TW201619298A - Red pigment dispersion liquid for color filters and method for producing the same, photosensitive red resin composition for color filters and method for producing the same, color filter, liquid crystal display device - Google Patents

Abstract

An object is to provide a red pigment dispersion liquid and photosensitive red resin composition for color filters, both of which provide high luminance and satisfy requests for high contrast. The red pigment dispersion liquid for color filters comprises a diketopyrrolopyrrole-based red pigment, a sulfonated yellow pigment derivative, a pigment dispersing agent which is a block copolymer comprising a tertiary amine salt or quaternary ammonium salt, and a solvent. The photosensitive red resin composition for color filters comprises the pigment dispersion liquid.

Description

Red pigment dispersion liquid for color filter and manufacturing method thereof, red photosensitive resin composition for color filter, manufacturing method thereof, color filter, liquid crystal display device and organic light emitting display device

The present invention relates to a pigment dispersion liquid, a method for producing the same, a red photosensitive resin composition for a color filter using the pigment dispersion liquid, and a red photosensitive resin composition for a color filter using the method for producing the pigment dispersion liquid. A manufacturing 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, with the development of personal computers, especially the development of portable personal computers, the demand for liquid crystal displays has increased. Moreover, the popularity of LCD TVs for home use has also increased recently, and the market for liquid crystal displays has been expanding. Further, in the performance of the liquid crystal display, it is also strongly desired to improve the further high image quality such as contrast and color reproducibility and the reduction in power consumption.

In such a situation, in a color filter having a color display function for a liquid crystal display, high luminance, high contrast, and improved color reproducibility are also expected. especially, Recently, for television use, the reduction in power consumption of the backlight and the characteristics of the LED backlight have also increased the expectation of high luminance.

Moreover, the above-mentioned problem is also the same in the organic EL display which is predicted to be popular in the future, and improvement in high luminance and color reproducibility is also a problem to be solved in the display.

Here, the color filter generally has a transparent substrate, a colored layer composed of red, green, and blue primary coloring patterns formed on the transparent substrate, and a coloring layer formed on the transparent substrate to separate the colored patterns. Shading section.

As a method of forming such a coloring layer, a pigment dispersion method, a dyeing method, an electrodeposition method, a printing method, and the like are known. Among them, a pigment dispersion method having an excellent average property is most widely used from the viewpoints of spectral characteristics, durability, pattern shape, and precision.

In general, a color filter in which a pigment is dispersed is a problem in which the degree of polarization of liquid crystal control is disturbed due to light scattering caused by a pigment or the like. In other words, when light is blocked (OFF state), light leaks, and when light must be transmitted (ON state), light is weakened, so that the luminance ratio (contrast) on the display device in the ON state and the OFF state is low. problem.

In order to achieve high contrast of the color filter, it has been reviewed until now that the pigment contained in the colored layer is refined. As an attempt to refine the pigment, a pigment preparation obtained by combining a pigment and a pigment derivative having a structure similar to a pigment has been used. For the red colored layer, a diketopyrrolopyrrole pigment derivative obtained by introducing a substituent such as sulfonamide into a diketopyrrolopyrrole pigment derivative has been used as a pigment dispersant, and is combined with a diketopyrrole. Attempts to combine pyrrole pigments (for example, Patent Document 1). However, if a diketopyrrolopyrrole pigment derivative as described above is combined with a diketopyrrolopyrrole pigment, the pigment may be finely dispersed, but the above-mentioned diketopyrrolopyrrole pigment derivative is mostly electronic. The influence of the attracting group becomes a color that is more bluish than the color of the mixed diketopyrrolopyrrole pigment (becomes absorbed to a longer wavelength), and a diketone such as the above is used in combination. The red colored layer of the pyridolopyrrole pigment derivative has a problem that the compound having absorption at the breakthrough wavelength of the diketopyrrolopyrrole pigment is absorbed, so that the brightness is lowered. According to the trend of high brightness developed in recent years, pigment derivatives having reduced brightness will become unusable. Further, in the above-described pigment derivative, although the diketopyrrolopyrrole pigment can be finely dispersed, the photosensitive resin composition produced by using the dispersion has a problem of precipitation of crystals during baking.

In order to solve the problem of precipitation of crystals during baking, Patent Document 2 discloses a composition of a diketopyrrolopyrrole pigment produced by cyclizing at least two kinds of a benzonitrile compound and a succinic acid diester. The diketoppyrrolopyrrole pigment composition (particle) obtained by adding a dye derivative as a crystal growth inhibitor when the crude crystal is treated with an organic solvent. The above-mentioned dye derivative used in the formation of a diketopyrrolopyrrole pigment composition (particle) has been described as being useful for improving the hue, but the hue is different from the chroma and brightness, and in particular, it is impossible to associate with Change the hue to increase the brightness. Further, in the technique specifically described in Patent Document 2, a red benzindole derivative is used as a dye derivative, and the brightness is insufficient, and the improvement of the pigment dispersibility in preparing the pigment dispersion liquid is also insufficient.

Further, in Patent Document 3, it is disclosed that in the case of forming a color film having excellent contrast and a reduced surface roughness, in the diketopyrrolopyrrole pigment, the quinone imide alkylated diketone group is mixed during salt milling. A pigment dispersion composition obtained by alkylating quinophthalone with pyrrolopyrrole and quinone. However, in the technique of Patent Document 3 in which a red pigment derivative is blended in a diketopyrrolopyrrole pigment to prepare a red pigment dispersion composition, there is a problem that the brightness is insufficient.

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open Publication No. 2001-214085

Patent Document 2: International Publication No. 2009/081930

Patent Document 3: Japanese Patent Laid-Open Publication No. 2009-251586

The present invention has been accomplished under such circumstances, and an object thereof is to provide a red pigment dispersion liquid for a color filter which achieves a particularly high brightness and which also achieves high contrast; and a method for producing the same; achieving a particularly high brightness and Further, a red photosensitive resin composition for a color filter having a high contrast color layer, a method for producing the same, a color filter formed using the photosensitive resin composition, and a liquid crystal display device having the color filter and Organic light emitting display device.

The present inventors have repeated efforts to achieve the above object, and have found that a diketopyrrolopyrrole red pigment is present in a solvent in the presence of a sulfonated derivative of a yellow pigment and a specific pigment dispersant. By dispersing, it is possible to obtain a pigment dispersion liquid and a photosensitive resin composition which achieve particularly high brightness and improve the dispersibility and dispersion stability of the diketopyrrolopyrrole red pigment, and which are required to have high brightness and high contrast.

The present invention has been completed in accordance with such findings.

A red pigment dispersion liquid for a color filter of the present invention, which comprises: a diketopyrrolopyrrole red pigment, a sulfonated derivative of a yellow pigment, a salt containing a tertiary amine or a tetrabasic ammonium salt. a pigment dispersant of a segment copolymer and a solvent.

Further, a method for producing a red pigment dispersion liquid for a color filter of the present invention is characterized by the step of: a sulfonated derivative of a yellow pigment in a solvent, and a salt containing a tertiary amine or a grade 4 In the presence of a pigment dispersant of a block copolymer of an ammonium salt, the above The step of dispersing the diketopyrrolopyrrole red pigment.

Moreover, the red photosensitive resin composition for a color filter of the present invention is characterized by comprising the red pigment dispersion liquid for a color filter of the present invention and a photosensitive adhesive component.

Further, a method for producing a red photosensitive resin composition for a color filter of the present invention is characterized by the step of: a sulfonated derivative of a yellow pigment and a salt containing a tertiary amine in a solvent; Or a step of dispersing the above-mentioned diketopyrrolopyrrole red pigment to prepare a red pigment dispersion in the presence of a pigment dispersant of a block copolymer of a fourth-order ammonium salt; and bonding the red pigment dispersion to the photosensitive material The step of mixing the ingredients.

In the red pigment dispersion liquid for a color filter of the present invention, a method for producing the same, and a red photosensitive resin composition for a color filter of the present invention, and a method for producing the same, a particularly high luminance is achieved, and a diketone group is improved. The sulfonated derivative of the above yellow pigment is preferably a sulfonated derivative of CI Pigment Yellow 138 in terms of dispersibility and dispersion stability of the pyrrolopyrrole red pigment and high brightness and high contrast requirements.

In the red pigment dispersion liquid for color filter of the present invention, the method for producing the same, and the red photosensitive resin composition for a color filter of the present invention, and the method for producing the same, even in the color filter step Further, after the heating step, aggregation of the pigment can be suppressed, and in view of particularly high brightness and high contrast, a ruthenium alkylated derivative further containing a diketopyrrolopyrrole red pigment is preferred.

In the red pigment dispersion liquid for color filter of the present invention, the method for producing the same, and the red photosensitive resin composition for a color filter of the present invention, and the method for producing the same, even in the color filter step After the heating step, the aggregation of the pigment can also be inhibited, and in terms of particularly high brightness and high contrast, it is preferred to sulfonate the yellow pigment. The content of the substance is 1 to 25 parts by weight based on 100 parts by weight of the diketopyrrolopyrrole red pigment, and the quinone imine alkylated derivative of the above diketopyrrolopyrrole red pigment The content is 0 to 15 parts by weight based on 100 parts by weight of the diketopyrrolopyrrole red pigment.

In the red pigment dispersion liquid for a color filter of the present invention, a method for producing the same, and a red photosensitive resin composition for a color filter of the present invention, and a method for producing the same, a particularly high luminance is achieved, and a diketone group is improved. The dispersibility and dispersion stability of the pyrrolopyrrole red pigment, and in terms of high brightness and high contrast, it is preferred that the above pigment dispersant has a repeating unit represented by the following general formula (I) (1) And a repeating unit (2) represented by the following general formula (II), wherein at least a part of the amine group of the repeating unit (1) is formed by forming a salt with an organic acid compound and/or a halogenated hydrocarbon. Block copolymer.

[In the formulae (I) and (II), R ¹ is a hydrogen atom or a methyl group, and R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and A is a carbon number of 1 to 8 Alkyl, -[CH(R ⁶ )-CH(R ⁷ )-O] _x -CH(R ⁶ )-CH(R ⁷ )- or -[(CH ₂ ) _y -O] _z -(CH ₂ ) _y - the divalent group shown, R ⁴ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, -[CH(R ⁶ )-CH(R ⁷ ) -O] _x -R ⁸ or -[(CH ₂ ) _y -O] _z -R ⁸ represents a monovalent group; R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group, and R ⁸ is a hydrogen atom, or An alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, -CHO, -CH ₂ CHO, or a monovalent group represented by -CH ₂ COOR ⁹ , and R ⁹ is hydrogen An atom or an alkyl group having 1 to 5 carbon atoms; the above alkyl group, alkenyl group, aralkyl group, and aryl group each may have a substituent; x represents an integer of 1 to 18, y represents an integer of 1 to 5, and z represents 1 An integer of ~18; m represents an integer from 3 to 200, and n represents an integer from 10 to 200. ]

Moreover, the present invention provides a color filter comprising a coloring layer formed by curing the color filter with a red photosensitive resin composition.

Furthermore, the present invention provides a liquid crystal display device comprising the color filter, the 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 above-described color filter and an organic light-emitting body.

According to the present invention, it is possible to provide a red pigment dispersion liquid for a color filter which achieves particularly high brightness and which also achieves high contrast.

According to the present invention, it is possible to provide a red photosensitive resin composition for a color filter which achieves a particularly high luminance and which can form a high contrast coloring layer. A pigment dispersion liquid and a photosensitive resin composition obtained by dispersing a diketopyrrolopyrrole red pigment of the present invention in the presence of a sulfonated derivative of a yellow pigment and a specific pigment dispersant can be used. The red pixel portion of the high-brightness and high-contrast color filter.

Further, according to the present invention, it is possible to provide a liquid crystal display device and an organic light-emitting display device having high luminance and high contrast by using the above-described color filter.

1‧‧‧Transparent substrate

2‧‧‧Lighting Department

3‧‧‧Colored layer

10‧‧‧Color filters

20‧‧‧ opposite substrate

30‧‧‧Liquid layer

40‧‧‧Liquid crystal display device

50‧‧‧Organic protective layer

60‧‧‧Inorganic oxide film

71‧‧‧Transparent anode

72‧‧‧ hole injection layer

73‧‧‧ hole transport layer

74‧‧‧Lighting layer

75‧‧‧Electronic injection layer

76‧‧‧ cathode

80‧‧‧Organic emitters

100‧‧‧Organic light-emitting display device

Fig. 1 is a schematic view showing an example of a color filter of the present invention.

Fig. 2 is a schematic view showing an example of a liquid crystal display device of the present invention.

Fig. 3 is a schematic view showing an example of the organic light-emitting display device of the present invention.

Hereinafter, the red pigment dispersion liquid for a color filter, the red photosensitive resin composition for a color filter, a color filter, a liquid crystal display device, and an organic light-emitting display device according to the present invention will be described in order.

Further, the light system according to the present invention includes electromagnetic waves having wavelengths in the visible and non-visible regions, and radiation, and the radiation system 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, the term "(meth)acrylic" means either acrylic or methacrylic, and the term "(meth)acrylate" means either acrylate or methacrylate.

1. Red pigment dispersion liquid for color filter, and manufacturing method thereof

A red pigment dispersion liquid for a color filter of the present invention, which comprises: a diketopyrrolopyrrole red pigment, a sulfonated derivative of a yellow pigment, a salt containing a tertiary amine or a tetrabasic ammonium salt. a pigment dispersant of a segment copolymer and a solvent.

The red color pigment dispersion liquid of the color filter of the present invention is used in the above solvent, and the diketopyrrolopyrrole red pigment is dispersed in the presence of the sulfonated derivative of the yellow pigment and the specific pigment dispersant. The winner is better.

When the red pigment diketopyrrolopyrrole red pigment is dispersed in a solvent, a pigment dispersant is obtained by a sulfonated derivative of a yellow pigment, a block copolymer with a salt of a tertiary amine or a grade 4 ammonium salt. When the dispersion is carried out in the presence of the combined pigment dispersant, it is possible to achieve a particularly high brightness, and to improve the dispersibility and dispersion stability of the diketopyrrolopyrrole red pigment, and to achieve high brightness and high contrast requirements. A pigment dispersion and a photosensitive resin composition.

The effect of the above effects by the above specific combination has not yet been elucidated, but Speculated as follows.

According to the present invention, when a diketopyrrolopyrrole red pigment is dispersed in a solvent, a sulfonated derivative of a yellow pigment is used. The sulfonated derivative of the yellow pigment has high affinity with the diketopyrrolopyrrole red pigment, and the surface of the red pigment is made acidic by adsorption to the surface of the red pigment, so that the affinity with the pigment dispersant is better than that of the diketone group. The pyrrolopyrrole red pigment itself is more enhanced and exerts an intermediate effect with the pigment dispersant. Further, the sulfonated derivative of the yellow pigment is different from the sulfonated derivative of the red pigment, since the original color is yellow having a low coloring power, so it is absorbed to a shorter wavelength than the diketoppyrrolopyrrole red pigment. On the wavelength side, the effect of increasing the brightness of the red pigment dispersion without greatly changing the color of the red pigment is exhibited.

Further, according to the present invention, the pigment dispersant used in combination with the sulfonated derivative of the yellow pigment is a salt type block copolymer containing a salt of a tertiary amine or a salt of a tertiary ammonium salt, whereby the salt type block is used. In the copolymer, the block having the constituent unit of the salt-forming portion is highly adsorbable to the pigment and the sulfonated derivative of the yellow pigment adsorbed on the surface of the pigment, and contains a constituent unit having no salt-forming portion. The block is soluble in the solvent.

When such a pigment dispersant and a sulfonated derivative of a yellow pigment are used in combination, the diketopyrrolopyrrole red pigment can be made fine, and the surface of the pigment which is exposed by miniaturization is suitable for sulfonation of the yellow pigment. The pigment and the pigment dispersant can be used to stabilize the pigment in the solvent, and it is presumed that the diketopyrrolopyrrole red pigment can be more uniformly and finely refined. As a result, a coating film with improved contrast can be obtained.

The red pigment dispersion liquid for color filter of the present invention contains at least: a diketopyrrolopyrrole red pigment, a sulfonated derivative of a yellow pigment, a salt containing a tertiary amine or a block copolymer of a 4-grade ammonium salt. The pigment dispersant and the solvent are included as essential components, and may contain other components as needed.

Hereinafter, each component of the red pigment dispersion liquid of the present invention will be described in detail.

(diketopyrrolopyrrole red pigment)

The diketopyrrolopyrrole red pigment has a structure represented by the following chemical formula.

(X independently represents a halogen atom, a hydrogen atom, a phenyl group, or a methyl group.)

Examples of the halogen atom in X in the above formula include Cl, Br, and the like.

Examples of the diketopyrrolopyrrole-based red pigment include C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Red 264, C.I. Pigment Red 272, C.I. Pigment Red 270, and the like. Among them, from the viewpoint of brightness, as the diketopyrrolopyrrole red pigment, C.I. Pigment Red 254 is preferably used.

C.I. Pigment Red 254 has a configuration shown by the following chemical formula.

The average primary particle diameter of the pigment such as the diketopyrrolopyrrole red pigment used in the present invention is not particularly limited as long as it is a coloring layer of a color filter. The limitation is also preferably in the range of 10 to 70 nm, and more preferably in the range of 10 to 50 nm, depending on the type of the pigment to be used. When the average primary particle diameter of the pigment is in the above range, the liquid crystal display device and the organic light-emitting display device which are produced by using the red pigment dispersion liquid for color filter of the present invention and the photosensitive resin composition can be made high. Contrast and high quality. Further, in the case of the conventional pigment dispersant, a large amount of the pigment dispersant is required as the particle size of the pigment is miniaturized, and there is a problem that the alkali developability is lowered and the residue is increased, but the color filter of the present invention is used. The pigment dispersant used in the red pigment dispersion liquid and the photosensitive resin composition is excellent in alkali developability when an organic acid compound is used to form a salt, and thus such a problem is less likely to occur. Therefore, the average particle diameter of the pigment is as described above, and the smaller the ratio is, the more the characteristics of the photosensitive resin composition for a color filter of the present invention are exhibited.

Further, the average particle diameter of the above pigment can be determined by an electron micrograph using a direct measurement method to determine the size of the primary particles. Specifically, the minor axis diameter and the major axis diameter of each primary particle are measured, and the average thereof is taken as the particle diameter of the particle. Next, the volume (weight) of each particle is determined as a cube which approximates the particle diameter of 100 or more particles, and the volume average particle diameter is calculated|required as an average particle diameter. In addition, the electron microscope can obtain the same result regardless of whether either a penetrating type (TEM) or a scanning type (SEM) is used.

The average dispersed particle diameter of the pigment in the pigment dispersion liquid varies depending on the type of the pigment to be used, and 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 diameter of the pigment in the pigment dispersion liquid is a dispersion particle diameter of the pigment particles dispersed in a dispersion medium containing at least a solvent, and is measured by a laser light scattering particle size distribution meter. As the measurement of the particle diameter by the laser light scattering particle size distribution meter, the pigment dispersion liquid can be appropriately diluted to a concentration (for example, 1000 times or the like) which can be measured by a laser light scattering particle size distribution meter. Further, it was measured by a dynamic light scattering method at 23 ° C using a laser light scattering particle size distribution meter (for example, Nanotrack particle size distribution measuring apparatus UPA-EX150 manufactured by Nikkiso Co., Ltd.). The average dispersed particle diameter here is a volume average particle diameter.

The diketopylpyryrazole-based red pigment used in the present invention can be produced by a known method such as recrystallization or solvent salt polishing. Also, a commercially available diketopyrrolopyrrole can also be used. A red pigment, for example, a commercially available C.I. Pigment Red 254 (for example, IRGAPHOR Red B-CF manufactured by Ciba Specialty Chemicals, etc.) is ground.

In the red pigment dispersion liquid for color filters of the present invention, the content of the diketopyrrolopyrrole-based red pigment is not particularly limited as long as it is appropriately adjusted. In general, the pigment content of the diketopyrrolopyrrole-based red pigment is preferably in the range of 5 to 40% by weight, and 10 to 20% by weight based on the total amount of the red pigment dispersion liquid for the color filter. The range is better.

(sulfonated derivative of yellow pigment)

As the yellow pigment derived from the sulfonated derivative of the yellow pigment used in the pigment dispersion of the present invention, CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16 can be cited. , 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, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, and the like.

In the above, the yellow pigment which is a sulfonated derivative derived from a yellow pigment has a high luminance and a high affinity with a diketopyrrolopyrrole red pigment such as CI Pigment Red 254, and is a CI pigment yellow. 138, 139, 150, 215 are preferred. Furthermore, in particular, it has high affinity and high affinity with a diketopyrrolopyrrole red pigment such as CI Pigment Red 254, and does not greatly change the hue, and can easily achieve high brightness and high contrast. CI Pigment Yellow 138, 139 is used, with CI Pigment Yellow 138 being particularly preferred.

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 further, a part or all of the sulfonic acid group may also be via an amine. A salt is formed with ammonium hydroxide, chloride, bromide, etc., and a metal to form a sulfonate.

The sulfonamide group as the sulfonate group of the sulfonate group is preferably a sulfonamide group represented by the following chemical formulas (1) to (3).

Chemical formula (1): -SO ₂ NH-(CH ₂ ) _m -NR'R"

Chemical formula (2): -SO ₂ NH-(CH ₂ ) _m -COOH

Chemical formula (3): -SO ₂ NH-(CH ₂ ) _m -SO ₃ H

In the chemical formula (1), R' and R" each independently represent a hydrogen atom, a saturated or unsaturated aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 20 carbon atoms, or may be bonded together with a neighboring nitrogen atom. A heterocyclic ring further containing a nitrogen, oxygen, or sulfur atom is formed.

In the chemical formulae (1) to (3), m is 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" of the above chemical formula (1) Listed are piperidinylmethyl, dimethylamine ethyl, diethylamine ethyl, dimethylaminopropyl, diethylamine propyl, dibutylaminopropyl, piperidinylethyl, methylpiperidinyl, Phenylethyl, piperidinylpropyl, methylpiperidinylpropyl, diethylamine hexyl, diethylamine ethoxypropyl, diethylamine butyl, trimethylammoniopentyl, NN-methyl-lauryl-amine C Base, 2-ethylhexylamine ethyl, stearylamine ethyl, oleyl ethyl and the like.

Furthermore, it may be a -SO ₂ NH- group, a combination of p-dimethylamine ethylamine sulfonate phenyl, p-diethylamine ethylamine sulfonate phenyl, p-dimethylaminopropyl sulfonate. A sulfonylamino group such as phenyl or p-diethylamine ethylamine formazanyl.

In the case where a sulfonic acid group which does not form a salt exists, a salt is formed by a tertiary amine moiety of a block copolymer type pigment dispersant to be described later, and dispersion can be improved by ion interaction. The pigment adsorption power of the agent is preferred in terms of contrast improvement.

Further, in the sulfonated derivative of the yellow pigment, in addition to the sulfonic acid group, the sulfonamide group, and the sulfonate, other functional groups such as a quinone imino group may be further substituted.

In the case of the sulfonamide group represented by the chemical formula (1) and the sulfonate salt forming a salt with the amine group having a long-chain alkyl group having 3 or more carbon atoms, the solvent resolubility is good. It is better. Here, the solvent resolubility means a property in which a solid portion of a temporarily dried photosensitive resin composition is dissolved again in a solvent. When the solvent resolubility is good, the dried product of the photosensitive resin composition adhered to the color filter can be easily removed and cleaned, which is a great advantage in manufacturing.

The number of substitutions in the molecule of the yellow pigment of the sulfonic acid group (-SO ₃ H) or the sulfonamide group is preferably from 1 to 3, wherein in terms of steric hindrance and affinity with the dispersing agent, 1~ 2 is better, and 1 is better.

The sulfonated derivative of the yellow pigment which is suitably used in the present invention may, for example, be the following structure of C.I.Pigment Yellow 138, at least a combination of a sulfonic acid group, a sulfonylamino group and a sulfonate.

(In the formula (4), 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 ) One selected from the group consisting of _m -SO ₃ H and sulfonate, R' and R" each independently represent a hydrogen atom, a saturated or unsaturated aliphatic hydrocarbon group having a carbon number of 1 to 20 which may be substituted Or an aromatic hydrocarbon group or a heterocyclic ring further containing a nitrogen, oxygen or sulfur atom, and m may be independently an integer of 1 to 6. n represents the number of substituents and represents an integer of 1 to 4. .)

As a substituent to be suitably used, a 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 (4), the number of substituents n is preferably from 1 to 2, and among them, it is preferable to form a salt with the amine moiety of the third component of the pigment dispersant.

A sulfonated derivative of a yellow pigment, for example, can be produced by subjecting a yellow pigment to concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid or a mixture thereof to carry out a sulfonation reaction. After the sulfonation reaction, the reaction solution is diluted with a large amount of water or neutralized with an aqueous amine solution in the preparation of the amine salt, and the resulting suspension is filtered, washed with an aqueous washing solution, and dried. The amine salt of the sulfonic acid can be introduced as appropriate by appropriate selection of the amine of the aqueous amine solution used. Further, in the case of producing sulfonic acid decylamine, the sulfonate of the yellow pigment obtained by the above method is treated with sulfinium chloride to form sulfonium chloride and then mixed with an amine, whereby sulfonated guanamine can be introduced as appropriate.

When sulfonation is carried out by the above method, the amount of introduction of the sulfonic acid group and the sulfonamide group per molecule can be controlled by adjusting the concentration of the reaction liquid, the reaction temperature, the reaction time, and the like.

The sulfonated derivative of the yellow pigment may be used alone or in combination of two or more. For example, a sulfonated derivative in which two or more kinds of sulfonic acid groups and sulfonamide groups are substituted, a substitution position or a different number of substitutions may be used in combination.

In the present invention, the sulfonated derivative of the yellow pigment is preferably 1 to 25 parts by weight based on 100 parts by weight of the above-mentioned diketopyrrolopyrrole red pigment. Wherein the sulfonated derivative of the yellow pigment is 100 parts by weight relative to the above-mentioned diketopyrrolopyrrole red pigment; It is preferably 1 to 15 parts by weight, more preferably 3 to 10 parts by weight. By using such a content, it is possible to produce a coating film which does not greatly change the hue and achieves high brightness and high contrast.

(pigment dispersant)

The pigment dispersant used in the present invention is a block copolymer containing a salt of a tertiary amine or a salt of a tertiary ammonium. In such a block copolymer, a block portion containing a salt of a tertiary amine or a salt of a fourth-order ammonium salt is adsorbed to a sulfonated derivative of a pigment and a yellow pigment, and does not contain a salt of a tertiary amine or a ammonium 4-phosphate. The block portion of the salt has solubility in a solvent, so that the dispersibility of the pigment can be improved. In particular, in the present invention, since a yellow pigment derivative having a sulfonic acid group and/or a sulfonamide group is used in combination with a pigment dispersant composed of a salt type block copolymer, diketopyrrole can be achieved. The pyrrole red pigment is refined to improve contrast.

When a pigment dispersant composed of a block copolymer is used, the size of the pigment adsorbing portion and the solvent soluble portion can be designed to be smaller than that of the graft polymer type pigment dispersing agent, and the finer pigment can be improved. The dispersion effect.

Examples of the salt of the tertiary amine include a tertiary amine moiety such as dimethylaminoethyl acrylate which forms a block copolymer, and a salt is formed by an acid such as a phosphoric acid compound or a sulfonic acid compound. Further, examples of the fourth-order ammonium salt include a tertiary amine moiety such as dimethylaminoethyl acrylate which forms a block copolymer, and an allylic halide and/or an aralkyl halide. Ammonium salt.

Further, in the block portion containing a salt of a tertiary amine or a salt of a tertiary ammonium salt, an amine which does not form a salt may be contained.

As the amount of the tertiary amine salt or the tertiary ammonium salt in the copolymer, the number of repeating units is preferably from 1 to 50%, and more preferably from 1 to 20%, based on all repeating units of the block copolymer. good.

Examples of the main chain structure of the polymer include (meth)acrylic resin and styrene B. An olefin resin or the like. Among them, in terms of ease of synthesis of the block copolymer, a (meth)acrylic resin is also preferred.

The block copolymer having a tertiary amine salt or a tertiary ammonium salt used in the present invention preferably has a weight average molecular weight Mw in the range of 500 to 20,000, more preferably in the range of 1,000 to 15,000, and is 3,000. It is even better in the 12000 range. When it is in the above range, the wettability and dispersion stability of the pigment at the initial stage of dispersion in which the pigment is uniformly dispersed can be achieved. Here, the weight average molecular weight can be determined by gel permeation chromatography (GPC) in the form of a standard styrene equivalent value.

A commercially available product may be used as the pigment dispersant comprising a block copolymer of a quaternary amine salt or a quaternary ammonium salt, and examples thereof include DISPERBYK-2000 manufactured by BYK Chem.

As in the case of DISPERBYK-2000 described above, a part of the amine group forms a salt and is specified in comparison with a block copolymer containing a tertiary amine salt or a tertiary ammonium salt of about 4 parts of the amine group. A block copolymer containing a salt of a tertiary amine or a salt of a tertiary amine which remains in the form of an amine without forming a salt, in the present invention, the synergistic effect with the combination of the above-mentioned sulfonated derivative is higher, and is further improved It is better in terms of dispersibility. Specifically, a block copolymer containing a salt of a tertiary amine or a salt of a tertiary amine of 0.2 to 0.8 mole equivalent salt is preferably formed with respect to the tertiary amine group contained. From the above, in the present invention, LPN-6919 manufactured by BYK Chem having a block portion containing a tertiary amino group in the constituent unit is preferably used, and a predetermined portion of the tertiary amine moiety is preferably formed into a salt.

The pigment dispersant used in the present invention has the repeating unit (1) represented by the following general formula (I) and the repeating unit (2) represented by the following general formula (II), and the above repeating A block copolymer of at least a part of an amine group of the unit (1) forming a salt with an organic acid compound and/or a halogenated hydrocarbon. Hereinafter, the salt type block copolymer having the specific repeating unit will be described in detail.

[In the formulae (I) and (II), R ¹ is a hydrogen atom or a methyl group, and R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and A is a carbon number of 1 to 8 Alkyl, -[CH(R ⁶ )-CH(R ⁷ )-O] _x -CH(R ⁶ )-CH(R ⁷ )- or -[(CH ₂ ) _y -O] _z -(CH ₂ ) _y - the divalent group shown, R ⁴ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, -[CH(R ⁶ )-CH(R ⁷ ) -O] _x -R ⁸ or -[(CH ₂ ) _y -O] _z -R ⁸ represents a monovalent group. R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group, and R ⁸ is a hydrogen atom, or 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, - A monovalent group represented by CH ₂ CHO or -CH ₂ COOR ⁹ , and R ⁹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. The alkyl group, the alkenyl group, the aralkyl group, and the aryl group each may have a substituent.

x represents an integer from 1 to 18, y represents an integer from 1 to 5, and z represents an integer from 1 to 18. m represents an integer from 3 to 200, and n represents an integer from 10 to 200. ]

<block copolymer>

The block copolymer has the repeating unit (1) represented by the above general formula (I) and the repeating unit (2) represented by the above general formula (II).

In the above general formula (I), R ¹ represents a hydrogen atom or a methyl group, and R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Here, the alkyl group having 1 to 8 carbon atoms may be any of a linear chain, a branched chain, and a cyclic chain. Examples of such an alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-butyl, various pentyl groups, various hexyl groups, and various octyl groups. , cyclopentyl, cyclohexyl, cyclooctyl and the like. Among them, methyl and ethyl are preferred.

In the present invention, the above R ² and R ³ may be the same as each other, or may be different.

A represents an alkylene group having 1 to 8 carbon atoms, _* -[CH(R ⁶ )-CH(R ⁷ )-O] _x -CH(R ⁶ )-CH(R ⁷ )- _** , or _* -[ (CH ₂ ) _y -O] _z -(CH ₂ ) _y - _{** is a} divalent group. Here, _* represents a linking site on the ester bonding side, and _** represents a linking site on the amine group side. Further, the alkylene group having 1 to 8 carbon atoms may be linear or branched, and examples thereof include a methylene group, an ethyl group, a trimethylene group, a propyl group, various kinds of butyl groups, and various kinds of butyl groups. Base, various extensions, various extensions, etc.

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. z is an integer of 1 to 18, preferably an integer of 1 to 4, more preferably an integer of 1 to 2. In the present invention, when x, y, and z are within the above range, the red pigment dispersion liquid for a color filter of the present invention is excellent in pigment dispersibility.

The above A is preferably an alkylene group having 1 to 8 carbon atoms, and more preferably a methylene group or an ethylidene group. When the carbon number is in the range of 1 to 8, the dispersibility of the pigment can be favorably maintained.

In the above general formula (II), R ⁴ represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, -[CH(R ⁶ )-CH(R ⁷ ) -O] _x -R ⁸ or -[(CH ₂ ) _y -O] _z -R ⁸ .

The alkyl group having 1 to 18 carbon atoms may be any of a linear chain, a branched chain, and a cyclic chain, and examples thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. Second butyl, tert-butyl, various pentyl, various hexyl groups, various octyl groups, various fluorenyl groups, various dodecyl groups, various tetradecyl groups, various hexadecyl groups, various octadecyl groups, rings Pentyl, cyclohexyl, cyclooctyl, cyclododecyl, Basis A group, a dicyclopentanyl group, an adamantyl group, an adamantyl group substituted with a lower alkyl group, and the like.

The alkenyl group having 2 to 18 carbon atoms may be any of a linear chain, a branched chain, and a cyclic chain. As Examples of such an alkenyl group include a vinyl group, an allyl group, a propenyl group, various butenyl groups, various hexenyl groups, various octenyl groups, various nonenyl groups, various dodecenyl groups, and various tetradecenes. A group, various hexadecenyl groups, various octadecenyl groups, cyclopentenyl groups, cyclohexenyl groups, cyclooctenyl groups, and the like. The position of the double bond of the alkenyl group is not limited, and from the viewpoint of reactivity of the obtained polymer, it is preferred that the terminal of the alkenyl group has a double bond.

Examples of the aryl group which may have a substituent include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, and a xylyl group. The carbon number of the aryl group is preferably from 6 to 24, more preferably from 6 to 12.

Examples of the aralkyl group which may have a substituent include a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group and the like. The aralkyl group has a carbon number of 7 to 20, more preferably 7 to 14.

Examples of the substituent of the aromatic ring such as an aryl group and an aralkyl group include an alkyl group, a nitro group, and a halogen atom, in addition to a linear or branched alkyl group having 1 to 4 carbon atoms.

Further, the above preferred carbon number does not include the carbon number of the substituent.

R ⁶ and R ^{7 are the} same as defined above, and R ⁸ is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms which may have a substituent, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, or -CHO. -CH ₂ CHO or a monovalent group represented by -CH ₂ COOR ⁹ , and R ⁹ is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 5 carbon atoms.

The monovalent group represented by the above R ⁸ may, for example, be a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms, or a halogen such as F, Cl or Br. Atoms, etc.

The alkyl group having 1 to 18 carbon atoms and the alkenyl group, aralkyl group and aryl group having 2 to 18 carbon atoms in the above R ⁸ are as shown in the above R ⁴ .

In the above R ⁴ , x, y and z are as described in the above A.

Further, R ⁴ in the repeating unit (2) represented by the above general formula (II) may be the same as each other or may be different.

In the present invention, it is preferable that the above-mentioned R ⁴ is excellent in solubility in a solvent to be described later, and specifically, depending on the repeating unit constituting the block copolymer, etc., the solvent is tetrahydrofuran. In the case of toluene or the like, a methyl group, an ethyl group, a benzyl group or the like is preferably used, and when the solvent is a lower polarity such as pentane or hexane, a pentyl group, a hexyl group, a heptyl group or the like is preferably used. The solvent is generally used as a solvent such as an ether alcohol acetate type, an ether type or an ester type as a solvent for a color filter, and is preferably a methyl group, an ethyl group, an n-butyl group, a 2-ethylhexyl group or a benzyl group. Base is better. Further, the solvent is preferably a lower polarity such as pentane or hexane, and a pentyl group, a hexyl group, a heptyl group or the like is preferably used.

Here, the reason why R ⁴ is set as described above is that the repeating unit (2) containing the above R ⁴ is soluble in the solvent, and the amine group of the repeating unit (1), and the organic acid compound and/or halogenated later described. The salt-forming portion of the hydrocarbon formation has high adsorptivity to the pigment, so that the dispersibility and stability of the pigment can be made particularly excellent.

Further, the above R ⁴ may be a substituent such as an alkoxy group, a hydroxyl group, a carboxyl group, an amine group, an epoxy group, an isocyanate group or a hydrogen bond-forming group, without impeding the dispersion property of the block copolymer or the like. Alternatively, the above substituent may be added after reacting the above-mentioned block copolymer with a compound having the above substituent. Further, after synthesizing a block copolymer having such a substituent, a polymerizable group can be added by reacting a compound having a functional group reactive with the substituent and a polymerizable group. For example, a block copolymer having a carboxyl group is reacted with glycidyl (meth)acrylate, and a block copolymer having an isocyanate group is reacted with hydroxyethyl (meth)acrylate to form a polymerizable group.

The ratio m/n of the unit number m of the constituent unit (1) and the unit number n of the constituent unit (2) used in the present invention is preferably in the range of 0.01 to 1, and more preferably in the range of 0.05 to 0.5. good. When the ratio m/n is within the above range, the adsorptivity to the pigment is improved, and the solubility in the solvent is not lowered by the above-mentioned constituent unit (2), and the dispersibility and stability of the pigment are not caused. Reduced sex.

The molecular size of the block copolymer used in the present invention is such that the number m of the repeating units (1) is an integer of from 3 to 200, preferably an integer of from 3 to 50. The number n of the above repeating unit (2) is an integer of 10 to 200, preferably an integer of 20 to 100, and more preferably an integer of 20 to 70. In the present invention, when m and n are each in the above range, the solvent-soluble portion and the solvent-insoluble portion can effectively act, and the red color pigment dispersion liquid of the color filter of the present invention can be excellent in pigment dispersibility.

Further, the weight average molecular weight Mw of the block copolymer is preferably in the range of 500 to 20,000, more preferably in the range of 1,000 to 15,000, and particularly preferably in the range of 3,000 to 12,000. When it is in the above range, the wettability and dispersion stability of the pigment at the initial stage of dispersion in which the pigment is uniformly dispersed can be achieved.

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

The order of binding of the block copolymer used in the present invention is not particularly limited as long as it has the above-mentioned repeating unit (1) and the above-mentioned repeating unit (2), and is stable in the above-mentioned repeating unit ( 1) It is preferred to bond only to one end of the above block copolymer. That is, the above repeating unit (1) and the above repeating unit (2) may be combined in the order of repeating unit (1)-repeat unit (2), and may also be in repeating unit (1)-repeat unit ( 2) - the order of the repeating unit (1), or the repeating unit (1) - repeating unit (2) is a repeater, in the present invention, preferably, the repeating unit (1) - repeat The order of units (2) is combined. its The reason is that the adsorption property to the pigment is excellent, and the aggregation of the pigment dispersants using such a block copolymer can be effectively suppressed.

In the case where the constituent unit (1) and the constituent unit (2) are contained in two or more types, the block copolymer may be bonded in the order of the constituent unit (1)-constituting unit (2')-constituting unit (2"). a block copolymer in which the constituent units (1') - constituent units (1") - constituent units (2) are bonded, and constituent units (1') - constituent units (1") - constituent units (2) ') - a block copolymer or the like in which the unit (2") is bonded in the order.

<Organic acid compound>

A salt is formed as an amine group which is a constituent unit (1) of the block copolymer having the structural unit (1) represented by the above general formula (I) and the structural unit (2) represented by the general formula (II). Examples of the organic acid compound include an organic phosphoric acid compound having a structure represented by the following general formula (III) and/or an organic sulfonic acid compound having a structure represented by the following general formula (IV).

[In the formulae (III) and (IV), R ^a and R ^{a '} are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, or an aryl group. , -[CH(R ^c )-CH(R ^d )-O] _s -R ^e , -[(CH ₂ ) _t -O] _u -R ^e , or -OR ^a" , a monovalent group, R Any of ^a and R ^a' contains a carbon atom. R ^a" is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, -[CH(R ^c ) -CH(R ^d )-O] _s -R ^e , [(CH ₂ ) _t -O] _u -R ^e represents a monovalent group.

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 -OR ^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 a 1-valent 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, or 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, - a monovalent group represented by CH ₂ CHO, -CO-CH=CH ₂ , -CO-C(CH ₃ )=CH ₂ or -CH ₂ COOR ^f , and R ^f is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms .

In R ^a , R ^{a '} and R ^b , the alkyl group, the alkenyl group, the aralkyl group and the aryl group may each have a substituent.

s represents an integer from 1 to 18, t represents an integer from 1 to 5, and u represents an integer from 1 to 18. ]

In the present invention, by using the above organic acid compound and/or a halogenated hydrocarbon to be described later, the pigment dispersant can be excellent in pigment dispersibility and stability. Further, in the case of using an organic acid compound, the salt-forming portion has high solubility in an alkaline aqueous solution at the time of alkaline development, and thus a photosensitive resin composition excellent in basic developability can be obtained.

In the above general formula (III), 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 group, and -[ CH(R ^c )-CH(R ^d )-O] _s -R ^e , -[(CH ₂ ) _t -O] _u -R ^e , or -OR ^a" , and any of R ^a and R ^a' One contains carbon atoms.

The alkyl group having 1 to 18 carbon atoms, the alkenyl group having 2 to 18 carbon atoms, an aryl group and an aralkyl group are represented by the above R ⁴ . The position of the double bond of the alkenyl group is not limited, and from the viewpoint of reactivity, it is preferred that the terminal of the alkenyl group has a double bond.

The alkyl group and the alkenyl group may have a substituent, and examples of the substituent include a halogen atom such as F, Cl, and Br, a nitro group, and the like.

In addition, examples of the substituent of the aromatic ring such as the aryl group and the aralkyl group include an alkenyl group, a nitro group, and a halogen atom, in addition to a linear or branched alkyl group having 1 to 4 carbon atoms.

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, or -CHO. a monovalent group represented by -CH ₂ CHO, -CO-CH=CH ₂ , -CO-C(CH ₃ )=CH ₂ or -CH ₂ COOR ^f , and R ^f is a hydrogen atom or a carbon number of 1 to 5 A linear, branched, or cyclic alkyl group.

The monovalent group represented by the above R ^e may, for example, be a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms, or a halogen such as F, Cl or Br. Atoms, etc.

The alkyl group having 1 to 18 carbon atoms in the above R ^{e is} represented by the above R ⁴ , and the alkenyl group, the aralkyl group and the aryl group having 2 to 18 carbon atoms are represented by R ^a and R ^a' described above.

When R ^a and/or R ^{a '} is -OR ^a" , it is an acidic phosphate. The above 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 aromatic group. a monovalent group represented by -[CH(R ^c )-CH(R ^d )-O] _s -R ^e and -[(CH ₂ ) _t -O] _u -R ^e .

The alkyl group having 1 to 18 carbon atoms, the alkenyl group having 2 to 18 carbon atoms, an aralkyl group, and an aryl group are represented by R ^a and R ^a' described above. Further, when R ^{a "} has an aromatic ring, the aromatic ring may have an appropriate substituent, for example, a linear or branched alkyl group having 1 to 4 carbon atoms.

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 preferably an integer of 1 to 4, more preferably 1 An integer of ~2, t is preferably an integer of 1 to 4, more preferably 2 or 3. u is preferably an integer of 1 to 4, more preferably an integer of 1 to 2.

In the above general formula (IV), R ^b represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, -[CH(R ^c )-CH(R ^d ) -O] _s -R ^e , -[(CH ₂ ) _t -O] _u -R ^e , or -OR ^b' .

The alkyl group having 1 to 18 carbon atoms, the alkenyl group having 2 to 18 carbon atoms, an aralkyl group and an aryl group are represented by the above R ^a and R ^{a '} .

In the case where R ^b is -OR ^b' , it is an acidic sulfate. The above 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 represents a monovalent group.

In R ^b and R ^{b '} , the alkyl group, the alkenyl group, the aralkyl group, and the aryl group may each have a substituent.

The above-mentioned alkyl group having 1 to 18 carbon atoms, alkenyl group having 2 to 18 carbon atoms, aralkyl group, aryl group, -[CH(R ^c )-CH(R ^d )-O] _s -R ^e , -[( CH ₂ ) _t —O] _u —R ^e is as shown in the above R ^a , R ^a′ and R ^a” .

Further, the above R ^c , R ^d and R ^e are as shown in the above R ^a , R ^{a '} and R ^a′ .

In the above R ^b and R ^{b '} , s is an integer from 1 to 18, t is an integer from 1 to 5, and u is an integer from 1 to 18. Preferably, s, t, and u are the same as R ^a , R ^{a '} and R ^{a '} .

As the organic acid compound represented by the above formula (III), R ^a and R ^{a '} in the above general formula (III) are each independently a hydrogen atom, a hydroxyl group, a methyl group, an ethyl group, and an aryl group which may have a substituent. Or aralkyl, vinyl, allyl, -[CH(R ^c )-CH(R ^d )-O] _s -R ^e , or -[(CH ₂ ) _t -O] _u -R ^e , or ^a monovalent group represented by -OR ^a" , any of R ^a and R ^a' containing a carbon atom, and R ^{a '} is a methyl group, an ethyl group, an aryl group or an aralkyl group which may have a substituent , vinyl, allyl, -[CH(R ^c )-CH(R ^d )-O] _s -R ^e , or -[(CH ₂ ) _t -O] _u -R ^e , R ^c and R ^d If it is independently a hydrogen atom or a methyl group, and R ^e is -CO-CH=CH ₂ or -CO-C(CH ₃ )=CH ₂ , it is preferable to be excellent in pigment dispersibility.

Further, as the organic acid compound represented by the general formula (IV), R ^b in the general formula (IV) is a methyl group, an ethyl group, an aryl group or an aralkyl group which may have a substituent, a vinyl group, an allylic group. a group, -[CH(R ^c )-CH(R ^d )-O] _s -R ^e , or -[(CH ₂ ) _t -O] _u -R ^e , or a -valent group represented by -OR ^b' , R ^{b '} is methyl, ethyl, aryl or aralkyl which may also have a substituent, vinyl, allyl, -[CH(R ^c )-CH(R ^d )-O] _s -R ^e , or -[(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 -CO-CH=CH ₂ or -CO-C (CH ₃ In the case of =CH ₂ , it is preferable to be excellent in pigment dispersibility.

Wherein the organic acid compound represented by the above general formula (III) and general formula (IV), as R ^a , R ^a′ and/or R ^a′′ , and/or R ^b and/or R ^b′ , is dispersed in pigment In terms of nature, it is preferred to have an aromatic ring. At least one of R ^a , R ^{a '} and R ^a′ , or R ^b or R ^b′ may be an aryl or aralkyl group which may have a substituent, Specifically, a benzyl group, a phenyl group, a tolyl group, a naphthyl group, or a biphenyl group is preferable in terms of pigment dispersibility. In the above general formula (III), one of R ^a and R ^{a '} has an aromatic ring, and the other of R ^a and R ^{a '} is a hydrogen atom or a hydroxyl group.

Further, in terms of heat resistance and chemical resistance, as an organic acid compound represented by the above general formula (III) and general formula (IV), a compound directly bonded to phosphorus (P) and sulfur (S) by carbon atoms Preferably, R ^a and R ^{a '} are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, -[CH(R ^c )- CH(R ^d )-O] _s -R ^e , -[(CH ₂ ) _t -O] _u -R ^e represents a monovalent group, and any of R ^a and R ^{a '} is preferably a carbon atom . Further, 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 The monovalent group represented by -[(CH ₂ ) _t -O] _u -R ^{e is} preferred.

Further, the organic acid compound represented by the above general formula (III) and general formula (IV) has, as R ^a , R ^{a '} and/or R ^a′′ , and/or R ^b and/or R ^b′ Polymeric group, ie, vinyl, allyl or -[CH(R ^c )-CH(R ^d )-O] _s -R ^e , or -[(CH ₂ ) _t -O] _u -R ^e And R ^e is -CO-CH=CH ₂ or -CO-C(CH ₃ )=CH ₂ is preferred, especially R ^a , R ^{a '} and/or R ^a" , and/or R ^b and / or R ^{b '} is preferably a vinyl group, an allyl group, a 2-methylpropenyloxyethyl group or a 2-propenyloxyethyl group.

In this case, when the photosensitive resin composition for a color filter of the present invention is used for exposure to form a colored layer, the polymerizable groups and/or the polymerizable group and the color filter of the present invention are used. The alkali-soluble resin, the polyfunctional monomer, and the like contained in the photosensitive resin composition can be easily polymerized, and the pigment dispersant can be stably present in the coloring layer of the color filter. When a liquid crystal display device is manufactured using such a color filter, it is possible to prevent the above-described pigment dispersant from oozing out to the liquid crystal layer or the like.

Further, since the organic acid compound contains a polymerizable group, the polymerizable groups of the organic acid compound can be polymerized before being used to form the coloring layer, and as a result, the pigment dispersant is highly polymerized, so that a colored layer is formed. Color filter at the unexposed area The photosensitive resin composition can be particularly excellent in alkaline development.

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

<halogenated hydrocarbon>

The halogenated hydrocarbon used in the present invention is a repeating unit (1) of a block copolymer having a repeating unit (1) represented by the above general formula (I) and a repeating unit (2) represented by the general formula (II). The amine group has a salt.

In the present invention, the salt-forming site formed by the pigment dispersant is excellent in the adsorptivity of the pigment by using the above-mentioned halogenated hydrocarbon, so that high dispersibility can be exhibited, and heat resistance, alkali resistance, and development of the dispersant can be improved. Pattern defect tolerance.

Examples of the halogenated hydrocarbon include a halogen atom of a chlorine atom, a bromine atom, and an iodine atom, which may be substituted for a hydrogen atom of a saturated or unsaturated linear, branched or cyclic hydrocarbon. Among them, in terms of improving the dispersibility of the pigment, an allyl halide and/or an aralkyl halide is preferred.

Further, the number of carbon atoms of the halogenated hydrocarbon is preferably from 1 to 30, more preferably from 1 to 25, still more preferably from 1 to 18.

In the above-mentioned halogenated hydrocarbon, examples of the alkyl halide include those having 1 to 18 carbon atoms, but are not particularly limited. Specific examples thereof include methyl chloride, methyl bromide, ethyl chloride, ethyl bromide, methyl iodide, ethyl iodide, n-butyl chloride, hexyl chloride, octyl chloride, and dodecyl chloride. Tetradecyl chloride, cetyl chloride, and the like. Further, examples of the allyl halide include allyl chloride, allyl bromide, and allyl iodide. In addition, examples of the aralkyl group of the aralkyl halide include a carbon number of 7 to 18, but are not particularly limited. Specific examples thereof include benzyl chloride, benzyl bromide, benzyl iodide, naphthylmethyl chloride, pyridylmethyl chloride, naphthylmethyl bromide, and pyridylmethyl bromide. Further, examples of the aryl halide include those having 6 to 18 carbon atoms, but are not particularly limited. Specifically, for example, chlorinated benzene or the like can be mentioned.

Among them, at least one selected from the group consisting of allyl chloride, allyl bromide, allyl iodide, benzyl chloride, benzyl bromide, and benzyl iodide, is easy to form and react with salt formation reaction. It is preferable that the salt formation site is excellent in the adsorptivity of the pigment.

The content of the organic acid compound and/or the halogenated hydrocarbon in the block copolymer used in the present invention is not particularly limited as long as it exhibits good dispersion stability, and is generally shown in the above general formula (I). The tertiary amine group is preferably 0.05 to 1.0 mole equivalent.

Among them, the content of the organic acid compound and/or the halogenated hydrocarbon is preferably 0.2 to 0.8 mol equivalents based on the tertiary amino group. Thus, for the tertiary amine group, a portion of the specified amount forms a salt, and a portion of the specified amount remains in the block copolymer in the form of an amine group, thereby enhancing the adsorption of the pigment, and the sulfonated derivative of the yellow pigment. Interaction makes the pigment dispersibility and pigment dispersion stability more excellent. Further, it is less effective in suppressing the viscosity of the pigment dispersant and the resin composition as compared with the effect of lowering the viscosity. Further, the solubility in the solvent and the resolubility after the resin composition is temporarily dried are also greatly improved.

In addition, when two or more kinds of the above organic acid compound and/or halogenated hydrocarbon are used in combination, the total content thereof may be within the above range.

<Manufacture of Pigment Dispersant>

In the present invention, as a method for producing a block copolymer used as a pigment dispersant, an amine group having the above repeating unit (1) and repeating unit (2) and having the above repeating unit (1) can be produced. The salt may be formed with the above organic acid compound and/or halogenated hydrocarbon, and is not particularly limited. In the present invention, for example, the repeating unit (1) and the repeating unit (2) are polymerized by a known polymerization means, and then dissolved or dispersed in a solvent to be described later, and then, the organic acid compound and/or the organic acid compound are added to the solvent. The pigment dispersant can be produced by halogenating the hydrocarbon and stirring.

As the above-mentioned polymerization means, the above-mentioned repeating unit (1) and repeating unit (2) can be used as The number required for polymerization and the desired molecular weight is not particularly limited, and a method generally used for polymerization of a compound having a vinyl group can be used. For example, anionic polymerization, living radical polymerization, or the like can be used. In the present invention, a method of performing living polymerization by group transfer polymerization (GTP) as disclosed in "J. Am. Chem. Soc." 105, 5706 (1983) is preferred. According to this method, the molecular weight, the molecular weight distribution, and the like can be easily made into a desired range, so that the dispersibility of the pigment dispersant can be made uniform.

In the red pigment dispersion liquid for a color filter of the present invention, one type of the above-mentioned block copolymer may be used as the pigment dispersant, or two or more types may be used in combination. Further, the content thereof is not particularly limited as long as the pigment can be uniformly dispersed, and for example, it can be used in an amount of 10 to 150 parts by weight based on 100 parts by weight of the pigment. Further, it is preferred to formulate a ratio of 15 to 45 parts by weight based on 100 parts by weight of the pigment, and particularly preferably a ratio of 15 to 40 parts by weight. When the content of the salt type graft copolymer is within the above range, the pigment can be uniformly dispersed. Further, in the present invention, when the content other than the pigment derivative is specified, the pigment contains a pigment derivative in addition to the pigment, and for example, a sulfonated derivative of a yellow pigment.

(solvent)

The red pigment dispersion liquid for color filters of the present invention contains a solvent for dispersing the pigment. The solvent to be used as the pigment dispersion liquid is not particularly limited as long as it does not react with each component in the pigment dispersion liquid and can dissolve or disperse the organic solvent.

The solvent used for the pigment dispersion liquid of the present invention may, for example, be an alcohol solvent such as methanol, ethanol, n-propanol or isopropanol; or a Cyrus solvent such as methoxy alcohol or ethoxylated alcohol; a carbitol solvent such as oxyethoxyethanol or ethoxyethoxyethanol; an ester of ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate or ethyl lactate a solvent; a ketone solvent such as acetone, methyl isobutyl ketone or cyclohexanone; methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl Surfactant-based solvent such as acetate, 3-methoxybutyl acetate, methoxybutyl acetate, ethoxyethyl acetate, ethyl celecoxib acetate; methoxyB a carbitol acetate solvent such as oxyethyl acetate, ethoxyethoxyethyl ester or butyl carbitol acetate (BCA); diethyl ether, ethylene glycol dimethyl ether, diethylene glycol An ether solvent such as dimethyl ether, propylene glycol monomethyl ether or tetrahydrofuran; aproticity such as N,N-dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidone Ammonium a solvent such as a lactone such as γ-butyrolactone; an unsaturated hydrocarbon solvent such as benzene, toluene, xylene or naphthalene; or an organic solvent such as a saturated hydrocarbon solvent such as n-heptane, n-hexane or n-octane; . Among these solvents, methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, B Surfacacetate solvent such as oxyethyl acetate or ethyl sirolimus acetate; methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, butyl carbitol acetate ( BCA) and other carbitol acetate solvent; ether solvent such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether or propylene glycol monomethyl ether; methyl methoxypropionate, ethoxypropionic acid An ester solvent such as ethyl ester or ethyl lactate; and a ketone solvent such as cyclohexanone is suitable for use. 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 One or more selected from the group consisting of benzyl-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, and cyclohexanone, in terms of solubility and coating suitability of other components It is better.

These solvents may be used alone or in combination of two or more.

The pigment dispersion liquid of the present invention is usually prepared by using a solvent as described above in a ratio of 60 to 85% by weight based on the total amount of the pigment dispersion liquid containing the solvent. If the amount of the solvent is too small, the viscosity increases and the pigment dispersibility is liable to lower. Further, if the amount of the solvent is too large, the pigment concentration is lowered, and it may be difficult to achieve a chromaticity coordinate in which the resin composition is a target after preparation.

(other pigment derivatives)

Other pigment derivatives may be contained as long as the effects of the present invention are not impaired. Such a pigment derivative is a compound having a function of imparting a functional group to a pigment skeleton and adding various functions to the pigment. When a pigment derivative is added to a pigment during pigment dispersion, a similar pigment skeleton of the pigment derivative is adsorbed or bonded to the surface of the pigment, thereby imparting polarity to the surface of the pigment, improving affinity between the dispersant and the pigment, and ensuring dispersibility. Decentralized stability.

In the pigment dispersion of the present invention, a sulfonium imide alkylated derivative of a diketopyrrolopyrrole red pigment can be further used, and the pigment can be inhibited even after the high temperature heating step in the color filter step. With agglutination, a particularly high brightness and high contrast can be achieved. In addition, a ruthenium imide alkylated derivative of a yellow pigment can also be used.

<Indoleimide alkylated derivatives of diketopyrrolopyrrole red pigment>

A quinone imine alkylated derivative of a diketopyrrolopyrrole red pigment having a structure in which at least one quinone imine alkyl group is bonded to a diketopyrrolopyrrole red pigment. For example, in the case of using C.I. Pigment Red 254 as a pigment, it is preferred to use a C.I. Pigment Red 254 quinone imine alkylated derivative and/or a C.I. Pigment Red 255 quinone imine alkylated derivative. In addition, the bismuth imide alkylated derivative of CI Pigment Red 254 and/or the ruthenium alkylated derivative of CI Pigment Red 255 has at least one sulfhydryl alkyl group bonded to CI Pigment Red 254. Or the construction of CI Pigment Red 255.

Examples of the alkyl group of the sulfimine alkyl group include a linear or branched alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and a hexyl group. Among them, in terms of ease of production, an alkyl group having a methyl group as a quinone imine group is preferred.

It is presumed that the quinone imide alkylated derivative is intramolecular or intermolecular, and forms a hydrogen bond with the hydrogen bonding site of the diketopyrrolopyrrole red pigment, thereby using the diketopyrrolopyrrole red pigment. The hydrogen bonding site is blocked, making other diketopyrrolopyrrole red Pigments are not close to the molecular level, making it difficult to grow crystals.

Further, it is preferable that the substitution number n of the quinone imine group is from 1 to 2, and it is preferable that the ratio of the easy adsorption of the pigment and the heat resistance are improved.

The quinone imine alkylated derivative of the diketopyrrolopyrrole red pigment, for example, is a diketopyrrolopyrrole red pigment which is reacted with formaldehyde and quinone in sulfuric acid. Can be manufactured. This synthesis method is described in detail in Japanese Patent Laid-Open Publication No. 2004-501911, which is incorporated herein by reference. The quinone imine alkylated derivative of the diketopyrrolopyrrole-based red pigment may be used alone or in combination of two or more. For example, a quinone imine alkylated derivative in which two or more types of alkyl groups, a substitution position or a substitution number of a quinone imine group are different may be used in combination.

In the present invention, the quinone imine alkylated derivative of the diketopyrrolopyrrole red pigment is contained in an amount of from 0 to 15 parts by weight based on 100 parts by weight of the diketopyrrolopyrrole red pigment. In addition, the quinone imine alkylated derivative of the diketopyrrolopyrrole red pigment is contained in an amount of 1 to 15 parts by weight, more preferably, based on 100 parts by weight of the diketopyrrolopyrrole red pigment. 3 to 15 parts by weight is preferred. By using such a content, even if the aggregation of the pigment can be suppressed after the high-temperature heating step in the color filter step, particularly high brightness and high contrast can be achieved.

Further, the content ratio of the sulfonated derivative of the yellow pigment to the ruthenium alkylated derivative of the diketopyrrolopyrrole red pigment is from 20:1 to 20:40, wherein The hue is greatly changed, and the aggregation of the pigment can be suppressed even after the high-temperature heating step in the color filter step, and it is preferable to achieve a particularly high brightness and a high contrast ratio of 20:1 to 20:30.

When the sulfonated derivative of the above yellow pigment and the quinone imide alkylated derivative of the diketopyrrolopyrrole red pigment are used in combination, the synergistic effect can be suppressed and used alone. When the red pigment derivative is changed in hue, it is also possible to increase the brightness, improve the heat resistance, and suppress the crystallization of the diketopyrrolopyrrole red pigment during baking.

(other pigments)

In the pigment dispersion liquid of the present invention, other pigments may be further contained as long as the effects of the present invention are not impaired. The other pigment is, for example, a yellow pigment in terms of a specific color tone necessary for achieving a red colored layer of a color filter as described in the red photosensitive resin composition described later. However, when the diketopyrrolopyrrole red pigment is dispersed, a sulfonated derivative of a yellow pigment and a pigment dispersant containing a block copolymer of a tertiary amine or a tertiary ammonium salt are preferred. That is, the red pigment dispersion liquid of the present invention is suitably used in the form of a red pigment dispersion liquid mixed with another yellow pigment dispersion liquid when preparing a red photosensitive resin composition.

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

In addition, it is preferable to select one or more selected from the group consisting of C.I. Pigment Red 177 and C.I. Pigment Red 242 in order to achieve a specific color tone of the color filter.

(other ingredients)

In the pigment dispersion of the present invention, the pigment dispersion auxiliary resin and other components may be further formulated as needed.

The pigment-dispersing auxiliary resin may, for example, be an alkali-soluble resin exemplified as the photosensitive resin composition described later. Due to the steric hindrance of the alkali-soluble resin, the pigment particles become difficult to contact each other, and the effect of reducing the dispersant is sometimes caused by the dispersion stabilization and the effect of the dispersion stabilization.

Further, other pigment dispersants may be contained as long as the effects of the present invention are not impaired.

Further, examples of the other component include a surfactant for improving wettability, and A decane coupling agent, an antifoaming agent, a collapse preventing agent, an antioxidant, an aggregation preventing agent, an ultraviolet absorber, and the like for improving adhesion.

<Method for Producing Pigment Dispersion>

The pigment dispersion liquid of the present invention is contained in the above solvent, in the presence of a sulfonated derivative of the yellow pigment, and a pigment dispersant containing a block copolymer of a tertiary amine or a tertiary ammonium salt. A step of dispersing the above diketopyrrolopyrrole red pigment.

In the dispersion step, as the dispersing machine for performing the dispersion treatment, a ball mill such as two rolls or three rolls, a ball mill such as a ball mill or a vibratory ball mill, a paint conditioner, a continuous disc type bead mill, and a continuous ring may be mentioned. A pellet mill such as a bead mill. As a preferable dispersion condition of the bead mill, the bead diameter used is preferably 0.03 to 2.00 mm, and more preferably 0.10 to 1.0 mm.

Specifically, it is pre-dispersed by 2 mm zirconia beads having a large bead diameter, and further dispersed by 0.1 mm zirconia beads having a small bead diameter. Further, after dispersion, it is preferably filtered through a membrane filter of 0.5 to 0.1 μm.

In the present invention, the dispersion time of dispersion by a known dispersing machine can be appropriately adjusted and is not particularly limited, and the pigment is obtained by a method in which the average dispersed particle diameter of the pigment is about 15 to 50 nm, for example, using a paint shaker. In terms of miniaturization and high contrast, it is preferably 5 to 50 hours.

By doing so, a pigment dispersion liquid excellent in dispersibility of the pigment particles is obtained. This pigment dispersion liquid is used as a pre-modulation for preparing a red photosensitive resin composition for a color filter excellent in pigment dispersibility.

2. Red photosensitive resin composition for color filter

The red photosensitive resin composition for a color filter of the present invention is characterized by comprising at least the red pigment dispersion liquid for a color filter of the present invention and a photosensitive adhesive component.

Since the red photosensitive resin composition for a color filter of the present invention contains the above-described pigment dispersion liquid of the present invention, it is possible to form a color filter which achieves particularly high brightness and which is required to achieve high contrast.

Hereinafter, the components used in the red photosensitive resin composition for a color filter of the present invention will be described.

In addition, the component contained in the red pigment dispersion liquid for a color filter of the present invention can be used in the same manner as the above-mentioned pigment dispersion liquid portion, and therefore, other pigments and other pigment dispersants are omitted here. Description.

(other pigments)

The red photosensitive resin composition for a color filter of the present invention may contain other yellow as long as the chromaticity necessary for the use and method of the color filter can be achieved without impairing the effects of the present invention. Pigments, even other pigments such as orange.

As the other pigment, it is preferable to contain a yellow pigment in terms of the specific color tone necessary for achieving the red colored layer of the color filter and to improve the contrast.

<yellow pigment>

As the yellow pigment, one or more selected from the group consisting of C.I. Pigment Yellow 150 or its derivative pigment, C.I. Pigment Yellow 138, and C.I. Pigment Yellow 139 are preferred.

Here, as the derivative pigment of the CI Pigment Yellow 150, specifically, a azo compound which acts as a host of at least one guest compound and which is one of the following chemical formulas or tautomeric structures thereof, The second, third and tetraanions correspond to the metals Li, Cs, Mg, Cd, Co, Al, Cr, Sn, Pb, particularly suitably Na, K, Ca, Sr, Ba, Zn, Fe, Ni, Cu, Mn And La metal complex.

[Chemistry 7] [In the above chemical formula, R and R' are independently OH, NH ₂ , NH-CN, amidino or arylamine, and R ^a and R ^{a' are} independently -OH or -NH ₂ ].

The above-mentioned derivative pigments can be referred to Japanese Patent Laid-Open No. 2001-354869, Japanese Patent Laid-Open No. Hei No. 2005-325350, Japanese Patent Laid-Open No. Hei. No. 2007-25687, Japanese Patent Laid-Open No. Hei. Japanese Laid-Open Patent Publication No. 2007-23288 and Japanese Patent Laid-Open No. 2008-24927.

(photosensitive adhesive component)

In the present invention, in terms of imparting sufficient strength, durability, and adhesion to the coating film, the coating film can be cured by a polymerization reaction after forming a pattern on a substrate by coating, transfer, or the like. Adhesive ingredients. In addition to the photosensitive adhesive component described below, a thermosetting adhesive such as an epoxy resin which can be polymerized and hardened by heating can be further used. When the resin composition of the present invention having the above pigment dispersion having excellent pigment dispersibility is used to prepare the resin composition of the present invention, it is necessary to select an appropriate binder component so as not to impede such excellent pigment dispersibility.

In the photosensitive adhesive component, the photocurable resin which can be polymerized and cured by light such as ultraviolet rays or electron beams is contained, and the exposed portion can be formed by curing the exposed portion and dissolving and removing the unexposed portion. The negative photosensitive adhesive component of the pattern.

In the red photosensitive resin composition for a color filter of the present invention, a negative photosensitive adhesive component is preferable in that a pattern can be easily formed by photolithography using an existing step.

A negative photosensitive adhesive component containing a photocurable resin which can be polymerized and cured by light such as ultraviolet rays or electron beams, and is formulated with (i) an alkali-soluble resin, (ii) a polyfunctional monomer, and (iii) photopolymerization. Starting agent, sensitizer, etc.

(i) alkali soluble resin

The alkali-soluble resin of the present invention has a carboxyl group in the side chain, and can be suitably used as long as it functions as a binder resin and is soluble in a developing solution used for patterning, particularly preferably in an alkaline developing solution.

The alkali-soluble resin which is preferable in the present invention is a resin having a carboxyl group, and specific examples thereof include an acrylic copolymer having a carboxyl group, an epoxy (meth)acrylate resin having a carboxyl group, and the like. Among them, 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 are preferred. This is because the film strength of the formed cured film is improved by containing a photopolymerizable functional group. Further, these acrylic copolymers and epoxy acrylate resins may be used in combination of two or more kinds.

An acrylic copolymer having a carboxyl group is obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group and an ethylenically unsaturated monomer.

The acrylic copolymer having a carboxyl group may further contain a constituent unit having an aromatic carbocyclic ring. The aromatic carbocyclic ring functions as a component that imparts coating properties to the photosensitive resin composition.

The acrylic copolymer having a carboxyl group may further contain a constituent unit having an ester group. The constituent unit having an ester group functions not only as a component for suppressing the alkali solubility of the photosensitive resin composition, but also as a component for improving the solubility in a solvent and further improving the solvent resolubility.

Examples of the acrylic copolymer having a carboxyl group include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and (methyl). ) n-butyl acrylate, dibutyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-amyl (meth)acrylate, (meth)acrylic acid Ester, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, n-decyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, (A) Phenyloxyethyl acrylate, cyclohexyl (meth) acrylate, (meth) acrylate Ester, dicyclopentanyl (meth)acrylate, 1-adamantyl (meth)acrylate, allyl (meth)acrylate, 2,2'-oxybis(methylene)bis-2-acrylic acid Ester, styrene, γ-methylstyrene, glycidyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-dimethylaminoethyl (meth)acrylate, N-ethylene Selected from 2-yl-2-pyrrolidone, N-methylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, etc. One or more kinds, and (meth)acrylic acid, acrylic acid dimer (for example, M-5600 manufactured by East Asian Synthetic Chemical Co., Ltd.), itaconic acid, crotonic acid, maleic acid, and antibutene A copolymer composed of one or more selected from the group consisting of an acid, a vinyl acetate, and an anhydrous substance. In addition, the above-mentioned copolymer, for example, a polymer obtained by adding an ethylenically unsaturated compound having a reactive functional group such as a glycidyl group or a hydroxyl group, and introducing an ethylenically unsaturated bond, may be exemplified, but is not limited thereto. this.

In addition, a polymer obtained by adding an ethylenically unsaturated compound having a glycidyl group or a hydroxyl group to a copolymer, and introducing an ethylenically unsaturated bond, etc., can be polymerized with a polyfunctional monomer described later upon exposure. It is particularly suitable in terms of a more stable coloring layer.

The copolymerization ratio of the carboxyl group-containing ethylenically unsaturated monomer in the carboxyl group-containing copolymer is usually 5 to 50% by weight, preferably 10 to 40% by weight. In this case, when the copolymerization ratio of the carboxyl group-containing ethylenically unsaturated monomer is less than 5% by weight, the solubility of the obtained coating film for the alkaline developing solution is lowered, and it is difficult to form a pattern. Moreover, when the copolymerization ratio exceeds 50% by weight, when the image is developed with an alkaline developing solution, the formed pattern tends to fall off from the substrate and the surface film of the pattern tends to be rough.

The preferred molecular weight of the carboxyl group-containing copolymer is preferably in the range of 1,000 to 500,000, more preferably 3,000 to 200,000. If it is less than 1,000, the patterning function after hardening is remarkably lowered. When it exceeds 500,000, when it develops with an alkali developing liquid, it may become difficult to form a pattern.

The epoxy (meth) acrylate resin having a carboxyl group is not particularly limited, but an epoxy (meth) acrylate compound obtained by reacting an epoxy compound with a reaction product of an unsaturated group-containing monocarboxylic acid and an acid anhydride To be appropriate.

The epoxy compound is not particularly limited, and examples thereof include a bisphenol A epoxy compound, a bisphenol F epoxy compound, a bisphenol S epoxy compound, a phenol novolak epoxy compound, and a cresol novolak ring. An epoxy compound such as an oxygen compound, an aliphatic epoxy compound, or a bisphenol fluorene epoxy compound. These may be used alone or in combination of two or more.

Examples of the carboxylic acid having an unsaturated group include (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl decanoic acid, and (methyl). Propylene oxiranyl hexahydrophthalic acid, (meth)acrylic acid dimer, β-mercaptoacrylic acid, β-styrene acrylic acid, cinnamic acid, crotonic acid, α-cyanocinnamic acid, and the like. These monocarboxylic acids containing an unsaturated group may be used alone or in combination of two or more.

Examples of the acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, decanoic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, and methyl group. a dibasic acid anhydride such as methylenetetrahydrophthalic anhydride, chloro-bromic anhydride, methyltetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, and Aromatic polyvalent carboxylic anhydride such as phenyl ether tetracarboxylic acid, 5-(2,5-dioxytetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, inner bicyclic ring a polyvalent carboxylic anhydride derivative such as [2,2,1]-hept-5-ene-2,3-dicarboxylic anhydride or the like. These may be used alone or in combination of two or more.

Molecular weight of the obtained epoxy (meth) acrylate compound having a carboxyl group There is no particular limitation, and it is preferably from 1,000 to 40,000, more preferably from 2,000 to 5,000.

(ii) Polyfunctional monomer

Examples of the polyfunctional monomer in the present invention include di(meth)acrylates of alkylene glycols such as ethylene glycol and propylene glycol; and polyalkylenes such as polyethylene glycol and polypropylene glycol. a di(meth) acrylate of a diol; a poly(meth) acrylate of a ternary or higher polyhydric alcohol such as glycerin, trimethylolpropane, pentaerythritol or dipentaerythritol; a dicarboxylic acid modified product; an oligo(meth)acrylate of a polyester, an epoxy resin, a urethane resin, an alkyd resin, a polyoxyxylene resin, a spiro resin, or the like; a di(meth)acrylate of a two-terminal hydroxylated polymer of 3-butadiene, a two-terminal hydroxypolyisoprene, a two-terminal hydroxypolycaprolactone, or the like; a bis(2-(methyl) propylene group; Oxyxyethyl) phosphate and the like.

Among these polyfunctional monomers, poly(meth)acrylates of a trihydric or higher polyhydric alcohol and tricarboxylic acid modified products thereof are preferable, specifically, trimethylolpropane tri(methyl) Acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate succinic acid modification, pentaerythritol tetra(meth)acrylate, dipentaerythritol IV (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are preferred. These polyfunctional monomers may be used alone or in combination of two or more.

The amount of the polyfunctional monomer used in the present invention is usually 5 to 500 parts by weight, preferably 20 to 300 parts by weight, per 100 parts by weight of the alkali-soluble resin. When the content of the polyfunctional monomer is less than the above range, the photocuring may not be sufficiently performed, and the exposed portion may be eluted. When the content of the polyfunctional monomer is more than the above range, the basic developability is lowered. possibility.

(iii) photopolymerization initiator, and sensitizer

Among the negative photosensitive adhesive components, usually, a photopolymerization initiator which is active for the wavelength of the light source used is formulated. Photopolymerization initiators are considered to have photopolymerizable aggregates. The difference between the form of the reaction of the complex and the photopolymerizable monomer (for example, radical polymerization, cationic polymerization, etc.) and the type of each material is not particularly limited.

The photopolymerization initiator is, for example, a compound which generates a free radical via ultraviolet energy, and examples thereof include a biimidazole compound, a benzoin compound, an acetophenone compound, a benzophenone compound, and an α-diketone system. Compound, multinuclear oxime compound, xanthone compound, thioxanthone compound, three Compound, ketal compound, azo compound, peroxide, 2,3-dialkyldiketone compound, disulfide compound, thiram compound, fluoroamine compound, oxime ester A compound or the like. These may be used alone or in combination of two or more.

The content of the photopolymerization initiator used in the red photosensitive resin composition for a color filter of the present invention is usually about 0.01 to 100 parts by weight, preferably 5, based on 100 parts by weight of the polyfunctional monomer. ~60 parts by weight. When the content is less than the above range, the polymerization reaction may not be sufficiently formed. Therefore, the hardness of the colored layer may not be sufficient. On the other hand, if the content is more than the above range, the red photosensitive resin composition for the color filter is used. The content of the pigment or the like in the solid portion is relatively small, and a sufficient coloring concentration may not be obtained.

Furthermore, in the present invention, one or more selected from the group consisting of a sensitizer and a curing accelerator may be used in combination with the photopolymerization initiator. Specific examples of the sensitizer include 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, and 4-diethylaminoethyl hydrazine. Benzene, 4-dimethylaminopropionylbenzene, ethyl-4-dimethylaminobenzoate, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-double (4-diethylaminobenzylidene)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzhydrazide) coumarin, 4-(diethylamino)arylpropene Aromatic hydrocarbons, etc. Further, specific examples of the curing accelerator include 2-hydrothiobenzimidazole, 2-hydrothiobenzothiazole, and 2-hydrothiobenzoene. Azole, 2,5-dihydrothio-1,3,4-thiadiazole, 2-hydrothio-4,6-dimethylaminopyridine, 1-phenyl-5-hydroxythio-1H- A chain shifting agent such as tetrazole or 3-hydrothio-4-methyl-4H-1, 2,4-triazole.

(Other pigment dispersants)

In the photosensitive resin composition, other pigments such as a yellow pigment can be further used as the pigment in terms of adjusting the chromaticity of the colored layer. In order to disperse the other pigment, the pigment dispersant used in the above-described pigment dispersion liquid of the present invention may be used, but other pigment dispersants may be used, and other pigment dispersants may be contained in the photosensitive resin composition.

The other pigment dispersant is not particularly limited, and for example, a surfactant such as a cationic system, an anionic system, a nonionic system, an amphoteric, a polyfluorene-based or a fluorine-based surfactant can be used. Among the surfactants, a polymer surfactant (polymer dispersant) exemplified below is also preferred. Further, as the pigment dispersant, a pigment derivative which is dissolved in a small amount in a solvent can also be used.

The pigment dispersant is appropriately selected for use in order to disperse the pigment to be used. Specific examples can be exemplified by decane decylamine, nonane decylamine, dodecyl decylamine, N-dodecylhexadecaneamine, N-octadecylpropionamide, N,N-dimethyl-10- Amidoxime compound such as dialkylamine and N,N-dihexylacetamide, diethylamine, diheptylamine, dibutylhexadecaneamine, N,N,N',N'-tetramethylmethane Amine compounds such as amine, triethylamine, tributylamine and trioctylamine, monoethanolamine, diethanolamine, triethanolamine, N,N,N',N'-(tetrahydroxyethyl)-1,2-diamine Ethylethane, N,N,N'-tris(hydroxyethyl)-1,2-diaminoethane, N,N,N',N'-tetrakis(hydroxyethylpolyoxyethylene)-1, 2-diaminoethane, 1,4-bis(2-hydroxyethyl)peri And 1-(2-hydroxyethyl) piperidine Examples of the amine having a hydroxyl group and the like include compounds such as piperidinamide, isopiperidiniumamine, and nicotinamide.

Further, examples thereof include (co)polymers of unsaturated carboxylic acid esters such as polyacrylates; (partial) amine salts (partially) ammonium salts of (co)polymers of unsaturated carboxylic acids such as polyacrylic acid; (partial) alkylamine salts; (co)polymers of hydroxyl group-containing unsaturated carboxylic acid esters such as hydroxyl group-containing polyacrylates and modified substances thereof; polyurethanes; unsaturated polyamines; Polyoxyalkylenes; long chain polyamine phthalamide phosphates; poly(lower alkylene imine) and free carboxyl groups The guanamine and its salts obtained by the reaction of the polyester.

(optional addition)

In the red photosensitive resin composition for a color filter of the present invention, various additives may be contained as needed without impairing the object of the present invention. Examples of the additive include a polymerization stopper, a chain shifting agent, a leveling agent, a plasticizer, a surfactant, an antifoaming agent, a decane coupling agent, an ultraviolet absorber, and an adhesion promoter.

Among them, examples of the surfactant that can be used include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene decyl phenyl ether, and poly Ethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, fatty acid modified polyester, tertiary amine modified polyurethane, and the like. Further, a fluorine-based surfactant may also be used.

Further, examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, and xylyl ester. Examples of the antifoaming agent and the leveling agent include a quinone-based, fluorine-based, and acrylic-based compound.

<Preparation ratio of each component in the photosensitive resin composition>

The total content of the pigments is preferably 10 to 40% by weight, more preferably 15 to 35% by weight, based on the total amount of the solid content of the photosensitive resin composition. When the amount of the pigment is too small, the photosensitive resin composition is applied to a predetermined film thickness (usually 1.0 to 4.0 μm), and the penetration concentration is insufficient, and if the pigment is too large, the photosensitive resin composition is applied to the photosensitive resin composition. When the substrate is hardened, the adhesion to the substrate, the surface roughness of the cured film, the hardness of the coating film, and the like are insufficient as the characteristics of the coating film, and the dispersion ratio of the pigment used in the photosensitive resin composition is dispersed. There are also many, so the characteristics of imaging and heat resistance are not sufficient. Further, in the present invention, the solid portion is a substance other than the above solvent, and also includes a polyfunctional monomer dissolved in a solvent.

Further, the total content of the pigment dispersant is preferably in the range of 1 to 60% by weight based on the total amount of the solid content of the photosensitive resin composition, and more preferably in the range of 5 to 50% by weight. When the content is less than 1% by weight based on the total amount of the solid content of the photosensitive resin composition, it is difficult to uniformly disperse the pigment, and when it exceeds 60% by weight, the curability and the display property are lowered. After that.

The alkali-soluble resin, the polyfunctional monomer, and the photoinitiator are blended in a ratio of 15 to 95% by weight, preferably 25 to 80% by weight, based on the total amount of the solid content of the photosensitive resin composition. good.

Further, the content of the solvent is not particularly limited as long as the coloring layer can be formed with good precision. The total amount of the photosensitive resin composition containing the solvent is preferably 65 to 95% by weight, more preferably 75 to 88% by weight. When the content of the solvent is within the above range, it can be excellent in coatability.

(Manufacture of red photosensitive resin composition for color filter)

The method for producing a red photosensitive resin composition for a color filter of the present invention comprises the steps of: a sulfonated derivative of a yellow pigment in a solvent, and a salt containing a tertiary amine or a 4-grade ammonium salt. a step of dispersing the diketopyrrolopyrrole red pigment to prepare a red pigment dispersion in the presence of a pigment dispersant of a block copolymer; and mixing the red pigment dispersion with a photosensitive binder component .

In order to achieve a necessary color tone for the red colored layer of the color filter, if necessary, other pigments different from the pigment contained in the red pigment dispersion of the present invention are further used, and the pigment dispersion of the present invention is additionally used. The liquid production method is preferably carried out, and it is preferred to prepare another pigment dispersion liquid in advance.

In this case, as a method for producing the photosensitive resin composition of the present invention, a pigment dispersion liquid of the present invention, another pigment dispersion liquid, and a photosensitive adhesive agent may be added. A method of further adding a solvent, various additives, and mixing as needed.

In the red photosensitive resin composition for a color filter of the present invention, since a pigment dispersion liquid prepared in advance is used, it is preferable to prevent aggregation of the pigment and to uniformly disperse the pigment.

Next, a color filter relating to the present invention will be described.

[Color Filter]

The color filter of the present invention is characterized in that it has a coloring layer formed by curing the color filter of the present invention with a red photosensitive resin composition.

The color filter of the present invention will be described with reference to the drawings. Fig. 1 is a schematic cross-sectional view showing an example of a 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 portion 2, and a colored layer 3.

(colored layer)

The coloring layer used in the color filter of the present invention is not particularly limited as long as the color filter of the present invention is cured with a red photosensitive resin composition, and is usually a transparent substrate to be described later. The opening portion of the light-shielding portion is formed, and the coloring pattern contained in the red photosensitive resin composition for the color filter is composed of three or more colored patterns.

Further, the arrangement of the colored layer is not particularly limited, and for example, a general arrangement such as a stripe type, a mosaic type, a triangular type, or a four-pixel arrangement type can be employed. Further, the width, area, and the like of the colored layer can be arbitrarily set.

The thickness of the colored layer is appropriately controlled by adjusting the coating method, the solid content concentration of the photosensitive resin composition for a color filter, the viscosity, and the like, and is usually preferably in the range of 1 to 5 μm.

This colored layer can be formed, for example, according to the following method.

First, the red color photosensitive resin composition of the color filter of the present invention is coated on a transparent substrate, which will be described later, by a coating means such as a spray coating method, a dip coating method, a bar coating method, a cold coating method or a spin coating method. It is coated to form a wet coating film.

Next, the wet coating film is dried by a hot plate, an oven, or the like, and then exposed to a mask having a predetermined pattern, and an alkali-soluble resin and a polyfunctional monomer are photopolymerized to form a color filter. The film is coated with a red photosensitive resin composition. Examples of the light source used for the 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 amount of exposure can be appropriately adjusted depending on the thickness of the light source and the coating film used, and the like.

Further, in order to promote the polymerization reaction after the exposure, heat treatment may be performed. The heating conditions can be appropriately selected depending on the blending ratio of each component in the red photosensitive resin composition used for the color filter to be used, the thickness of the coating film, and the like.

Next, development processing is carried out using a developing liquid, and a coating film is formed in a desired pattern by dissolving and removing the unexposed portion. As the developing liquid, a solution in which a base is dissolved in water and a water-soluble solvent is usually used. In this alkaline solution, a surfactant or the like may be added in an appropriate amount. Also, the development method can adopt a general method.

After the development processing, usually, the developing solution is washed and the cured coating film of the photosensitive resin composition is dried to form a colored layer. Further, after the development treatment, heat treatment may be performed in order to sufficiently cure the coating film. The heating conditions are not particularly limited and may be appropriately selected depending on the application of the coating film.

(lighting part)

The light-shielding portion of the color filter of the present invention is formed into a pattern on a transparent substrate to be described later, and can be formed in the same manner as a light-shielding portion used 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 a metal film in which a black pigment is dispersed or dissolved in a binder resin, and a metal film such as chromium or chromium oxide. The metal thin film may be a CrO _x film (x is an arbitrary number) and a Cr film may be laminated in two layers, or may be a CrO _x film (x is an arbitrary number) or a CrN _y film (y) having a lower reflectance. It is an arbitrary number) and the Cr film is laminated in three layers.

In the case where the light-shielding portion is dispersed or dissolved in the adhesive resin, the method of forming the light-shielding portion is not particularly limited as long as it can form a pattern of the light-shielding portion, and for example, shading is used. A photolithography method, a printing method, an inkjet method, or the like for the photosensitive resin composition.

In the case of the above, when the printing method and the inkjet method are used as the method of forming the light-shielding portion, examples of the binder resin include polymethyl methacrylate resin, polyacrylate resin, polycarbonate resin, and polyvinyl alcohol resin. , polyvinylpyrrolidone resin, hydroxyethyl 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 case of the above-mentioned method, when the photolithography method is used as the method of forming the light-shielding portion, for example, an acrylate-based, methacrylate-based, polyvinyl-cinnamate-based or cyclized rubber-based resin can be used as the binder resin. A photosensitive resin having a reactive vinyl group. In this case, a photopolymerization initiator may be added to the photosensitive resin composition containing a black pigment such as carbon black or titanium black as a pigment and a light-shielding portion of the photosensitive resin, and a sensitizer may be added as needed. , a coating improver, a development improver, a crosslinking agent, a polymerization inhibitor, a plasticizer, a flame retardant, and the like.

On the other hand, the light-shielding part is a metal thin film, and the method of forming the light-shielding portion is not particularly limited as long as it can form a light-shielding portion pattern, and for example, photolithography or steaming using a photomask Plating method, printing method, etc.

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

(transparent substrate)

The transparent substrate in the color filter of the present invention is not particularly limited as long as it is a transparent substrate for visible light, and a transparent substrate for a general color filter can be used. Specifically, a flexible transparent hard material such as quartz glass, an alkali-free glass, or a synthetic quartz plate, or a flexible transparent material such as a transparent resin film or an optical resin plate can be used.

The thickness of the transparent substrate is not particularly limited, and for the use of the color filter of the present invention, for example, about 100 μm to 1 mm can be used.

Further, the color filter of the present invention may have, for example, a cover layer and a transparent electrode layer, an alignment film, a columnar spacer, and the like in addition to the transparent substrate, the light shielding portion, and the coloring layer.

Next, a liquid crystal display device relating to the present invention will be described.

[Liquid Crystal Display Device]

A liquid crystal display device of the present invention is characterized by comprising the color filter of the present invention, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.

The 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 a liquid crystal display device of the present invention. As illustrated in FIG. 2, the liquid crystal display device 40 of the present invention has a color filter 10, an opposite substrate 20 having a TFT array substrate, and the like, and a formation between the color filter 10 and the opposite substrate 20. Liquid crystal layer 30.

Further, the liquid crystal display device of the present invention is not limited to the configuration shown in Fig. 2, and can be formed into a known configuration of a liquid crystal display device used for a general color filter.

The driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method used in a general liquid crystal display device can be employed. Examples of such a driving method include a TN method, an IPS method, an OCB method, and an MVA method. In the present invention, any of these methods is suitable for use.

Moreover, the counter substrate can be appropriately selected and used according to the driving method of the liquid crystal display device of the present invention.

Further, as the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropy and a mixture thereof can be used according to the driving method of the liquid crystal display device of the present invention.

As a method of forming the liquid crystal layer, a method generally used as a method for producing 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 form an isotropic liquid, and the liquid crystal is injected into the liquid crystal cell in an isotropic liquid state by a capillary effect. The liquid crystal layer can be formed by blocking with an adhesive. Thereafter, the liquid crystal cell is gradually cooled to a normal temperature, whereby the sealed liquid crystal can be aligned.

Further, in the liquid crystal dropping method, for example, a sealant is applied around the color filter, and the color filter is heated until the liquid crystal becomes a temperature of an isotropic phase, and the liquid crystal is an isotropic liquid using a disperser or the like. The liquid crystal layer is formed by dropping the color filter and the counter substrate under pressure and adhering to the sealing agent. Thereafter, the liquid crystal cell is allowed to cool to a normal temperature, whereby the sealed liquid crystal can be aligned.

Next, an organic light emitting display device relating to the present invention will be described.

[Organic light-emitting display device]

An organic light-emitting display device of the present invention is characterized by comprising the color filter of the present invention and an organic light-emitting body.

The organic light-emitting display device of the present invention will be described with reference to the drawings. Fig. 3 is a schematic view showing 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 has a color filter 10 and an organic light-emitting body 80.

The organic protective layer 50 and the inorganic oxide film 60 may be provided between the color filter 10 and the organic light-emitting body 80.

As a method of laminating the organic light-emitting body 80, for example, a transparent anode 71, a hole injection layer 72, a hole transport layer 73, a light-emitting layer 74, an electron injection layer 75, and a cathode 76 are sequentially formed on the color filter. The method and the method of bonding the organic light-emitting body 80 formed on the other substrate to the inorganic oxide film 60, and the like. 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 in the organic light-emitting body 80, and other structures can be suitably used. The organic light-emitting display device 100 manufactured in this manner can be applied to, for example, a passive driving type organic EL display, and can also be applied to an active driving type organic EL display.

Further, the organic light-emitting display device of the present invention is not limited to the configuration shown in Fig. 3, and can be formed into a known configuration of an organic light-emitting display device used for a general color filter.

[Examples]

Hereinafter, the present invention will be described in further detail based on examples, but the present invention is not limited by the examples.

(Production Example 1 Preparation of Dispersant Solution a)

A pigment dispersant (trade name: BYK-LPN6919, manufactured by BYK Chem Co., Ltd.) was added to 20.1 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) in a 100 ml round bottom flask. (Block copolymer having the repeating unit (1) represented by the above general formula (I) and the repeating unit (2) represented by the above general formula (II), a weight average molecular weight of 7,800, an amine value of 130, and a solid content of 60 (% by weight) 1.45 parts by weight, phenylphosphonic acid (trade name: PPA, manufactured by Nissan Chemical Co., Ltd.) 0.1 parts by weight (0.3 molar equivalent to the tertiary amine group), and ultrasonically treated for 15 minutes to form a partial portion. A dispersant solution a of a salt block copolymerized dispersant.

At this time, the amine group of the block copolymer (BYK-LPN6919) forms a salt by an acid-base reaction with a phosphonic acid group of PPA.

(Production Example 2 Preparation of Dispersant Solution b)

A pigment dispersant (trade name: BYK-LPN6919, manufactured by BYK Chem Co., Ltd.) was added to 23.8 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) in a 100 ml round bottom flask (having the above general formula (I)). The repeating unit (1), the block copolymer of the repeating unit (2) represented by the above general formula (II), the weight average molecular weight of 7,800, the amine value of 130, the solid content of 60% by weight, 1.68 parts by weight, and the phenylphosphine. Acid (trade name: PPA, manufactured by Nissan Chemical Co., Ltd.) 0.12 parts by weight (0.3 molar equivalents relative to the 3-stage amine group), and ultrasonically treated for 15 minutes to form a partially salt-forming block copolymer-type dispersant. Dispersant solution b.

At this time, the amine group of the block copolymer (BYK-LPN6919) forms a salt by an acid-base reaction with a phosphonic acid group of PPA.

As the yellow pigment sulfonated derivative, a yellow pigment sulfonated derivative 1 to 5 having a different substituent X shown by the following formula is used.

[化8]

(Synthesis Example 1) yellow pigment sulfonated derivative 1 (the above formula X = SO ₃ H)

374.76 g of 11 wt% fuming sulfuric acid was stirred while cooling to 10 ° C, and 13874.96 g of pigment yellow was added. Next, it was stirred at 90 ° C for 6 hours.

The reaction solution was added to 1600 g of ice water, and after stirring for 15 minutes, the precipitate was filtered. The resulting wet cake was washed 3 times with 800 ml of water. The wet cake was dried under vacuum at 80 ° C to give a yellow product. The molecular weight of the target was confirmed by TOF-MS.

(Synthesis Example 2) yellow pigment sulfonated derivative 2 (the above formula X = SO ₂ NHC ₂ H ₄ COOH)

Pigment yellow 138 62.46 g was added to 374.75 g of chlorosulfate. Next, after 2 hours at 120 ° C, 38.75 g of sulfinium chloride was dropped at 75 ° C. Thereafter, stirring was carried out at 80 ° C for 3 hours.

The reaction liquid was added to 1093 g of ice water while cooling to 3 ° C or lower. An additional 1300 g of ice was added and stirred for 15 minutes, and the precipitate was filtered. The resulting wet cake was washed with 660 ml of ice water while being cold. After 11.77 g of sodium hydroxide, 23.92 g of water and 24.30 g of β-alanine were prepared, 259.78 g of ice water was added, and the wet cake was added while keeping the temperature below 5 °C. 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 make pH 2. The precipitate was filtered and washed twice with 560 ml of water. Drying at 80 ° C under vacuum gave a yellow product. The molecular weight of the target was confirmed by TOF-MS.

(Synthesis Example 3) yellow pigment sulfonated derivative 3 (the above formula X = SO ₃ ^- NH(CH ₃ ) ₂ (C ₁₈ H ₃₇ ) ₂ ⁺ )

374.76 g of 11% fuming sulfuric acid was stirred while cooling to 10 ° C, and pigment yellow 138 74.96 g was added. Next, it was stirred at 90 ° C for 6 hours.

The reaction solution was added to 1600 g of ice water, and after stirring for 15 minutes, the precipitate was filtered. The resulting wet cake was washed 3 times with 800 ml of water. 600 ml of water was added to the wet cake and stirred at 60 ° C for 1 hour. 55.60 g 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 ml of water. Drying at 80 ° C under vacuum gave a yellow product. The molecular weight of the target was confirmed by TOF-MS.

(Synthesis Example 4) yellow pigment sulfonated derivative 4 (the above formula X = SO ₃ H, recombined with one quinone imine methyl group)

After adding 5.14 g of formaldehyde and 17.71 g of quinone imine to 338.67 g of 3.6% fuming sulfuric acid at 25 ° C, it was stirred at 50 ° C for 30 minutes. Next, Pigment Yellow 138 69.404 g was added and stirred at 100 ° C for 3 hours.

The reaction solution was added to 2400 g of ice water, and after stirring at 60 ° C for 30 minutes, the precipitate was filtered. The resulting wet cake was washed 3 times with 1 liter of warm water at 60 °C. The wet cake was dried under vacuum at 80 ° C to give a yellow product.

200.00 g of 20% fuming sulfuric acid was stirred while cooling to 10 ° C, and 40.00 g of a yellow product was added. Next, it was stirred at 80 ° C for 6 hours.

The reaction solution was added to 2000 g of ice water, and after stirring for 15 minutes, the precipitate was filtered and washed three times with 250 ml of water. Drying at 80 ° C under vacuum gave a yellow product. The molecular weight of the target was confirmed by TOF-MS.

(Synthesis Example 5) yellow pigment sulfonated derivative 5 (the above formula X = SO ₂ NHC ₃ H ₆ N(C ₂ H ₅ ) ₂ )

Pigment yellow 138 41.64 g was added to 250.44 g of chlorosulfuric acid. Next, after 2 hours at 120 ° C, 25.70 g of sulfinium chloride was dropped at 75 ° C. Thereafter, stirring at 80 ° C for 3 small Time.

The reaction liquid was added to 730 g of ice water while cooling to 3 ° C or lower. An additional 1100 g of ice was added and stirred for 15 minutes, and the precipitate was filtered. The resulting wet cake was washed with 500 ml of ice water while being cold. 420 g of ice water was added while being kept below 2 ° C to add a wet cake. Next, 15.65 g of diethylamine propylamine was added dropwise, and the mixture was stirred at 2 ° C or lower for 1 hour. The precipitate was filtered, washed with water (500 ml) and filtered twice. Drying at 80 ° C under vacuum gave a yellow product. The molecular weight of the target was confirmed by TOF-MS.

(Synthesis Example 6) Red pigment sulfonated derivative 1

300.0 g of 20% fuming sulfuric acid was stirred while cooling to 10 ° C, and pigment red 254 30.0 g was added. Next, it was stirred at 63 ° C for 6 hours.

The reaction solution was added to 3000 g of ice water, and after stirring for 15 minutes, the precipitate was filtered. The resulting wet cake was washed with 2000 ml of water and filtered. Drying at 80 ° C under vacuum gave a red product. The molecular weight of the object represented by the following structural formula (n=1) was confirmed by TOF-MS.

(Synthesis Example 7) Red pigment quinone imine methyl derivative

461.2 g of 96% sulfuric acid was stirred, and the pigment 255 23.08 g was added while cooling. Next, while stirring for 1 hour while cooling, 461.2 g of 100% sulfuric acid and 28.37 g of N-hydroxymethylimine were added. After stirring at room temperature for one night, the reaction solution was added to ice water. 3800 g and the precipitate was removed by filtration.

The obtained wet cake was washed three times with warm water, and dried in a vacuum to be pulverized to obtain a red pigment quinone imine derivative in which pigment red 255 was substituted with a quinone imine methyl group.

(Example 1) (1) Adjustment of color filter red pigment dispersion

Mixed with the fine pigment (CI Pigment Red 254 (PR254: average primary particle diameter 15 to 50 nm) 3.705 parts by weight, yellow pigment sulfonated derivative 1 0.195 parts by weight as a yellow pigment sulfonated derivative, mixed production example 1 Dispersant solution a 21.6 parts by weight and alkali-soluble resin (styrene / benzyl methacrylate / acrylic acid / 2-hydroxymethyl acrylate copolymer (mole ratio 30 / 40/10/20, acid value: 70 mg KOH / g, Molecular weight 6000, solid content 44.1% by weight, diluted with propylene glycol monomethyl ether acetate) 4.4 parts by weight, and dispersed in a coating shaker with 2 mm zirconia beads for 1 hour, and then dispersed with 0.1 mm zirconia beads for 10 hours. A red pigment dispersion A having a pigment concentration of 13% was obtained, and the bead filling ratio in the container at the time of dispersion was 50%.

The dispersed average particle diameter of the mixed pigment particles was diluted 1000 times with propylene glycol monomethyl ether acetate, and the particle size distribution measuring device UPA-EX150 was measured using a Nano track manufactured by Nikkiso Co., Ltd., according to dynamic light scattering. The method was measured at 23 °C. Further, the viscosity of the produced dispersion was measured at 6 rpm by a Rheometer MCR-301 (Corn Plate CP50-1, 23 ° C measurement) manufactured by Anton Paar. The dispersed average particle diameter and viscosity were measured by storing the dispersion at 40 ° C for one week.

(2) Modulation of a red photosensitive resin composition for a color filter

In the 4.06 parts by weight of the red pigment dispersion A obtained above, 2.22 parts by weight of the following binder composition, 3.72 parts by weight of propylene glycol monomethyl ether acetate, 0.01 part by weight of a surfactant RO8MH (manufactured by DIC), and a decane coupling agent. KBM503 (made by Shin-Etsu Silicone) 0.05 parts by weight of the mixture was added and mixed, and pressure filtration was carried out to obtain a red photosensitive resin composition for a color filter of Example 1.

<Binder composition>

‧ Alkali-soluble resin (styrene / benzyl methacrylate / acrylic acid / 2-hydroxymethyl acrylate copolymer (mol ratio 30 / 40/10/20, acid value: 70 mg KOH / g, molecular weight 6000)): 11.0 weight Share

‧4 functional acrylate monomer (trade name: Aronix M450, manufactured by Toagos Corporation): 8.2 parts by weight

‧Photopolymerization initiator (2-methyl-1[4-(methylthio)phenyl]-2- Orolinylpropan-1-one (trade name: Irugacure 907, manufactured by Ciba Specialty Chemicals Co., Ltd.): 1.0 part by weight

‧Photopolymerization initiator (2-benzyl-2-dimethylamino-1-(4- Polinylphenyl)-1-butanone (trade name Irugacure 369, manufactured by Ciba Specialty Chemicals Co., Ltd.): 2.4 parts by weight

‧Photosensitizer (4,4'-bis(dimethylamino)benzophenone): 0.7 parts by weight

‧ solvent (propylene glycol monomethyl ether acetate): 43.2 parts by weight

(evaluation result) <Contrast and Hue, Brightness Evaluation>

The obtained color filter was coated with a red photosensitive resin composition on a glass substrate (manufactured by NH Technoglass Co., Ltd., "NA35") having a thickness of 0.7 mm using a spin coater. Thereafter, it was dried by heating on a hot plate at 80 ° C for 3 minutes. Exposure (60 mJ) was performed using a small aligner to obtain a photocured film (red colored layer). The cured film was heated in an oven at 230 ° C for 30 minutes to prepare a cured film after post-baking. The film thickness after photohardening was prepared so that the target chromaticity after baking was x=0.650.

The brightness measurement was performed using a pot-and-electricity contrast measuring device CT-1, a light source: a cold cathode-to-C10 lamp, and a luminance meter: LS-100 manufactured by Konica-Minolta. Contrast is used The measured value of the brightness is derived according to the following formula.

Contrast = parallel brightness (cd/m ² ) / vertical brightness (cd/m ² )

The hue (x, y) and the brightness (Y) were measured using a "microscopic spectroscopic measuring device OSP-SP200" manufactured by Olympus Co., Ltd.

(Examples 2 to 5)

In the first embodiment, except that the yellow pigment sulfonated derivative 1 was changed to the yellow pigment sulfonated derivative 2 to 5, the same procedure as in Example 1 was carried out to prepare a dispersion liquid and a cured film after post-baking, and a dispersion liquid was prepared. The dispersion particle size, viscosity, and optical properties of the cured film after post-baking were evaluated. The results are shown in Table 1.

(Example 6)

In Example 1, except that a yellow pigment sulfonated derivative and the same part by weight of a PR 255 酞醯iminomethyl derivative (Synthesis Example 7) were added, the same procedure as in Example 1 was carried out to prepare a dispersion and post-baking. After the cured film, the dispersed particle size, viscosity, and optical properties of the cured film after post-baking were evaluated. The results are shown in Table 1.

(Comparative Example 1)

The dispersion was prepared in the same manner as in Example 1 except that the yellow pigment sulfonated derivative was not used, and the fine pigment Pigment Pigment Red 254 (PR254: average primary particle diameter: 15 to 50 nm) was 3.9 parts by weight. The cured film was subjected to evaluation of the dispersed particle size, viscosity, and optical properties of the cured film after post-baking. The results are shown in Table 1.

(Comparative Example 2)

In the same manner as in Example 1, except that the yellow pigment sulfonated derivative was changed to the red pigment sulfonated derivative 1 obtained in Synthesis Example 6, a dispersion liquid and a cured film after post-baking were prepared, and the dispersed particle diameter of the dispersion liquid was Evaluation of the optical properties of the cured film after viscosity and post-baking. The results are shown in Table 1.

(Comparative Example 3)

The dispersion was prepared in the same manner as in Example 1 except that the yellow pigmented derivative was changed to the red pigment quinone imine methyl derivative obtained in Synthesis Example 7. However, since the dispersion was agglomerated and the viscosity was drastically increased, the cured film could not be evaluated.

As is clear from Table 1, in the diketopyrrolopyrrole-based red pigment, when the yellow pigment sulfonated derivative is dispersed, it is added, and the hue is not greatly changed and finely dispersed. As a result, both contrast and brightness can be achieved. Among them, in particular, in the diketopyrrolopyrrole red pigment, Example 6 using a yellow pigment sulfonated derivative and a red pigment quinone imide methylated derivative can exhibit particularly high brightness and achieve high contrast. Claim. It is presumed that this is due to the multiplication effect of the yellow pigment sulfonated derivative and the red pigment quinone imide methylated derivative, and the aggregation of the pigment is suppressed even after the high-temperature heating step in the color filter step.

On the other hand, in Comparative Example 1 in which the yellow pigment sulfonated derivative was not used, the dispersion stability was poor and the contrast was largely lowered. Further, in Comparative Example 2 in which a red pigment sulfonated derivative was used, the y value became small and the hue became blue, and the luminance was lowered. Further, in Comparative Example 3 using only the red pigment quinone imine methyl derivative, the pigment was aggregated and the pigment dispersion liquid was gelated.

(Example 7) (1) Modulation of color filter with red pigment dispersion

2.5% by weight of the micronized pigment CI Pigment Red 255 (PR255: average primary particle diameter 30 to 60 nm), 0.15 parts by weight of the yellow pigment sulfonated derivative 1 as a yellow pigment sulfonated derivative, and the red pigment of Synthesis Example 7. 0.15 parts by weight of the quinone imine methyl derivative, 25.6 parts by weight of the dispersant solution b prepared in Preparation Example 2, and an alkali-soluble resin (styrene/benzyl methacrylate/acrylic acid/2-hydroxymethyl acrylate copolymer ( Mohr ratio 30/40/10/20, acid value: 70 mgKOH/g, molecular weight 6000, solid content 44.1% by weight, diluted with propylene glycol monomethyl ether ester) 1.36 parts by weight, and 2 mm as a coating shaker The zirconia beads were dispersed for 1 hour, and further dispersed in 0.1 mm of zirconia for 10 hours to obtain a red pigment dispersion having a pigment concentration of 10%, and the bead filling ratio in the container at the time of dispersion was 50%.

(2) Modulation of a red photosensitive resin composition for a color filter

In the 5.28 parts by weight of the red pigment dispersion obtained above, 2.39 parts by weight of the binder composition described in Example 1, 2.34 parts by weight of propylene glycol monomethyl ether acetate, 0.01 part by weight of a surfactant RO8MH (manufactured by DIC), and decane. 0.05 parts by weight of a coupling agent KBM503 (manufactured by Shin-Etsu Silicone) was added and mixed, and subjected to pressure filtration to obtain a red photosensitive resin composition for a color filter of Example 7.

In the same manner as in Example 1, a dispersion liquid and a cured film after post-baking were prepared, and the dispersed particle diameter, viscosity, and optical characteristics of the cured film after post-baking were evaluated.

The dispersed particle diameter of the dispersion was 59 nm immediately after the dispersion and 60 (nm) after one week at 40 °C. The viscosity was 11.2 (mPa ‧ s) immediately after dispersion and 9.8 (mPa ‧ s) after one week at 40 ° C. Thus, even if C.I. Pigment Red 255 was used, the dispersion stability was good. Further, as a result of evaluation of optical characteristics of the cured film after post-baking, good results of x = 0.6350, y = 0.373, Y = 24.7, and contrast of 1478 were obtained.

(Comparative Example 4)

The same example except that the yellow pigment sulfonated derivative and the red pigment quinone imine methyl derivative were not used, and the fine pigment Pigment Pigment Red 255 (PR255: average primary particle diameter 30 to 60 nm) was set to 3 parts by weight. 7 Treatment, preparation of a dispersion liquid and a cured film after post-baking, dispersion particle size, viscosity, and evaluation of optical properties of the cured film after post-baking.

However, in the pigment dispersion liquid of Comparative Example 4, since the dispersion liquid agglomerated and the viscosity was drastically increased, the cured film could not be evaluated.

(assessment) <solvent resolubility>

In the evaluation method, the photosensitive resin composition of Examples 1 to 7 and the photosensitive resin of Comparative Examples 1 and 2 were each immersed in a longitudinally 2 cm portion of a glass substrate having a length of 100 mm and a width of 5 mm. Composition and pull up at 25 ° C, 70% RH The constant temperature and humidity layer was dried for 30 minutes. Next, the glass substrate to which the dried coating film adhered was immersed in PGMEA for 15 seconds while stirring. At this time, according to the re-dissolved state of the dried coating film, the following three stages were evaluated.

‧ ○: The dried film was completely dissolved during the immersion.

‧ △: A part of the dried coating film remained even after immersion for 15 seconds.

‧×: The dried coating film was almost or completely undissolved even after immersion for 15 seconds.

As a result, Examples 3 and 5 were ○, Examples 1, 2, 6, and 7 were Δ, and Example 4 and Comparative Examples 1 and 2 were ×.

From the above, it is understood that a sulfonated derivative having a sulfonamide group and a sulfonated derivative having a salt with a long-chain alkyl group are excellent in solvent resolubility.

Claims (12)

A red pigment dispersion liquid for color filter, comprising: a diketopyrrolopyrrole red pigment, a sulfonated derivative of an organic yellow pigment, a block copolymer containing a tertiary amine salt or a 4-grade ammonium salt Pigment dispersant, and solvent. A red pigment dispersion liquid for a color filter according to claim 1 which is in the above solvent, wherein the diketopyrrolopyrrole is red in the presence of the sulfonated derivative of the yellow pigment and the pigment dispersant The pigment is obtained by dispersion. A red pigment dispersion liquid for a color filter according to claim 1, wherein the sulfonated derivative of the yellow pigment contains a sulfonated derivative of a yellow pigment of an isoindole structure. A red pigment dispersion liquid for a color filter according to claim 1, which further comprises a quinone imine alkylated derivative of a diketopyrrolopyrrole red pigment. The red color pigment dispersion liquid of the color filter of claim 1, wherein the content of the sulfonated derivative of the yellow pigment is 1 to 25 by weight based on 100 parts by weight of the above-mentioned diketopyrrolopyrrole red pigment. The content of the quinone imide alkylated derivative of the diketopyrrolopyrrole red pigment is 0 to 15 parts by weight based on 100 parts by weight of the above-mentioned diketopyrrolopyrrole red pigment. The red pigment dispersion liquid for a color filter according to claim 1, wherein the pigment dispersant has a repeating unit (1) represented by the following general formula (I) and a general formula (II): a repeating unit (2), which is a block copolymer obtained by forming at least a part of an amine group of the above repeating unit (1) with an organic acid compound and/or a halogenated hydrocarbon; [Chemical Formula 1] [In the formulae (I) and (II), R ¹ is a hydrogen atom or a methyl group, and R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and A is a carbon number of 1 to 8 Alkyl, -[CH(R ⁶ )-CH(R ⁷ )-O] _x -CH(R ⁶ )-CH(R ⁷ )- or -[(CH ₂ ) _y -O] _z -(CH ₂ ) _y - the divalent group shown, R ⁴ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, -[CH(R ⁶ )-CH(R ⁷ ) -O] _x -R ⁸ or -[(CH ₂ ) _y -O] _z -R ⁸ represents a monovalent group; R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group, and R ⁸ is a hydrogen atom, or An alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, -CHO, -CH ₂ CHO, or a monovalent group represented by -CH ₂ COOR ⁹ , and R ⁹ is hydrogen An atom or an alkyl group having 1 to 5 carbon atoms; the above alkyl group, alkenyl group, aralkyl group, and aryl group each may have a substituent; x represents an integer of 1 to 18, y represents an integer of 1 to 5, and z represents 1 An integer of ~18; m represents an integer from 3 to 200, and n represents an integer from 10 to 200]. A method for producing a red pigment dispersion for a color filter, which comprises the steps of: a sulfonated derivative of a yellow pigment in a solvent, and a block copolymer of a salt containing a tertiary amine or a ammonium salt of a 4-stage ammonium salt A step of dispersing the above-mentioned diketopyrrolopyrrole-based red pigment in the presence of a pigment dispersant. A red photosensitive resin composition for a color filter comprising at least a red pigment dispersion liquid for a color filter of claim 1 and a photosensitive adhesive component. A method for producing a red photosensitive resin composition for a color filter, which has the following steps: Dispersing the above diketopyrrolopyrrole red pigment in the presence of a sulfonated derivative of a yellow pigment and a pigment dispersant containing a block copolymer of a tertiary amine or a tertiary ammonium salt in a solvent And a step of preparing a red pigment dispersion; and mixing the red pigment dispersion with the photosensitive binder component. A color filter having a coloring layer formed by hardening a color filter of claim 8 with a red photosensitive resin composition. A liquid crystal display device comprising the color filter of claim 10, an opposite substrate, and a liquid crystal layer formed between the color filter and the counter substrate. An organic light-emitting display device comprising the color filter of claim 10 and an organic light-emitting body.