 15 to 50 nm)) was changed to 3.9 parts by weight. It was.
(2) Preparation of red photosensitive resin composition for color filter In Example 1, in place of the red pigment dispersion liquid A for color filter, the same procedure as in Example 1 except that the red pigment dispersion liquid G for color filter was used was used. In the same manner as in Example 1, a red photosensitive resin composition for color filter of Comparative Example 2 was obtained.

(Comparative Example 3)
(1) Preparation of red pigment dispersion for color filter In Example 1, the asymmetric diketopyrrolopyrrole derivative 1 was used without using the yellow pigment sulfonated derivative 1, and a red pigment having a diphenyl diketopyrrolopyrrole skeleton. A red pigment dispersion H for a color filter was prepared in the same manner as in Example 1 except that 3.9 parts by weight of CI pigment red 254 (PR254: average primary particle size 15 to 50 nm) was changed to 3.9 parts by weight. Obtained.
(2) Preparation of red photosensitive resin composition for color filter In Example 1, in place of the red pigment dispersion liquid A for color filter, the red pigment dispersion liquid H for color filter obtained above was used instead of the above. In the same manner as in Example 1, a red photosensitive resin composition for a color filter of Comparative Example 3 was obtained.

(Comparative Example 4)
(1) Preparation of Red Pigment Dispersion for Color Filter In Example 1, using a graft type dispersant PB822 (Ajinomoto Fine Chemical) as a dispersant, a refined pigment of red pigment having a diphenyl diketopyrrolopyrrole skeleton (C.I. I. Pigment Red 254 (PR254: average primary particle size 15 to 50 nm) was used in the same manner as in Example 1 except that 3.9 parts by weight was obtained.
(2) Preparation of red photosensitive resin composition for color filter In Example 1, in place of the red pigment dispersion liquid A for color filter, the above procedure was performed except that the red pigment dispersion liquid I for color filter obtained above was used. In the same manner as in Example 1, a red photosensitive resin composition for color filter of Comparative Example 4 was obtained.

(Comparative Example 5)
(1) Preparation of red pigment dispersion for color filter In Example 1, instead of the asymmetrical diketopyrrolopyrrole derivative 1, the asymmetrical diketopyrrolopyrrole comparative derivative 1 obtained in Synthesis Example 6 was used to prepare diphenyl. A red pigment having a diketopyrrolopyrrole skeleton (C.I. Pigment Red 254 (PR254: average primary particle size 15 to 50 nm)) was changed to 3.9 parts by weight in the same manner as in Example 1, A red pigment dispersion J for color filters was obtained.
(2) Preparation of red photosensitive resin composition for color filter In Example 1, in place of the red pigment dispersion liquid A for color filter, the same procedure as in Example 1 except that the red pigment dispersion liquid J for color filter was used was used. In the same manner as in Example 1, a red photosensitive resin composition for color filter of Comparative Example 5 was obtained.

(Comparative Example 6)
(1) Preparation of red pigment dispersion for color filter In Example 1, instead of the yellow pigment sulfonated derivative 1, the red pigment sulfonated derivative 1 obtained in Synthesis Example 9 was used to prepare a diphenyl diketopyrrolopyrrole skeleton. Red pigment for color filters in the same manner as in Example 1 except that the pigment refined pigment (CI Pigment Red 254 (PR254: average primary particle size 15 to 50 nm)) was 3.9 parts by weight. Dispersion K was obtained.
(2) Preparation of red photosensitive resin composition for color filter In Example 1, in place of red pigment dispersion liquid A for color filter, the same procedure as in Example 1 except that red pigment dispersion liquid K for color filter was used was used. In the same manner as in Example 1, a red photosensitive resin composition for color filter of Comparative Example 6 was obtained.

(Reference Example 1)
(1) Preparation of red pigment dispersion for color filter In Example 1, instead of the asymmetric diketopyrrolopyrrole derivative 1, the asymmetric diketopyrrolopyrrole comparative derivative 2 obtained in Synthesis Example 7 was used to prepare diphenyl. A red pigment having a diketopyrrolopyrrole skeleton (C.I. Pigment Red 254 (PR254: average primary particle size 15 to 50 nm)) was changed to 3.9 parts by weight in the same manner as in Example 1, A red pigment dispersion L for color filters was obtained.
(2) Preparation of red photosensitive resin composition for color filter In Example 1, in place of the red pigment dispersion liquid A for color filter, the red pigment dispersion liquid L for color filter obtained above was used instead of the above. In the same manner as in Example 1, the red photosensitive resin composition for color filter of Reference Example 1 was obtained.

(Evaluation results)
(1) Pigment dispersibility and dispersion stability The pigment dispersibility and dispersion stability were evaluated using the pigment dispersions obtained in each of Examples and Comparative Examples.
The dispersion average particle diameter of the mixed pigment particles was diluted 23 times with a propylene glycol monomethyl ether acetate with a pigment dispersion, and 23 ° C. by a dynamic light scattering method using a nanotrack particle size distribution analyzer UPA-EX150 manufactured by Nikkiso Co., Ltd. Measured with Further, the viscosity of the produced dispersion was measured at 6 rpm with an Anton Paar rheometer MCR-301 (cone plate CP50-1, measured at 23 ° C.). Dispersion average particle size and viscosity are measured again when the dispersion is stored at 40 ° C. for 1 week, and it is confirmed whether the dispersion average particle size has increased by 5 nm or more or whether the viscosity has increased by 10 mPa · s or more. The dispersion stability x was determined when it was applied, the dispersion stability Δ was applied when only one was applicable, and the dispersion stability ◯ was given when there was no problem. Further, the case where the pigment dispersion gelled during preparation and the viscosity could not be measured was defined as xx.
The evaluation results of each example and comparative example are shown in Table 1.

(2) Contrast, Hue, and Luminance Evaluation A red photosensitive resin composition for a color filter obtained in each Example and Comparative Example was prepared by using a glass substrate having a thickness of 0.7 mm (“NA35” manufactured by NH Techno Glass Co., Ltd.). On top, it was applied using a spin coater. Then, it heat-dried for 3 minutes on an 80 degreeC hotplate. A photocured film (red colored layer) was obtained by exposure (60 mJ) using a small aligner. The cured film was heated in an oven at 230 ° C. for 30 minutes to obtain a cured film after post-baking. The film thickness after photocuring was adjusted so that the target chromaticity after post-baking would be x = 0.650.
Luminance was measured using a contrast measurement device CT-1 manufactured by Aisaka Electric Co., Ltd., light source: F10 lamp between cold cathodes, and luminance meter: LS-100 manufactured by Konica Minolta. The contrast can be derived from the following formula using the measured luminance value.
Contrast = parallel luminance (cd / m ² ) / orthogonal luminance (cd / m ² )
Hue (x, y) and luminance (Y) were measured using “Microspectroscope OSP-SP200” manufactured by Olympus Corporation.
In each example and comparative example, as a result of measuring the hue, brightness and contrast (Cont) for the photocured film (red colored layer) after exposure, as a result of measuring the hue, brightness and contrast of the cured film after post-baking, Table 1 shows the evaluation results of the contrast retention ratio (contrast after heating / contrast after exposure × 100 (%)).

(3) Evaluation of heat resistance The obtained red photosensitive resin composition for a color filter was applied on a 0.7 mm-thick glass substrate (“NA Techno Glass Co., Ltd.,“ NA35 ”) using a spin coater. . Then, it heat-dried for 3 minutes on an 80 degreeC hotplate. Mask exposure (30 mJ) using a small aligner, alkali development with Disperse H (manufactured by Henkel) 100-fold diluted for 1 minute, followed by a pure 2 minute rinse, resolution on the glass A photocuring pattern with a 90 μm line & space red coloring composition was formed. After the light-hardened glass substrate was heated in an oven at 260 ° C. for 30 minutes, the pattern was observed with a microscope, and the pattern and the glass were observed. Evaluation of heat resistance when no crystals were deposited on the pattern or glass after heating, x when the crystals were deposited on the pattern or on the glass, and Δ when crystals were deposited only on the glass. did. The coating film thickness was applied at the same rotational speed as that adjusted so that the target chromaticity after post-baking was x = 0.650 in the evaluation of contrast, hue, and luminance. The evaluation results of each example and comparative example are shown in Table 1.

(4) Measurement of retardation As retardation of the colored layer, retardation in the thickness direction (Rth) calculated by the following formula was used as an index.
Retardation (Rth) was measured using a retardation layer measuring device (Axoscan ^™ Mueller Matrix Polarimeter manufactured by AXOMETRICS) at a measurement wavelength of 620 nm.
Rth = ((Nx + Ny) / 2−Nz) d
nx: Refractive index in the in-plane slow axis direction ny: Refractive index in the in-plane fast axis direction nz: Refractive index in the thickness direction d: Film thickness (nm)

  From Table 1, the red pigment dispersion and photosensitive resin composition of the present invention are C.I., which is a red pigment having a diphenyl diketopyrrolopyrrole skeleton. I. It was clarified that by adding a specific yellow pigment sulfonated derivative 1 to Pigment Red 254 at the time of dispersion, it can be finely dispersed without greatly changing the hue, and as a result, both contrast and brightness can be improved. . Further, C.I. which is a red pigment having a diphenyl diketopyrrolopyrrole skeleton. I. Since Pigment Red 254 uses an asymmetric diketopyrrolopyrrole derivative having steric hindrance on one side together with a yellow pigment sulfonated derivative, the heat resistance is particularly improved, and the demand for high brightness and high contrast can be achieved. This is presumably because the aggregation and crystal precipitation of the pigment were suppressed even after the high-temperature heating step in the color filter step due to the synergistic effect of the yellow pigment sulfonated derivative and the diketopyrrolopyrrole derivative.

On the other hand, in Comparative Example 1 in which the yellow pigment sulfonated derivative and the asymmetric type diketopyrrolopyrrole derivative are not used, the dispersibility is poor, the heat resistance is poor, crystals are precipitated after high-temperature heating, and the contrast is lowered. It was.
Further, in Comparative Example 2 in which a yellow pigment sulfonated derivative was used but no asymmetric type diketopyrrolopyrrole derivative was used, the contrast after exposure was good, but the heat resistance was greatly deteriorated, and crystals were not formed after heating at high temperature. As it was deposited, the contrast was greatly reduced and the phase difference was increased.
Moreover, although the asymmetric type diketopyrrolopyrrole derivative was used, in Comparative Example 3 in which the yellow pigment sulfonated derivative was not used, the heat resistance was good, but the dispersibility was poor and the contrast was low.
In Comparative Example 4, the dispersibility was good and the contrast after exposure was improved. However, it is considered that crystal precipitation and contrast reduction occurred after baking because of different dispersants.
In Comparative Example 5, an asymmetric type diketopyrrolopyrrole derivative was used, but the steric hindrance chloro group was not at an angle with respect to the diketopyrrolopyrrole plane, so crystal precipitation was suppressed without causing sufficient steric hindrance. It is thought that it was not possible. Further, the dispersibility was greatly reduced, and the contrast after exposure was lowered.
In Comparative Example 6, the dispersibility is good, but since the red pigment sulfonated derivative is bluish red, the dispersion is also C.I. I. It became blue (y was smaller) than the color of Pigment Red 254, and the luminance was lowered.

  In Reference Example 1, the dispersibility and the heat resistance were good, but it was revealed that the luminance was lowered. The asymmetric diketopyrrolopyrrole derivative used in Reference Example 1 uses a phenyl group substituted with a relatively bulky t-butyl group as a substituent of the diketopyrrolopyrrole derivative, and one of the terminal methyl groups is diketo Since it has an angle of 50 degrees with respect to the plane of pyrrolopyrrole, it is estimated that crystal growth during heating could be suppressed. However, since it is not substituted with a polycyclic compound, C.I. I. It is presumed that the color of the pigment red 254 is bluish (y is smaller) and the luminance is lowered.

  From the results of Examples 1 to 5 and Reference Example 1 and Comparative Example 5, in the asymmetric diketopyrrolopyrrole derivative, a dihedral angle or twist angle of 10 degrees or more with respect to the planar structure of diketopyrrolopyrrole. It is presumed that the presence of the substituent has a tendency to suppress crystal growth by suppressing the hydrogen bonding sites on the surface of the PR254 pigment, to improve the heat resistance, and to increase the effect of suppressing a decrease in contrast and an increase in phase difference during heating. The

  Further, from the results of Examples 1 to 5, among them, when a polycyclic compound containing a heterocyclic ring is directly bonded to the diketopyrrolopyrrole derivative, the crystal precipitation suppressing effect is particularly high, and contrast, luminance, It has been clarified that functions such as phase difference are enhanced.

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

Claims (10)

(A) a red pigment having a diphenyl diketopyrrolopyrrole skeleton, (B) an asymmetric diketopyrrolopyrrole derivative represented by the following general formula (1), and (C) C.I. I. A block comprising a sulfonated derivative of one or more yellow pigments selected from the group consisting of CI Pigment Yellow 138, 139, 150, 215, and derivative pigments thereof; and (D) a salt of a tertiary amine or a quaternary ammonium salt A red pigment dispersion for a color filter, comprising a pigment dispersant which is a copolymer and (E) a solvent.

(In general formula (1), Pc represents a polycyclic compound group which may have a substituent and may contain a hetero atom. X represents a halogen atom, a benzyl group, a phenyl group, and And a substituent selected from the group consisting of linear or branched alkyl groups having 1 to 10 carbon atoms, and n represents an integer of 0 to 5. When n is 2 or more, a plurality of Xs are the same. Or different.)   In the solvent (E), in the presence of (B) an asymmetric diketopyrrolopyrrole derivative represented by the following general formula (1), a sulfonated derivative of the (C) yellow pigment, and the (D) pigment dispersant. The red pigment dispersion for a color filter according to claim 1, obtained by dispersing the (A) red pigment having a diphenyl diketopyrrolopyrrole skeleton. The pigment dispersant has a repeating unit (1) represented by the following general formula (I) and a repeating unit (2) represented by the following general formula (II), and further the repeating unit (1) The red pigment dispersion for a color filter according to claim 1 or 2, which is a block copolymer in which at least a part of the amino group possessed by the organic acid compound and / or halogenated hydrocarbon forms a salt.

[In Formula (I) and Formula (II), R ¹ is a hydrogen atom or a methyl group, R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and A is a carbon atom having 1 carbon atom. To 8 alkylene groups, — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —CH (R ⁶ ) —CH (R ⁷ ) — or — [(CH ₂ ) _y —O] _z — ( CH _{2) y} - ₂ monovalent group represented by, ^{R 4} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl ^{group, - [CH (R 6)} -CH It is a monovalent group represented by (R ⁷ ) —O] _x —R ⁸ or — [(CH ₂ ) _y —O] _z —R ⁸ . R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group, and R ⁸ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, It is a monovalent group represented by —CHO, —CH ₂ CHO, or —CH ₂ COOR ⁹ , and R ⁹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. The alkyl group, alkenyl group, aralkyl group, and aryl group each may have a substituent.
x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18. m represents an integer of 3 to 200, and n represents an integer of 10 to 200. ] The red pigment dispersion for a color filter according to any one of claims 1 to 3, wherein the (B) asymmetric diketopyrrolopyrrole derivative is an asymmetric diketopyrrolopyrrole derivative represented by the following general formula (2): liquid.

(In the general formula (2), Ar ^{1 to} Ar ⁵ are each independently a hydrogen atom, a halogen atom, or an organic group, which may be bonded to form a cyclic structure. Provided that at least one of Ar ^{1 to} Ar ⁵ is an aryl group which may have a substituent or a heteroaryl group which may have a substituent, and / or (At least two of Ar ^{1 to} Ar ⁵ are bonded to form a cyclic structure. X and n are the same as those in the general formula (1).)   The sulfonated derivative of the (C) yellow pigment is C.I. I. The red pigment dispersion for color filters according to any one of claims 1 to 4, which is a sulfonated derivative of CI Pigment Yellow 138.   (A) The red pigment having a diphenyl diketopyrrolopyrrole skeleton is C.I. I. Pigment red 254 or C.I. I. The red pigment dispersion for a color filter according to claim 1, which is CI Pigment Red 255. The pigment dispersant is a block copolymer in which at least a part of the amino group of the repeating unit (1) and an organic acid compound form a salt, and the organic acid compound is represented by the following general formula (III) And a red pigment dispersion for a color filter according to claim 3, which is at least one selected from the group consisting of organic acids represented by the following general formula (IV):

[In Formula (III) and Formula (IV), R ^a and R ^{a ′} are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, or an aryl group. 1 represented by the group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — [(CH ₂ ) _t —O] _u —R ^e , or —O—R ^{a ″.} the valence of the group, one of R ^a and R ^{a 'comprises} a carbon atom. R ^{a ″} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e. ,-[(CH ₂ ) _t —O] _u —R ^e .
R ^b is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — [(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. ]   A red photosensitive resin composition for a color filter, comprising at least the red pigment dispersion for a color filter according to any one of claims 1 to 7 and (F) a photosensitive binder component.   A color filter comprising a colored layer formed by curing the red photosensitive resin composition for a color filter according to claim 8.   A liquid crystal display device comprising: the color filter according to claim 9; a counter substrate; and a liquid crystal layer formed between the color filter and the counter substrate.

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