JP2012220637A - Red pigment dispersion liquid for color filter and production method of the liquid, red photosensitive resin composition for color filter and production method of the composition, color filter, liquid crystal display device, and organic light-emitting display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a red pigment dispersion liquid for a color filter and a method for producing the dispersion liquid, the liquid showing excellent dispersibility and dispersion stability, particularly achieving high luminance and satisfying demands for obtaining high contrast, and to provide a photosensitive resin composition for a color filter and a method for producing the composition, the composition having excellent dispersibility and dispersion stability, particularly achieving high luminance, allowing formation of a color layer with high contrast, and having excellent alkali developability.SOLUTION: The red pigment dispersion liquid for a color filter includes a red pigment having an anthraquinone skeleton, a sulfonated derivative as a yellow pigment, a pigment dispersant consisting of a block copolymer containing a tertiary amine salt, and a solvent. The red photosensitive resin composition for a color filter comprises the above pigment dispersion liquid and a photosensitive binder component.

Description

  The present invention relates to a red pigment dispersion and a method for producing the same, a red photosensitive resin composition for a color filter using the pigment dispersion, and a red photosensitive resin composition for a color filter using the method for producing the red pigment dispersion. And a liquid crystal display device and an organic light-emitting display device having the color filter, and a color filter formed using the photosensitive resin composition.

In recent years, with the development of personal computers, particularly portable personal computers, the demand for liquid crystal displays has increased. The penetration rate of home-use liquid crystal televisions is also increasing, and the market for liquid crystal displays is expanding. Recently, an organic light-emitting display device such as an organic EL display having high visibility due to self-emission has been attracting attention as a next-generation image display device. In the performance of these image display devices, further improvement in image quality such as improvement in contrast and color reproducibility and reduction in power consumption are strongly desired.
Color filters are used in these liquid crystal display devices and organic light emitting display devices. For example, in the formation of a color image of a liquid crystal display device, the light passing through the color filter is colored as it is into the color of each pixel constituting the color filter, and the light of those colors is synthesized to form a color image. In the organic light emitting display device, when a color filter is used for the white light emitting organic light emitting element, a color image is formed as in the liquid crystal display device.
Under such circumstances, demands for higher luminance, higher contrast, and improved color reproducibility are increasing in color filters. Recently, particularly for television applications, there is a growing demand for higher brightness due to reduced power consumption of the backlight and the characteristics of the LED backlight.

Here, the color filter is generally formed on a transparent substrate, a transparent layer formed on the transparent substrate, and composed of a colored layer of three primary colors of red, green, and blue, and on the transparent substrate so as to partition each colored pattern. And a light shielding portion formed.
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 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, 4,4′-diamino-1,1′-bianthraquinone and 4,4′-diamino-1,1′-bianthraquinone-3, which are red pigments having an anthraquinone skeleton, Attempts have been made to disperse 3′-disulfonic acid in the presence of a cationic polymer dispersant (for example, Patent Document 1). According to the combination as described above, it is described that high spectral transmittance and high contrast are exhibited. However, in the characteristic evaluation of the color resist ink described in Patent Document 1, the chromaticity in the xy coordinate system is determined depending on the presence or absence of 4,4′-diamino-1,1′-bianthraquinone-3,3′-disulfonic acid. The x value and the y value vary and do not indicate the spectral transmission with the same color index. That is, the high spectral transmittance in Patent Document 1 merely indicates an improvement in transmittance due to a decrease in the dispersed particle diameter of the pigment due to an improvement in dispersibility and a decrease in scattered light, and the spectral spectrum itself. It is not shown about the improvement of the brightness which represents the change of. Actually, when the x value in the xy coordinate system is fixed depending on whether or not 4,4′-diamino-1,1′-bianthraquinone-3,3′-disulfonic acid having a fixed x value in the xy coordinate system is added. In comparison, the y value becomes small (shifts greatly to blue) and the luminance decreases. Further, this is easily estimated by comparing the x value and the y value in the example and the comparative example in Patent Document 1.
When the red pigment having an anthraquinone skeleton is combined with a sulfonated derivative of a red pigment having an anthraquinone skeleton as described above, the absorption wavelength of the sulfonated derivative is shifted by a longer wavelength than the original red pigment due to the sulfo group that is an electron withdrawing group. As a result, there is a problem in that the spectral spectrum of the original red pigment becomes more bluish and the transmittance decreases.

  In addition, C.I. I. Pigment red 254 and C.I. I. Patent Document 2 discloses that C.I. Pigment Red 177 solves the problem that these pigments easily aggregate. I. Pigment red 254 and C.I. I. An ink for color filter that combines Pigment Red 177 and a specific sulfonated derivative is disclosed. As the specific sulfonated derivative, a structure in which a sulfonic acid is bonded to a compound having a quinoline structure and a phthalimide structure is described. In Patent Document 2, it is described that aggregation of pigments in ink is prevented and dispersibility and dispersion stability are improved. By using a dispersant having an acid value in combination with a dispersant having an amine value, the pigment dispersion stability is improved. It is described that the property is further improved. However, in the ink using the dispersant described in Patent Document 2, particularly when Pigment Red 177 is used alone, the dispersibility and the dispersion stability are not sufficient. Further, the ink described in Patent Document 2 has a problem that developability with respect to an alkaline developer is insufficient.

Japanese Patent Laid-Open No. 10-338832 JP 2009-145804 A

  The present invention has been made under such circumstances, and is excellent in dispersibility and dispersion stability, in particular, achieves a high brightness and achieves a demand for high contrast, and a red pigment dispersion for a color filter and its RED PHOTOSENSITIVE RESIN COMPOSITION FOR COLOR FILTER WHICH IS EXCELLENT IN MANUFACTURING METHOD, DISPERSABILITY AND DISTRIBUTION STABILITY, WHICH RESULTS IN HIGHLY BRIGHTNESS, CAN BE FORMED WITH HIGH CONTRAST COLOR LAYER AND EXCELLENT IN ALKALINE DEVELOPER An object of the present invention is to provide a color filter formed using the photosensitive resin composition and a liquid crystal display device having the color filter.

As a result of intensive studies to achieve the above object, the present inventors have found that a red pigment having an anthraquinone skeleton is present as a sulfonated derivative of a yellow pigment and a block copolymer containing a salt of a tertiary amine. When dispersed in a solvent, the dispersibility and dispersion stability are improved even with a red pigment having a miniaturized anthraquinone skeleton while achieving particularly high brightness, and there is a demand for high brightness and high contrast. It was found that a pigment dispersion and a photosensitive resin composition excellent in alkali developability can be obtained.
The present invention has been completed based on such findings.

A red pigment dispersion for a color filter according to the present invention comprises a red pigment having an anthraquinone skeleton, a sulfonated derivative of a yellow pigment, a pigment dispersant that is a block copolymer containing a tertiary amine salt, and a solvent. It is characterized by containing.
The method for producing a red pigment dispersion for a color filter according to the present invention includes a step of dispersing the red pigment having an anthraquinone skeleton in a solvent in the presence of a sulfonated derivative of a yellow pigment and the pigment dispersant. It is characterized by having.

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 a photosensitive binder component, It is characterized by the above-mentioned.
Furthermore, the method for producing a red photosensitive resin composition for a color filter according to the present invention comprises dispersing a red pigment having an anthraquinone skeleton in a solvent in the presence of a sulfonated derivative of a yellow pigment and the pigment dispersant. And a step of preparing a red pigment dispersion,
It has the process of mixing the said red pigment dispersion and a photosensitive binder component, It is characterized by the above-mentioned.

  In the red pigment dispersion for color filters according to the present invention and the method for producing the same, and the red photosensitive resin composition for color filters according to the present invention and the method for producing the same, the sulfonated derivative of the yellow pigment contains C.I. I. A sulfonated derivative of CI Pigment Yellow 138 is preferable from the viewpoint that the dispersibility and dispersion stability of the red pigment having an anthraquinone skeleton are improved, and a demand for high brightness and high contrast can be achieved.

  In the red pigment dispersion for a color filter according to the present invention and the production method thereof, and the red photosensitive resin composition for the color filter according to the present invention and the production method thereof, the content of the sulfonated derivative of the yellow pigment is The dispersibility and dispersion stability of the red pigment having the anthraquinone skeleton are improved so that the red pigment having the anthraquinone skeleton is 1 to 25 parts by weight with respect to 100 parts by weight of the red pigment having the anthraquinone skeleton. This is preferable because the requirements can be achieved.

  In the red pigment dispersion for a color filter according to the present invention and the production method thereof, and the red photosensitive resin composition for a color filter according to the present invention and the production method thereof, the pigment dispersant is represented by the following general formula (I): A repeating unit (1) represented by formula (II) and a repeating unit (2) represented by the following general formula (II), and at least part of the amino group of the repeating unit (1) and an organic acid compound Is a block copolymer in which a salt is formed, and the dispersibility and dispersion stability of the red pigment having the anthraquinone skeleton are improved while achieving particularly high brightness, and it has excellent alkali developability and high brightness. And it is preferable from the point which can achieve high contrast.

［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 an alkyl group having 1 to 8 carbon atoms, and A is an alkyl group having 1 to 8 carbon atoms. An alkylene group, — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —CH (R ⁶ ) —CH (R ⁷ ) — or — [(CH ₂ ) _y —O] _z — (CH ₂ ) _a divalent group represented by _y— , R ⁴ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ⁶ ) —CH (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 particular, the organic acid compound in the pigment dispersant 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). However, the red pigment having an anthraquinone skeleton is preferable in that the dispersibility and dispersion stability are improved, the alkali developability is excellent, the brightness is high, and the high contrast can be achieved.

［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. ]

  The color filter according to the present invention has a colored layer formed using the red photosensitive resin composition for a color filter.

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.
In addition, the present invention provides an organic light emitting display device comprising the color filter and an organic light emitter.

  According to the present invention, a red pigment dispersion for a color filter that is excellent in dispersibility and dispersion stability, particularly achieves high brightness and also achieves a high contrast requirement, and a method for producing the same, dispersibility and dispersion stability. Using the photosensitive resin composition, a red photosensitive resin composition for a color filter that achieves excellent, particularly high brightness, can form a colored layer with high contrast, and is excellent in alkali developability, a method for producing the same, and the photosensitive resin composition A formed color filter and a liquid crystal display device having the color filter can be provided.

FIG. 1 is a schematic view showing an example of the color filter of the present invention. FIG. 2 is a schematic view showing an example of the liquid crystal display device of the present invention. FIG. 3 is a schematic view illustrating an example of the organic light emitting display device of the present 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.
In addition, C.I. I. Pigment Red as “PR”, C.I. I. Pigment Yellow may be abbreviated as “PY”.

1. A red pigment dispersion for a color filter and a method for producing the same The red pigment dispersion for a color filter according to the present invention is a block copolymer containing a red pigment having an anthraquinone skeleton, a sulfonated derivative of a yellow pigment, and a tertiary amine salt. It contains a pigment dispersant as a polymer and a solvent.

The red pigment dispersion for a color filter of the present invention was obtained by dispersing the red pigment having the anthraquinone skeleton in the solvent in the presence of the sulfonated derivative of the yellow pigment and the specific pigment dispersant. It is preferable.
When dispersing a red pigment having an anthraquinone skeleton in a solvent, in the presence of a pigment dispersant that combines a sulfonated derivative of a yellow pigment and a pigment dispersant that is a block copolymer containing a tertiary amine salt. Dispersion improves the dispersibility and dispersion stability of the red pigment having an anthraquinone skeleton while achieving particularly high brightness, and the pigment dispersion that can achieve the demand for high brightness and high contrast, photosensitivity A resin composition is obtained.

Although it is unclear as an effect | action which exhibits the above effects by said specific combination, it is estimated as follows.
According to the present invention, a sulfonated derivative of a yellow pigment is used when a red pigment having an anthraquinone skeleton is dispersed in a solvent. Since many sulfonated derivatives of yellow pigments have a nitrogen atom or a carbonyl group in the conjugated system, the red pigment having an anthraquinone skeleton having an amino group or a carbonyl group in the conjugated system is compatible with hydrogen bonds or similar skeletons. By adsorbing to the surface of the red pigment by improving the properties, the surface of the red pigment is made acidic, and the intermediary with the pigment dispersant increases the affinity with the pigment dispersant than the red pigment itself having an anthraquinone skeleton. It is estimated that In addition, the sulfonated derivative of the yellow pigment is different from the sulfonated derivative of the red pigment, and since the original color is yellow with low coloring power, it has a shorter wavelength than the transmission wavelength of the red pigment having an anthraquinone skeleton. By transmitting the light, it plays a role of improving the luminance of the red pigment dispersion without largely changing the color of the red pigment.

According to the present invention, the pigment dispersant used in combination with the sulfonated derivative of the yellow pigment is a salt type block copolymer containing a salt of a tertiary amine. The block of the structural unit having a salt-forming site is highly adsorbable to the pigment and, in particular, to the sulfonated derivative of the yellow pigment adsorbed on the pigment surface, while the block containing the structural unit having no salt-forming site is used as a solvent. It has solubility.
When such a pigment dispersant and a sulfonated derivative of a yellow pigment are used in combination, the sulfonated derivative of the yellow pigment and the pigment dispersion are dispersed on the surface of the finely exposed pigment while miniaturizing the red pigment having an anthraquinone skeleton It is presumed that the agent can be adsorbed appropriately to stabilize the pigment in the solvent, and the red pigment having an anthraquinone skeleton can be made finer and more uniform. As a result, a coating film with improved contrast can be obtained.

The red pigment dispersion for a color filter of the present invention comprises a red pigment having at least an anthraquinone skeleton, a sulfonated derivative of a yellow pigment, a pigment dispersant that is a block copolymer containing a tertiary amine salt, and a solvent. It is contained as an essential component, and may contain other components as necessary.
Hereinafter, each component of the red pigment dispersion of the present invention will be described in detail.

(Red pigment with anthraquinone skeleton)
Examples of the red pigment having an anthraquinone skeleton used in the present invention include C.I. I. Pigment red 83, C.I. I. Pigment red 84, C.I. I. Pigment red 89, C.I. I. Pigment red 168, C.I. I. Pigment red 216, C.I. I. And CI Pigment Red 177.

  Among them, the red pigment having an anthraquinone skeleton is C.I. represented by the following chemical formula (1). I. The pigment 177 is preferable from the viewpoint of easily realizing high luminance and high contrast.

The average primary particle size of a pigment such as a red pigment having an anthraquinone skeleton used in the present invention is not particularly limited as long as it can produce a desired color when used as a colored layer of a color filter. Although it varies depending on the type of pigment, it is preferably in the range of 10 to 70 nm, more preferably 10 to 50 nm. When the average primary particle size of the pigment is in the above range, a display device including a color filter manufactured using the red pigment dispersion for color filter of the present invention and the photosensitive resin composition can be provided with high contrast and high It can be of quality. Further, in the case of a conventional pigment dispersant, a large amount of pigment dispersant is required as the particle size of the pigment is reduced, which may cause problems such as a decrease in alkali developability and an increase in residue. The pigment dispersant used in the red pigment dispersion for color filters and the photosensitive resin composition is a block copolymer containing a tertiary amine salt, and is excellent in alkali developability, and may cause such problems. Less is. Therefore, as the average particle diameter of the pigment is within 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 each of 100 or more particles, the volume (mass) of each particle was obtained by approximating a rectangular parallelepiped having the obtained particle size, and the volume average particle size was obtained and used as the average particle size. Note that 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 distribution particle size here is a volume average particle size.

  The red pigment having an anthraquinone skeleton used in the present invention can be produced by a known method such as a recrystallization method or a solvent salt milling method. Further, a commercially available red pigment having an anthraquinone skeleton (for example, chromophthal red A2B manufactured by BASF) may be milled and used.

In the red pigment dispersion for the color filter of the present invention, the content of the red pigment having an anthraquinone skeleton may be appropriately adjusted and is not particularly limited. Usually, the content of the pigment containing a red pigment having an anthraquinone skeleton is preferably in the range of 5 to 40% by mass, more preferably 10 to 20% by mass, based on the total amount of the red pigment dispersion for color filters.
As a red pigment which has an anthraquinone skeleton, it can be used individually by 1 type or in mixture of 2 or more types.

(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 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 144, 146, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 17 , And the like 175,176,177,179,180,181,182,185,187,188,193,194,199,213,214.

  Among the above, as a yellow pigment for deriving a sulfonated derivative of a yellow pigment, C.I. I. Pigment Yellow 138, 139, 150, and 215 are preferable from the viewpoint of high luminance and high affinity with a red pigment having an anthraquinone skeleton. I. Pigment Yellow 138, 139 is used. I. It is preferable to use CI Pigment Yellow 138 because it has particularly high brightness, high affinity with a red pigment having an anthraquinone skeleton, and high brightness and high contrast can be easily realized without greatly changing the hue.

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 yellow pigment, and a part or all of the sulfonic acid group. May be formed into a salt with an amine, ammonium hydroxide, chloride, bromide, or the like, or a metal to form a sulfonate.

As a sulfonamide group which is an amide compound of a sulfonic acid group, sulfonamide groups represented by the following chemical formulas (1) to (3) are preferable.
Chemical Formula (1): —SO ₂ NH— (CH ₂ ) _m —NR′R ″
Chemical formula _{(2): -SO 2 NH- (} CH 2) m -COOH
Chemical formula _{(3): -SO 2 NH- (} CH 2) m -SO 3 H
In the chemical formula (1), R ′ and R ″ are each independently 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 (1) to (3), 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 above chemical formula (1) 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.

  From the viewpoint of dispersibility and developability, a sulfonic acid group is preferred. On the other hand, from the viewpoint of solvent resolubility, a sulfonamide group is preferable, and in particular, in the case of the sulfonamide group represented by the chemical formula (1), and an amino group and a salt containing a long-chain alkyl group having 3 or more carbon atoms. In the case of the sulfonate formed, it is preferable from the viewpoint of good solvent resolubility. Here, the solvent re-solubility means the property that the solid content of the photosensitive resin composition once dried dissolves again in the solvent. If the solvent resolubility is good, it becomes easy to remove and clean the dried product of the photosensitive resin composition adhering at the time of manufacturing the color filter, which is a great merit in manufacturing.

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.

（上記式（２）において、Ｘ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 the above formula (2), X represents 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 or a C 1-20 substituent. Represents a saturated or unsaturated aliphatic hydrocarbon group or aromatic hydrocarbon group, or a heterocyclic ring that may further contain nitrogen, oxygen, or sulfur atoms together with an adjacent nitrogen atom, and each m represents Independently, it is 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 3 - N (CH 3) 2 (C 18 H 37) 2 +, -SO 2 NHC 3 H 6 N ( _{C 2 H 5) 2, SO} 3 - N (CH 3) 4 + and the like.

  In the above formula, the number n of substituents is preferably 1 to 2, and 1 is particularly preferable because salt formation with the tertiary amine moiety of the pigment dispersant is easy.

  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.

  The sulfonated derivative of the yellow pigment may further have other substituents. Examples of the other substituent include an imidoalkyl group represented by the following chemical formula.

（式（３）中、Ｒは、炭素数１〜６のアルキレン基を表し、Ｘは、アリーレン基を表し、当該アリーレン基は、ハロゲン原子、アリールスルホニル基、アシル基、又は−（Ｃ＝Ｏ）−Ｃ_６Ｈ_４−（Ｃ＝Ｏ）−により置換されていても良い。）

(In Formula (3), R represents an alkylene group having 1 to 6 carbon atoms, X represents an arylene group, and the arylene group is a halogen atom, an arylsulfonyl group, an acyl group, or — (C═O). ) May be substituted by —C ₆ H ₄ — (C═O) —.

  Among the imide alkyl groups, other substituents of the yellow pigment sulfonated derivative are preferably phthalimidoalkyl groups and more preferably phthalimidomethyl groups from the viewpoint of achieving high contrast.

  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 mass with respect to 100 parts by mass of the red pigment having the anthraquinone skeleton. Among them, the sulfonated derivative of the yellow pigment is preferably contained in an amount of 1 to 15 parts by mass, and more preferably 3 to 10 parts by mass with respect to 100 parts by mass of the red pigment having the anthraquinone 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.

(Pigment dispersant)
The pigment dispersant used in the present invention is a block copolymer containing a tertiary amine salt. In such a block copolymer, a block portion containing a tertiary amine salt is adsorbed on a sulfonated derivative of a pigment and a yellow pigment, and a block portion containing no tertiary amine salt is dissolved in a solvent. Therefore, the dispersibility of the pigment can be improved. For this reason, it becomes possible to realize the miniaturization of the red pigment having an anthraquinone skeleton, and the contrast can be improved. In particular, in the present invention, a block copolymer containing a tertiary amine salt, 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. Therefore, dispersibility is remarkably improved as compared with nonionic block copolymers (for example, Dispersic 166 etc.) in which the interaction between the derivative and the acid-base does not occur.
Further, by using a block copolymer containing a salt of a tertiary amine, the developability is excellent as compared with a block copolymer containing a quaternary ammonium salt.
In addition, when a pigment dispersant made of a block copolymer is used, the size of the pigment adsorbing part and the solvent-soluble part can be designed to be smaller than when a graft polymer type pigment dispersant is used. Increases effectiveness.

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.
The block portion containing a tertiary amine salt may contain an amine that does not form a salt.

  The amount of the tertiary amine salt contained in the copolymer is preferably 1 to 50%, more preferably 1 to 20% in terms of the number of repeating units, based on the total number of repeating units of the block copolymer. More preferably.

  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 mass average molecular weight Mw of the block copolymer containing a tertiary amine salt used in the present invention is preferably in the range of 500 to 20000, more preferably in the range of 1000 to 15000, 3000 to More preferably, it is within the range of 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 mass average molecular weight can be obtained as a standard polystyrene equivalent value by gel permeation chromatography (GPC).

  As the pigment dispersant comprising a block copolymer containing a tertiary amine salt, for example, a commercially available product LPN-6919 manufactured by Big Chemie may be used, and the tertiary amine moiety may be used as a salt.

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), The block copolymer in which at least a part of the amino group of the repeating unit (1) and the organic acid compound form a salt improves dispersibility and dispersion stability of the red pigment having the anthraquinone skeleton. In view of excellent alkali developability, high brightness and high contrast.
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 an alkyl group having 1 to 8 carbon atoms, and A is an alkyl group having 1 to 8 carbon atoms. An alkylene group, — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —CH (R ⁶ ) —CH (R ⁷ ) — or — [(CH ₂ ) _y —O] _z — (CH ₂ ) _a divalent group represented by _y— , R ⁴ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ⁶ ) —CH (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 general formula (I), R ¹ represents a hydrogen atom or a methyl group, and R ² and R ³ each independently represent an alkyl group having 1 to 8 carbon atoms. Here, the alkyl group having 1 to 8 carbon atoms may be linear, branched or cyclic. Examples of such alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, various pentyl groups, various hexyl groups, and various octyl groups. Group, cyclopentyl group, cyclohexyl group, cyclooctyl group and the like. Among these, a methyl group and an ethyl group are preferable.
In the present invention, R ² and R ³ may be the same as or different from each other.

A 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. 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. In the case where 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 in the case where the solvent is a less polar one such as pentane or hexane, It is preferable to use a pentyl group, hexyl group, heptyl group or the like.
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 This is because the dispersibility and stability of the pigment can be made particularly excellent when the salt-forming site formed by the compound has high adsorptivity to the pigment.

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

  The 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, the pigment dispersant can be made excellent in dispersibility and stability of the pigment. Furthermore, by using an organic acid compound, 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.

  The content of the organic acid compound in the block copolymer used in the present invention is not particularly limited as long as good dispersion stability is exhibited, and is generally represented by the general formula (I). 0.05-1.0 molar equivalent is preferable with respect to a tertiary amino group. Furthermore, the organic acid compound content is a tertiary amino group from the viewpoint of excellent pigment adsorbing power, solubility in a solvent, interaction with a sulfonated derivative of a yellow pigment, pigment dispersibility and pigment dispersion stability. On the other hand, it is preferably 0.2 to 0.8 molar equivalent. In addition, when using 2 or more types of the said organic acid compounds 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. Any method can be used as long as it can produce a salt formed with the organic acid compound. 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. The pigment dispersant can be produced by adding the compound 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, in particular, 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. In addition, the content is not particularly limited as long as the pigment can be uniformly dispersed, and for example, 10 to 150 parts by mass can be used with respect to 100 parts by mass of the pigment. Furthermore, it is preferable to mix | blend in the ratio of 15-45 mass parts with respect to 100 mass parts of pigments, and it is preferable to mix | blend especially in the ratio of 15-40 mass parts. If the content of the pigment dispersant is within the above range, the pigment can be uniformly dispersed. In the present invention, the pigment used to define the content other than the pigment derivative includes a pigment derivative in addition to the pigment, for example, a sulfonated derivative of a yellow pigment.

(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 solvent as described above usually at a ratio of 60 to 85% by mass 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 pigment derivatives)
Other pigment derivatives may be included as long as the effect of the present invention is not impaired. Such a pigment derivative is a compound having a role of imparting a functional group to the pigment skeleton and adding various functions to the pigment. When a pigment derivative is added to the pigment at the time of pigment dispersion, the pigment-like skeleton of the pigment derivative is adsorbed or bonded to the surface of the pigment, whereby the surface of the pigment becomes polar, so that the affinity between the dispersant and the pigment is increased. It is considered that the dispersibility and dispersion stability can be secured.
Examples of other pigment derivatives include phthalimide alkylated derivatives of yellow pigments. The phthalimide alkylated derivative of the pigment is preferably used from the viewpoint of suppressing aggregation of the pigment and achieving high brightness and high contrast.

  When the phthalimide alkylated derivative of the pigment is used as the other pigment derivative, examples of the alkyl group of the phthalimide alkyl group include linear or branched alkyl groups having 1 to 6 carbon atoms, such as methyl group, ethyl group, and the like. Group, propyl group, hexyl group and the like. Among these, from the viewpoint of easy production, the alkyl group of the phthalimidoalkyl group is preferably a methyl group.

  Moreover, it is preferable that the substitution number of a phthalimide alkyl group is 1-2, and it is preferable that it is 1 especially from the point which can be easy to adsorb | suck a pigment and can improve heat resistance.

  A phthalimidoalkylated derivative of a pigment can be produced, for example, by reacting a pigment with paraformaldehyde and phthalimide in sulfuric acid. This synthesis method is described in detail in JP-T-2004-501911 and can be referred to. As the phthalimide alkylated derivative of the pigment, one kind can be used alone, or two or more kinds can be mixed and used. For example, two or more types of phthalimide alkylated derivatives having different types of alkyl groups, phthalimidoalkyl group substitution positions or substitution numbers may be used.

  The phthalimide alkylated derivative of the pigment is preferably contained in an amount of 0 to 15 parts by mass with respect to 100 parts by mass of the red pigment having the anthraquinone skeleton. Especially, it is preferable to contain 1-15 mass parts with respect to 100 mass parts of the red pigment which has the said anthraquinone frame | skeleton, Furthermore, 3-15 mass parts is contained. By using in such a content, the aggregation of the pigment is suppressed even after the high-temperature heating step in the color filter step, and particularly high brightness and high contrast can be achieved.

Further, the hue ratio of the sulfonated derivative of the yellow pigment and the phthalimide alkylated derivative of the pigment is 20: 1 to 20:40, particularly 20: 1 to 20:30. Without change, the aggregation of the pigment is suppressed even after the high-temperature heating step in the color filter step, which is preferable because it is particularly possible to achieve high brightness and high contrast.
When the sulfonated derivative of the yellow pigment and the phthalimide alkylated derivative of the pigment are used in combination, a change in hue when the red pigment derivative is used alone can be suppressed due to their synergistic effect, and the luminance can be improved, and Heat resistance can be improved.

(Other pigments)
The pigment dispersion of the present invention 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 an anthraquinone skeleton, it is preferable that a pigment dispersant which is a block copolymer containing a sulfonated derivative of a yellow pigment and a salt of a tertiary amine is 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. I. Pigment red 1, C.I. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 4, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment red 8, C.I. I. Pigment red 9, C.I. I. Pigment red 10, C.I. I. Pigment red 11, C.I. I. Pigment red 12, C.I. I. Pigment red 14, C.I. I. Pigment red 15, C.I. I. Pigment red 16, C.I. I. Pigment red 17, C.I. I. Pigment red 18, C.I. I. Pigment red 19, C.I. I. Pigment red 21, C.I. I. Pigment red 22, C.I. I. Pigment red 23, C.I. I. Pigment red 30, C.I. I. Pigment red 31, C.I. I. Pigment red 32, C.I. I. Pigment red 37, C.I. I. Pigment red 38, C.I. I. Pigment red 40, C.I. I. Pigment red 41, C.I. I. Pigment red 42, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 48: 2, C.I. I. Pigment red 48: 3, C.I. I. Pigment red 48: 4, C.I. I. Pigment red 49: 1, C.I. I. Pigment red 49: 2, C.I. I. Pigment red 50: 1, C.I. I. Pigment red 52: 1, C.I. I. Pigment red 53: 1, C.I. I. Pigment red 57, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 57: 2, C.I. I. Pigment red 58: 2, C.I. I. Pigment red 58: 4, C.I. I. Pigment red 60: 1, C.I. I. Pigment red 63: 1, C.I. I. Pigment red 63: 2, C.I. I. Pigment red 64: 1, C.I. I. Pigment red 81: 1, C.I. I. Pigment red 88, C.I. I. Pigment red 90: 1, C.I. I. Pigment red 97, C.I. I. Pigment red 101, C.I. I. Pigment red 102, C.I. I. Pigment red 104, C.I. I. Pigment red 105, C.I. I. Pigment red 106, C.I. I. Pigment red 108, C.I. I. Pigment red 112, C.I. I. Pigment red 113, C.I. I. Pigment red 114, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 144, C.I. I. Pigment red 146, C.I. I. Pigment red 149, C.I. I. Pigment red 150, C.I. I. Pigment red 151, C.I. I. Pigment red 166, C.I. I. Pigment red 168, C.I. I. Pigment red 170, C.I. I. Pigment red 171, C.I. I. Pigment red 172, C.I. I. Pigment red 174, C.I. I. Pigment red 175, C.I. I. Pigment red 176, C.I. I. Pigment red 178, C.I. I. Pigment red 179, C.I. I. Pigment red 180, C.I. I. Pigment red 185, C.I. I. Pigment red 187, C.I. I. Pigment red 188, C.I. I. Pigment red 190, C.I. I. Pigment red 193, C.I. I. Pigment red 194, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 207, C.I. I. Pigment red 208, C.I. I. Pigment red 209, C.I. I. Pigment red 215, C.I. I. Pigment red 216, C.I. I. Pigment red 220, C.I. I. Pigment red 224, C.I. I. Pigment red 226, C.I. I. Pigment red 242, C.I. I. Pigment red 243, C.I. I. Pigment red 245, C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 264, C.I. I. And CI Pigment Red 265.

  Among these, from the viewpoint of achieving a specific color necessary for the red colored layer of the color filter, C.I. I. Pigment red 242, and C.I. I. You may use in combination with 1 or more types selected from the group which consists of pigment red 254.

  In the pigment dispersion, the content of the red pigment having an anthraquinone skeleton in all pigments excluding the sulfonated derivative of the yellow pigment may be appropriately selected according to the desired chromaticity. Since it is low, it is preferably 70% by mass or more and more preferably 80% by mass or more from the viewpoint of securing process suitability such as developability in the flow of thinning with a high pigment concentration.

(Other ingredients)
If necessary, the pigment dispersion liquid of the present invention may further contain a pigment dispersion auxiliary resin and other components.
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 pigment dispersion of the present invention is a red color having the anthraquinone skeleton in the presence of a sulfonated derivative of the yellow pigment in the solvent and a pigment dispersant that is a block copolymer containing a salt of the tertiary amine. A step of dispersing the pigment.
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 comprises at least the red pigment dispersion for color filter according to the present invention and a photosensitive binder component. And

Since the red photosensitive resin composition for a color filter according to the present invention includes the pigment dispersion according to the present invention, it is possible to form a color filter that achieves particularly high brightness and also achieves a high contrast requirement. .
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 another pigment, it is preferable to contain a yellow pigment from the viewpoint of improving contrast while achieving a specific color necessary for the red colored layer of the color filter.

<Yellow pigment>
Examples of yellow pigments include C.I. I. Pigment Yellow 150 or a derivative pigment thereof, C.I. I. Pigment yellow 138 and C.I. I. It is preferably at least one selected from the group consisting of CI Pigment Yellow 139.
Here, C.I. I. As pigment pigments of CI Pigment Yellow 150, specifically, mono-, di-, tri-, and tetraanions of azo compounds according to the following chemical formula or one of its tautomeric structures that serve as hosts for at least one guest compound and metals 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 are mentioned. be able to.

［式（４）中、Ｒ^ｇおよびＲ^ｇ’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^ｈおよびＲ^ｈ’は、独立して、−ＯＨまたは−ＮＨ_２である］

[In formula (4), R ^g and R ^g ′ are independently OH, NH ₂ , NH—CN, acylamino or arylamino, and R ^h and R ^h ′ are independently —OH Or is —NH ₂ ]

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

(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- Hydroxylethyl (meth) acrylate, 2-dimethylaminoethyl (
At least one selected from (meth) acrylate, N-vinyl-2-pyrrolidone, N-methylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, (meth) acrylic acid, acrylic acid A dimer (for example, M-5600 manufactured by Toagosei Kagaku Co., Ltd.), itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, and one or more copolymers selected from these anhydrides Can be illustrated. 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 mass, preferably 10 to 40% by mass. In this case, when the copolymerization ratio of the carboxyl group-containing ethylenically unsaturated monomer is less than 5% by mass, 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 mass, 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 novolak 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 products of (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like are preferable. 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 mass parts normally with respect to 100 mass parts of alkali-soluble resin, Preferably it is 20-300 mass parts. 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.

  Content of the photoinitiator used in the red photosensitive resin composition for color filters of this invention is about 0.01-100 mass parts normally with respect to 100 mass parts of said polyfunctional monomers, Preferably it is 5-60. Part by mass. 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-diamino Examples thereof include amines having a hydroxy group such as tan, 1,4-bis (2-hydroxyethyl) piperazine and 1- (2-hydroxyethyl) piperazine, and others such as nipecotamide, isonipecotamide, and nicotinamide. A compound can be mentioned.

  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 mass, more preferably 15 to 35% by mass, 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.

The content of the red pigment having an anthraquinone skeleton in all the pigments excluding the sulfonated derivative of the yellow pigment may be appropriately selected according to the desired chromaticity. However, since the coloring power of the derivative is low, the high pigment From the viewpoint of securing process suitability such as developability, the concentration is preferably 70% by mass or more, and more preferably 80% by mass or more, in the flow of thinning as a concentration.
Further, the total content of the pigment dispersant is preferably in the range of 1 to 60% by mass, particularly in the range of 5 to 50% by mass with respect to the total solid content of the photosensitive resin composition. Preferably there is. When the content is less than 1% by mass relative to the total solid content of the photosensitive resin composition, it may be difficult to uniformly disperse the pigment. When the content exceeds 60% by mass, , The curability and developability may be lowered.
The total amount of the alkali-soluble resin, polyfunctional monomer, and photoinitiator is 15 to 95% by mass, preferably 25 to 80% by mass, 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 mass, particularly preferably in the range of 75 to 88% by mass, with respect to 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)
In the presence of a method for producing a red photosensitive resin composition for a color filter of the present invention, and a pigment dispersant which is a block copolymer containing a sulfonated derivative of a yellow pigment and a tertiary amine salt in a solvent, A step of dispersing a red pigment having the anthraquinone skeleton to prepare a red pigment dispersion;
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 has a colored layer formed using the above-described red photosensitive resin composition for a color filter of the present invention.
Such a color filter of the present invention will be described with reference to the drawings. FIG. 1 is a schematic sectional view showing an example of the color filter of the present invention. According to FIG. 1, the color filter 10 of the present invention has a transparent substrate 1, a light shielding part 2, and a colored layer 3.

(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, 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.

Next, the organic light emitting display device of the present invention will be described.
[Organic light emitting display]
The organic light emitting display device of the present invention includes the above-described color filter of the present invention and an organic light emitter.
Such an organic light emitting display device of the present invention will be described with reference to the drawings. FIG. 3 is a schematic view illustrating an example of the organic light emitting display device of the present invention. As illustrated in FIG. 3, the organic light emitting display device 100 of the present invention includes a color filter 10 and an organic light emitter 80.
An organic protective layer 50 and an inorganic oxide film 60 may be provided between the color filter 10 and the organic light emitter 80.

As a method for laminating the organic light emitter 80, for example, the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, and the cathode 76 are sequentially formed on the upper surface of the color filter. Examples thereof include a method and a method in which an organic light emitter 80 formed on another substrate is bonded onto the inorganic oxide film 60. As the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, the cathode 76, and other configurations in the organic light emitting body 80, known structures can be appropriately used. The organic light emitting display device 100 manufactured as described above can be applied to, for example, a passive drive type organic EL display or an active drive type organic EL display.
Note that the organic light emitting display device of the present invention is not limited to the configuration shown in FIG. 3, and may be a known configuration as an organic light emitting display device that generally uses a color filter.

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

(Production Example 1) Preparation of Dispersant Solution a In a 100 mL round bottom flask, 20.1 parts by mass of propylene glycol monomethyl ether acetate (PGMEA), the repeating unit (1) represented by the above general formula (I), A block copolymer having a repeating unit (2) represented by the above general formula (II) (trade name: BYK-LPN6919, manufactured by Big Chemie) (mass average molecular weight 7920, amine value 120 mgKOH / g, solid content 60 mass) %) 1.45 parts by mass, phenylphosphonic acid (trade name: PPA, manufactured by Nissan Chemical Co., Ltd.) 0.1 parts by mass (0.3 molar equivalents with respect to the tertiary amino group), and treated with ultrasound for 15 minutes Thus, a dispersant solution a containing a block copolymer type dispersant containing a tertiary amine, which was partially salted, was obtained.
At this time, the amino group of the block copolymer (BYK-LPN6919) is salt-formed by an acid / base reaction with the phosphonic acid group of phenylphosphonic acid.

  As yellow pigment sulfonated derivatives, yellow pigment sulfonated derivatives 1 to 5 represented by the following formula and having different substituents X were used.

Synthesis Example 1 Yellow Pigment Sulfonated Derivative 1
374.76 g of 11 mass% 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 yellow pigment sulfonated derivative 1 represented by the following formula. The molecular weight of the target product was confirmed by TOF-MS.

（式中、Ｘは１又は２である。）

(In the formula, X is 1 or 2.)

(Synthesis Example 2) Yellow pigment sulfonated derivative 2 (the formula ^{_{X = SO 3 - N (CH}} 3) 2 (C 18 H 37) 2 +)
374.76 g of 11% 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. Add 600 ml of water to the wet cake and stir at 60 ° C. for 1 hour. Distearyl ammonium chloride 55.60g was added and it stirred at 60 degreeC for 1 hour. The precipitate was filtered and washed twice with 600 ml of water. Vacuum drying at 80 ° C. gave a yellow product. The molecular weight of the target product was confirmed by TOF-MS.

(Synthesis Example 3) Yellow Pigment Sulfonated Derivative 3 (Formula X = SO ₃ H, In addition, one phthalimidomethyl group is bonded)
After adding 5.14 g of paraformaldehyde and 17.71 g of phthalimide to 338.67 g of 3.6% fuming sulfuric acid at 25 ° C., the mixture was stirred at 50 ° C. for 30 minutes. Subsequently, 69.40 g of Pigment Yellow 138 was added, and the mixture was stirred at 100 ° C. for 3 hours.
The reaction solution was added to 2400 g of ice water and stirred at 60 ° C. for 30 minutes, and then the precipitate was filtered. The obtained wet cake was washed three times with 1 L of warm water at 60 ° C. The wet cake was vacuum dried at 80 ° C. to obtain a yellow product.
200.00 g of 20% fuming sulfuric acid was stirred while being cooled to 10 ° C., and 40.00 g of a yellow product was added. Subsequently, it stirred at 80 degreeC for 6 hours.
The reaction solution was added to 2000 g of ice water and stirred for 15 minutes, and then the precipitate was filtered and washed with 250 ml of water three times. Vacuum drying at 80 ° C. gave a yellow product. The molecular weight of the target product was confirmed by TOF-MS.

Synthesis Example 4 Yellow Pigment Sulfonated Derivative 4 (Formula X = SO ₂ NHC ₃ H ₆ N (C ₂ H ₅ ) ₂ )
41.64 g of Pigment Yellow 138 was added to 250.44 g of chlorosulfuric acid. Then, after 2 hours at 120 ° C., 25.70 g of thionyl chloride was added dropwise at 75 ° C. Then, it stirred at 80 degreeC for 3 hours.
The reaction solution was added to 730 g of ice water while cooling to 3 ° C. or lower. Further, 1100 g of ice was added and stirred for 15 minutes, and the precipitate was filtered. The obtained wet cake was washed with 500 ml of ice water while cooling with ice. The wet cake was added while keeping 420 g of ice water at 2 ° C. or lower. Next, 15.65 g of diethylaminopropylamine was added dropwise, and the mixture was stirred at 2 ° C. or lower for 1 hour. The precipitate was filtered, washed twice with 500 ml of water and filtered. Vacuum drying at 80 ° C. gave a yellow product. The molecular weight of the target product was confirmed by TOF-MS.

(Synthesis Example 5) Yellow pigment sulfonated derivative 5 (the above formula ^{_{X = SO 3 - N (CH}} 3) 4 +)
374.76 g of 11% 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. Add 265 ml of water to the wet cake and stir at 25 ° C. for 1 hour. Tetramethylammonium chloride 4.81g was added and it stirred at 25 degreeC for 1 hour. The precipitate was filtered and washed twice with 600 ml of water. Vacuum drying at 80 ° C. gave a yellow product. The molecular weight of the target product was confirmed by TOF-MS.

Synthesis Example 6 Red Pigment Sulfonated Derivative 1
300.0 g of 20% fuming sulfuric acid was stirred while being cooled to 10 ° C., and 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 compound represented by the following structural formula (n = 1) was confirmed by TOF-MS.

Example 1
(1) Preparation of red pigment dispersion for color filter C.I. which is a red pigment having an anthraquinone skeleton I. Pigment Red 177 (PR177, average particle diameter: 40 nm or less) 3.705 parts by mass, 0.195 parts by mass of yellow pigment sulfonated derivative 1 as a yellow pigment sulfonated derivative, dispersant solution a21.6 prepared in Production Example 1 Parts by mass and an 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, solid content 44. 4.4 parts by weight of 1% by weight diluted with propylene glycol monomethyl ether acetate) is mixed and dispersed in a paint shaker for 1 hour with 2 mm zirconia beads and for another 6 hours with 0.1 mm zirconia beads. % Of the red pigment dispersion liquid A of Example 1. Beads filling rate of the Le was 50%.

<Evaluation of dispersion average particle size and viscosity>
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
Moreover, 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.).
The dispersion average particle diameter and viscosity were measured again after the dispersion was stored at 40 ° C. for 1 week, and changes in the dispersion average particle diameter and viscosity immediately after dispersion were confirmed. The results are shown in Table 1.
[Evaluation criteria for dispersion stability]
○: Increase in dispersion average particle diameter was less than 5 nm, and increase in viscosity was less than 10 mP · s.
Δ: Increase in dispersion average particle size was less than 5 nm, or increase in viscosity was less than 10 mP · s.
X: Increase in dispersion average particle diameter was 5 nm or more, and increase in viscosity was 10 mP · s or more.

(2) Preparation of Red Photosensitive Resin Composition for Color Filter To 4.06 parts by mass of the red pigment dispersion A of Example 1 obtained above, 2.22 parts by mass of the following binder composition, propylene glycol monomethyl ether acetate 3 72 parts by mass, 0.01 parts by mass of surfactant R08MH (manufactured by DIC), and silane coupling agent KBM503 (manufactured by Shin-Etsu Silicone) were added and mixed, followed by pressure filtration, and a red photosensitive resin composition for color filters. Got.
<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 mass Tetrafunctional acrylate monomer (trade name: Aronix M450, manufactured by Toagosei Co., Ltd.): 8.2 parts by mass / 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 mass / photopolymerization initiator (2-benzyl-2-dimethylamino-1- (4-morpholino) Phenyl) -1-butanone (trade name Irgacure 369, manufactured by Ciba Specialty Chemicals Co., Ltd.): 2.4 parts by mass / photosensitization (4,4'-bis (dimethylamino) benzophenone): 0.7 parts by mass Solvent (propylene glycol monomethyl ether acetate): 43.2 parts by weight

(Evaluation results)
<Contrast, hue, and luminance evaluation>
The red photosensitive resin composition for a color filter obtained by using the red pigment dispersion of Example 1 was applied to a spin coater on a 0.7 mm thick glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.). It applied using. 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 “Microspectrometer OSP-SP200” manufactured by Olympus Corporation. The results are shown in Table 1.

(Examples 2 to 5)
In Example 1, a dispersion and a post-baked cured film were prepared and dispersed in the same manner as in Example 1 except that the yellow pigment sulfonated derivative 1 was changed to yellow pigment sulfonated derivatives 2 to 5, respectively. The dispersion particle size of the liquid, the viscosity, and the optical properties of the post-baked post-baked film were evaluated. The results are shown in Table 1.

(Comparative Example 1)
A red pigment having an anthraquinone skeleton was used without using a yellow pigment sulfonated derivative. I. Pigment Red 177 (PR177, average particle size: 40 nm or less) was prepared in the same manner as in Example 1 except that 3.9 parts by mass was used, and a dispersion and a post-baked cured film were prepared. Viscosity and optical properties of the post-baked cured film were evaluated. The results are shown in Table 1.

(Comparative Example 2)
A dispersion and a post-baked cured film were prepared in the same manner as in Example 1 except that the yellow pigment sulfonated derivative was changed to the red pigment sulfonated derivative 1, and the dispersion particle size, viscosity, post-baked post-bake cured The optical properties of the film were evaluated. The results are shown in Table 1.

(Comparative Example 3)
Instead of 21.6 parts by mass of the dispersant solution a prepared in Production Example 1, 2.34 parts by mass of Ajisper PB822 (manufactured by Ajinomoto Fine-Techno), which is a graft type dispersant, was used, and further 19.26 of propylene glycol monomethyl ether acetate. A dispersion and a post-baked cured film were prepared in the same manner as in Example 1 except that parts by mass were added, and the dispersion particle size and viscosity of the dispersion and the optical properties of the post-baked cured film were evaluated. The results are shown in Table 1.

(Comparative Example 4)
Instead of 21.6 parts by mass of the dispersant solution a prepared in Production Example 1, 3.3 parts by mass of Dispersic 166 (manufactured by BYK Chemie, solid content 29.5%) was used, and further 18.3 of propylene glycol monomethyl ether acetate When a dispersion was prepared in the same manner as in Example 1 except that mass parts were added, it was agglomerated and gelled when dispersed with 2 mm beads.

  From Table 1, it is clear that by adding a yellow pigment sulfonated derivative to a red pigment having an anthraquinone skeleton at the time of dispersion, it becomes possible to finely disperse without greatly changing the hue, and as a result, both contrast and luminance can be achieved. It was done. In Comparative Example 1 in which the yellow pigment sulfonated derivative was not used, thickening and an increase in the dispersed particle diameter were confirmed after the storage stability test, whereas in Example 1 in which the yellow pigment sulfonated derivative was used, the dispersibility was increased. The dispersion stability was good.

<Solvent resolvability>
As an evaluation method, the photosensitive resin composition of Examples 1-7 and the photosensitive resin composition of Comparative Examples 1-2 in which the cured film was evaluated on a length of 2 cm of a glass substrate cut to a length of 100 mm and a width of 5 mm. Each thing was dipped and what was pulled up was dried for 30 minutes in a constant temperature and humidity layer of 25 ° C. and 70% RH. Next, the glass substrate to which the dried coating film adhered was immersed in PGMEA with stirring for 15 seconds. At this time, it evaluated in the following three steps by the redissolved state of the dry coating film.
-○: All the dried coating films were dissolved during immersion.
Δ: A part of the dried coating film remained even after immersion for 15 seconds.
X: The dry coating film hardly or not dissolved even after dipping for 15 seconds.
As a result, Examples 2 and 4 and Comparative Example 3 were ◯, Examples 1, 5 and Comparative Examples 1 and 2 were Δ, and Example 3 and Comparative Example 4 were ×.
From the above, excluding the influence of PB822, which has a structure in which the dispersant is particularly easily dissolved in PGMEA, sulfonated derivatives having sulfonamide groups and sulfonated derivatives salted with long-chain alkyl groups are soluble in solvents. It was revealed that it was excellent.

DESCRIPTION OF SYMBOLS 1 Transparent substrate 2 Light-shielding part 3 Colored layer 10 Color filter 20 Opposite substrate 30 Liquid crystal layer 40 Liquid crystal display device 50 Organic protective layer 60 Inorganic oxide film 71 Transparent anode 72 Hole injection layer 73 Hole transport layer 74 Light emitting layer 75 Electron injection layer 76 Cathode 80 Organic light emitter 100 Organic light emitting display device

A red pigment dispersion for a color filter according to the present invention comprises a red pigment having an anthraquinone skeleton, a sulfonated derivative of a yellow pigment, a pigment dispersant that is a block copolymer containing a tertiary amine salt, and a solvent. And the red pigment having the anthraquinone skeleton is 80% by mass or more in all pigments excluding the sulfonated derivative of the yellow pigment, and the sulfonated derivative of the yellow pigment has 100 parts by mass of the anthraquinone skeleton. It is 1-10 mass parts with respect to a red pigment, The said pigment dispersant is a repeating unit (1) represented by the following general formula (I), and a repeating unit (2 represented by the following general formula (II) (2) And 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 pigment dispersant contains Takes said organic acid compound, characterized in that at least one selected from the group consisting of organic acids represented by the following general formula (III) and Formula (IV).
The method for producing a red pigment dispersion for a color filter according to the present invention includes a step of dispersing the red pigment having an anthraquinone skeleton in a solvent in the presence of a sulfonated derivative of a yellow pigment and the pigment dispersant. A red pigment dispersion for a color filter , wherein the red pigment having an anthraquinone skeleton is 80% by mass or more in all pigments excluding the sulfonated derivative of the yellow pigment, and the yellow pigment sulfone 1 to 10 parts by mass with respect to the red pigment having 100 parts by mass of the anthraquinone skeleton, and the pigment dispersant is a repeating unit (1) represented by the following general formula (I): The repeating unit (2) represented by the general formula (II), and at least a part of the amino group of the repeating unit (1) and the organic acid compound Wherein the organic acid compound in the pigment dispersant 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) It is characterized by being.

[In formula (I) and formula (II), R ¹ Is a hydrogen atom or a methyl group, R ² And R ³ Are each independently an alkyl group having 1 to 8 carbon atoms, A is an alkylene group having 1 to 8 carbon atoms, and — [CH (R ⁶ ) -CH (R ⁷ -O] _x -CH (R ⁶ ) -CH (R ⁷ )-Or-[(CH ₂ ) _y -O] _z -(CH ₂ ) _y A divalent 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 (R ⁷ -O] _x -R ⁸ Or-[(CH ₂ ) _y -O] _z -R ⁸ It is a monovalent group shown by these. 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, —CHO, —CH ₂ CHO or -CH ₂ COOR ⁹ A monovalent group represented by 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 formula (III) and formula (IV), R ^a And R ^{a ’} Each independently represents 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 "} A monovalent group represented by R ^a And R ^{a ’} Any of which contains 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 It is a monovalent group shown by these.
  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 -O-R ^{b ’} It is a monovalent group shown by these. 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-[(CH ₂ ) _t -O] _u -R ^e It is a monovalent group shown by these.
  R ^c And R ^d Are each independently a hydrogen atom or a methyl group, and R ^e Is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, —CHO, —CH ₂ CHO, -CO-CH = CH ₂ , -CO-C (CH ₃ ) = CH ₂ Or -CH ₂ COOR ^f A monovalent group represented by R ^f Is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
R ^a , R ^{a ’} And R ^b In the above, 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. ]

  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 a photosensitive binder component, It is characterized by the above-mentioned.
  Furthermore, the method for producing a red photosensitive resin composition for a color filter according to the present invention comprises dispersing a red pigment having an anthraquinone skeleton in a solvent in the presence of a sulfonated derivative of a yellow pigment and the pigment dispersant. And a step of preparing a red pigment dispersion,
  A method for producing a red photosensitive resin composition for a color filter, comprising the step of mixing the red pigment dispersion and a photosensitive binder component, wherein the red pigment having the anthraquinone skeleton is sulfonated of the yellow pigment 80% by mass or more in the total pigment excluding the derivative, the sulfonated derivative of the yellow pigment is 1 to 10 parts by mass with respect to 100 parts by mass of the red pigment having the anthraquinone skeleton, and the pigment dispersant is And the repeating unit (1) represented by the general formula (I) and the repeating unit (2) represented by the general formula (II), and further the amino group of the repeating unit (1). A block copolymer in which at least a part of the organic acid compound forms a salt, and the organic acid compound in the pigment dispersant is represented by the general formula (III) and the general formula ( Characterized in that from the group consisting of organic acids represented by V) is at least one selected.

In the red pigment dispersion for color filters according to the present invention and the method for producing the same, and the red photosensitive resin composition for color filters according to the present invention and the method for producing the same, the sulfonated derivative of the yellow pigment is represented by the following chemical formula (2 And a content of the organic acid compound in the pigment dispersant is 0.05 to 0.3 mol with respect to the amino group of the repeating unit (1). It is preferable that it is equivalent.

(In the above formula (2), X 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 or unsaturated aliphatic group having 1 to 20 carbon atoms. A hydrocarbon group or an aromatic hydrocarbon group, or a group that forms a heterocyclic ring that may further contain a nitrogen, oxygen, or sulfur atom together with an adjacent nitrogen atom, and each m independently represents 1-6 (It is an integer. N represents the number of substituents and represents an integer of 1 to 4.)

  In the red pigment dispersion for color filters according to the present invention and the method for producing the same, and the red photosensitive resin composition for color filters according to the present invention and the method for producing the same, the sulfonated derivative of the yellow pigment contains C.I. I. A sulfonated derivative of CI Pigment Yellow 138 is preferable from the viewpoint that the dispersibility and dispersion stability of the red pigment having an anthraquinone skeleton are improved, and a demand for high brightness and high contrast can be achieved.

Claims (13)

  A red pigment dispersion for a color filter, comprising a red pigment having an anthraquinone skeleton, a sulfonated derivative of a yellow pigment, a pigment dispersant that is a block copolymer containing a salt of a tertiary amine, and a solvent.   The red pigment dispersion for a color filter according to claim 1, obtained by dispersing the red pigment having the anthraquinone skeleton in the solvent in the presence of the sulfonated derivative of the yellow pigment and the pigment dispersant. .   The sulfonated derivative of the yellow pigment is C.I. I. The red pigment dispersion for a color filter according to claim 1 or 2, which is a sulfonated derivative of CI Pigment Yellow 138.   The red pigment having the anthraquinone skeleton is C.I. I. The red pigment dispersion for a color filter according to any one of claims 1 to 3, which is CI Pigment Red 177.   5. The color filter according to claim 1, wherein the content of the sulfonated derivative of the yellow pigment is 1 to 25 parts by mass with respect to 100 parts by mass of the red pigment having the anthraquinone skeleton. Red pigment dispersion. 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 any one of claims 1 to 5, which is a block copolymer in which at least a part of the amino group contained in the organic acid compound 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 an alkyl group having 1 to 8 carbon atoms, and A is an alkyl group having 1 to 8 carbon atoms. An alkylene group, — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —CH (R ⁶ ) —CH (R ⁷ ) — or — [(CH ₂ ) _y —O] _z — (CH ₂ ) _a divalent group represented by _y— , R ⁴ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ⁶ ) —CH (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 color filter according to claim 6, wherein the organic acid compound in the pigment dispersant 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). Red pigment dispersion.

[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 method for producing a red pigment dispersion for a color filter, comprising the step of dispersing the red pigment having an anthraquinone skeleton in a solvent in the presence of a sulfonated derivative of a yellow pigment and the pigment dispersant.   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 a photosensitive binder component. A step of preparing a red pigment dispersion by dispersing the red pigment having an anthraquinone skeleton in a solvent in the presence of a sulfonated derivative of a yellow pigment and the pigment dispersant;
A method for producing a red photosensitive resin composition for a color filter, comprising a step of mixing the red pigment dispersion and a photosensitive binder component.   It forms using the photosensitive resin composition obtained by the manufacturing method of the red photosensitive resin composition for color filters of the said Claim 9, or the red photosensitive resin composition for color filters of the said Claim 10. A color filter having a colored layer formed thereon.   12. A liquid crystal display device comprising: the color filter according to claim 11; a counter substrate; and a liquid crystal layer formed between the color filter and the counter substrate.   12. An organic light emitting display device comprising the color filter according to claim 11 and an organic light emitter.

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