JP7019235B2 - Pigment compositions for color filters, coloring compositions for color filters, and color filters - Google Patents

Description

The present invention relates to a pigment composition for a color filter used in a color liquid crystal display device, a color image pickup device, or the like.

Generally, in a color liquid crystal display device, a transparent electrode for driving a liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for orienting the liquid crystal in a certain direction is further formed on the transparent electrode. There is. The manufacturing process for forming a color filter from these transparent electrodes and alignment films generally requires high temperature treatment at 200 ° C. or higher, preferably 230 ° C. or higher. For this reason, the mainstream of pigment compositions for color filters is a pigment dispersion method using a pigment having excellent light resistance and heat resistance as a colorant.

In the pigment dispersion method, it is common to use a pigment having excellent light resistance and heat resistance such as diketopyrrolopyrrole pigment, anthraquinone pigment, perylene pigment, and disazo pigment as a colorant alone or in combination for the red filter segment. Is.

Among the diketopyrrolopyrrole pigments, C.I. I. Pigment Red 254 is well known as a colorant for red color filters, and in recent years, a brominated diketopyrrolopyrrole pigment, which is a bromine analog thereof, has been used in C.I. I. It is disclosed that it gives a higher brightness than Pigment Red 254 (for example, Patent Document 1 and Patent Document 2).

Since color filters are pursued to have high brightness and high contrast, a pigmentation step (also called a conditioning or finishing step) is required to reduce the primary particle size of the diketopyrrolopyrrole pigment and to adjust the crystal shape. .. However, the finely divided diketopyrrolopyrrole pigment has problems of deterioration of dispersibility due to an increase in the specific surface area of the pigment and heat resistance in which crystals of the pigment are precipitated by high temperature treatment.

In Patent Document 3, C.I. I. Pigment Red 254 and a diketopyrrolopyrrole pigment having at least one specific structural formula are disclosed as a pigment composition.

Japanese Unexamined Patent Publication No. 2010-47748 Japanese Unexamined Patent Publication No. 2016-180042 Japanese Unexamined Patent Publication No. 2009-215361

However, although the conventional pigment composition for a color filter has a certain degree of dispersibility and heat resistance, there is a problem that the contrast and the brightness are insufficient.

An object of the present invention is to provide a pigment composition for a color filter, a coloring composition for a color filter, and a color filter capable of producing a color filter having good dispersibility and heat resistance and good brightness and contrast.

The pigment composition for a color filter of the present invention contains a diketopyrrolopyrrole pigment represented by the general formula (1) and a diketopyrrolopyrrole pigment represented by the general formula (2).

General formula (1) General formula (2)

[In the formula, R1 is a chlorine atom or a bromine atom, R2 is -SR3 or -CON (R3) R4, and R3 and R4 are independently hydrogen atoms and 1 to 20 carbon atoms. It is an alkyl group or a phenyl group which may have a substituent. ]

According to the present invention, it is possible to provide a pigment composition for a color filter, a coloring composition for a color filter, and a color filter capable of producing a color filter having good dispersibility and heat resistance and good brightness and contrast.

Hereinafter, the present invention will be described in detail. In addition, "CI" mentioned below means a color index (CI).

<Diketopyrrolopyrrole pigment composition>
The pigment composition for a color filter of the present invention (hereinafter referred to as a pigment composition) contains, as a colorant, a diketopyrrolopyrrole pigment represented by the general formula (1) and a diketopyrrolopyrrole pigment represented by the general formula (2). contains.

In the present specification, the pigment composition can be used for paints, inks, and various other coloring applications, and is preferably used for color filter applications in which excellent brightness and contrast can be obtained.

General formula (1) General formula (2)

[In the formula, R1 is a chlorine atom or a bromine atom, R2 is -SR3 or -CON (R3) R4, and R3 and R4 are independently hydrogen atoms and 1 to 20 carbon atoms. It is an alkyl group or a phenyl group which may have a substituent. ]

The alkyl group having 1 to 20 carbon atoms is linear or branched, and is, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and the like. Examples thereof include a hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group, a hexadecyl group, an octadecyl group, an icosyl group, a 1,5-dimethylhexyl group, a 1,6-dimethylheptyl group and a 2-ethylhexyl group. Among these, an alkyl group having 4 to 8 carbon atoms is preferable from the viewpoint of contrast and crystal precipitation suppressing effect.

The phenyl group which may have the above substituents is, for example, an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, a halogen atom, a nitro group, a cyano group, a carbamoyl group, a sulfamoyl group and 1 to 4 carbon atoms. Examples thereof include a phenyl group having a substituent such as an alkoxyl group. More specifically, for example, phenyl group, p-methylphenyl group, 4-tert-butylphenyl group, p-nitrophenyl group, p-methoxyphenyl group, p-chlorophenyl group, 2,4-dichlorophenyl group, 3 -Ccarbamoylphenyl group and the like can be mentioned. Among these, a phenyl group substituted with a halogen atom or an alkoxyl group having 1 to 4 carbon atoms or an unsubstituted phenyl group is preferable, and an unsubstituted phenyl group is more preferable.

As the above R3 and R4, a hydrogen atom, a phenyl group or an alkyl group having 4 to 8 carbon atoms is preferable, and an alkyl group having 4 to 8 carbon atoms is more preferable, respectively, from the viewpoint of contrast and crystal precipitation suppressing effect.

Specific examples of the diketopyrrolopyrrole pigment of the general formula (2) are given below, but the present invention is not limited thereto.

The diketopyrrolopyrrole pigment represented by the general formula (1) can be produced, for example, by a succinic acid ester synthesis method, or a commercially available product can be used. In the succinic acid ester synthesis method, 2 mol of 4-bromobenzonitrile or 2 mol of 4-chlorobenzonitrile is added to 1 mol of the succinate diester in an inert organic solvent such as tert-amyl alcohol, and the alkali metal or In the presence of the alkali metal alkoxide, a condensation reaction is carried out at a high temperature of 80 to 110 ° C. to form an alkali metal salt of the diketopyrrolopyrrole compound, and subsequently, with respect to the alkali metal salt of the diketopyrrolopyrrole compound. A diketopyrrolopyrrole pigment can be synthesized by protonation with water, an alcohol, an acid or the like. During the synthesis, the size of the obtained primary particle size can be controlled by the temperature in protonation, the type, ratio and amount of water, alcohol or acid.

The diketopyrrolopyrrole pigment represented by the general formula (2) can be produced by a succinic acid ester synthesis method like the diketopyrrolopyrrole pigment represented by the general formula (1). To give an example of the synthesis method, in the above succinate synthesis method, for example, 2 mol of 4-bromobenzonitrile or 2 mol of 4-chlorobenzonitrile is 2 mol of a benzonitrile compound represented by the following general formula (3). Alternatively, it may be synthesized by changing to 2 mol of the benzonitrile compound represented by the following general formula (4).

[In the formula, R3 and R4 are phenyl groups which may independently have a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a substituent. ]

In the present specification, the pigment composition has a mass ratio of the diketopyrrolopyrrole pigment represented by the general formula (1) to the diketopyrrolopyrrole pigment represented by the general formula (2) of 99.99: 0.01 to 80: It is preferably 20. When the diketopyrrolopyrrole pigment represented by the general formula (2) exceeds 0.01% by mass, the contrast is further improved and crystal precipitation can be further suppressed. Further, when the content is 20% by mass or less, the brightness is further improved. The mass ratio of the diketopyrrolopyrrole pigment represented by the general formula (1) to the diketopyrrolopyrrole pigment represented by the general formula (2) is more preferably 99.9: 0.1 to 85:15.

The mass ratio of the diketopyrrolopyrrole pigment represented by the general formula (1) to the diketopyrrolopyrrole pigment represented by the general formula (2) is analyzed using HPLC, TOF-MASS, FD-MASS, LC-MASS or NMR. be able to. Alternatively, as disclosed in Japanese Patent Application Laid-Open No. 08-199085, the diketopyrrolopyrrole pigment composition is obtained by stirring the diketopyrrolopyrrole pigment composition in tetrahydrofuran with di-tert-butyl dicarbonate and 4-dimethylaminopyridine at room temperature. After conversion to a soluble diketopyrrolopyrrole compound, analysis using NMR, MASS, LC-MASS or the like may be performed. Alternatively, the hydrogen of the NH group of the pyrrolopyrrole ring may be replaced with an alkyl group using an alkyl halide or the like to convert it into a soluble diketopyrrolopyrrole compound, and then the above analysis may be performed.

(Dye derivative)
As the pigment composition in the present specification, a dye derivative can be used. As a result, the pigment crystal growth is further suppressed and the pigment dispersibility is further improved. Examples of the dye derivative include a diketopyrrolopyrrole derivative, a benzoisoindole derivative, an anthraquinone derivative, a dianthraquinone derivative, a thiazineindigo derivative, an azo dye derivative, a quinophthalone derivative, and a quinacridone derivative. Further, as the structure of the dye derivative, for example, the dye derivative represented by the following formula (5) can be mentioned.
P-Lm formula (5)
[In formula (5), P is a diketopyrrolopyrrole residue, a benzoisoindole residue, an anthraquinone residue, a dianthraquinone residue, a thiazineindigo residue, an azo dye residue, a quinophthalone residue, or a quinacridone residue. It is a group, m is an integer of 1 to 4, and L is independently -OH; -SO ₃ H, and -COOH, and their monovalent to trivalent metal salts, and these. Alkylammonium salt; phthalimidemethyl group which may have a substituent; a group represented by the following formula (a), (b), (c), (d), (e), or (f), where X is , -SO _2- , -CO-, -CH _2- , -CH _{2 NHCOCH 2-, -CH 2 NHSO 2 CH 2- ,} or a direct bond, where Y is -NH-, -O-, -S. -Or a direct bond, n is an integer of 1 to 10, and R ¹⁶ and R ¹⁷ are each independently an alkyl group having 1 to 30 carbon atoms and may have a hydrogen atom and a substituent. , An alkenyl group having 2 to 30 carbon atoms which may have a substituent, or a substituent which is a combination of R ¹⁶ and R ¹⁷ and further contains a nitrogen, oxygen, or sulfur atom. It is a heterocyclic ring, and each of R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² independently has a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and a substituent. It may be an alkenyl group having 2 to 20 carbon atoms, R ²³ is a substituent represented by the formula (a) or the formula (b), and R ²⁴ is a chlorine atom, —OH, an alkoxyl group, a formula. (A) or a substituent represented by the formula (b), Z is -CONH-, -NHCO-, -SO ₂ NH-, or -NHSO _2- , and R ²⁵ is a hydrogen atom, -NH. ₂ , -NHCOCH ₃ , -NHR ²⁶ , or a substituent represented by the formula (c), wherein R ²⁶ has an alkyl group having 1 to 20 carbon atoms and a substituent which may have a substituent. Is also a good alkenyl group with 2 to 20 carbon atoms. ]

Examples of the monovalent to trivalent metal include sodium, potassium, magnesium, calcium, iron, aluminum and the like. The alkylammonium salt is, for example, an ammonium salt of a long-chain monoalkylamine such as octylamine, laurylamine, stearylamine; palmityltrimethylammonium salt; dilauryldimethylammonium salt; a quaternary alkyl such as distearyldimethylammonium salt. Ammonium salt can be mentioned.

The substituent of the phthalimide methyl group which may have a substituent, the alkyl group which may have a substituent, the alkenyl group which may have a substituent, or the substituent of a heterocycle which may have a substituent is. For example, a halogen atom, a nitro group, a cyano group, a carbamoyl group, an N-substituted carbamoyl group, a sulfamoyl group, an N-substituted sulfamoyl group, an alkoxyl group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms and the like can be mentioned. ..

The dye derivative is sulfonated by heating in sulfuric acid or fuming sulfuric acid, phthalimide methylation reaction by dehydration condensation with N-hydroxymethylphthalimide in sulfuric acid, chlorsulfonated with chlorsulfonic acid and thionyl chloride, and then chlorsulfonated. It is synthesized by a known production method such as a sulfon amidation reaction in which an amine component such as dimethylaminopropylamine is reacted.

The amine component used to form the substituents represented by the above formulas (a), (b) and (c) is, for example, dimethylamine, diethylamine, methylethylamine, N, N-ethylisopropylamine, and the like. N, N-ethylpropylamine, N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butylethylamine, N, N-tert-butylethylamine, diisopropylamine, dipropylamine, N, Nsec- Butylpropylamine, dibutylamine, di-sec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisoamylamine, dihexylamine, dicyclohexylamine, di (2-ethylhexyl) amine, dioctylamine , N, N-methyloctadecylamine, didecylamine, diallylamine, N, N-ethyl-1,2-dimethylpropylamine, N, N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine , N, N-dimethylaminoethylamine, N, N-dimethylaminoamylamine, N, N-dimethylaminobutylamine, N, N-diethylaminoethylamine, N, N-diethylaminopropylamine, N, N-diethylaminohexylamine, N , N-diethylaminobutylamine, N, N-diethylaminopentylamine, N, N-dipropylaminobutylamine, N, N-dibutylaminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-diisobutylaminopentylamine, N, N-methyl-laurylaminopropylamine, N, N-ethyl-hexylaminoethylamine, N, N-distearylaminoethylamine, N, N-diorailaminoethylamine, N, N- Distearylaminobutylamine, piperidine, 2-pipecholine, 3-pipecholine, 4-pipecholine, 2,4-lupetidine, 2,6-lupetidine, 3,5-lupetidine, 3-piperidinmethanol, pipecoronic acid, isonipecotic acid, isonipecotin Methyl acid, ethyl isonipecotate, 2-piperidinethanol, pyrrolidine, 3-hydroxypyrrolidin, N-aminoethylpiperidin, N-aminoethyl-4-pipecholine, N-aminoethylmorpholin, N-aminopropylpiperidin, N-aminopropyl －2-Pipe Colin, N-aminopropyl-4-pipecholine, N-aminopropylmorpholine, N-methylpiperazine, N-butylpiperazine, N-methylhomopiperazine, 1-cyclopentylpiperazin, 1-amino-4-methylpiperazine, 1-cyclopentyl Examples include piperazine.

Further, when a substituent is introduced into the azo dye, the azo dye derivative can also be produced by introducing the substituent into the diazo component or the coupling component in advance and then carrying out a coupling reaction.

Diketopyrrolopyrrole pigments can be used in a method of mixing with a pigment when the diketopyrrolopyrrole pigment is dispersed in a pigment carrier, a method of mixing in water or an organic solvent during pigment production, and co-dissolution during dissolution and precipitation. Examples thereof include a method of precipitating and a method of adding during wet kneading. The method of mixing the dye derivative in water or an organic solvent at the time of pigment production, the method of co-precipitating at the time of dissolution and precipitation, and the method of adding at the time of wet kneading exhibit the effect of suppressing the crystal growth of the diketopyrrolopyrrole pigment. In order to exert the effect of suppressing crystal growth, it is required that the dye derivative is efficiently adsorbed on the surface of the diketopyrrolopyrrole pigment and is not easily desorbed. For this reason, the structure of the dye derivative is often considered to have a partial chemical structure similar to that of the pigment used. For this reason, when producing a diketopyrrolopyrrole pigment, a dye derivative having a diketopyrrolopyrrole structure, a thiazine indigo structure, a benzoisoindole structure, or a quinacridone structure is generally preferable.

Further, when a dye derivative is used, it is preferable that the color tone of the diketopyrrolopyrrole pigment is not impaired as much as possible. From the viewpoint of hue, it is preferable to use a diketopyrrolopyrrole derivative, a benzoisoindole derivative, a thiazineindigo derivative, an azo dye derivative, or a quinophthalone derivative which is yellow, orange, or red.

The blending amount of the dye derivative is preferably 0.5 to 40% by mass in 100% by mass of the pigment composition. 3 to 35% by mass is more preferable. By blending 0.5 to 40% by mass, the dispersibility is further improved and the color tone of the pigment is further improved.

Hereinafter, specific examples of the dye derivative will be described.

(Diketopyrrolopyrrole derivative)
A diketopyrrolopyrrole derivative will be described as an example of a dye derivative. As the diketopyrrolopyrrole derivative, for example, a compound represented by the following formula (6) or formula (7) is preferable.

(Benzoisoindole derivative)
A benzoisoindole derivative will be described as an example of a dye derivative. As the benzoisoindole derivative, for example, the compound represented by the following formula (8) is preferable.

(Anthraquinone derivative)
Anthraquinone derivatives will be described as an example of dye derivatives. As the anthraquinone derivative, for example, the compound represented by the following formula (9) is preferable.

(Dianthraquinone derivative)
A dianthraquinone derivative will be described as an example of a dye derivative. As the dianthraquinone derivative, for example, the compound represented by the following formula (10) is preferable.

(Chiadin indigo derivative)
A thiazine indigo derivative will be described as an example of a dye derivative. As the thiazine indigo derivative, for example, the compound represented by the following formula (11) is preferable.

(Azo dye derivative)
An azo dye derivative will be described as an example of the dye derivative. The azo dye derivative is preferably, for example, a compound represented by the following formula (12), formula (13), or formula (14).

(Kinophthalone derivative)
A quinophthalone derivative will be described as an example of a dye derivative. As the quinophthalone derivative, for example, compounds represented by the following formulas (15-1) to (15-17) are preferable.

(Quinacridone derivative)
A quinacridone derivative will be described as an example of a dye derivative. As the quinacridone derivative, for example, the compound represented by the following formula (16) is preferable.

<Manufacturing method of diketopyrrolopyrrole pigment composition>
The pigment composition of the present specification can be produced, for example, by using the diketopyrrolopyrrole pigment represented by the formula (1) and the diketopyrrolopyrrole pigment represented by the formula (2) in combination when performing the pigmentation step. In addition, another production method is, for example, in a step of protonating an alkali metal salt of a diketopyrrolopyrrole compound in the step of succinate ester synthesis method to precipitate pigment particles in order to produce a diketopyrrolopyrrole pigment. , A method of mixing the metal salt of the diketopyrrolopyrrole pigment represented by the formula (1) and the metal salt of the diketopyrrolopyrrole pigment represented by the formula (2) can also be mentioned. Further, the formula (2) separately adjusted with respect to the metal salt of the diketopyrrolopyrrole pigment represented by the formula (1) obtained in the process of producing the diketopyrrolopyrrole pigment represented by the formula (1) by the succinic acid ester synthesis method. A method of mixing a metal salt of the diketopyrrolopyrrole pigment shown in (1) and protonating the obtained mixed solution with water, alcohol, acid or the like can also be mentioned. At this time, a pigmentation step may be further added to the water-containing cake or dried product of the obtained diketopyrrolopyrrole pigment composition.

The pigmentation step is, for example, a salt milling treatment in which a water-soluble inorganic salt and a water-soluble organic solvent are added to the pigment and kneaded, a solvent heat treatment in which the pigment is heated and stirred in the presence of the organic solvent, and the pigment is dissolved in a good solvent. Examples thereof include a dissolution precipitation treatment in which the mixture is reprecipitated with a poor solvent. It is preferable to carry out a salt milling treatment for producing the pigment composition.

In the salt milling treatment, a mixture of a pigment, a water-soluble inorganic salt and a water-soluble organic solvent is heated using a kneader such as a kneader, a trimix, a 2-roll mill, a 3-roll mill, a ball mill, an attritor, or a sand mill. This is a treatment in which the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water after mechanically kneading. The water-soluble inorganic salt acts as a crushing aid, and it is considered that the pigment is crushed by utilizing the high hardness of the inorganic salt during salt milling, which causes an active surface and crystal growth. There is. Therefore, during kneading, crushing of the pigment and crystal growth occur at the same time, and the primary particle size of the pigment obtained differs depending on the kneading conditions.

In order to promote crystal growth by heating, a heating temperature of 35 to 150 ° C. is preferable. When the heating temperature is set to 35 to 150 ° C., crystal growth and crushing are balanced, and it is easy to obtain a pigment having an appropriate primary particle size. The kneading time of the salt milling treatment is preferably about 2 to 24 hours from the viewpoint of the balance between the particle size distribution of the primary particles of the salt milling treatment pigment and the cost required for the salt milling treatment.

By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution.

Further, as the water-soluble inorganic salt used for the salt milling treatment, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of price. The water-soluble inorganic salt has a total of 100 parts by mass of the diketopyrrolopyrrole pigment represented by the general formula (1) and the diketopyrrolopyrrole pigment represented by the general formula (2) in terms of both treatment efficiency and production efficiency. It is preferable to use 50 to 2000 parts by mass, and more preferably 300 to 1200 parts by mass.

The water-soluble organic solvent has a function of wetting the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent easily evaporates, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety.

Examples of the water-soluble organic solvent include 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and triethylene glycol. Triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, etc. Can be mentioned. As the water-soluble organic solvent, 5 to 1000 parts by mass may be used with respect to a total of 100 parts by mass of the diketopyrrolopyrrole pigment represented by the general formula (1) and the diketopyrrolopyrrole pigment represented by the general formula (2). It is preferably 50 to 500 parts by mass, more preferably 50 to 500 parts by mass.

In the salt milling treatment, the above-mentioned dye derivative may be used in combination in order to improve the kneading efficiency, which is very effective for making the pigment finer and sizing. In the miniaturization of the diketopyrrolopyrrole pigment composition of the present invention, it is preferable to use the above-mentioned dye derivative, but the present invention is not limited thereto. The amount of the dye derivative used is such that it does not affect the color tone, that is, with respect to a total of 100 parts by mass of the diketopyrrolopyrrole pigment represented by the general formula (1) and the diketopyrrolopyrrole pigment represented by the general formula (2). , 0.5-40 parts by mass is preferably used.

In addition, a resin can be added as needed during the salt milling treatment. Examples of the resin include natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like. The resin is preferably solid and water-insoluble and water-insoluble at room temperature (25 ° C.), and more preferably partially soluble in the above organic solvent. It is preferable to use 5 to 200 parts by mass of the resin with respect to a total of 100 parts by mass of the diketopyrrolopyrrole pigment represented by the general formula (1) and the diketopyrrolopyrrole pigment represented by the general formula (2).

Further, in the salt milling treatment, an additive such as a resin-type dispersant and / or a surfactant may be contained, if necessary. As the additive, for example, a resin-type dispersant and / or a surfactant described later are preferable. The amount of the additive used is 0.1 to 55 parts by mass with respect to a total of 100 parts by mass of the diketopyrrolopyrrole pigment represented by the general formula (1) and the diketopyrrolopyrrole pigment represented by the general formula (2). It is preferably 0.1 to 45 parts by mass, more preferably 0.1 to 45 parts by mass.

The coloring composition for a color filter (hereinafter, also referred to as a coloring composition) of the present specification preferably contains a diketopyrrolopyrrole pigment composition, a binder resin, and an organic solvent.

<Other colorants>
The coloring composition may contain other colorants. This makes it easier to adjust the chromaticity of the coloring composition. Other colorants are pigments and dyes other than the diketopyrrolopyrrole pigment represented by the general formula (1) and the diketopyrrolopyrrole pigment represented by the general formula (2). Specific examples of other colorants are shown below. The term "colorant" as used herein includes the diketopyrrolopyrrole pigment represented by the general formula (1), the diketopyrrolopyrrole pigment represented by the general formula (2), and other colorants.

Other colorants include, for example, C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 146, 168 , 169, 176, 177, 178, 179, 184, 185, 187, 200, 202, 208, 20, 242, 246, 255, 264, 270, 272, 273, 274, 276, 277, 278, 279, Examples include red pigments such as 280, 281, 282, 283, 284, 285, 286, or 287. Examples of the red dye include xanthene-based, azo-based (pyridone-based, barbituric acid-based, metal complex-based, etc.), disazo-based, and anthraquinone-based dyes. Among these, the red dye is C.I. I. Salt-forming compounds of xanthene-based acid dyes such as Acid Red 52, 87, 92, 289, 338 are preferable.

In addition, C.I. I. Pigment Orange An orange pigment such as 43, 71, or 73 and / or C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 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, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 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, Examples include yellow pigments such as 193, 194, 198, 199, 213, 214, 218, 219, 220, or 221. Examples of the orange dye and / or the yellow dye include quinoline-based dyes, azo-based dyes (pyridone-based, barbituric acid-based, metal complex-based, etc.), disazo-based dyes, and methine-based dyes.

Among these, C.I. I. Pigment Red 177 , 242, C.I. I. Pigment Yellow 139, 150, 185 are preferred.

The diketopyrrolopyrrole pigment composition preferably contains 40 to 100% by mass, more preferably 60 to 100% by mass, in 100% by mass of the total colorant.

<Binder resin>
Examples of the binder resin include conventionally known thermoplastic resins and thermosetting resins. The spectral transmittance of the binder resin is preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region.

The thermoplastic resin is, for example, an acrylic resin, a butyral resin, a styrene-maleic acid copolymer, a chlorinated polyethylene, a chlorinated polypropylene, a polyvinyl chloride, a vinyl chloride-vinyl acetate copolymer, a polyvinyl acetate, a polyurethane resin, and the like. Examples thereof include polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resin.

Further, as the binder resin, it is preferable to use an alkali-soluble resin obtained by copolymerizing an ethylenically unsaturated monomer containing an acidic group. When this binder resin is used, it can be preferably used for an alkali-developed colored resist of a color filter. The alkali-soluble resin can be photoreactive by adding an ethylenically unsaturated active double bond.

The alkali-soluble resin is preferably a resin having an acidic group such as a carboxyl group or a sulfone group, for example. The alkali-soluble resin is, for example, an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or an isobutylene /. (Anhydrous) maleic acid copolymer and the like can be mentioned. Among these, an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer are preferable, and an acrylic resin having an acidic group is more preferable.

The alkali-soluble resin having an ethylenically unsaturated active double bond is, for example, a polymer having a reactive substituent such as a hydroxyl group, a carboxyl group or an amino group and a reactive substituent such as an isocyanate group, an aldehyde group or an epoxy group. A resin in which a photoreactive group such as a (meth) acryloyl group or a styryl group is introduced into the polymer by reacting with a (meth) acrylic compound or silicic acid having the above is preferable. Alternatively, a polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is half-estered with a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. The resin is also preferable.

As the thermoplastic resin, those having both alkali-soluble performance and energy ray-curing performance are also preferable as the photosensitive coloring composition for a color filter.

Examples of the thermosetting resin include epoxy resin, benzoguanamine resin, rosin-modified maleic acid resin, rosin-modified fumaric acid resin, melamine resin, urea resin, and phenol resin. Among these, epoxy resin and melamine resin are more preferably used from the viewpoint of improving heat resistance.

The weight average molecular weight (Mw) of the binder resin is preferably 5,000 to 80,000, more preferably 7,000 to 50,000. The number average molecular weight (Mn) is preferably 2,500 to 40,000. The molecular weight dispersion (Mw / Mn) is preferably 10 or less. For the weight average molecular weight (Mw) and the number average molecular weight (Mn), four separation columns are connected in series in the gel permeation chromatography "HLC-8120GPC" manufactured by Tosoh Corporation, and Tosoh stocks are used as fillers in order. It is a polystyrene-equivalent molecular weight measured by using a company-made "TSK-GEL SUPER H5000", "H4000", "H3000", and "H2000" and using tetrahydrofuran as a mobile phase.

When the binder resin has an acid value, an acid value of 20 to 300 mgKOH / g is preferable. When used in this range, the solubility in a developing solution is further improved, and it becomes easy to form a fine resist pattern.

It is preferable to use 20 to 500% by mass of the binder resin with respect to 100 parts by mass of the colorant. When an appropriate amount of the binder resin is used, it becomes easy to form a film of the color filter, and it is easy to obtain a good color tone.

<Organic solvent>
The coloring composition of the present specification preferably contains an organic solvent. As a result, the solubility of the non-volatile component of the coloring composition is improved, and the coatability of the coloring composition is further improved.

Examples of the organic solvent include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, and the like. 2-Heptanone, 2-Methyl-1,3-Propanediol, 3,5,5-trimethyl-2-Cyclohexene-1-one, 3,3,5-trimethylcyclohexanone, Ethyl 3-ethoxypropionate, 3-Methyl -1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m -Diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propylacetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene Glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotersial butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl Ether acetate, Diisobutylketone, Diethylene glycol diethyl ether, Diethylene glycol dimethyl ether, Diethylene glycol monoisopropyl ether, Diethylene glycol monoethyl ether acetate, Diethylene glycol monobutyl ether, Diethylene glycol monobutyl ether acetate, Diethylene glycol monomethyl ether, Cyclohexanol, Cyclohexanol acetate, Cyclohexanone, Dipropylene glycol dimethyl ether , Dipropylene glycol methyl ether acetate, Dipropylene glycol monoethyl ether, Dipropylene Propylene Glycol Monobutyl Ether, Dipropylene Glycol Monopropyl Ether, Dipropylene Glycol Monomethyl Ether, Diacetone Alcohol, Triacetin, Tripropylene Glycol Monobutyl Ether, Tripropylene Glycol Monomethyl Ether, Propylene Glycol Diacetate, Propylene Glycolphenyl Ether, Propylene Glycol Monoethyl Ether, Propylene Glycol Monoethyl Ether Acetate, Propylene Glycol Monobutyl Ether, Propylene Glycol Monopropyl Ether, Propylene Glycol Monomethyl Ether, Propylene Glycol Monomethyl Ether Acetate, Propylene Glycol Monomethyl Ether Propionate, benzyl Alcohol, Methyl Isobutyl Ketone, Methyl Cyclohexanol, Examples thereof include n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid ester and the like.

Among these, glycol acetates such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate; aromatic alcohols such as benzyl alcohol; ketones such as cyclohexanone; Is preferable.

The organic solvent can be used alone or in combination of two or more.

The organic solvent is preferably 500 to 4000% by mass with respect to 100 parts by mass of the colorant. When an appropriate amount of organic solvent is used, it is easy to form a filter segment having a uniform film thickness.

<Preparation of coloring composition>
The coloring composition can be prepared by finely dispersing the colorant carrier composed of the pigment composition, the binder resin, and the organic solvent by using a dispersion means. Examples of the dispersion means include a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annual bead mill, and an attritor.

Further, when the colorant is dispersed in the colorant carrier, a dispersion aid such as the above-mentioned dye derivative, resin type dispersant, or surfactant may be appropriately contained. Since the dispersion aid has a great effect of preventing the reaggregation of the colorant after dispersion, the coloring composition using the dispersion aid further improves the contrast and viscosity stability.

(Resin type dispersant and surfactant)
The resin-type dispersant has a pigment-affinitive moiety having a property of adsorbing to the colorant and a moiety compatible with the colorant carrier, and is adsorbed on the colorant to disperse the colorant on the colorant carrier. Stabilize. Resin-type dispersants include, for example, polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, and poly. Oiliness of amides and salts thereof of reactants of siloxane, long-chain polyaminoamidophosphates, and hydroxyl group-containing polycarboxylic acid esters, and modified products thereof; poly (lower alkyleneimine) and polyester having a free carboxyl group. Dispersant; (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, water-soluble resin such as polyvinylpyrrolidone, or water-soluble Examples thereof include a sex polymer compound, a polyester type, a modified polyacrylate type, an ethylene oxide / propylene oxide addition compound, and a phosphoric acid ester type.

The resin type dispersant can be used alone or in combination of two or more.

Commercially available resin-type dispersants include, for example, Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166 manufactured by Big Chemie Japan. , 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155, or Anti-Terra-U, 203, 204, Or BYK-P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykuman, etc., SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000 , 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., EFKA-46, 47, manufactured by BASF. 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc. , PB824 and the like.

Surfactants include, for example, sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salts of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalrine sulfonate, alkyldiphenyl ether disulfonic acid. Anionic surfactants such as sodium, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate, etc. Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; Chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyl betaines such as alkyldimethylaminoacetic acid betaine and amphoteric surfactants such as alkylimidazolin can be mentioned.

The surfactant can be used alone or in combination of two or more.

When a resin-type dispersant or a surfactant is added, 0.1 to 55 parts by mass is preferable, and 0.1 to 45 parts by mass is more preferable with respect to 100 parts by mass of the colorant. Dispersibility is further improved by blending an appropriate amount of a resin-type dispersant or a surfactant.

The coloring composition herein further preferably contains a photopolymerizable monomer and a photopolymerization initiator. Thereby, the coloring composition can be used as a photosensitive coloring composition.

<Photopolymerizable monomer>
The photopolymerizable monomer includes a monomer and an oligomer that react with ultraviolet rays, heat, or the like.
The blending amount of the photopolymerizable monomer is preferably 5 to 400% by weight, more preferably 10 to 300% by weight, based on 100 parts by weight of the colorant. When an appropriate amount of the photopolymerizable monomer is used, the photocurability and developability are further improved.

Examples of the monomer include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, and tri. Various acrylic acid esters such as cyclodecanyl (meth) acrylate, ester acrylate, (meth) acrylic acid ester of methylolated melamine, epoxy (meth) acrylate, urethane acrylate, and methacrylic acid ester, (meth) acrylic acid, styrene, acetic acid. Examples thereof include vinyl, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, and acrylonitrile.
Examples of the oligomer include polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, and trimethyl propantri (meth). Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether Examples thereof include di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate.

<Photopolymerization initiator>
The photopolymerization initiator is, for example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one, 1 -Hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl]- Acetphenone compounds such as 1- [4- (4-morpholinyl) phenyl] -1-butanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one; benzoin, benzoin Benzoin compounds such as methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl dimethyl ketal; benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylicized benzophenone, 4-benzoyl-4'- Benzophenone compounds such as methyldiphenylsulfide, 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorthioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropyl Thioxanthone compounds such as thioxanthone, 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxy) Phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloro) Methyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(4-methoxy-naphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloromethyl-( Triazine compounds such as 4'-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], O- (acetyl) )-N- (1-Phenyl-2-oxo-2- (4'-methoxy-naphthyl) ethylidene) oxime ester compounds such as hydroxylamine; bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2 , 4,6-trimethylbenzoyldiphenylphosphine oxide and other phosphine compounds; 9,10-phenanthrene quinone, camphorquinone, ethylanthraquinone and other quinone compounds; borate compounds; carbazole compounds; imidazole compounds; titanosen compounds Examples include compounds.

The photopolymerization initiator can be used alone or in combination of two or more.

The blending amount of the photopolymerization initiator is preferably 2 to 200% by mass, more preferably 3 to 150% by mass from the viewpoint of photocurability and developability, based on 100 parts by mass of the total amount of the colorant.

<Sensitizer>
The coloring composition can further include a sensitizer.
Examples of the sensitizer include unsaturated ketones such as chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives and anthraquinone. Polymethine dyes such as derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonoal derivatives, aclysine derivatives, azine derivatives, thiadine derivatives, oxadin derivatives, indolin derivatives. , Azulene derivative, Azurenium derivative, Squalylium derivative, Porphyrin derivative, Tetraphenylporphyrin derivative, Triarylmethane derivative, Tetrabenzoporphyrin derivative, Tetrapyrazinoporphyrazine derivative, Phthalocyanin derivative, Tetraazaporphyrazine derivative, Tetraquinoxalyloporphyrazine Derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrilium derivatives, tetraphyllin derivatives, anuren derivatives, spiropyrane derivatives, spiroxazine derivatives, thiospiropyrane derivatives, metal arene complexes, organic ruthenium complexes, or Mihiler ketone derivatives, α-acyloxy Esters, acylphosphine oxides, methylphenylgrioxylates, benzyls, 9,10-phenanthrene quinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalofenone, 3,3', or 4,4 '-Tetra (t-butylperoxycarbonyl) benzophenone, 4,4'-diethylaminobenzophenone and the like can be mentioned.

Also, edited by Nobu Okawara et al., "Dye Handbook" (1986, Kodansha), edited by Nobu Okawara et al., "Chemistry of Functional Dyes" (1981, CMC), edited by Chuzaburo Ikemori et al., And "Special Functional Materials". Also mentioned is the sensitizer described in (1986, CMC).

The sensitizer can be used alone or in combination of two or more.

The blending amount of the sensitizer is preferably 3 to 60% by mass, more preferably 5 to 50% by mass, based on 100 parts by mass of the photopolymerization initiator. When an appropriate amount of sensitizer is added, the photocurability and developability are further improved.

<Amine compounds>
The coloring composition can further contain an amine-based compound. Amine compounds function as antioxidants.

Amine compounds include, for example, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, and the like. Examples thereof include 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine and the like.

<Leveling agent>
The coloring composition can further include a leveling agent. This makes it possible to produce a smoother filter segment.
Examples of the leveling agent include dimethylsiloxane having a polyether structure or a polyester structure in the main chain. Examples of commercially available products of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning and BYK-333 manufactured by Big Chemie. Examples of commercially available products of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by Big Chemie.

The leveling agent can be used alone or in combination of two or more.

The blending amount of the leveling agent is preferably 0.003 to 0.5% by mass in 100% by mass of the non-volatile content of the coloring composition.

Anionic, cationic, nonionic, amphoteric, fluorinated or silicone-based surfactants can be used in combination with the leveling agent. Anionic surfactants include, for example, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalline sulfonate, sodium alkyldiphenyl ether disulfonate, and monoethanol lauryl sulfate. Examples thereof include amine, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether phosphate ester.

Examples of the chaotic surfactant include an alkyl quaternary ammonium salt and an ethyleneoxy group adduct thereof. Nonionic surfactants include, for example, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate. Can be mentioned. Examples of the benign surfactant include alkyl betaine such as alkyldimethylaminoacetic acid betaine and alkyl imidazoline. The fluorine-based surfactant is, for example, a surfactant having a fluorocarbon chain, and the silicone-based surfactant is, for example, a linear polymer composed of a siloxane bond or an organic group introduced into a side chain or a terminal. Examples include modified siloxane polymers.

The surfactant can be used alone or in combination of two or more.

<Curing agent, curing accelerator>
The coloring composition can further contain a curing agent and a curing accelerator. This further improves the curability of the thermosetting resin.
Examples of the curing agent include phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, and sulfonic acid compounds. Among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine-based curing agent are preferable. Further, the curing accelerator is, for example, an amine compound (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl). -N, N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (eg, triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (eg, dimethylamine, etc.), imidazole derivative bicyclic amidin compounds and salts thereof (eg, eg). Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2- Ethyl-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), guanamine compounds (eg, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (eg, 2,4-diamino-6). -Methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine-isosianulic acid adduct, 2,4-diamino-6- Methacryloyloxyethyl-S-triazine, isocyanuric acid adduct, etc.) is preferable.

The curing agent and curing accelerator can be used alone or in combination of two or more.

The content of the curing accelerator is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the thermosetting resin.

<Other additive components>
The coloring composition can further contain other additive components. Examples of other additive components include storage stabilizers, adhesion improvers and the like.
When a storage stabilizer is contained, the viscosity of the coloring composition over time during storage is unlikely to change. Further, when the adhesion improving agent is contained, the coloring composition further improves the adhesion to the transparent substrate or the like.

Storage stabilizers include, for example, quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and phosphoric acid, and their methyl ethers, t-butylpyrocatechol, tetraethylphosphine, tetraphenylphosphine and the like. Examples thereof include organic phosphine and phosphite.

The content of the storage stabilizer is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the colorant.

The adhesion improver is preferably a silane coupling agent. The silane coupling agent is, for example, vinyl silane such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, vinyltrimethoxysilane; (meth) acrylic silane such as γ-methacryloxypropyltrimethoxysilane; β- (3, 4-Epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane; N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) ) Γ-Aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysisilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyl Aminosilanes such as trimethoxysilane and N-phenyl-γ-aminopropyltriethoxysilane; thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane; and the like can be mentioned.

The content of the adhesion improver is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the colorant.

<Removal of coarse particles>
The coloring composition preferably removes coarse particles mixed or generated during production. The colored composition was mixed with coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more, using means such as centrifugation, filtration with a sintering filter or a membrane filter. It is preferable to remove dust.

<Color filter>
The color filters herein preferably include a red filter segment, a green filter segment, and a blue filter segment. The red filter segment preferably contains a pigment composition or is a cured product of a coloring composition.

The green filter segment can be formed using a conventional green coloring composition containing a green pigment and a colorant carrier. The green pigment is, for example, C.I. I. Pigment Green 7, 10, 36, 37, 58 and the like.

Further, a yellow pigment can be used in combination with the green coloring composition. The yellow pigment is, for example, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 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, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 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, 198, 199, 213, 214, 218, 219, 220, 221 and the like can be mentioned. In addition, a salt-forming compound of a basic dye or an acid dye that exhibits yellow color can be used in combination.

The blue filter segment can be formed using a conventional blue coloring composition containing a blue pigment and a colorant carrier. The blue pigment is, for example, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64 and the like. Further, a purple pigment can be used in combination with the blue coloring composition. The purple pigment is, for example, C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50 and the like. In addition, salt-forming compounds of basic dyes and acid dyes that exhibit blue or purple can be used. When a dye is used, a xanthene dye is preferable in terms of heat resistance and lightness.

<Manufacturing method of color filter>
The color filter can be manufactured by a printing method or a photolithography method using the coloring composition.
Since the formation of the filter segment by the printing method can be patterned only by repeating printing and drying of the coloring composition prepared as the printing ink, it is low cost and excellent in mass productivity as a manufacturing method of the color filter. Furthermore, it is possible to form a fine pattern having high dimensional accuracy and smoothness. For printing, it is preferable that the composition is such that the ink does not dry or solidify on the printing plate or on the blanket. Further, in order to control the fluidity of the ink on the printing machine, the ink viscosity can be adjusted with a dispersant or an extender pigment.

When the filter segment is formed by the photolithography method, the colored composition prepared as a solvent-developed type or an alkali-developed type is dried on a transparent substrate by a coating method such as spray coating, spin coating, slit coating, or roll coating. A film is formed by applying so that the film thickness is 0.2 to 5 μm. The film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or without contact with the film. Then, after immersing in a solvent or an alkaline developer or spraying the developer with a spray or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. .. Further, in order to promote the polymerization of the coloring composition, heating can be applied as needed. The photolithography method can be used to produce color filters with higher accuracy than the printing method.

For development, an aqueous solution of sodium carbonate, sodium hydroxide or the like can be used as the alkaline developer. Further, organic alkalis such as dimethylbenzylamine and triethanolamine can also be used. Further, an antifoaming agent or a surfactant can be added to the developing solution. In order to increase the UV exposure sensitivity, the colored resist was applied and dried, and then a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin was applied and dried to form a film for preventing polymerization inhibition by oxygen. Later, UV exposure can also be performed.

The color filter can be manufactured by an electrodeposition method, a transfer method, or the like in addition to the above method. The electrodeposition method is a method of manufacturing a color filter by electrodepositing each color filter segment on the transparent conductive film by electrophoresis of colloidal particles using the transparent conductive film formed on the substrate. .. Further, the transfer method is a method in which a filter segment is formed in advance on the surface of a peelable transfer base sheet, and the filter segment is transferred to a desired substrate.

A black matrix can be formed in advance before forming each color filter segment on the transparent substrate or the reflective substrate. As the black matrix, a multilayer film of chromium or chromium / chromium oxide, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but the black matrix is not limited thereto. Further, it is also possible to form a thin film transistor (TFT) in advance on the transparent substrate or the reflective substrate, and then form each color filter segment. Further, an overcoat film, a transparent conductive film, or the like is formed on the color filter of the present invention, if necessary.

Examples of the material of the transparent substrate and the reflective substrate include a glass plate and a transparent resin plate.

The thickness of the transparent substrate and the reflective substrate is about 50 μm to 1 mm.

The color filter is preferably used, for example, in a display device such as a liquid crystal display device or an organic EL display device, or in a camera application.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In Examples and Comparative Examples, "part" means "part by mass" and "%" means "% by mass".

<Mass ratio of diketopyrrolopyrrole pigment>
The content of the diketopyrrolopyrrole pigment represented by the general formula (1) and the diketopyrrolopyrrole pigment represented by the general formula (2) in the pigment composition was quantified by using HPLC. The measurement conditions are as follows.

Device: JASCO Gulliver series detector: JASCO UV-970 detector Column: Waters Symmetry C18 (5 μm, 2.1 mm φ × 150 mm)
Mobile phase A solution: dimethylformamide / water (1: 1)
Mobile phase B liquid: dimethylformamide / water (97.5: 2.5)
Gradient (Liquid B): 47% → (15 min) → 47% → (5 min) → 100% → (25 min) → 100%
Wavelength: 510 nm
Column temperature: 35 ° C
Flow rate: 0.3 mL / min
Sample injection volume: 5 μL (dissolved in N-methylpyrrolidone / 28% sodium methoxide methanol solution)

<Mass average molecular weight (Mw) of binder resin>
The mass average molecular weight (Mw) of the binder resin is converted to polystyrene measured by using a TSKgel column (manufactured by Tosoh Corporation) and a GPC (manufactured by Tosoh Corporation, HLC-8120GPC) equipped with an RI detector and using tetrahydrofuran as a developing solvent. Is the mass average molecular weight (Mw) of.

<Manufacturing method of diketopyrrolopyrrole pigment>
[Production Example 1] (Production of diketopyrrolopyrrole pigment represented by the formula (1-1))
To a stainless steel reaction vessel equipped with a reflux tube, 200 parts of molecularly dehydrated tert-amyl alcohol and 140 parts of sodium-tert-amyl alkoxide were added under a nitrogen atmosphere, and the mixture was heated to 100 ° C. with stirring to prepare an alcoholate solution. Prepared. On the other hand, 88 parts of diisopropyl succinate and 153.6 parts of 4-bromobenzonitrile were added to a glass flask and heated to 90 ° C. with stirring to dissolve them to prepare a solution of a mixture thereof. The heated solution of this mixture was uniformly added dropwise over 2 hours to the above alcoholate solution heated to 100 ° C. with vigorous stirring. After completion of the dropping, heating and stirring were continued at 90 ° C. for 2 hours to obtain an alkali metal salt of a diketopyrrolopyrrole compound. Further, 600 parts of methanol, 600 parts of water, and 304 parts of acetic acid were added to the reaction vessel with a glass jacket, and the mixture was cooled to −10 ° C. The cooled mixture was cooled to 75 ° C. using a high-speed stirring disperser while rotating a share disk having a diameter of 8 cm at 4000 rpm, and the alkali metal salt of the previously obtained diketopyrrolopyrrole compound was cooled therein. The solution was added in small portions. At this time, the rate of adding the alkali metal salt of the diketopyrrolopyrrole compound at 75 ° C. while cooling so that the temperature of the mixture consisting of methanol, acetic acid, and water is always maintained at -5 ° C. or lower. Was added in small portions over approximately 120 minutes. After the addition of the alkali metal salt, red crystals were precipitated and a red suspension was formed. Subsequently, the obtained red suspension was washed with an ultrafiltration device at 5 ° C. and then filtered off to obtain a red paste. This paste was redistributed in 3500 parts of methanol cooled to 0 ° C. to prepare a suspension having a methanol concentration of about 90%, and the mixture was stirred at 5 ° C. for 3 hours to perform particle sizing and washing with crystal transition. Subsequently, the water paste of the obtained diketopyrrolopyrrole compound was filtered off with an extraneous filter, dried at 80 ° C. for 24 hours, and pulverized to obtain the diketopyrrolopyrrole represented by the following formula (1-1). A pyrrolopyrrole pigment was obtained.

[Production Example 2] (Production of diketopyrrolopyrrole pigment represented by the formula (1-2))
The same procedure as in Production Example 1 was carried out except that 153.6 parts of 4-bromobenzonitrile was changed to 117.4 parts of 4-chlorobenzonitrile to obtain a diketopyrrolopyrrole pigment represented by the formula (1-2). ..

[Production Example 3] (Production of diketopyrrolopyrrole pigment represented by the formula (2-1))
The procedure was carried out in the same manner as in Production Example 1 except that 153.6 parts of 4-bromobenzonitrile was changed to 124.7 parts of 4-cyanobenzamide to obtain a diketopyrrolopyrrole pigment represented by the formula (2-1).

[Production Example 4] (Production of diketopyrrolopyrrole pigment represented by the formula (2-3))
The same procedure as in Production Example 1 was carried out except that 153.6 parts of 4-bromobenzonitrile was changed to 172.6 parts of N-butyl-4-cyanobenzamide to obtain a diketopyrrolopyrrole pigment represented by the formula (2-3). rice field.

[Production Example 5] (Production of diketopyrrolopyrrole pigment represented by the formula (2-7))
The same procedure as in Production Example 1 was carried out except that 153.6 parts of 4-bromobenzonitrile was changed to 189.6 parts of N-phenyl-4-cyanobenzamide to obtain a diketopyrrolopyrrole pigment represented by the formula (2-7). rice field.

[Production Example 6] (Production of diketopyrrolopyrrole pigment represented by the formula (2-11))
The same procedure as in Production Example 1 was carried out except that 153.6 parts of 4-bromobenzonitrile was changed to 172.6 parts of N-butyl-3-cyanobenzamide to obtain a diketopyrrolopyrrole pigment represented by the formula (2-11). rice field.

[Production Example 7] (Production of diketopyrrolopyrrole pigment represented by the formula (2-15))
The same procedure as in Production Example 1 was carried out except that 153.6 parts of 4-bromobenzonitrile was changed to 220.4 parts of N, N-dibutyl-4-cyanobenzamide, and the diketopyrrolopyrrole pigment represented by the formula (2-15) was used. Got

[Production Example 8] (Production of diketopyrrolopyrrole pigment represented by the formula (2-22))
The same procedure as in Production Example 1 was carried out except that 153.6 parts of 4-bromobenzonitrile was changed to 163.2 parts of 4- (butylthio) benzonitrile, and the diketopyrrolopyrrole pigment represented by the formula (2-22) was used. Obtained.

[Production Example 9] (Production of diketopyrrolopyrrole pigment represented by the formula (2-24))
The same procedure as in Production Example 1 was carried out except that 153.6 parts of 4-bromobenzonitrile was changed to 211.1 parts of 4- (octylthio) benzonitrile, and the diketopyrrolopyrrole pigment represented by the formula (2-24) was used. Obtained.

[Production Example 10] (Production of diketopyrrolopyrrole pigment represented by the formula (2-27))
The same procedure as in Production Example 1 was carried out except that 153.6 parts of 4-bromobenzonitrile was changed to 180.3 parts of 4- (phenylthio) benzonitrile, and the diketopyrrolopyrrole pigment represented by the formula (2-27) was used. Obtained.

[Production Example 11] (Production of diketopyrrolopyrrole pigment represented by the formula (2-34))
The same procedure as in Production Example 1 was carried out except that 153.6 parts of 4-bromobenzonitrile was changed to 211.1 parts of 3- (octylthio) benzonitrile, and the diketopyrrolopyrrole pigment represented by the formula (2-34) was used. Obtained.

[Production Example 12] (Production of Diketopyrrolopyrrole Pigment Represented by Formula (17))
The same procedure as in Production Example 1 was carried out except that 153.6 parts of 4-bromobenzonitrile was changed to 149.5 parts of 3-butoxybenzonitrile to obtain a diketopyrrolopyrrole pigment represented by the following formula (17).

[Production Example 13] (Production of Diketopyrrolopyrrole Pigment Represented by Formula (18))
The procedure was carried out in the same manner as in Production Example 1 except that 153.6 parts of 4-bromobenzonitrile was changed to 88.0 parts of benzonitrile to obtain a diketopyrrolopyrrole pigment represented by the following formula (18).

[Production Example 14] (Production of Diketopyrrolopyrrole Pigment Represented by Formula (19))
The procedure was carried out in the same manner as in Production Example 1 except that 153.6 parts of 4-bromobenzonitrile was changed to 152.9 parts of 4-cyanobiphenyl to obtain a diketopyrrolopyrrole pigment represented by the following formula (19).

<Manufacturing method of binder resin solution>
[Production Example 15] (Preparation of Acrylic Resin Solution 1)
196 parts of cyclohexanone was charged in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer in a separable 4-neck flask, the temperature was raised to 80 ° C., the inside of the reaction vessel was replaced with nitrogen, and then dropped. From the tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, 20.7 parts of paracumylphenol ethylene oxide-modified acrylate ("Aronix M110" manufactured by Toa Synthetic Co., Ltd.) , 2,2'-Azobisisobutyronitrile 1.1 parts mixture was added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain a solution of acrylic resin. After cooling to room temperature, an acrylic resin solution 1 having a weight average molecular weight (Mw) of 26000 was obtained by adjusting with methoxypropyl acetate so that the non-volatile content was 20% by mass.

[Production Example 16] (Preparation of Acrylic Resin Solution 2)
207 parts of cyclohexanone was charged in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer in a separable 4-neck flask, the temperature was raised to 80 ° C., the inside of the reaction vessel was replaced with nitrogen, and then dropped. From the tube, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toa Synthetic Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2'-azobis. A mixture of 1.33 parts of isobutyronitrile was added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain a copolymer resin solution. Next, for the entire amount of the obtained copolymer solution, nitrogen gas was stopped, dry air was injected for 1 hour, and the mixture was stirred, cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Showa Denko's Karenz). A mixture of 6.5 parts of MOI), 0.08 part of dibutyltin laurate and 26 parts of cyclohexanone was added dropwise at 70 ° C. over 3 hours. After completion of the dropping, the reaction was continued for another 1 hour to obtain a solution of acrylic resin. After cooling to room temperature, the acrylic resin solution 2 having a weight average molecular weight (Mw) of 18,000 was obtained by adjusting with cyclohexanone so that the non-volatile content was 20% by mass.

<Manufacturing method of diketopyrrolopyrrole pigment composition>
[Example 1] (Production of Diketopyrrolopyrrole Pigment Composition (R-1))
95.0 parts of the diketopyrrolopyrrole pigment of the formula (1-1), 5.0 parts of the diketopyrrolopyrrole pigment of the formula (2-1), 1000 parts of sodium chloride, and 120 parts of diethylene glycol are added to a 1-gallon kneader made of stainless steel. It was charged in (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 10 hours. Next, the kneaded mixture was put into warm water, stirred for 1 hour while heating at about 80 ° C. to form a slurry, filtered and washed with water to remove salt and diethylene glycol, dried at 80 ° C. overnight, and pulverized. The diketopyrrolopyrrole pigment composition (R-1) was obtained.

[Example 2] (Production of diketopyrrolopyrrole pigment composition (R-2))
The same procedure as in Example 1 was carried out except that 5.0 parts of the diketopyrrolopyrrole pigment of the formula (2-1) was changed to 5.0 parts of the diketopyrrolopyrrole pigment of the formula (2-3). A pyrrolopyrrole pigment composition (R-2) was obtained.

[Example 3] (Production of Diketopyrrolopyrrole Pigment Composition (R-3))
The same procedure as in Example 1 was carried out except that 5.0 parts of the diketopyrrolopyrrole pigment of the formula (2-1) was changed to 5.0 parts of the diketopyrrolopyrrole pigment of the formula (2-7). A pyrrolopyrrole pigment composition (2-7) was obtained.

[Example 4] (Production of Diketopyrrolopyrrole Pigment Composition (R-4))
The same procedure as in Example 1 was carried out except that 5.0 parts of the diketopyrrolopyrrole pigment of the formula (2-1) was changed to 5.0 parts of the diketopyrrolopyrrole pigment of the formula (2-11). A pyrrolopyrrole pigment composition (R-4) was obtained.

[Example 5] (Production of diketopyrrolopyrrole pigment composition (R-5))
The same procedure as in Example 1 was carried out except that 5.0 parts of the diketopyrrolopyrrole pigment of the formula (2-1) was changed to 5.0 parts of the diketopyrrolopyrrole pigment of the formula (2-15). A pyrrolopyrrole pigment composition (R-5) was obtained.

[Example 6] (Production of Diketopyrrolopyrrole Pigment Composition (R-6))
The same procedure as in Example 1 was carried out except that 5.0 parts of the diketopyrrolopyrrole pigment of the formula (2-1) was changed to 5.0 parts of the diketopyrrolopyrrole pigment of the formula (2-22). A pyrrolopyrrole pigment composition (R-6) was obtained.

[Example 7] (Production of diketopyrrolopyrrole pigment composition (R-7))
The same procedure as in Example 1 was carried out except that 5.0 parts of the diketopyrrolopyrrole pigment of the formula (2-1) was changed to 5.0 parts of the diketopyrrolopyrrole pigment of the formula (2-24). A pyrrolopyrrole pigment composition (R-7) was obtained.

[Example 8] (Production of Diketopyrrolopyrrole Pigment Composition (R-8))
The same procedure as in Example 1 was carried out except that 5.0 parts of the diketopyrrolopyrrole pigment of the formula (2-1) was changed to 5.0 parts of the diketopyrrolopyrrole pigment of the formula (2-27). A pyrrolopyrrole pigment composition (R-7) was obtained.

[Example 9] (Production of diketopyrrolopyrrole pigment composition (R-9))
The same procedure as in Example 1 was carried out except that 5.0 parts of the diketopyrrolopyrrole pigment of the formula (2-1) was changed to 5.0 parts of the diketopyrrolopyrrole pigment of the formula (2-34). A pyrrolopyrrole pigment composition (R-7) was obtained.

[Example 10] (Production of Diketopyrrolopyrrole Pigment Composition (R-10))
The same procedure as in Example 1 was carried out except that 95.0 parts of the diketopyrrolopyrrole pigment of the formula (1-1) was changed to 95.0 parts of the diketopyrrolopyrrole pigment of the formula (1-2). A pyrrolopyrrole pigment composition (R-10) was obtained.

[Example 11] (Production of diketopyrrolopyrrole pigment composition (R-11))
95.0 parts of the diketopyrrolopyrrole pigment of the formula (1-1), 5.0 parts of the diketopyrrolopyrrole pigment of the formula (2-1), and 95.0 of the diketopyrrolopyrrole pigment of the formula (1-2). The same procedure as in Example 1 was carried out except that the portion was changed to 5.0 parts of the diketopyrrolopyrrole pigment of the formula (2-3) to obtain a diketopyrrolopyrrole pigment composition (R-11).

[Example 12] (Production of Diketopyrrolopyrrole Pigment Composition (R-12))
95.0 parts of the diketopyrrolopyrrole pigment of the formula (1-1), 5.0 parts of the diketopyrrolopyrrole pigment of the formula (2-1), and 95.0 of the diketopyrrolopyrrole pigment of the formula (1-2). The same procedure as in Example 1 was carried out except that the portion was changed to 5.0 parts of the diketopyrrolopyrrole pigment of the formula (2-15) to obtain a diketopyrrolopyrrole pigment composition (R-12).

[Example 13] (Production of Diketopyrrolopyrrole Pigment Composition (R-13))
95.0 parts of the diketopyrrolopyrrole pigment of the formula (1-1), 5.0 parts of the diketopyrrolopyrrole pigment of the formula (2-1), and 95.0 of the diketopyrrolopyrrole pigment of the formula (1-2). The same procedure as in Example 1 was carried out except that the portion was changed to 5.0 parts of the diketopyrrolopyrrole pigment of the formula (2-24) to obtain a diketopyrrolopyrrole pigment composition (R-13).

[Example 14] (Production of diketopyrrolopyrrole pigment composition (R-14))
95.0 parts of the diketopyrrolopyrrole pigment of the formula (1-1), 5.0 parts of the diketopyrrolopyrrole pigment of the formula (2-1), and 95.0 of the diketopyrrolopyrrole pigment of the formula (1-2). The same procedure as in Example 1 was carried out except that the portion was changed to 5.0 parts of the diketopyrrolopyrrole pigment of the formula (2-27) to obtain a diketopyrrolopyrrole pigment composition (R-14).

[Example 15] (Production of Diketopyrrolopyrrole Pigment Composition (R-15))
95.0 parts of the diketopyrrolopyrrole pigment of the formula (1-1), 5.0 parts of the diketopyrrolopyrrole pigment of the formula (2-1), and 99.99 of the diketopyrrolopyrrole pigment of the formula (1-1). The same procedure as in Example 1 was carried out except that the portion was changed to 0.01 part of the diketopyrrolopyrrole pigment of the formula (2-15) to obtain a diketopyrrolopyrrole pigment composition (R-15).

[Example 16] (Production of Diketopyrrolopyrrole Pigment Composition (R-16))
95.0 parts of the diketopyrrolopyrrole pigment of the formula (1-1), 5.0 parts of the diketopyrrolopyrrole pigment of the formula (2-1), and 80.0 of the diketopyrrolopyrrole pigment of the formula (1-1). The same procedure as in Example 1 was carried out except that the portion was changed to 20.0 parts of the diketopyrrolopyrrole pigment of the formula (2-15) to obtain a diketopyrrolopyrrole pigment composition (R-16).
However, Example 16 is a reference example.

[Example 17] (Production of diketopyrrolopyrrole pigment composition (R-17))
95.0 parts of the diketopyrrolopyrrole pigment of the formula (1-1), 5.0 parts of the diketopyrrolopyrrole pigment of the formula (2-1), and 70.0 of the diketopyrrolopyrrole pigment of the formula (1-1). The same procedure as in Example 1 was carried out except that the portion was changed to 30.0 parts of the diketopyrrolopyrrole pigment of the formula (2-15) to obtain a diketopyrrolopyrrole pigment composition (R-17).
However, Example 17 is a reference example.

[Example 18] (Production of Diketopyrrolopyrrole Pigment Composition (R-18))
95.0 parts of the diketopyrrolopyrrole pigment of the formula (1-1), 5.0 parts of the diketopyrrolopyrrole pigment of the formula (2-1), and 85.5 parts of the diketopyrrolopyrrole pigment of the formula (1-1). The same procedure as in Example 1 was carried out except that the part was changed to 4.5 parts of the diketopyrrolopyrrole pigment of the formula (2-15) and 10.0 parts of the benzoisoindole derivative of the formula (8-1). A pyrrolopyrrole pigment composition (R-18) was obtained.

[Example 19] (Production of diketopyrrolopyrrole pigment composition (R-19))
95.0 parts of the diketopyrrolopyrrole pigment of the formula (1-1), 5.0 parts of the diketopyrrolopyrrole pigment of the formula (2-1), and 85.5 parts of the diketopyrrolopyrrole pigment of the formula (1-1). The same procedure as in Example 1 was carried out except that the part was changed to 4.5 parts of the diketopyrrolopyrrole pigment of the formula (2-15) and 10.0 parts of the thiazineindigo derivative of the formula (11-6). A pyrrolopyrrole pigment composition (R-19) was obtained.

[Example 20] (Production of Diketopyrrolopyrrole Pigment Composition (R-20))
95.0 parts of the diketopyrrolopyrrole pigment of the formula (1-1), 5.0 parts of the diketopyrrolopyrrole pigment of the formula (2-1), and 85.5 parts of the diketopyrrolopyrrole pigment of the formula (1-1). The same procedure as in Example 1 was carried out except that the pigment was changed to 4.5 parts of the diketopyrrolopyrrole pigment of the formula (2-15) and 10.0 parts of the diketopyrrolopyrrole derivative of the formula (7-6). A ketopyrrolopyrrole pigment composition (R-20) was obtained.

[Example 21] (Production of Diketopyrrolopyrrole Pigment Composition (R-21))
95.0 parts of the diketopyrrolopyrrole pigment of the formula (1-1), 5.0 parts of the diketopyrrolopyrrole pigment of the formula (2-1), and 85.5 parts of the diketopyrrolopyrrole pigment of the formula (1-1). Diketopyrrolopyrrole was carried out in the same manner as in Example 1 except that the pigment was changed to 4.5 parts of the diketopyrrolopyrrole pigment of the formula (2-15) and 10.0 parts of the quinophthalone derivative of the formula (15-1). A pigment composition (R-21) was obtained.

[Example 22] (Production of Diketopyrrolopyrrole Pigment Composition (R-22))
549.6 parts of an alkali metal salt solution of the diketopyrrolopyrrole compound prepared by the method described in Production Example 1 and an alkali metal salt of the diketopyrrolopyrrole compound prepared by the method described in Production Example 7 in a stainless steel container. 24.0 parts of the solution was added, and the mixture was stirred and mixed at 75 ° C. for 30 minutes to prepare an alkali metal salt mixed solution of the diketopyrrolopyrrole compound. Further, 600 parts of methanol, 600 parts of water, and 304 parts of acetic acid were added to the reaction vessel with a glass jacket, and the mixture was cooled to −10 ° C. A small amount of the previously obtained alkali metal salt mixed solution of the diketopyrrolopyrrole compound was added to the cooled mixture while rotating the share disk having a diameter of 8 cm at 4000 rpm using a high-speed stirring disperser. Added one by one. At this time, the rate of adding the alkali metal salt of the diketopyrrolopyrrole compound at 75 ° C. while cooling so that the temperature of the mixture consisting of methanol, acetic acid, and water is always maintained at -5 ° C. or lower. Was added in small portions over approximately 120 minutes. After the addition of the alkali metal salt, red crystals were precipitated and a red suspension was formed. Subsequently, the obtained red suspension was washed with an ultrafiltration device at 5 ° C. and then filtered off to obtain a red paste. This paste was redistributed in 3500 parts of methanol cooled to 0 ° C. to prepare a suspension having a methanol concentration of about 90%, and the mixture was stirred at 5 ° C. for 3 hours to perform particle sizing and washing with crystal transition. Subsequently, the water paste of the obtained diketopyrrolopyrrole compound was filtered off with an ultrafiltrationr, dried at 80 ° C. for 24 hours, and pulverized to obtain a diketopyrrolopyrrole pigment composition (R-22). ) Was obtained.

[Comparative Example 1] (Production of Diketopyrrolopyrrole Pigment Composition (R-23))
95.0 parts of the diketopyrrolopyrrole pigment of the formula (1-1), 5.0 parts of the diketopyrrolopyrrole pigment of the formula (2-1), and 100.0 of the diketopyrrolopyrrole pigment of the formula (1-1). Diketopyrrolopyrrole pigment (R-23) was obtained in the same manner as in Example 1 except that the parts were changed to parts.

[Comparative Example 2] (Production of Diketopyrrolopyrrole Pigment Composition (R-24))
95.0 parts of the diketopyrrolopyrrole pigment of the formula (1-1), 5.0 parts of the diketopyrrolopyrrole pigment of the formula (2-1), and 100.0 of the diketopyrrolopyrrole pigment of the formula (1-2). Diketopyrrolopyrrole pigment (R-24) was obtained in the same manner as in Example 1 except that the parts were changed to parts.

[Comparative Example 3] (Production of Diketopyrrolopyrrole Pigment Composition (R-25))
95.0 parts of the diketopyrrolopyrrole pigment of the formula (1-1), 5.0 parts of the diketopyrrolopyrrole pigment of the formula (2-1), and 95.0 of the diketopyrrolopyrrole pigment of the formula (1-2). The same procedure as in Example 1 was carried out except that the portion was changed to 5.0 parts of the diketopyrrolopyrrole pigment of the formula (17) to obtain a diketopyrrolopyrrole pigment (R-25).

[Comparative Example 4] (Production of Diketopyrrolopyrrole Pigment Composition (R-26))
95.0 parts of the diketopyrrolopyrrole pigment of the formula (1-1), 5.0 parts of the diketopyrrolopyrrole pigment of the formula (2-1), and 95.0 of the diketopyrrolopyrrole pigment of the formula (1-2). The same procedure as in Example 1 was carried out except that the portion was changed to 5.0 parts of the diketopyrrolopyrrole pigment of the formula (18) to obtain a diketopyrrolopyrrole pigment (R-26).

[Comparative Example 5] (Production of Diketopyrrolopyrrole Pigment Composition (R-27))
95.0 parts of the diketopyrrolopyrrole pigment of the formula (1-1), 5.0 parts of the diketopyrrolopyrrole pigment of the formula (2-1), and 95.0 of the diketopyrrolopyrrole pigment of the formula (1-2). The same procedure as in Example 1 was carried out except that the portion was changed to 5.0 parts of the diketopyrrolopyrrole pigment of the formula (19) to obtain a diketopyrrolopyrrole pigment (R-27).

Table 1 shows the contents of the produced diketopyrrolopyrrole pigment compositions 1 to 27.

<Manufacturing method of coloring composition for color filter>
[Example 23] (Preparation of coloring composition (RP-1))
The following mixture is stirred and mixed so as to be uniform, and then dispersed for 5 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then a 5 μm filter. The mixture was filtered with (RP-1) to prepare a colored composition (RP-1).
Diketopyrrolopyrrole pigment composition (R-1) 11.0 parts Dye derivative formula (15-1) 1.0 part Acrylic resin solution 1 40.0 parts Propylene glycol monomethyl ether acetate 48.0 parts

[Examples 24 to 44] (Coloring compositions (RP-2 to 22))
The diketopyrrolopyrrole pigment composition (R-1) was changed to the diketopyrrolopyrrole pigment composition (R-2 to 22) shown in Table 2 in the same manner as in Example 23, and the coloring composition was carried out. The thing (RP-2-22) was obtained.
However, Examples 38 and 39 are reference examples.

[Comparative Examples 6 to 10] (Coloring Compositions (RP-23 to 27))
The diketopyrrolopyrrole pigment composition (R-1) was changed to the diketopyrrolopyrrole pigment composition (R-23 to 27) shown in Table 2 in the same manner as in Example 23, and the coloring composition was carried out. A thing (RP-23-27) was obtained.

<Evaluation of coloring composition for color filter>
The obtained coloring compositions (RP-1 to 27) were evaluated as follows. The evaluation results are shown in Table 2.

(Contrast ratio evaluation of coating film)
The obtained coloring composition was applied onto a glass substrate having a thickness of 100 mm × 100 mm and a thickness of 0.7 mm to a film thickness such that x = 0.640 with a C light source, and dried. Further, a red coating film was obtained by heating at 230 ° C. for 60 minutes. The contrast of the obtained red coating film was measured by the following method.

A method for measuring the contrast ratio of the coating film will be described. The light emitted from the backlight unit for a liquid crystal display passes through a polarizing plate, is polarized, passes through a dry coating film of a colored composition coated on a glass substrate, and reaches the polarizing plate. If the polarizing plate and the polarizing plane of the polarizing plate are parallel, the light passes through the polarizing plate, but if the polarizing plane is orthogonal, the light is blocked by the polarizing plate. However, when the light polarized by the polarizing plate passes through the dry coating film of the coloring composition, scattering by pigment particles or the like occurs and a part of the polarizing surface is displaced. When the polarizing plates are parallel, the light is polarized. The amount of light transmitted through the plate is reduced, and when the polarizing plate is orthogonal, part of the light is transmitted through the polarizing plate. This transmitted light was measured as the brightness on the polarizing plate, and the ratio (contrast ratio) between the brightness when the polarizing plates were parallel and the brightness when the polarizing plates were orthogonal was calculated.
(Contrast ratio) = (Brightness when parallel) / (Brightness when orthogonal)
Therefore, when scattering occurs due to the pigment in the coating film, the brightness when parallel is reduced and the brightness when orthogonal is increased, so that the contrast ratio is lowered. A color luminance meter (“BM-5A” manufactured by Topcon Corporation) was used as the luminance meter, and a polarizing plate (“NPF-G1220DUN” manufactured by Nitto Denko Corporation) was used as the polarizing plate. At the time of measurement, a black mask having a 1 cm square hole was applied to the measurement portion in order to block unnecessary light.

(Evaluation of initial viscosity)
The viscosity of the coloring composition was measured at 25 ° C. using an E-type viscometer (“ELD-type viscometer” manufactured by Toki Sangyo Co., Ltd.) on the day of adjusting the coloring composition.
◯: Initial viscosity is 50 mPa ・ s or less Good Δ: Initial viscosity is 50 or more and less than 150 mPa ・ s Practical use ×: Initial viscosity is 150 mPa ・ s or more Practical use is not possible

(Evaluation of viscosity over time)
For those that had been allowed to stand at 40 ° C. for 7 days counting from the day of adjusting the coloring composition, after returning the sample temperature to 25 ° C., the viscosity over time was measured according to the above viscosity measurement method, and the viscosity increase rate over time was obtained from the following formula. rice field.
Viscosity over time = (viscosity over time) / (initial viscosity) x 100 (%)
The stability of viscosity over time was evaluated by the rate of thickening over time. The evaluation criteria are shown below.
◯: Time-dependent thickening rate 90% or more and less than 110% Good Δ: Time-related thickening rate 80% or more and less than 90%, or 110% or more and less than 120% No practical problem ×: Time-related thickening rate less than 80% or 120% Not practical

<Method for producing other coloring compositions>
(Preparation of Coloring Composition (RP-28))
The mixture having the composition shown below is uniformly stirred and mixed, dispersed with a picomill for 8 hours using zirconia beads having a diameter of 0.1 mm, and then filtered through a filter of 5 μm to prepare a colored composition (RP-28). did.
Dianthraquinone pigment (PR177-1) 10.8 parts Dye derivative represented by formula (9-5) 1.2 parts Acrylic resin solution 1 40.0 parts Propylene glycol monomethyl ether acetate 48.0 parts

<Method for producing photosensitive coloring composition>
[Example 45] (Preparation of photosensitive coloring composition (RR-1))
The mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare a photosensitive coloring composition 1 (RR-1).
Coloring composition (RP-1) 38.4 parts Coloring composition (RP-28) 3.6 parts Acrylic resin solution 2 13.2 parts Photopolymerizable monomer (“Aronix M400” manufactured by Toa Synthetic Co., Ltd.) 2. 8 parts Photopolymerization initiator (BASF "Irgacure 907") 2.0 parts Sensitizer (Hodoya Chemical Industry "EAB-F") 0.4 parts Ethylene glycol monomethyl ether acetate 39.6 parts

[Examples 46 to 66] (Preparation of photosensitive coloring compositions (RR-2 to 22))
The coloring composition (RP-1) is changed to the coloring composition (RP-2 to 22), and further, the coloring composition (RP-2 to 22) and the coloring composition so as to have the same chromaticity as in Example 45. A photosensitive coloring composition (RR-2 to 22) was prepared in the same manner as in Example 45 except that the ratio of (RP-28) was adjusted.
However, Examples 60 and 61 are reference examples.

[Comparative Examples 11 to 15] (Preparation of photosensitive coloring compositions (RR-23 to 27))
The coloring composition (RP-1) is changed to the coloring composition (RP-23 to 27), and further, the coloring composition (RP-23 to 27) and the coloring composition so as to have the same chromaticity as in Example 45. Photosensitive coloring compositions (RR-23 to 27) were prepared in the same manner as in Example 45 except that the ratio of (RP-28) was adjusted.

<Evaluation of photosensitive coloring composition>
The obtained photosensitive coloring compositions (RR-1 to 27) were evaluated as follows. The evaluation results are shown in Table 3.

(Evaluation of color characteristics)
The obtained photosensitive coloring composition was applied onto a glass substrate having a thickness of 100 mm × 100 mm and 0.7 mm to a thickness of x = 0.640 and y = 0.328 with a C light source, and after drying. , Ultraviolet rays of 300 mJ / cm ² were irradiated using an ultrahigh pressure mercury lamp. Further, a red coating film was obtained by heating at 230 ° C. for 60 minutes. Then, the brightness (Y) of the obtained coating film was measured with a microspectroscopy (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.).

(Evaluation of crystal precipitation on the coating film surface)
The obtained photosensitive coloring composition was applied onto a glass substrate having a thickness of 100 mm × 100 mm and 0.7 mm to a thickness of x = 0.640 and y = 0.328 with a C light source, and after drying. , Ultraviolet rays of 300 mJ / cm ² were irradiated using an ultrahigh pressure mercury lamp. Subsequently, the heat treatment at 230 ° C. for 60 minutes was performed, and then the heat treatment at 240 ° C. for 60 minutes was repeated twice. The surface of the coating film on the substrate after the heat treatment was observed with an optical microscope, and the presence or absence of crystal precipitation was determined according to the following criteria.
⊚: No crystal precipitation even after heat treatment at 230 ° C. for 60 minutes, further heat treatment at 240 ° C. for 60 minutes, and further heat treatment at 240 ° C. for 60 minutes Good ○: After heat treatment at 230 ° C. for 60 minutes, and heat treatment at 240 ° C. for 60 minutes. However, there is no crystal precipitation, but there is crystal precipitation in the second heat treatment at 240 ° C for 60 minutes. There is no problem in practical use. Impractical
×: Crystal precipitation occurs after heat treatment at 230 ° C for 60 minutes, which is not practical.

From the results in Table 3, in the examples using the pigment composition containing the diketopyrrolopyrrole pigment represented by the general formula (1) and the diketopyrrolopyrrole pigment represented by the general formula (2), the crystals of the pigment by the heating step were used. It can be seen that it has good heat resistance with suppressed precipitation and is excellent in brightness and contrast ratio.

<Manufacturing method of color filter>
[Production Example 18] (Preparation of Green Photosensitive Coloring Composition 1 (GR-1))
The mixture having the composition shown below is uniformly stirred and mixed, dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm, and then a 5 μm filter. The mixture was filtered with the above to prepare a green coloring composition 1 (GP-1).
Green pigment (CI Pigment Green 36) 6.8 parts Yellow pigment (CI Pigment Yellow 150) 5.2 parts Resin type dispersant (BASF "EFKA4300") 1.0 part Acrylic resin solution 1 part 35.0 parts propylene glycol monomethyl ether acetate 52.0 parts

The mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare a green photosensitive coloring composition 1 (GR-1).
Green coloring composition 1 (GP-1) 42.0 parts Acrylic resin solution 2 13.2 parts Photopolymerizable monomer (“Aronix M400” manufactured by Toa Synthetic Co., Ltd.) 2.8 parts Photopolymerization initiator (manufactured by BASF) "Irgacure 907") 2.0 parts Sensitizer ("EAB-F" manufactured by Hodoya Chemical Industry Co., Ltd.) 0.4 parts Ethylene glycol monomethyl ether acetate 39.6 parts

[Production Example 19] (Preparation of Blue Photosensitive Coloring Composition 1 (BR-1))
The mixture having the composition shown below is uniformly stirred and mixed, dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm, and then a 5 μm filter. The mixture was filtered with the above to prepare a blue coloring composition 1 (BP-1).
Blue pigment (CI Pigment Blue 15: 6) 7.2 parts Purple pigment (CI Pigment Violet 23) 4.8 parts Resin type dispersant (BASF "EFKA4300") 1.0 part Acrylic resin Solution 1 35.0 parts propylene glycol monomethyl ether acetate 52.0 parts

The mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare a blue photosensitive coloring composition 1 (BR-1).
Blue Coloring Composition 1 (BP-1) 34.0 parts Acrylic resin solution 2 15.2 parts Photopolymerizable monomer (“Aronix M400” manufactured by Toa Synthetic Co., Ltd.) 3.3 parts Photopolymerization initiator (manufactured by BASF) "Irgacure 907") 2.0 parts Sensitizer ("EAB-F" manufactured by Hodoya Chemical Industry Co., Ltd.) 0.4 parts Ethylene glycol monomethyl ether acetate 45.1 parts

(Making a color filter)
A black matrix is patterned on a glass substrate, and the photosensitive coloring composition (RR-5) of the present invention is coated on the substrate with a spin coater to a film thickness such that x = 0.640 and y = 0.328. It was applied to form a colored film. The film was irradiated with ultraviolet rays of 300 mJ / cm ² using an ultrahigh pressure mercury lamp via a photomask. Next, the unexposed portion was removed by spray development with an alkaline developer consisting of a 0.2% by mass aqueous sodium carbonate solution, washed with ion-exchanged water, and the substrate was heated at 230 ° C. for 20 minutes to obtain a red filter. Formed a segment. By the same method, the green photosensitive coloring composition 1 (GR-1) is applied to a film thickness such that x = 0.300 and y = 0.600, and the blue photosensitive coloring composition 1 (BR-1) is applied. It was applied to a film thickness such that x = 0.150 and y = 0.060, respectively, to form a green filter segment and a blue filter segment, respectively, to obtain a color filter.

It can be seen that when the pigment composition of the present specification is used, for example, a color filter having excellent brightness and contrast and having no pigment crystal precipitation in the heating step can be produced.

Claims (4)

A pigment composition for a color filter containing a diketopyrrolopyrrole pigment represented by the general formula (1) and a diketopyrrolopyrrole pigment represented by the general formula (2), and the diketopyrrolopyrrole represented by the general formula (1). A pigment composition for a color filter in which the mass ratio of the pigment to the diketopyrrolopyrrole pigment represented by the general formula (2) is 99.9: 0.1 to 85:15 .

[In the formula, R1 is a chlorine atom or a bromine atom, R2 is -SR3 or -CON (R3) R4, and R3 and R4 are independently hydrogen atoms and 1 to 20 carbon atoms. It is an alkyl group or a phenyl group which may have a substituent. ] A coloring composition for a color filter, which comprises the pigment composition for a color filter according to claim 1 , a binder resin and an organic solvent. The coloring composition for a color filter according to claim 2 , further comprising a photopolymerizable monomer and a photopolymerization initiator. A color filter comprising a filter segment which is a cured product of the coloring composition for a color filter according to claim 2 or 3 .