JP6078999B2 - Red pigment dispersion for color filter and production method thereof, red photosensitive resin composition for color filter and production method thereof, color filter, liquid crystal display device and organic light emitting display device - Google Patents

Description

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

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

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

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 dispersing agent described in Patent Document 2, the dispersibility and the dispersion stability are not sufficient when Pigment Red 177 is used alone, as in Comparative Examples described later.

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

  The present invention has been made under such circumstances, and is a red pigment dispersion for a color filter that is excellent in dispersibility and dispersion stability, and achieves the demands for high brightness and high contrast, a method for producing the same, and dispersibility And a red photosensitive resin composition for a color filter that is excellent in dispersion stability, can form a colored layer with high brightness and high contrast, and is excellent in alkali developability, a method for producing the same, and the photosensitive resin composition. An object of the present invention is to provide a formed color filter, a liquid crystal display device having the color filter, and an organic light emitting display device.

As a result of intensive studies to achieve the above object, the present inventors have obtained a red pigment having an anthraquinone skeleton in a solvent in the presence of a sulfonated derivative of a yellow pigment and a specific graft copolymer. When dispersed, even a red pigment having an anthraquinone skeleton is improved in dispersibility and dispersion stability, can achieve the demand for high brightness and high contrast, and further has excellent alkali developability. It has been found that a functional resin composition 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 contains a red pigment having an anthraquinone skeleton, a sulfonated derivative of a yellow pigment, a pigment dispersant, and a solvent, and the pigment dispersant is ethylenically unsaturated. A graft copolymer comprising , as a copolymerization component, a monomer having a double bond and an amino group, and a macromonomer containing a polymer chain and a group having an ethylenically unsaturated double bond at its terminal, The polymer chain of the monomer has at least a structural unit represented by the following general formula (IV), and further has at least a part of an amino group derived from a monomer having an ethylenically unsaturated double bond and an amino group, and an organic acid. The compound is a graft copolymer in which a salt is formed.

The method for producing a red dispersion for a color filter according to the present invention includes a step of dispersing the red pigment having the anthraquinone skeleton in a solvent in the presence of a sulfonated derivative of a yellow pigment and a pigment dispersant, The pigment dispersant contains, as a copolymerization component, a monomer having an ethylenically unsaturated double bond and an amino group, and a macromonomer containing a polymer chain and a group having an ethylenically unsaturated double bond at its terminal. It is a graft copolymer, and the polymer chain of the macromonomer is derived from a monomer having at least a structural unit represented by the following general formula (IV) and further having an ethylenically unsaturated double bond and an amino group It is a graft copolymer in which at least a part of the amino group and an organic acid compound form a salt.

  The red photosensitive resin composition for a color filter according to the present invention contains at least the red pigment dispersion for the color filter and a photosensitive binder component.

The method for producing a red photosensitive resin composition for a color filter according to the present invention comprises the steps of dispersing a red pigment having an anthraquinone skeleton in a solvent in the presence of a sulfonated derivative of a yellow pigment and a pigment dispersant. A step of preparing a pigment dispersion;
A step of mixing the red pigment dispersion and a photosensitive binder component, wherein the pigment dispersant is composed of a monomer having an ethylenically unsaturated double bond and an amino group, a polymer chain, and an ethylenic group at its end. A graft copolymer containing, as a copolymerization component, a macromonomer containing a group having an unsaturated double bond , wherein the polymer chain of the macromonomer comprises a structural unit represented by the following general formula (IV) It is a graft copolymer in which at least a part of an amino group derived from a monomer having at least an ethylenically unsaturated double bond and an amino group and an organic acid compound form a salt.

(In the formula (IV), R ⁴ Is a hydrogen atom or a methyl group, R ⁵ Is an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, a cyano group, — [CH (R ⁶ ) -CH (R ⁷ -O] _x -R ⁸ ,-[(CH ₂ ) _y -O] _z -R ⁸ ,-[CO- (CH ₂ ) _y -O] _z -R ⁸ , -CO-O-R ⁹ Or -O-CO-R ¹⁰ It is a monovalent group shown by these. R ⁶ And R ⁷ Are each independently a hydrogen atom or a methyl group.
  R ⁸ Is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, —CHO, —CH ₂ CHO or -CH ₂ COOR ¹¹ A monovalent group represented by R ⁹ Is an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, a cyano group, — [CH (R ⁶ ) -CH (R ⁷ -O] _x -R ⁸ ,-[(CH ₂ ) _y -O] _z -R ⁸ Or-[CO- (CH ₂ ) _y -O] _z -R ⁸ It is a monovalent group shown by these. R ¹⁰ Is an alkyl group having 1 to 18 carbon atoms and R ¹¹ Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. )

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 because it is excellent in dispersibility and dispersion stability, and easily satisfies the demands for high brightness and high contrast.
In the red pigment dispersion for a color filter according to the present invention and a method for producing the same, and the red photosensitive resin composition for a color filter according to the present invention and the method for producing the same, the red pigment having an anthraquinone skeleton is C.I. I. Pigment Red 177 is preferable in that it has excellent dispersibility and dispersion stability, and can easily achieve the demands for high brightness and high contrast.

  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 It is preferably 1 to 25 parts by mass with respect to 100 parts by mass of the red pigment having an anthraquinone skeleton because it is excellent in dispersibility and dispersion stability, and it is easy to achieve demands for high luminance and high contrast.

  In the red pigment dispersion for a color filter according to the present invention and a method for producing the same, and the red photosensitive resin composition for a color filter according to the present invention and the method for producing the same, in the pigment dispersant, It is preferable that the monomer having a heavy bond and an amino group is represented by the following general formula (I) because it is excellent in dispersibility and dispersion stability and easily achieves high brightness and high contrast requirements.

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

  In the red pigment dispersion for a color filter according to the present invention and a method for producing the same, and the red photosensitive resin composition for a color filter according to the present invention and the method for producing the same, in the pigment dispersant, the organic acid compound is Represented by the following general formula (II) and / or the following general formula (III), it is excellent in dispersibility and dispersion stability, easily achieves demands for high brightness and high contrast, and has excellent developability. Is preferable.

(In Formula (II) and Formula (III), R ^a and R ^{a ′} are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, or an aryl group. 1 represented by the group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — [(CH ₂ ) _t —O] _u —R ^e , or —O—R ^{a ″.} R ^a and R ^{a ′} each contain ^a carbon atom. R ^{a ″} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, and an aryl group. , — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — [(CH ₂ ) _t —O] _u —R ^e .
R ^b is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — [(CH ₂ ) _t —O] _u —R ^e or a monovalent group represented by —O—R ^{b ′} . R ^{b ′} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , or _- it is a monovalent group represented by _{[(CH 2) t -O]} u -R e.
R ^c and R ^d are each independently a hydrogen atom or a methyl group, and R ^e is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, _{-CHO, -CH 2 CHO, -CO-} CH = CH 2, a monovalent group represented by _{-CO-C (CH 3) =} CH 2 or _-CH 2 COOR ^{f, R f} is hydrogen or C It is an alkyl group of formula 1-5.
In R ^a , R ^{a ′} , and R ^b , each of the alkyl group, alkenyl group, aralkyl group, and aryl group may have a substituent.
s is an integer of 1 to 18, t is an integer of 1 to 5, and u is an integer of 1 to 18. )

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

  According to the present invention, the red pigment dispersion for color filter that achieves the demands for high brightness and high contrast, excellent in dispersibility and dispersion stability, and its manufacturing method, excellent in dispersibility and dispersion stability, high brightness, A red photosensitive resin composition for a color filter that is capable of forming a high-contrast colored layer and has excellent alkali developability, a method for producing the same, a color filter formed using the photosensitive resin composition, and the color filter A liquid crystal display device and an organic light emitting display device 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. FIG. 4 is a schematic diagram showing an example of a preferred structure of the graft copolymer used in the present invention.

Hereinafter, the red pigment dispersion for a color filter and the production method thereof, the red photosensitive resin composition for the color filter and the production method thereof, the color filter, the liquid crystal display device and the organic light emitting display device 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. Red pigment dispersion for color filter and method for producing the same Red pigment dispersion for color filter according to the present invention contains a red pigment having an anthraquinone skeleton, a sulfonated derivative of a yellow pigment, a pigment dispersant, and a solvent. And the pigment dispersant comprises a monomer having an ethylenically unsaturated double bond and an amino group, and a macromonomer containing a polymer chain and a group having an ethylenically unsaturated double bond at its terminal as a copolymerization component. A graft copolymer containing a graft copolymer in which at least part of an amino group derived from a monomer having an ethylenically unsaturated double bond and an amino group and an organic acid compound form a salt (hereinafter, It may be referred to as a salt-type graft copolymer).

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 a red pigment having an anthraquinone skeleton is dispersed in a solvent, the dispersion is performed in the presence of a pigment dispersant that is a combination of a sulfonated derivative of a yellow pigment and a pigment dispersant that is the salt-type graft copolymer. As a result, the dispersibility and dispersion stability of the red pigment having an anthraquinone skeleton are improved, and a pigment dispersion and a photosensitive resin composition that can achieve the demand for high brightness and high contrast can be 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 includes a monomer having an ethylenically unsaturated double bond and an amino group, a polymer chain, and an ethylenically unsaturated diester at its terminal. A graft copolymer containing, as a copolymerization component, a macromonomer containing a group having a heavy bond, and at least a part of an amino group derived from a monomer having an ethylenically unsaturated double bond and an amino group, and organic Since the acid compound is a graft copolymer in which a salt is formed, in the salt-type graft copolymer, the salt-forming site is adsorbed on the sulfonated derivative of the pigment, and particularly the yellow pigment adsorbed on the pigment surface. On the other hand, the part derived from the macromonomer is soluble in the solvent.
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 at least a red pigment having an anthraquinone skeleton, a sulfonated derivative of a yellow pigment, a pigment dispersant that is the specific salt-type graft copolymer, and a solvent. And may contain other components as necessary.
Hereinafter, each component of the red pigment dispersion of the present invention will be described in detail.

(Red pigment with anthraquinone skeleton)
The red pigment having an anthraquinone skeleton used in the present invention is not particularly limited. For example, 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 177, C.I. I. Pigment Red 216 and the like.

  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 graft copolymer containing a salt of an amino group and an organic acid compound, and is excellent in alkali developability. Less likely to cause problems. 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 8 to 20% by mass, based on the total amount of the red pigment dispersion for color filters.
The red pigment having an anthraquinone skeleton can be used alone or in combination of two or more.

(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 109, 110, 138, 139, and 185 have high luminance. I. It is preferable because of its high affinity with a red pigment having an anthraquinone skeleton such as CI Pigment Red 177. Furthermore, C.I. I. Pigment Yellow 138, 139 is used. I. C.I. Pigment Yellow 138 is particularly high in luminance. I. This is preferable because it has a high affinity with a red pigment having an anthraquinone skeleton such as CI Pigment Red 177 and can easily achieve high brightness and high contrast 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 the sulfonamide group which is an amide compound of a sulfonic acid group, sulfonamide groups represented by the following chemical formulas (2) to (4) are preferable.
Chemical formula (2): —SO ₂ NH— (CH ₂ ) _m —NR′R ″
Chemical formula _{(3): -SO 2 NH- (} CH 2) m -COOH
Formula _{(4): -SO 2 NH- (} CH 2) m -SO 3 H
In the chemical formula (2), 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 (2) to (4), 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 dispersing agent is improved by the interaction with the tertiary amine site of the graft copolymer type pigment dispersing agent described later and salt formation or ions. Therefore, it is preferable from the viewpoint of improving the contrast.
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.

  In particular, in the case of the sulfonamide group represented by the chemical formula (2) and in the case of a sulfonate salt formed with an amino group containing a long-chain alkyl group having 3 or more carbon atoms, the solvent resolubility is good. This is preferable. 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 adhered during the production of the color filter, which is a great merit in production.

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.

In (Equation (5), 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 group having 1 to 20 carbon atoms. Or an unsaturated aliphatic hydrocarbon group or an aromatic hydrocarbon group, or a heterocyclic ring which may contain a nitrogen, oxygen or sulfur atom together with an adjacent nitrogen atom, and each m is independently And n represents an integer of 1 to 6. n represents the number of substituents and represents an integer of 1 to 4.)

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

  In the formula (5), the number of substituents n is preferably 1 to 2, and is preferably 1 from the viewpoint of high affinity with the salt-forming site of the pigment dispersant.

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

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

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

  In the present invention, the sulfonated derivative of the yellow pigment is preferably contained in an amount of 1 to 25 parts by 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 an 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 copolymer of a monomer having an ethylenically unsaturated double bond and an amino group and a macromonomer having a polymer chain and a group having an ethylenically unsaturated double bond at its terminal. A graft copolymer contained as a component, further comprising at least a part of an amino group derived from a monomer having an ethylenically unsaturated double bond and an amino group, and an organic acid compound forming a salt. is there.

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

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

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

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

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

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

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

Examples of the divalent linking group Q include, for example, an alkylene group having 1 to 8 carbon atoms, an arylene group, a -CONH-A- group, and a -COO-A- group (provided that A is a group having 1 to 8 carbon atoms). An alkylene group, — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —CH (R ⁶ ) —CH (R ⁷ ) — or — [(CH ₂ ) _y —O] _z — (CH ₂ ) _{and a} divalent group represented by y-, wherein R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group, x is an integer of 1 to 18, y is an integer of 1 to 5, and z is 1. -It shows the integer of -18.) Etc., and it is preferable that they are -CONH-A- group or -COO-A- group.

Here, the alkylene group having 1 to 8 carbon atoms may be linear or branched. For example, a methylene group, an ethylene group, a trimethylene group, a propylene group, various butylene groups, various pentylene groups, various types. A hexylene group, various octylene groups, etc. are mentioned. Examples of the arylene group include a phenylene group.
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, when x, y and z are in the above ranges, the pigment dispersion and the red photosensitive resin composition for a color filter of the present invention have excellent pigment dispersibility.
As this A, a C1-C8 alkylene group is preferable, and a methylene group and ethylene group are more preferable. If the carbon number is in the range of 1 to 8, the dispersibility of the pigment can be kept good.

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

(In general formula (I ′) and general formula (I ″), R ¹ is a hydrogen atom or a methyl group, R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and A is Each independently 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, R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group, x is an integer of 1 to 18, and y is (The integer of 1-5, z shows the integer of 1-18.)

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

  In the present invention, the monomer represented by the general formula (I) is an acrylamide type represented by the above general formula (I ″) from the viewpoint that the dispersibility and dispersion stability of the red pigment having an anthraquinone skeleton are particularly excellent. It is more preferable that it is a monomer.

Specific examples of the monomer represented by the formula (I) include dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminoethyl (meth) acrylate, diethylaminopropyl (meth) acrylate, pentamethylpiperidyl ( Nitrogen-containing (meth) acrylate monomers such as (meth) acrylate; structural units derived from acrylamide monomers such as dimethylaminopropyl acrylamide, and the like, but are not limited thereto.
The nitrogen-containing monomer represented by the general formula (I) can be used alone or in combination of two or more.

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

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

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

The alkyl group having 1 to 18 carbon atoms in R ⁵ may be linear, branched or cyclic, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, Isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, various hexyl groups, various octyl groups, various decyl groups, various dodecyl groups, various tetradecyl groups, various hexadecyl groups, various octadecyl groups, cyclopentyl groups, cyclohexyl groups , Cyclooctyl group, cyclododecyl group, bornyl group, isobornyl group, dicyclopentanyl group, adamantyl group, lower alkyl group-substituted adamantyl group and the like.

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

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

R ⁶ and R ⁷ are 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 aralkyl group, an aryl group, —CHO, —CH _2. A monovalent group represented by CHO or —CH ₂ COOR ¹¹ . R ¹¹ is a hydrogen atom or a linear, branched, or cyclic alkyl group having 1 to 5 carbon atoms, and R ¹⁰ is an alkyl group having 1 to 18 carbon atoms.
In the monovalent group represented by R ⁸ , the substituent that may be included is, for example, a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms, a halogen atom such as F, Cl, or Br. And so on.
The alkyl group having 1 to 18 carbon atoms, the aralkyl group, and the aryl group in R ¹⁰ and R ⁸ are as described above for R ⁵ .
In the above R ⁵ and R ⁹ , x, y and z are as described in the above A.

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

Furthermore, R ⁵ and R ⁹ are substituents such as an alkoxy group, a hydroxyl group, a carboxyl group, an amino group, an epoxy group, an isocyanate group, and a hydrogen bond-forming group as long as they do not interfere with the dispersion performance of the graft copolymer. It may be substituted by. Moreover, after synthesizing a graft copolymer having these substituents, a compound having a functional group that reacts with the substituent and a polymerizable group may be reacted to add a polymerizable group. For example, adding a polymerizable group by reacting a graft copolymer having a carboxyl group with glycidyl (meth) acrylate, or reacting a graft copolymer having an isocyanate group with hydroxyethyl (meth) acrylate. Can do.

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

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

  In consideration of the above points, the polymer chain of the macromonomer used in the present invention includes methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, cyclohexyl metallate, benzyl, among the above-described structural units. 1 selected from the group consisting of (meth) acrylate, phenyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, styrene, α-methylstyrene, and vinylcyclohexane The total amount of structural units derived from more than one monomer is preferably contained at 50% by mass or more of the entire polymer chain of the macromonomer, more preferably at least 70% by mass, Methyl methacrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, and / or isobornyl (meth) is more preferable that contains structural units derived from acrylate. However, it is not limited to these.

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

Furthermore, the macromonomer used for a graft copolymer may be used individually by 1 type, but may be used in mixture of 2 or more types.
When two or more kinds of macromonomers are used as a mixture, the macromonomer having a polymer chain having a glass transition temperature of 30 ° C. or higher is used in an amount of 50% by mass or more, further 70% by mass or more of the entire macromonomer. It is preferable.

  m is an integer of 1 to 5, preferably an integer of 2 to 5, more preferably an integer of 4 or 5. The number of units n and n ′ of the constituent units of the macromonomer may be an integer of 5 to 200, and is not particularly limited, but is preferably in the range of 5 to 100.

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

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

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

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

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

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

  The graft copolymer used in the present invention has the above-mentioned monomer having an amino group and a macromonomer as copolymer components, and further, a salt formed by the amino group and the organic acid compound of the monomer. There is a structure as shown in FIG. In FIG. 4, in the graft copolymer, a monomer unit 51 having an amino group forms a main chain by a polymerization reaction, and a polymerizable group site (group site having an ethylenically unsaturated double bond) of the macromonomer in the polymerization reaction. ) 52 is simultaneously polymerized with a monomer having an amino group (nitrogen-containing monomer), and the macromonomer forms a side chain as a polymer chain 53 while being connected to the group site having the ethylenically unsaturated double bond, The acid compound 54 forms a salt with the amino group of the monomer unit 51 having an amino group.

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

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

(In Formula (II) and Formula (III), R ^a and R ^{a ′} are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, or an aryl group. A monovalent group represented by a group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — [(CH ₂ ) _t —O] _u —R ^e , or —O—R ^{a ″.} R ^a and R ^{a ′} each contain ^a carbon atom. R ^{a ″} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , a monovalent group represented by — [(CH ₂ ) _t —O] _u —R ^e .
R ^b is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — [(CH ₂ ) _t —O] _u —R ^e or a monovalent group represented by —O—R ^{b ′} . R ^{b ′} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , or _- it is a monovalent group represented by _{[(CH 2) t -O]} u -R e.
R ^c and R ^d are each independently a hydrogen atom or a methyl group, and R ^e is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, _{-CHO, -CH 2 CHO, -CO-} CH = CH 2, a monovalent group represented by _{-CO-C (CH 3) =} CH 2 or _-CH 2 COOR ^{f, R f} is hydrogen or C It is an alkyl group of formula 1-5. In R ^a , R ^{a ′} , R ^b , R ^e and R ^f , each of the alkyl group, alkenyl group, aralkyl group and aryl group may have a substituent.
s is an integer of 1 to 18, t is an integer of 1 to 5, and u is an integer of 1 to 18. )

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

  The alkenyl group having 2 to 18 carbon atoms may be linear, branched or cyclic. Examples of such alkenyl groups include vinyl groups, allyl groups, propenyl groups, various butenyl groups, various hexenyl groups, various octenyl groups, various decenyl groups, various dodecenyl groups, various tetradecenyl groups, various hexadecenyl groups, various octadecenyl groups, A cyclopentenyl group, a cyclohexenyl group, a cyclooctenyl group, etc. can be mentioned. The position of the double bond of the alkenyl group is not limited, but from the viewpoint of the reactivity of the polymer obtained, it is preferable that there is a double bond at the terminal of the alkenyl group.

When R ^a and / or R ^{a ′} is —O—R ^{a ″} , it is an acidic phosphate ester. The R ^{a ″} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, A monovalent group represented by an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _a —R ^e , or — [(CH ₂ ) _b —O] _c —R ⁸ ; is there.
The alkyl group having 1 to 18 carbon atoms, the aralkyl group, and the aryl group are as described above for R ⁵ , and the alkenyl group having 2 to 18 carbon atoms are as described above for R ^a and R ^{a ′.} It is. In addition, when R ^{a ″} has an aromatic ring, it may have an appropriate substituent on the aromatic ring, such as a linear or branched alkyl group having 1 to 4 carbon atoms.

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

In the general formula (III), R ^b is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —. _O] a ^-R _e, - it shows a _{[(CH 2) b -O]} c -R e , or -O-R ^{b '.} In addition, when ^Rb has an aromatic ring, it may have an appropriate substituent on the aromatic ring, for example, a linear or branched alkyl group having 1 to 4 carbon atoms.
The alkyl group having 1 to 18 carbon atoms, the aralkyl group, and the aryl group are as described above for R ⁵ , and the alkenyl group having 2 to 18 carbon atoms are as described above for R ^a and R ^{a ′.} It is.
When R ^b is —O—R ^{b ′} , it is an acidic sulfate ester. R ^{b ′} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e. Or a monovalent group represented by — [(CH ₂ ) _t —O] _u —R ^e .
The alkyl group having 1 to 18 carbon atoms, the aralkyl group, and the aryl group are as described above for R ⁵ , and the alkenyl group having 2 to 18 carbon atoms are as described above for R ^a and R ^{a ′.} It is. When R ^{b ′} has an aromatic ring, it may have an appropriate substituent on the aromatic ring, for example, a linear or branched alkyl group having 1 to 4 carbon atoms.
The above R ^c , R ^d and R ^e are the same as described above.
In said ^Rb and ^{Rb '} , s is an integer of 1-18, t is an integer of 1-5, u is an integer of 1-18. Preferred s, t, and u are the same as R ^a , R ^{a ′,} and R ^{a ″} above.

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

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

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

In addition, from the viewpoint of heat resistance and chemical resistance, particularly alkali resistance, organic acid compounds represented by the above general formula (II) and general formula (III) include carbon (P), sulfur (S), and carbon. A compound in which atoms are directly bonded is preferable, and R ^a and R ^{a ′} each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl A monovalent group represented by a group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — [(CH ₂ ) _t —O] _u —R ^e , R ^a and Any of R ^{a ′} preferably contains a carbon atom. R ^b is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e. , — [(CH ₂ ) _t —O] _u —R ^e is preferably a monovalent group.
From the viewpoint of pigment dispersibility, heat resistance, chemical resistance, and alkali resistance, a compound in which an aryl group is directly bonded to phosphorus (P) or sulfur (S) is particularly preferable, and R ^a and R ^a It is preferable that either R ^′ or R ^b is an aryl group which may have a substituent.

The organic acid compound represented by the above general formula (II) and general formula ^{(III), R} a, R ^{a 'and} / or R ^a'', and / or as ^{R b} and / or R ^b' Has a polymerizable group, that is, a vinyl group, an allyl group, or — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , or — [(CH ₂ ) _t —O] _u. It is preferable that -R ^e and R ^e is -CO-CH = CH ₂ or -CO-C (CH ₃ ) = CH ₂ , especially R ^a , R ^{a ′} and / or R ^{a ′. '} And / or R ^b and / or R ^b' are preferably vinyl, allyl, 2-methacryloyloxyethyl, or 2-acryloyloxyethyl.
In such a case, the above-mentioned polymerizable groups and / or the above-mentioned polymerizable groups and the color of the present invention are exposed during exposure when a colored layer is formed using the red photosensitive resin composition for a color filter of the present invention. It is possible to easily polymerize an alkali-soluble resin, a polyfunctional monomer, and the like contained in a red photosensitive resin composition for a filter, and that the pigment dispersant is stably present in a colored layer of a color filter. Make it possible. 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 red 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.

The content of the organic acid compound in the graft copolymer used in the present invention is not particularly limited as long as good dispersion stability is exhibited. The amount is preferably 0.05 to 1.0 molar equivalent.
Especially, it is preferable that content of this organic acid compound is 0.2-0.8 molar equivalent with respect to the said amino group. In this way, a part of a predetermined amount with respect to the amino group is salt-formed, and a part of the predetermined amount remains in the graft copolymer as an amino group. The interaction with the derivative is enhanced, and the pigment dispersibility and the pigment dispersion stability are further improved. Moreover, there is an effect of suppressing an increase in the viscosity of the pigment dispersant or the resin composition, or rather reducing the viscosity.
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.

In the pigment dispersion of the present invention and the red photosensitive resin composition for a color filter, as described above, as a pigment dispersant, a monomer having an ethylenically unsaturated double bond and an amino group, a polymer chain, and its A graft copolymer containing a macromonomer composed of a group having an ethylenically unsaturated double bond at the end as a copolymerization component, and the amino group of the nitrogen-containing monomer and an organic acid compound form a salt A salt-type graft copolymer is used.
By using such a salt-type graft copolymer as a pigment dispersant, the pigment dispersion for a color filter of the present invention and the red photosensitive resin composition for a color filter are excellent in pigment dispersion stability. can do.

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

In the pigment dispersion for the color filter and the red photosensitive resin composition for the color filter of the present invention, as the pigment dispersant, the salt-type graft copolymer may be used alone or in combination of two or more. The content thereof may be appropriately selected according to the type of pigment used, the solid content concentration of the photosensitive resin composition, and the like. In the pigment dispersion for a color filter and the red photosensitive resin composition for a color filter of the present invention, the pigment dispersant is usually in the range of 5 to 200 parts by mass with respect to 100 parts by mass of the pigment. 100 parts by mass is preferable, and 20 to 80 parts by mass is more preferable. If the content of the salt-type graft copolymer is within the above range, the pigment can be uniformly dispersed. Moreover, in the photosensitive resin composition, a colored layer having sufficient hardness can be formed without relatively reducing the blending ratio of the alkali-soluble resin and the polyfunctional monomer.
In the present invention, the pigment used when the content other than the pigment derivative is defined includes a pigment derivative in addition to the pigment, 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 pigment surface, so that the surface of the pigment has polarity, 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 and red pigments. The phthalimide alkylated derivative of the pigment is preferably used because it suppresses the aggregation of the pigment and makes it easy to achieve particularly 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. The number of substitutions of the phthalimidoalkyl group is preferably 1 to 2, and is preferably 1 from the viewpoint that both easy adsorption of the pigment and improvement in heat resistance can be achieved.

  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.

(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. . In the present invention, C.I. I. Pigment dispersibility and dispersion stability are improved even if it does not contain a diketopyrrolopyrrole pigment such as CI Pigment Red 254 or does not contain a yellow pigment which is a raw material of the sulfonated derivative of the yellow pigment. It becomes.

  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 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 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. Pigment red 265, C.I. I. Pigment red 270, C.I. I. And CI Pigment Red 272.

(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, and may have the effect of stabilizing the dispersion or reducing the dispersant due to the dispersion stabilizing effect.
Moreover, as long as the effect of this invention is not impaired, the other pigment dispersant may be included.
Other components include, for example, surfactants for improving wettability, silane coupling agents for improving adhesion, antifoaming agents, repellency inhibitors, antioxidants, anti-aggregation agents, and UV absorbers. Etc.

<Method for producing pigment dispersion>
The method for producing a pigment dispersion for a color filter according to the present invention includes a monomer having the ethylenically unsaturated double bond and an amino group in the solvent, a polymer chain, and an ethylenically unsaturated double bond at the terminal thereof. A graft copolymer containing a macromonomer containing a group as a copolymerization component, and further comprising at least a part of an amino group derived from a monomer having an ethylenically unsaturated double bond and an amino group, and an organic acid compound A step of dispersing the red pigment having an anthraquinone skeleton in the presence of a pigment dispersant which is a graft copolymer formed with a salt and a sulfonated derivative of the yellow 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, or a bead mill such as a continuous annular type bead mill. 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 0.05 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 0.1-5.0 micrometers membrane filter after dispersion | distribution.

In the present invention, the dispersion time for dispersion using a known disperser is appropriately adjusted and is not particularly limited. 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 3 to 8 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 suitably used as a preliminary preparation for preparing the red photosensitive resin composition for a color filter according to the present invention having excellent pigment dispersibility.
In other words, the pigment dispersion is a pigment composition having a high ratio (prepared in the composition / solid content other than the pigment in the composition) that is preliminarily prepared in the stage before preparing the photosensitive resin composition described later. It is. Specifically, the ratio of (pigment content in composition / solid content other than pigment in composition) is usually 1.0 or more. By mixing the pigment dispersion and at least the binder component, a red resin composition for a color filter having excellent pigment dispersibility can be prepared.

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. Moreover, it is excellent also in alkali developability.
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, another pigment 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 the chromaticity required for use and specifications in a color filter, and other yellow pigments and other red pigments as long as the effects of the present invention are not impaired. Further, other pigments such as orange may be contained.
Examples of other pigments include the same pigments as those described in the red pigment dispersion for color filters of the present invention. Among them, it is preferable that other pigments 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. Specific examples of the pigment pigment of CI Pigment Yellow 150 include mono-, di-, tri-, and tetra-azo compounds of the azo compound according to the following chemical formula (6) or one of its tautomeric structures that serve as a host of at least one guest compound. Anions and metals Li, Cs, Mg, Cd, Co, Al, Cr, Sn, Pb, particularly preferably metals corresponding to Na, K, Ca, Sr, Ba, Zn, Fe, Ni, Cu, Mn and La Mention may be made of complexes.

(In the above chemical formula (6), R ^g and R ^g ′ are independently —OH, —NH ₂ , —NH—CN, an acylamino group or an arylamino group, and R ^h and R ^h ′ are Independently —OH or —NH _2. )

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

(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 re-solubility.

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

  The copolymerization ratio of the carboxyl group-containing ethylenically unsaturated monomer in the carboxyl group-containing copolymer is usually 5 to 50% by 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 in the range of 1,000 to 500,000, more preferably 3,000 to 200,000. If it is less than 1,000, the binder function after curing is remarkably lowered, and if it exceeds 500,000, pattern formation may be difficult during development with an alkaline developer.

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

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

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

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

  Of these polyfunctional monomers, poly (meth) acrylates of polyhydric alcohols having three or more valences and their dicarboxylic acid-modified products are preferable. Specifically, trimethylolpropane tri (meth) acrylate, pentaerythritol tris. Succinic acid modified product of (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol penta (meth) ) Succinic acid modified products of 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, sensitizer, etc. 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 (for example, radical polymerization or cationic polymerization) of the polymer having photopolymerization or the photopolymerization monomer 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 5-5. 60 parts 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 of the present invention, other pigments such as a yellow pigment can be further used as a pigment from the viewpoint of adjusting the chromaticity of the colored layer. 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 red photosensitive resin composition for color filters. If the amount of the pigment is too small, there is a possibility that the transmission density when the photosensitive resin composition is applied to a predetermined film thickness (for example, 1.0 to 3.0 μm) may not be sufficient. There is a possibility that the properties as a coating film such as adhesion to the substrate when the resin composition is applied and cured on the substrate, surface roughness of the cured film, and coating film hardness may be insufficient, and its photosensitivity. Since the ratio of the amount of the dispersant used for dispersing the pigment in the resin composition increases, characteristics such as developability and heat resistance may be insufficient. In addition, in this invention, solid content is all things other than the solvent mentioned above, and the polyfunctional monomer etc. which are melt | dissolving in the solvent are also contained.
Further, the total content of the pigment dispersant is preferably in the range of 1 to 60% by 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, , There is a risk of lowering curability and developability.
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)
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 a pigment dispersant. Preparing a dispersion;
A step of mixing the red pigment dispersion and a photosensitive binder component, wherein the pigment dispersant is composed of a monomer having an ethylenically unsaturated double bond and an amino group, a polymer chain, and an ethylenic group at its end. A graft copolymer containing, as a copolymerization component, a macromonomer containing a group having an unsaturated double bond, and further comprising at least one amino group derived from a monomer having an ethylenically unsaturated double bond and an amino group It is a graft copolymer in which a part and an organic acid compound form a salt.

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 by curing 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 by curing the above-described red photosensitive resin composition for a color filter of the present invention, and is usually a transparent substrate described later. Depending on the type of pigment formed in the opening of the light-shielding part and contained in the red photosensitive resin composition for color filter, it is composed of a coloring pattern of three or more colors.
In addition, the arrangement of the colored layers is not particularly limited, and for example, a general arrangement such as a stripe type, a mosaic type, a triangle type, or a four-pixel arrangement type can be used. Moreover, the width | variety, area, etc. of a colored layer can be set arbitrarily.
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 3 μm in the case where a black colorant is dispersed or dissolved in a binder resin. Is set.

(Transparent substrate)
The transparent substrate in the color filter of the present invention is not particularly limited as long as it is a base material transparent to visible light, and a transparent substrate used for a general color filter can be used. Specific examples include inflexible transparent rigid materials such as quartz glass, alkali-free glass, and synthetic quartz plates, or transparent flexible materials having flexibility such as transparent resin films and optical resin plates. It is done.
Although the thickness of the said transparent substrate is not specifically limited, According to the use of the color filter of this invention, the thing of about 100 micrometers-1 mm can be used, for example.
The color filter of the present invention may be one in which, for example, an overcoat layer, a transparent electrode layer, an alignment film, a columnar spacer, or the like is formed in addition to the transparent substrate, the light shielding portion, and the colored layer. .

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

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

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

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 further in detail, this invention is not limited at all by these examples.

  As yellow pigment sulfonated derivatives, yellow pigment sulfonated derivatives A to C represented by the following formula (7) and having different substituents X were used.

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

(Production Example 2 Synthesis of Yellow Pigment Sulfonated Derivative B (Formula X = SO ₂ NHC ₂ H ₄ COOH))
62.46 parts by mass of Pigment Yellow 138 was added to 374.75 parts by mass of chlorosulfuric acid. Then, after 2 hours at 120 ° C., 38.75 parts by mass of thionyl chloride was added dropwise at 75 ° C. Then, it stirred at 80 degreeC for 3 hours.
The reaction solution was added to 1093 parts by mass of ice water while cooling to 3 ° C. or lower. Further, 1300 parts by mass of ice was added and stirred for 15 minutes, and the precipitate was filtered. The obtained wet cake was washed with 660 parts by mass of ice water while cooling with ice. After 11.77 parts by mass of sodium hydroxide, 23.92 parts by mass of water and 24.30 parts by mass of β-alanine were mixed, 259.78 parts by mass of ice water was added, and a wet cake was added while maintaining the temperature at 5 ° C or lower. After stirring at 5 ° C or lower for 1 hour, the mixture was stirred at 25 ° C for 30 minutes, then at 50 ° C for 30 minutes, and further at 70 ° C for 30 minutes. After allowing to cool, 10% hydrochloric acid was added to adjust to pH 2. The precipitate was filtered and washed twice with 560 parts by mass of water. Vacuum drying at 80 ° C. gave a yellow pigment sulfonated derivative B. The molecular weight of the target product was confirmed by TOF-MS.

(- Synthesis of _{N (CH 3) 2 (C} 18 H 37) 2 +) Production Example 3 yellow pigment sulfonated derivative C (the formula _X ⁼ SO ₃₎
While cooling 374.76 parts by mass of 11% fuming sulfuric acid to 10 ° C., 74.96 parts by mass of Pigment Yellow 138 was added. Subsequently, it stirred at 90 degreeC for 6 hours.
The reaction solution was added to 1600 parts by mass of ice water and stirred for 15 minutes, and then the precipitate was filtered. The obtained wet cake was washed three times with 800 parts by mass of water. 600 parts by weight of water was added to the wet cake and stirred at 60 ° C. for 1 hour. 55.60 parts by mass of distearyl ammonium chloride was added, and the mixture was stirred at 60 ° C. for 1 hour. The precipitate was filtered and washed twice with 600 parts by mass of water. It was vacuum dried at 80 ° C. to obtain a yellow pigment sulfonated derivative C. The molecular weight of the target product was confirmed by TOF-MS.

(Production Example 4 Synthesis of Red Pigment Sulfonated Derivative A)
300.0 parts by mass of 20% fuming sulfuric acid was stirred while being cooled to 10 ° C., and 30.0 parts by mass of Pigment Red 254 was added. Subsequently, it stirred at 63 degreeC for 6 hours.
The reaction solution was added to 3000 parts by mass of ice water and stirred for 15 minutes, and then the precipitate was filtered. The obtained wet cake was washed with 2000 parts by mass of water and filtered. It was vacuum dried at 80 ° C. to obtain a red pigment sulfonated derivative A represented by the following chemical formula (9) (n = 1). The molecular weight of the target product was confirmed by TOF-MS.

(Production Example 5 Synthesis of Binder Resin A)
A polymerization tank was charged with 130 parts by mass of diethylene glycol ethyl methyl ether (EMDG) as a solvent, heated to 110 ° C. in a nitrogen atmosphere, and then 32 parts by mass of methyl methacrylate (MMA) and 22 parts by mass of cyclohexyl methacrylate (CHMA). , 24 parts by weight of methacrylic acid (MAA), 2 parts by weight of α, α′-azobisisobutyronitrile (AIBN) as an initiator, and 4.5 parts by weight of n-dodecyl mercaptan as a chain transfer agent, It was dripped continuously over 1.5 hours.
Thereafter, the reaction was continued while maintaining the synthesis temperature, and 0.05 parts by mass of p-methoxyphenol was added as a polymerization inhibitor 2 hours after the completion of the dropping.
Next, 22 parts by mass of glycidyl methacrylate (GMA) was added while blowing air, the temperature was raised to 110 ° C., 0.2 parts by mass of triethylamine was added, and an addition reaction was carried out at 110 ° C. for 15 hours to obtain a binder. Resin A (solid content: 44% by mass) was obtained.
The obtained binder resin A had a mass average molecular weight of 8,500 and an acid value of 85 mgKOH / g. The mass average molecular weight was calculated by gel permeation chromatography (GPC) using polystyrene as a standard substance and THF as an eluent, and the acid value was measured according to JIS-K0070.

(Production Example 6 Synthesis of Macromonomer MM-1)
A reactor equipped with a condenser, addition funnel, nitrogen inlet, mechanical stirrer, and digital thermometer was charged with 80.0 parts by mass of propylene glycol methyl ether acetate (abbreviated as PGMEA), and the temperature was maintained while stirring under a nitrogen stream. Warmed to 90 ° C. Methyl methacrylate 50.0 parts by mass, methacrylate-n-butyl 30.0 parts by mass, benzyl methacrylate 20.0 parts by mass, mercaptoethanol 4.0 parts by mass, PGMEA 30 parts by mass, α, α'-azobisiso A mixed solution of 1.0 part by mass of butyronitrile (abbreviation AIBN) was added dropwise over 1.5 hours, and the reaction was further continued for 3 hours. Next, the nitrogen stream was stopped, the reaction solution was cooled to 80 ° C., Karenz MOI (manufactured by Showa Denko KK) 8.74 parts by mass, dibutyltin dilaurate 0.125 parts by mass, p-methoxyphenol 0.125 mass parts and 10 mass parts of PGMEA were added and it stirred for 3 hours, and the 49.5 mass% solution (Tg = 64 degreeC) of macromonomer MM-1 was obtained. When the obtained macromonomer MM-1 was confirmed by GPC (gel permeation chromatography) under the conditions of N-methylpyrrolidone, 0.01 mol / L lithium bromide added / polystyrene standard, the mass average molecular weight (Mw 4010, number average molecular weight (Mn) 1910, molecular weight distribution (Mw / Mn) was 2.10.

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

(Production Example 8 Synthesis of Graft Copolymer GP-1)
A reactor equipped with a condenser, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer was charged with 80.0 parts by mass of PGMEA and heated to 85 ° C. while stirring under a nitrogen stream. Macromonomer MM-1 solution 75.76 parts by mass (effective solid content 37.5 parts by mass), 2- (dimethylamino) ethyl methacrylate (abbreviation DMA) 12.5 parts by mass, n-dodecyl mercaptan 1 in Production Example 6 A mixed solution mixed solution of 24 parts by mass, 20.0 parts by mass of PGMEA, and 0.5 parts by mass of AIBN was dropped over 1.5 hours, and the mixture was heated and stirred for 3 hours, then 0.10 parts by mass of AIBN and 10.0 parts by mass of PGMEA The mixed solution was added dropwise over 10 minutes, and further aged at the same temperature for 1 hour to obtain a 25.8 mass% solution of graft copolymer GP-1. As a result of GPC measurement, the obtained graft copolymer GP-1 had a mass average molecular weight (Mw) of 11480, a number average molecular weight (Mn) of 4650, and a molecular weight distribution (Mw / Mn) of 2.47. The amine value was 89 mgKOH / g.

(Production Example 9 Synthesis of Graft Copolymer GP-2)
A reactor equipped with a condenser, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer was charged with 80.0 parts by mass of PGMEA and heated to 85 ° C. while stirring under a nitrogen stream. Macromonomer MM-2 solution 75.30 parts by mass (effective solid content 37.5 parts by mass), DMA 12.5 parts by mass, n-dodecyl mercaptan 1.24 parts by mass, PGMEA 20.0 parts by mass, AIBN 0. After 5 parts by mass of the mixed solution mixed solution was added dropwise over 1.5 hours and heated and stirred for 3 hours, a mixed solution of 0.10 parts by mass of AIBN and 10.0 parts by mass of PGMEA was added dropwise over 10 minutes. Was then aged for 1 hour to obtain a 26.0 mass% solution of graft copolymer GP-2. As a result of GPC measurement, the obtained graft copolymer GP-2 had a mass average molecular weight (Mw) of 11230, a number average molecular weight (Mn) of 4350, and a molecular weight distribution (Mw / Mn) of 2.58. The amine value was 90 mgKOH / g.

(Production Example 10 Synthesis of Graft Copolymer GP-3)
A reactor equipped with a condenser, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer was charged with 80.0 parts by mass of PGMEA and heated to 85 ° C. while stirring under a nitrogen stream. 70.51 parts by mass of macromonomer MM-1 solution of Production Example 6 (effective solid content 25.0 parts by mass), 17.86 parts by mass of Plaxel FA-10L (manufactured by Daicel Chemical Industries, Ltd., hydroxyethyl acrylate 10 mol of caprolactone 10 mol) % Solution effective solid content 12.5 parts by mass), DMA 12.5 parts by mass, n-dodecyl mercaptan 1.24 parts by mass, PGMEA 30.0 parts by mass, AIBN 0.5 parts by mass over 1.5 hours After 3 hours of heating and stirring, a mixture of AIBN 0.10 parts by mass and PGMEA 10.0 parts by mass was added dropwise over 10 minutes, and further aged at the same temperature for 1 hour, so that the graft copolymer GP- 3 of 26.4% by weight was obtained. As a result of GPC measurement, the obtained graft copolymer GP-3 had a mass average molecular weight (Mw) of 12760, a number average molecular weight (Mn) of 4810, and a molecular weight distribution (Mw / Mn) of 2.65. The amine value was 90 mgKOH / g.

(Production Example 11 Synthesis of Graft Copolymer GP-4)
A reactor equipped with a condenser, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer was charged with 80.0 parts by mass of PGMEA and heated to 85 ° C. while stirring under a nitrogen stream. 75.76 parts by mass of macromonomer MM-1 solution of Production Example 6 (effective solid content 37.5 parts by mass), 12.5 parts by mass of dimethylaminopropylacrylamide (abbreviation DMAPAA, manufactured by Kojin Co., Ltd.), n- A mixed solution of 1.24 parts by mass of dodecyl mercaptan, 20.0 parts by mass of PGMEA, and 0.5 parts by mass of AIBN was added dropwise over 1.5 hours, followed by heating and stirring for 3 hours, and then 0.10 parts by mass of AIBN and 10.0 parts of PGMEA. A mixed solution of parts by mass was added dropwise over 10 minutes, and further aged at the same temperature for 1 hour, thereby obtaining a 25.6% by mass solution of the graft copolymer GP-4. As a result of GPC measurement, the obtained graft copolymer GP-4 had a mass average molecular weight (Mw) of 11150, a number average molecular weight (Mn) of 4620, and a molecular weight distribution (Mw / Mn) of 2.41. The amine value was 89 mgKOH / g.

(Production Example 12 Preparation of Dispersant Solution A)
In a 225 mL mayonnaise bottle, 28.90 parts by mass of PGMEA and 68.86 parts by mass of the graft copolymer GP-1 solution of Production Example 8 (effective solid content of 17.8 parts by mass) were dissolved, respectively, and phenylphosphonic acid (trade name) : PPA, manufactured by Nissan Chemical Co., Ltd.) 2.23 parts by mass (0.5 molar equivalent to the tertiary amino group of the graft copolymer) was added, and the mixture was stirred at room temperature for 30 minutes, thereby dispersing agent solution A (solid content 20% by mass) was prepared. The acid value of the resulting dispersant solution A was 79 mgKOH / g.
At this time, the amino group of the graft copolymer GP-1 is salt-formed by an acid / base reaction with the phosphonic acid group of PPA.

(Production Example 13 Preparation of Dispersant Solution B)
In a 225 mL mayonnaise bottle, 28.32 parts by mass of PGMEA and 69.65 parts by mass of the graft copolymer GP-1 solution of Production Example 8 (effective solid content 18.0 parts by mass) were dissolved, respectively, and phenylphosphinic acid (Tokyo Kasei) 2.03 parts by mass (0.5 mol equivalent to the tertiary amino group of the graft copolymer) was added, and the mixture was stirred at room temperature for 30 minutes to obtain Dispersant Solution B (solid content 20% by mass). Prepared. The acid value of Dispersant Solution B obtained was 41 mg KOH / g.
At this time, the amino group of the graft copolymer GP-1 is salt-formed by an acid / base reaction with the phosphinic acid group of phenylphosphinic acid.

(Production Example 14 Preparation of Dispersant Solution C)
In a 225 mL mayonnaise bottle, 29.43 parts by mass of PGMEA and 68.33 parts by mass of the graft copolymer GP-2 solution of Production Example 9 (effective solid content 17.8 parts by mass) were dissolved, respectively, and 2.23 parts by mass of PPA ( Dispersant solution C (solid content 20% by mass) was prepared by adding 0.5 molar equivalent) to the tertiary amino group of the graft copolymer and stirring at room temperature for 30 minutes. The acid value of Dispersant Solution C obtained was 79 mgKOH / g.
At this time, the amino group of the graft copolymer GP-2 is salt-formed by an acid / base reaction with the phosphonic acid group of PPA.

(Production Example 15 Preparation of Dispersant Solution D)
In a 225 mL mayonnaise bottle, 30.47 parts by mass of PGMEA and 67.30 parts by mass of the graft copolymer GP-3 solution of Production Example 10 (effective solid content of 17.8 parts by mass) were respectively dissolved, and 2.23 parts by mass of PPA ( Dispersant solution D (solid content 20% by mass) was prepared by adding 0.5 molar equivalent) to the tertiary amino group of the graft copolymer and stirring at room temperature for 30 minutes. The acid value of the resulting dispersant solution D was 80 mgKOH / g.
At this time, the amino group of the graft copolymer GP-3 is salt-formed by an acid / base reaction with the phosphonic acid group of PPA.

(Production Example 16 Preparation of Dispersant Solution E)
In a 225 mL mayonnaise bottle, 28.40 parts by mass of PGMEA and 69.35 parts by mass of the graft copolymer GP-4 solution of Production Example 11 (17.75 parts by mass of effective solid content) were dissolved, respectively, and phenylphosphonic acid (trade name) : PPA, manufactured by Nissan Chemical Co., Ltd.) 2.25 parts by mass (0.5 molar equivalent based on the tertiary amino group of the graft copolymer) and stirred at room temperature for 30 minutes to disperse solution E (solid content) 20% by mass) was prepared. The acid value of the resulting dispersant solution E was 80 mgKOH / g.
At this time, the amino group of the graft copolymer GP-4 is salt-formed by an acid / base reaction with the phosphonic acid group of PPA.

(Production Example 17 Preparation of Dispersant Solution F)
In a 200 mL flask equipped with a condenser, 27.74 parts by mass of PGMEA and 70.43 parts by mass of the graft copolymer GP-1 solution of Production Example 8 (effective solid content: 18.2 parts by mass) were dissolved, respectively. (Kanto Chemical Co., Inc.) 1.83 parts by mass (0.5 molar equivalent to the tertiary amino group of the graft copolymer) was added and reacted at 80 ° C. for 6 hours to obtain a dispersant solution F (solid content of 20 % By weight) was prepared. The acid value of the obtained dispersant solution F was 0 mgKOH / g.
At this time, the amino group of the graft copolymer GP-1 is salt-formed by a quaternization reaction with benzyl chloride.

Example 1
(1) Preparation of red pigment dispersion liquid A for color filter C.I. is a red pigment having an anthraquinone skeleton as a colorant component. I. Pigment Red 177 (PR177: average primary particle size 10 to 40 nm) 9.50 parts by mass, 0.50 parts by mass of the yellow pigment sulfonated derivative A obtained in Production Example 1, and dispersant solution A30.00 prepared in Production Example 12 Part by mass, 4.55 parts by mass of binder resin A of Production Example 5 and 55.45 parts by mass of PGMEA were mixed, and 1 hour with 2 mm zirconia beads and 3 hours with 0.1 mm zirconia beads on a paint shaker (manufactured by Asada Tekko Co., Ltd.) Dispersion was carried out to obtain a red pigment dispersion A. The bead filling rate during dispersion was 50%.

(2) Preparation of Red Photosensitive Resin Composition A for Color Filter To 52.76 parts by mass of the red pigment dispersion A of Example 1 obtained above, 18.76 parts by mass of the following binder composition and 28.48 parts by mass of PGMEA , Surfactant R08MH (manufactured by DIC) 0.02 parts by mass, silane coupling agent KBM503 (manufactured by Shin-Etsu Silicone) 0.20 parts by mass, mixed under pressure, filtered under pressure, and red photosensitive resin composition for color filter Product A was obtained.
<Binder composition (solid content 40%)>
Alkali-soluble resin (Binder resin A of Production Example 5, solid content 44% by mass): 23.18 parts by mass 3 to 4 functional acrylate monomer (trade name: Aronix M305, manufactured by Toagosei Co., Ltd.): 23.80 Mass parts / photopolymerization initiator (2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name: Irgacure 907, manufactured by Ciba Specialty Chemicals)) : 1.80 parts by mass-photopolymerization initiator (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone (trade name Irgacure 369, manufactured by Ciba Specialty Chemicals) ): 4.2 parts by mass / solvent (PGMEA): 47.02 parts by mass

(Examples 2 and 3)
(1) Preparation of red pigment dispersions B and C for color filters In Example 1 (1), yellow pigment sulfonated derivatives B and C obtained in Production Examples 2 and 3 were used instead of yellow pigment sulfonated derivative A. Except that it was used, red pigment dispersions B and C for color filters were obtained in the same manner as in Example 1 (1).

(2) Preparation of red photosensitive resin compositions B and C for color filters In Example 1 (2), instead of the red pigment dispersion A for color filters, the red pigment for color filters obtained in (1) above Except for using the dispersions B and C, red photosensitive resin compositions B and C for color filters were obtained in the same manner as in Example 1 (2).

(Examples 4 to 7)
(1) Preparation of red pigment dispersions D to G for color filters In Example 1 (1), the dispersant solutions B to E prepared in Production Examples 13 to 16 were used instead of the dispersant solution A. In the same manner as in Example 1 (1), red pigment dispersions D to G for color filters were obtained.

(2) Preparation of red photosensitive resin compositions D to G for color filter In Example 1 (2), instead of red pigment dispersion A for color filter, the red pigment for color filter obtained in (1) above Except having used dispersion liquid DG, it carried out similarly to Example 1 (2), and obtained red photosensitive resin composition DG for color filters.

(Comparative Example 1)
(1) Preparation of Red Pigment Dispersion Liquid H for Color Filter In Example 1 (1), a yellow pigment sulfonated derivative was not included as a color material component, and C.I. I. A red pigment dispersion H for color filters was obtained in the same manner as in Example 1 (1) except that 10.00 parts by mass of Pigment Red 177 was used.

(2) Preparation of red photosensitive resin composition H for color filter In Example 1 (2), instead of the red pigment dispersion A for color filters, the red pigment dispersion for color filters obtained in (1) above A red photosensitive resin composition H for color filters was obtained in the same manner as in Example 1 (2) except that H was used.

(Comparative Example 2)
(1) Preparation of red pigment dispersion liquid I for color filter In Example 1 (1), the procedure was carried out except that the red pigment sulfonated derivative A obtained in Production Example 4 was used instead of the yellow pigment sulfonated derivative A. In the same manner as in Example 1 (1), a red pigment dispersion I for color filters was obtained.

(2) Preparation of red photosensitive resin composition I for color filter In Example 1 (2), instead of the red pigment dispersion A for color filters, the red pigment dispersion for color filters obtained in (1) above A red photosensitive resin composition I for color filters was obtained in the same manner as in Example 1 (2) except that I was used.

(Comparative Example 3)
(1) Preparation of Red Pigment Dispersion Liquid J for Color Filter In Example 1 (1), 23.26 parts by mass of the graft copolymer GP-1 solution prepared in Production Example 8 instead of the dispersant solution A, PGMEA 62. A red pigment dispersion liquid J for color filters was obtained in the same manner as in Example 1 (1) except that the amount was 20 parts by mass.

(2) Preparation of red photosensitive resin composition J for color filter In Example 1 (2), instead of the red pigment dispersion A for color filters, the red pigment dispersion for color filters obtained in (1) above A red photosensitive resin composition J for color filters was obtained in the same manner as in Example 1 (2) except that J was used.

(Comparative Example 4)
(1) Preparation of Red Pigment Dispersion Liquid K for Color Filter Example 1 (1) except that in Example 1 (1), Dispersant Solution F prepared in Production Example 17 was used instead of Dispersant Solution A. In the same manner as above, a red pigment dispersion K for color filters was obtained.

(2) Preparation of red photosensitive resin composition K for color filter In Example 1 (2), instead of the red pigment dispersion A for color filters, the red pigment dispersion for color filters obtained in (1) above A red photosensitive resin composition K for color filters was obtained in the same manner as in Example 1 (2) except that K was used.

(Comparative Example 5)
(1) Preparation of Red Pigment Dispersion Liquid L for Color Filter In Example 1 (1), instead of the dispersant solution A, a commercially available dispersant that does not form a salt with an organic acid compound “Ajisper PB821” (Ajinomoto Fine Techno Co., Ltd.) The red pigment dispersion L for color filters was obtained in the same manner as in Example 1 (1) except that 6.00 parts by mass and PGMEA 79.45 parts by mass were obtained.

(2) Preparation of red photosensitive resin composition L for color filter In Example 1 (2), instead of the red pigment dispersion A for color filters, the red pigment dispersion for color filters obtained in (1) above Except having used L, it carried out similarly to Example 1 (2), and obtained the red photosensitive resin composition L for color filters.

(Comparative Example 6)
(1) Preparation of Red Pigment Dispersion Liquid M for Color Filter In Example 1 (1), instead of the dispersant solution A, a commercially available dispersant “BYK-LPN6919” that does not form a salt with an organic acid compound (BIC Chemie) (Manufactured, solid content concentration 60 mass%) A red pigment dispersion M for color filters was obtained in the same manner as in Example 1 except that 10.00 mass parts and PGMEA were changed to 75.45 mass parts.

(2) Preparation of red photosensitive resin composition M for color filter In Example 1 (2), instead of the red pigment dispersion A for color filters, the red pigment dispersion for color filters obtained in (1) above. A red photosensitive resin composition M for color filters was obtained in the same manner as in Example 1 (2) except that M was used.

(Comparative Example 7)
(1) Preparation of Red Pigment Dispersion Liquid N for Color Filter In Example 1 (1), instead of the dispersant solution A, a commercially available dispersant “DISPERBYK-166” (by Big Chemie, solid content concentration 29.5% by mass) ) 14.12 parts by mass, “DISPERBYK-111” (by Big Chemie, solid content concentration: 95% by mass) 1.93 parts by mass, PGMEA was the same as Example 1 (1) except that PGMEA was 69.40 parts by mass. Thus, a red pigment dispersion N for color filters was obtained.

(2) Preparation of red photosensitive resin composition N for color filter In Example 1 (2), instead of the red pigment dispersion A for color filters, the red pigment dispersion for color filters obtained in (1) above A red photosensitive resin composition N for color filters was obtained in the same manner as in Example 1 (2) except that N was used.

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

<Optical performance (chromaticity, brightness, contrast)>
The red photosensitive resin composition for a color filter obtained in each example and comparative example was applied on a glass substrate having a thickness of 0.7 mm (“OA-10G” manufactured by Nippon Electric Glass Co., Ltd.) using a spin coater. did. Then, it heat-dried for 3 minutes on an 80 degreeC hotplate. A cured film (red colored layer) was obtained by irradiating ultraviolet rays of 30 mJ / cm ² using an ultrahigh pressure mercury lamp. The film thickness after drying and curing was adjusted so that the target chromaticity x = 0.640. The glass plate on which the colored layer was formed was post-baked in a clean oven at 230 ° C. for 30 minutes, and the contrast, chromaticity (x, y) and luminance (Y) of the obtained colored substrate were measured. Contrast was measured using “Contrast measuring device CT-1B” manufactured by Aisaka Electric Co., Ltd., and chromaticity and luminance were measured using “Microspectroscopy measuring device OSP-SP200” manufactured by Olympus.
The results are shown in Table 2.

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

<Alkali developability>
The red photosensitive resin composition for a color filter obtained in each example and comparative example was applied on a glass substrate having a thickness of 0.7 mm using a spin coater. Then, it heat-dried for 3 minutes on an 80 degreeC hotplate. This colored layer was irradiated with ultraviolet rays of 30 mJ / cm ² through a photomask using an ultrahigh pressure mercury lamp. Thereafter, the glass plate on which the colored layer has been formed is shower-developed using a 0.05% by weight aqueous potassium hydroxide solution as an alkaline developer, and the time until the glass surface where the colored layer is formed appears is developed. Measured as time. If development was not possible even after development for 5 minutes or longer, development was prohibited.
The results are shown in Table 2.

<Alkali resistance evaluation>
The red photosensitive resin composition for a color filter obtained in each example and comparative example was applied on a glass substrate having a thickness of 0.7 mm using a spin coater. Then, it heat-dried for 3 minutes on an 80 degreeC hotplate. This colored layer was irradiated with ultraviolet rays of 30 mJ / cm ² using a super high pressure mercury lamp through a photomask on which a stripe pattern having a line and space of 80 μm was drawn. Thereafter, the glass plate on which the colored layer was formed was shower-developed for 60 seconds using a 0.05% by weight aqueous potassium hydroxide solution as an alkaline developer, and further washed with ultrapure water for 60 seconds. Post-baked in a clean oven for 30 minutes. If development was not possible in 60 seconds, shower development was performed until development was possible.
The obtained glass substrate on which the colored pattern was formed was immersed in a 5.0% by mass aqueous sodium hydroxide solution maintained at 40 ° C., and the time until the colored pattern peeled from the glass substrate was measured.
The results are shown in Table 2.

[Summary of results]
The red pigment dispersions of Examples 1 to 7 containing a red pigment having an anthraquinone skeleton, a sulfonated derivative of a yellow pigment, the above-described salt-type graft copolymer, and a solvent were used before and after the storage stability test. The change in the particle diameter and viscosity of the pigment was small, and the dispersibility and dispersion stability were excellent. Moreover, the red photosensitive resin composition of Examples 1-7 was excellent in developability, alkali resistance, and solvent resistance, and was able to form a high-brightness and high-contrast colored layer.
The red pigment dispersion of Example 7 using the graft copolymer GP-4 using an acrylamide-based monomer as a pigment dispersant is excellent in pigment dispersibility and dispersion stability among the examples, and obtained coloration. The layer had high contrast and was excellent in developability and solvent resistance.
In Comparative Example 1 in which a sulfonated derivative of a yellow pigment was not used, and in place of the sulfonated derivative of a yellow pigment, C.I. I. The photosensitive resin composition of Comparative Example 2 using the sulfonic acid derivative of Pigment Red 254 had poor dispersion stability, and the resulting colored layer had poor luminance and contrast.
In Comparative Example 3 in which a graft copolymer not forming a salt was used as a pigment dispersant, the dispersibility and dispersion stability were poor and the contrast was low.
The photosensitive resin composition of Comparative Example 4 using a graft copolymer salt-formed with benzyl chloride instead of an organic acid compound as a pigment dispersant was good in luminance and contrast, but could not be developed. It was.
In Comparative Examples 5 to 7 using a commercially available dispersant that does not form a salt with the organic acid compound, as in Examples 1 to 7, high brightness, high contrast, dispersibility, dispersion stability, and A photosensitive resin composition excellent in developability was not obtained.

<Solvent resolvability>
As an evaluation method, the photosensitive resin composition of Examples 1 to 3 and the photosensitive resin composition of Comparative Example 1 in which the cured film was evaluated on a 2 cm length of a glass substrate cut to a length of 100 mm × width of 5 mm. Each soaked and pulled up was dried in a constant temperature and humidity layer of 23 ° C. and 70% RH for 30 minutes. 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 the 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, Example 3 was ○, Examples 1 and 2 were Δ, and Comparative Example 1 was ×.
From the above, it was revealed that a sulfonated derivative salted with a long-chain alkyl group is excellent in solvent resolubility.

DESCRIPTION OF SYMBOLS 1 Transparent substrate 2 Light-shielding part 3 Colored layer 10 Color filter 20 Counter substrate 30 Liquid crystal layer 40 Liquid crystal display device 50 Organic protective layer 51 Monomer unit which has an amino group 52 Polymerizable part of macromonomer 53 Polymer chain by macromonomer 54 Organic acid compound 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

Claims (12)

A red pigment having an anthraquinone skeleton, a sulfonated derivative of a yellow pigment, a pigment dispersant, and a solvent, wherein the pigment dispersant has a monomer having an ethylenically unsaturated double bond and an amino group, and a polymer A graft copolymer containing, as a copolymerization component, a macromonomer containing a chain and a group having an ethylenically unsaturated double bond at its terminal, wherein the polymer chain of the macromonomer has the following general formula (IV) has in a structural unit represented by at least further is a graft copolymer and at least a part and an organic acid compound to form a salt of the amino group derived from a monomer having an ethylenically unsaturated double bond and an amino group Red pigment dispersion for color filters.
(In Formula (IV), R ⁴ is a hydrogen atom or a methyl group, R ⁵ is an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, a cyano group, — [CH (R ⁶ ) —CH (R _{^{7) -O] x -R 8,}} - [(CH 2) y -O] z -R 8, - [CO- (CH 2) y -O] z -R 8, -CO-O-R 9 or It is a monovalent group represented by —O—CO—R ^10. R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group.
R ⁸ is a hydrogen atom or a monovalent group represented by an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, —CHO, —CH ₂ CHO, or —CH ₂ COOR ¹¹ , and R ⁹ is C1-C18 alkyl group, aralkyl group, aryl group, cyano group, — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —R ⁸ , — [(CH ₂ ) _y —O] _z It is a monovalent group represented by —R ⁸ or — [CO— (CH ₂ ) _y —O] _z —R ⁸ . R ¹⁰ is an alkyl group having 1 to 18 carbon atoms, and R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. )   The sulfonated derivative of the yellow pigment is C.I. I. The red pigment dispersion for color filter according to claim 1, 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 color filters according to claim 1 or 2, which is CI Pigment Red 177.   The color filter red according to any one of claims 1 to 3, wherein a 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. Pigment dispersion. In the said pigment dispersant, the monomer which has the said ethylenically unsaturated double bond and an amino group is represented by the following general formula (I), For color filters as described in any one of Claims 1 thru | or 4 Red pigment dispersion.
(In Formula (I), R ¹ represents a hydrogen atom or a methyl group, R ² and R ³ each independently represent a hydrogen atom, or an optionally substituted cyclic or chain hydrocarbon group, or R ² and R ³ combine with each other to form a cyclic structure, Q represents a divalent linking group. The red pigment for a color filter according to any one of claims 1 to 5, wherein in the pigment dispersant, the organic acid compound is represented by the following general formula (II) and / or the following general formula (III). Dispersion.
(In Formula (II) and Formula (III), R ^a and R ^{a ′} are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, or an aryl group. 1 represented by the group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — [(CH ₂ ) _t —O] _u —R ^e , or —O—R ^{a ″.} R ^a and R ^{a ′} each contain ^a carbon atom. R ^{a ″} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, and an aryl group. , — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — [(CH ₂ ) _t —O] _u —R ^e .
R ^b is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — [(CH ₂ ) _t —O] _u —R ^e or a monovalent group represented by —O—R ^{b ′} . R ^{b ′} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , or _- it is a monovalent group represented by _{[(CH 2) t -O]} u -R e.
R ^c and R ^d are each independently a hydrogen atom or a methyl group, and R ^e is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, _{-CHO, -CH 2 CHO, -CO-} CH = CH 2, a monovalent group represented by _{-CO-C (CH 3) =} CH 2 or _-CH 2 COOR ^{f, R f} is hydrogen or C It is an alkyl group of formula 1-5. In R ^a , R ^{a ′} , and R ^b , each of the alkyl group, alkenyl group, aralkyl group, and aryl group may have a substituent.
s is an integer of 1 to 18, t is an integer of 1 to 5, and u is an integer of 1 to 18. ) 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 a pigment dispersant, the pigment dispersant comprising an ethylenically unsaturated double bond and an amino acid A graft copolymer containing, as a copolymerization component, a monomer having a group and a macromonomer containing a polymer chain and a group having an ethylenically unsaturated double bond at its terminal, the polymer chain of the macromonomer At least a part of the amino group derived from a monomer having at least a structural unit represented by the following general formula (IV) and further having an ethylenically unsaturated double bond and an amino group, and the organic acid compound is a salt. A method for producing a red pigment dispersion for a color filter, which is a formed graft copolymer.
(In Formula (IV), R ⁴ is a hydrogen atom or a methyl group, R ⁵ is an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, a cyano group, — [CH (R ⁶ ) —CH (R _{^{7) -O] x -R 8,}} - [(CH 2) y -O] z -R 8, - [CO- (CH 2) y -O] z -R 8, -CO-O-R 9 or It is a monovalent group represented by —O—CO—R ^10. R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group.
R ⁸ is a hydrogen atom or a monovalent group represented by an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, —CHO, —CH ₂ CHO, or —CH ₂ COOR ¹¹ , and R ⁹ is C1-C18 alkyl group, aralkyl group, aryl group, cyano group, — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —R ⁸ , — [(CH ₂ ) _y —O] _z It is a monovalent group represented by —R ⁸ or — [CO— (CH ₂ ) _y —O] _z —R ⁸ . R ¹⁰ is an alkyl group having 1 to 18 carbon atoms, and R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. ) 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 6 and a photosensitive binder component. A step of preparing a red pigment dispersion by dispersing the red pigment having the anthraquinone skeleton in a solvent in the presence of a sulfonated derivative of a yellow pigment and a pigment dispersant;
A step of mixing the red pigment dispersion and a photosensitive binder component, wherein the pigment dispersant is composed of a monomer having an ethylenically unsaturated double bond and an amino group, a polymer chain, and an ethylenic group at its end. A graft copolymer containing, as a copolymerization component, a macromonomer containing a group having an unsaturated double bond , wherein the polymer chain of the macromonomer comprises a structural unit represented by the following general formula (IV) A red photosensitivity for a color filter, which is a graft copolymer in which at least a part of an amino group derived from a monomer having an ethylenically unsaturated double bond and an amino group and an organic acid compound form a salt. A method for producing a resin composition.
(In Formula (IV), R ⁴ is a hydrogen atom or a methyl group, R ⁵ is an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, a cyano group, — [CH (R ⁶ ) —CH (R _{^{7) -O] x -R 8,}} - [(CH 2) y -O] z -R 8, - [CO- (CH 2) y -O] z -R 8, -CO-O-R 9 or It is a monovalent group represented by —O—CO—R ^10. R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group.
R ⁸ is a hydrogen atom or a monovalent group represented by an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, —CHO, —CH ₂ CHO, or —CH ₂ COOR ¹¹ , and R ⁹ is C1-C18 alkyl group, aralkyl group, aryl group, cyano group, — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —R ⁸ , — [(CH ₂ ) _y —O] _z It is a monovalent group represented by —R ⁸ or — [CO— (CH ₂ ) _y —O] _z —R ⁸ . R ¹⁰ is an alkyl group having 1 to 18 carbon atoms, and R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. ) A color filter comprising a colored layer formed using the red photosensitive resin composition for a color filter according to claim 8 . 11. A liquid crystal display device comprising: the color filter according to claim 10 ; a counter substrate; and a liquid crystal layer formed between the color filter and the counter substrate. 11. An organic light emitting display device comprising the color filter according to claim 10 and an organic light emitter.