JP6919234B2 - Diketopyrrolopyrrole pigment composition, composition for color filter using the pigment composition, and color filter - Google Patents

Description

The present invention relates to a pigment composition for a color filter used for manufacturing a color filter used for a color liquid crystal display device, a color image pickup device, and the like, a coloring composition, and a color filter formed by using the pigment composition and the coloring composition.

In Patent Document 1, by using a brominated diketopyrrolopyrrole pigment in combination with at least one diketopyrrolopyrrole pigment having a specific structural formula, high brightness, high contrast, and suppression of pigment crystal precipitation due to a heating step are suppressed. The pigment composition for a color filter has been disclosed. However, the market demand for improving optical characteristics in recent years is remarkable, and further improvement in brightness and contrast is required.

International Publication No. 2012/102399

The subject of the present invention is a diketopyrrolopyrrole pigment composition which has excellent dispersibility and dispersion stability, does not cause crystal precipitation of the pigment in the heating step, and is suitable for producing a high-brightness, high-contrast color filter. Is to provide.

As a result of intensive studies, the present inventors have found that brominated diketopyrrolopyrrole pigments and C.I. I. In a pigment composition containing Pigment Red 254 and a diketopyrrolopyrrole pigment in which a substituent is introduced asymmetrically in a specific structure in a specific ratio, the powder X-ray diffraction pattern exhibited by each of the diketopyrrolopyrrole pigments contained alone is exhibited. Or, it was found that the mixed crystals show a specific powder X-ray diffraction pattern, which is different from the superposition of those powder X-ray diffraction patterns. Indeed, surprisingly, the use of the diketopyrrolopyrrole pigment composition of the present invention in the color filter pigment composition is much higher than the conventionally known diketopyrrolopyrrole pigments and diketopyrrolopyrrole pigment compositions. We have found that it exhibits brightness and contrast and can solve the above-mentioned other problems, and has arrived at the present invention.

That is, the present invention comprises a diketopyrrolopyrrole pigment represented by the formula (1), a diketopyrrolopyrrole pigment represented by the formula (2), and a diketopyrrolopyrrole pigment represented by the general formula (3). The diketopyrrolopyrrole pigment composition contained therein, in which the mass ratio of the diketopyrrolopyrrole pigment represented by the formula (1) to the diketopyrrolopyrrole pigment represented by the formula (2) is 70:30 to 20. : 80, and the content of the diketopyrrolopyrrole pigment represented by the general formula (3) is 1% by mass to 20% by mass with respect to the total amount of the diketopyrrolopyrrole pigment composition, and CuKα ray. The present invention relates to a diketopyrrolopyrrole pigment composition having no maximum peak in the range of diffraction angle (2θ) = 5 to 12 ° in powder X-ray diffraction using the above.

[In the general formula (3), R ¹ is a hydrogen atom, a halogen atom or a cyano group, and R ² and R ³ are independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituent. It is a phenyl group which may have. ]

Further, in the present invention, the mass ratio of the diketopyrrolopyrrole pigment represented by the formula (1) to the diketopyrrolopyrrole pigment represented by the formula (2) is 50:50 to 20:80. Regarding the pyrrolop pigment composition.

Further, in the present invention, the content of the diketopyrrolopyrrole pigment represented by the general formula (3) is 1% by mass to 15% by mass with respect to the total amount of the diketopyrrolopyrrole pigment composition. The present invention relates to a pyrrolop pigment composition.

The present invention also relates to a coloring composition for a color filter containing the diketopyrrolopyrrole pigment composition, a binder resin and an organic solvent.

The present invention further relates to the coloring composition for a color filter, which further contains at least one selected from the group consisting of a photopolymerizable monomer and a photopolymerization initiator.

Furthermore, the present invention relates to a color filter including a filter segment formed of the coloring composition for a color filter.

According to the present invention, a diketopyrrolopyrrole pigment composition which has excellent dispersibility and dispersion stability, does not cause crystal precipitation of the pigment in the heating step, and is suitable for producing a high-brightness, high-contrast color filter. Can be provided.

FIG. 1 is an X-ray diffraction pattern of the diketopyrrolopyrrole pigment composition produced in Example 4. FIG. 2 is an X-ray diffraction pattern of the diketopyrrolopyrrole pigment produced in Comparative Example 1. FIG. 3 is an X-ray diffraction pattern of the diketopyrrolopyrrole pigment produced in Comparative Example 2. FIG. 4 is an X-ray diffraction pattern of the diketopyrrolopyrrole pigment composition produced in Comparative Example 11.

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

<Diketopyrrolopyrrole pigment composition>
First, the diketopyrrolopyrrole pigment composition of the present invention will be described.
The diketopyrrolopyrrole pigment composition of the present invention is represented by the diketopyrrolopyrrole pigment represented by the following formula (1), the diketopyrrolopyrrole pigment represented by the following formula (2), and the general formula (3). Contains the diketopyrrolopyrrole pigment.

[In the general formula (3), R ¹ is a hydrogen atom, a halogen atom or a cyano group, and R ² and R ³ are independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituent. It is a phenyl group which may have. ]

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Two or more types may be used in combination. Of these, chlorine atoms and bromine atoms are preferable.

From ^{the viewpoint of color characteristics, the R 1} is preferably a hydrogen atom, a chlorine atom, or a bromine atom, and the substitution position is preferably a para position.

The alkyl group having 1 to 12 carbon atoms may be linear or branched, and is not particularly limited, but is limited to a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, and the like. Examples thereof include a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group, a 1,5-dimethylhexyl group, a 1,6-dimethylheptyl group and a 2-ethylhexyl group. From the viewpoint of contrast and crystal precipitation suppressing effect, an alkyl group having 4 to 8 carbon atoms is preferable.

Examples of the phenyl group which may have the above-mentioned substituent include 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 an alkoxyl having 1 to 4 carbon atoms. Examples thereof include a phenyl group having a substituent such as a group. More specifically, phenyl group, p-methylphenyl group, 4-tert-butylphenyl group, p-nitrophenyl group, p-methoxyphenyl group, p-chlorophenyl group, 2,4-dichlorophenyl group, 3-carbamoyl. Examples thereof include a phenyl group, but the present invention is not particularly limited. Of 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 R ² and R ³ , hydrogen atoms, phenyl groups or alkyl groups having 4 to 8 carbon atoms are preferable independently from the viewpoint of contrast and crystal precipitation suppressing effect, respectively, and hydrogen atoms or alkyl having 4 to 8 carbon atoms are preferable. More preferably it is a group.

Specific examples of the diketopyrrolopyrrole pigment of the general formula (3) that can be used in the present invention are given below, but the present invention is not limited thereto.

The diketopyrrolopyrrole pigment represented by the formula (1) and the diketopyrrolopyrrole pigment represented by the formula (2) can be produced by a succinic acid ester synthesis method or various commercially available products can be used. can. In the succinate 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 was carried out at a high temperature of 80 to 110 ° C. to produce 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 obtained by protonation with water, alcohol, acid or the like. At this time, 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 method for producing the diketopyrrolopyrrole pigment is not limited to this method.

The diketopyrrolopyrrole pigment represented by the general formula (3) is described in, for example, the document Synth. Commun. , 1988, 18, 1213 and Tetrahedron, 58 (2002) 5457-5565. The method for producing the diketopyrrolopyrrole pigment represented by the general formula (3) is not limited to this method.

The diketopyrrolopyrrole pigment represented by the general formula (3) is a mixture with the diketopyrrolopyrrole pigment represented by the formula (1) or the diketopyrrolopyrrole pigment represented by the formula (2). It can also be synthesized as. This is possible by using a method using at least two structurally different benzonitrile compounds in the succinate ester synthesis method. Specifically, in the method described in International Publication No. 2009/081930, the plurality of benzonitrile compounds used are 4-bromobenzonitrile and a benzonitrile compound represented by the following general formula (4), or , 4-Chlorobenzonitrile and the benzonitrile compound represented by the following general formula (4), the diketopyrrolopyrrole pigment of the general formula (3) is a mixture with the brominated diketopyrrolopyrrole pigment, or C. I. It can be produced as a mixture with Pigment Red 254.

[In the general formula (4), R ² and R ³ are phenyl groups that may independently have a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituent. ]

The diketopyrrolopyrrole pigment composition of the present invention is characterized in that it does not have a maximum peak in the range of diffraction angle (2θ) = 5 to 12 ° in powder X-ray diffraction measurement using CuKα ray. Brominated diketopyrrolopyrrole pigments and C.I. I. In a diketopyrrolopyrrole pigment such as Pigment Red 254, the maximum peak in the range of the diffraction angle (2θ) = 5 to 12 ° in the powder X-ray diffraction measurement using CuKα ray is (0) of the diketopyrrolopyrrole pigment crystal lattice. 20) A signal indicating the degree of crystallization of the plane. The diketopyrrolopyrrole pigment composition of the present invention can be obtained by any production method as long as it does not have a maximum peak within the range of diffraction angle (2θ) = 5 to 12 °. However, when the diketopyrrolopyrrole pigment composition is obtained by the method for producing the diketopyrrolopyrrole pigment composition described later, the diketopyrrolopyrrole pigment represented by the formula (1) is represented by the formula (2). The coexistence of the diketopyrrolopyrrole pigment and the diketopyrrolopyrrole pigment represented by the general formula (3) results in mixed crystals, and the degree of crystallization of the (020) plane is significantly reduced, or (020). ) It is preferable because it has no crystallinity in the plane direction and does not have a maximum peak within the range of the diffraction angle (2θ) = 5 to 12 °.

The diketopyrrolopyrrole pigment composition of the present invention has a mass ratio of the diketopyrrolopyrrole pigment represented by the formula (1) and the diketopyrrolopyrrole pigment represented by the formula (2) from 70:30 to. It is characterized by being 20:80. When the mass ratio of the diketopyrrolopyrrole pigment represented by the formula (1) exceeds 70% by mass, the contrast and the effect of suppressing crystal precipitation are not sufficient. Further, when the mass ratio of the diketopyrrolopyrrole pigment represented by the formula (1) is less than 20% by mass, the brightness is not sufficient. At this time, the X-ray diffraction pattern of the diketopyrrolopyrrole pigment composition can be obtained by using the diketopyrrolopyrrole pigment represented by the formula (1) and the diketopyrrolopyrrole pigment represented by the formula (1) even through the method for producing the diketopyrrolopyrrole pigment composition described later. Each X-ray diffraction pattern of the diketopyrrolopyrrole pigment represented by the formula (2) is superposed according to the mass ratio, and a mixed crystal having a specific X-ray diffraction pattern, which is a feature of the present invention. However, it has a maximum peak in the range of diffraction angle (2θ) = 5 to 12 °.

That is, a diketo containing a diketopyrrolopyrrole pigment represented by the formula (1), a diketopyrrolopyrrole pigment represented by the formula (2), and a diketopyrrolopyrrole pigment represented by the general formula (3). In the pyrolopyrrolop pigment composition, preferably, in the process of producing the diketopyrrolopyrrole pigment composition described later, the diketopyrrolopyrrole pigment represented by the formula (1) and the diketo represented by the formula (2). When the mass ratio with the pyrrolopyrrolop pigment is 70:30 to 20:80, it becomes a mixed crystal having no maximum peak within the range of the diffraction angle (2θ) = 5 to 12 ° in the X-ray diffraction measurement, and the crystal is high. It is possible to obtain a diketopyrrolopyrrole pigment composition that has high contrast and does not cause crystal precipitation of the pigment in the heating step. In order to further increase the contrast ratio within a range that does not impair the brightness, the mass ratio of the diketopyrrolopyrrole pigment represented by the formula (1) and the diketopyrrolopyrrole pigment represented by the formula (2) is 50. : 50 to 20:80 is preferable.

In the diketopyrrolopyrrole pigment composition of the present invention, the content of the diketopyrrolopyrrole pigment represented by the general formula (3) is preferably 1% by mass to 15% by mass with respect to the total amount of the diketopyrrolopyrrole pigment composition. It is by mass, more preferably 3% by mass to 10% by mass. When the content of the diketopyrrolopyrrole pigment represented by the general formula (3) is 1% by mass or more and 15% by mass or less, the contrast, the crystal precipitation suppressing effect and the brightness are all good, which is preferable.

In the diketopyrrolopyrrole pigment composition of the present invention, the diketopyrrolopyrrole pigment represented by the formula (1), the diketopyrrolopyrrole pigment represented by the formula (2), and the diketopyrrolopyrrole pigment represented by the formula (3). The mass ratio of ketopyrrolopyrrole pigments can be analyzed using HPLC, TOF-MASS, FD-MASS, LC-MASS or NMR. 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 carried out.

(Dye derivative)
In the diketopyrrolopyrrole pigment composition of the present invention, a pigment derivative can be used for the purpose of suppressing pigment crystal growth and improving pigment dispersibility. Examples of the dye derivative used in the present invention include diketopyrrolopyrrole derivative, benzoisoindole derivative, anthraquinone derivative, dianthraquinone derivative, thiazineindigo derivative, azo dye derivative, quinophthalone derivative, and quinacridone derivative. Examples of the structure of the dye derivative include, but are not limited to, the dye derivative represented by the following formula (5).
P-Lm formula (5)
[In formula (5), P is a diketopyrrolopyrrole residue, a benzoisoindole residue, an anthraquinone residue, a dianthraquinone residue, a thiazine indigo residue, an azo dye residue, a quinophthalone residue, or a quinacridone residue. a group, m is an integer from 1 to 4, L is _{independently, -OH; -SO 3 H, -COOH} , 1 monovalent to trivalent metal salt thereof acidic groups, alkylammonium salt A phthalimidomethyl group which may have a substituent; a group represented by the following formulas (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, Y is, -NH -, - O -, - S- , Or a direct bond, n is an integer of 1 to 10, and R ₁₆ and R ₁₇ are independently hydrogen atoms and alkyl groups having 1 to 30 carbon atoms which may have substituents. An alkenyl group having 2 to 30 carbon atoms which may have a substituent _{, or a complex which may have a substituent in which R 16} and R ₁₇ are integrated and further contains a nitrogen, oxygen or sulfur atom. It is a ring, and R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ and R ₂₂ each independently have 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. It is a substituent represented by the formula (a) or 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 is an alkyl group having 1 to 20 carbon atoms which may have a substituent and is substituted. It is an alkenyl group having 2 to 20 carbon atoms which may have a group. ]

Examples of the monovalent to trivalent metal include sodium, potassium, magnesium, calcium, iron, aluminum and the like. Examples of the alkylammonium salt include ammonium salts of long-chain monoalkylamines such as octylamine, laurylamine, and stearylamine, or palmityltrimethylammonium salts, dilauryldimethylammonium salts, distearyldimethylammonium salts, and the like. A quaternary alkylammonium salt can be mentioned.

As a substituent of a phthalimidomethyl group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a heterocyclic which may have a substituent. , Halogen atom, nitro group, cyano group, carbamoyl group, N-substituted carbamoyl group, sulfamoyl group, N-substituted sulfamoyl group, alkoxyl group having 1 to 20 carbon atoms, alkylthio group having 1 to 20 carbon atoms and the like. , Not limited to these.

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 chlorosulfonic acid and thionyl chloride, and then chlorsulfonated. It is synthesized by a known production method such as a sulfonamide reaction in which an amine component such as dimethylaminopropylamine is reacted.

Examples of the amine component used to form the substituent represented by the above formula (a), formula (b), and formula (c) include dimethylamine, diethylamine, methylethylamine, N, N-ethyl. Isopropylamine, 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-dimethyl Aminomethylamine, N, N-dimethylaminoethylamine, N, N-dimethylaminoamylamine, N, N-dimethylaminobutylamine, N, N-diethylaminoethylamine, N, N-diethylaminopropylamine, N, N-diethylaminohexyl Amine, 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-piperidin methanol, pipecoronic acid, isonipecotin Acid, methyl isonipecotate, ethyl isonipecotate, 2-piperidinethanol, pyrrolidine, 3-hydroxypyrrolidin, N-aminoethylpiperidin, N-aminoethyl-4-pipecholine, N-aminoethylmorpholin, N-aminopropylpiperidin, N -Aminopropyl -2-Pipecholine, N-aminopropyl-4-pipecholine, N-aminopropylmorpholin, N-methylpiperazine, N-butylpiperazine, N-methylhomopiperazin, 1-cyclopentylpiperazin, 1-amino-4-methylpiperazine, Examples thereof include, but are not limited to, 1-cyclopentylpiperazin.

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 addition to the method of mixing with the pigment when dispersing the diketopyrrolopyrrole pigment in the pigment carrier, the method of mixing in water or an organic solvent during pigment production, and the co-dissolving during dissolution and precipitation. Examples thereof include a method of precipitating and a method of adding during wet kneading. The method of mixing the pigment derivative in water or an organic solvent at the time of pigment production, the method of co-precipitating at the time of dissolution 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 effective. be.

Further, when a dye derivative is used, it is necessary 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 are yellow, orange, or red.

The blending amount of the dye derivative is preferably in the range of 0.5 to 40% by mass based on the total amount of the pigment composition (100% by mass). More preferably, it is in the range of 3 to 35% by mass. If it is 0.5% by mass or less, the effect of suppressing crystal growth is not sufficient, and if it is 40% by mass or more, the good color tone of the diketopyrrolopyrrole pigment is impaired.

Specific examples of the dye derivative used in the present invention will be described below, but the present invention is not limited thereto.

(Specific example of diketopyrrolopyrrole derivative)
As the diketopyrrolopyrrole derivative, specifically, a compound represented by the following formula (6) or formula (7) can be used, but the diketopyrrolopyrrole derivative is not limited thereto.

(Specific example of benzoisoindole derivative)
Specifically, as the benzoisoindole derivative, a compound represented by the following formula (8) can be used, but the benzoisoindole derivative is not limited thereto.

(Specific examples of anthraquinone derivatives)
Specifically, as the anthraquinone derivative, a compound represented by the following formula (9) can be used, but the anthraquinone derivative is not limited thereto.

(Specific example of dianthraquinone derivative)
Specifically, as the dianthraquinone derivative, a compound represented by the following formula (10) can be used, but the dianthraquinone derivative is not limited thereto.

(Specific example of cheerleader indigo derivative)
Specifically, as the thiazine indigo derivative, a compound represented by the following formula (11) can be used, but the present invention is not limited thereto.

(Specific example of azo dye derivative)
Specifically, as the azo dye derivative, a compound represented by the following formula (12), formula (13), or formula (14) can be used, but the azo dye derivative is not limited thereto.

(Specific example of quinophthalone derivative)
Specifically, as the quinophthalone derivative, compounds represented by the following formulas (15-1) to (15-17) can be used, but the quinophthalone derivative is not limited thereto.

(Specific example of quinacridone derivative)
Specifically, as the quinacridone derivative, a compound represented by the following formula (16) can be used, but the derivative is not limited thereto.

<Manufacturing method of diketopyrrolopyrrole pigment composition>
The diketopyrrolopyrrole pigment composition of the present invention is a diketopyrrolopyrrole pigment represented by the formula (1) and the formula (2) when a known pigmentation step (also referred to as a conditioning or finishing step) is performed. ) And the diketopyrrolopyrrole pigment represented by the formula (3) coexist. Alternatively, the diketopyrrolopyrrole pigment composition of the present invention protonates an alkali metal salt of a diketopyrrolopyrrole compound to precipitate pigment particles in the process of succinic acid ester synthesis method for producing a diketopyrrolopyrrole pigment. It can also be obtained by mixing the metal salts of the diketopyrrolopyrrole pigments represented by the formulas (1) to (3) in the step of making the pigment. For example, 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 succinate synthesis method was separately adjusted. The metal salt of the diketopyrrolopyrrole pigment represented by the formula (2) and the metal salt of the diketopyrrolopyrrole pigment represented by the formula (3) are mixed, and water, alcohol, and water, alcohol, and the like are added to the obtained mixed solution. The diketopyrrolopyrrole pigment composition of the present invention in mixed crystals can be obtained by protonation with an acid or the like. At this time, a pigmentation step may be further added to the water-containing cake or dried product of the obtained diketopyrrolopyrrole pigment composition.

Known pigmentation steps include salt milling treatment in which a water-soluble inorganic salt and a water-soluble organic solvent are added to the pigment and kneaded, solvent heat treatment in which the pigment is heated and stirred in the presence of the organic solvent, and dissolution of the pigment in a good solvent. Examples thereof include a dissolution precipitation treatment in which the mixture is reprecipitated with a poor solvent. In the diketopyrrolopyrrole pigment composition of the present invention, it is preferable to carry out a salt milling treatment or a dissolution precipitation treatment, and it is more preferable to carry out a salt milling treatment.

Salt milling treatment involves heating a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent 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 process 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, the heating temperature is preferably 35 to 150 ° C. If the heating temperature is less than 35 ° C., crystal growth does not occur sufficiently and the shape of the pigment particles becomes close to amorphous, which is not preferable. On the other hand, when the heating temperature exceeds 150 ° C., crystal growth proceeds too much and the primary particle size of the pigment becomes large, which is not preferable as a colorant for a color filter. The kneading time of the salt milling treatment is preferably 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 the salt milling treatment of 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. From the viewpoint of both treatment efficiency and production efficiency, the water-soluble inorganic salt is preferably used in an amount of 50 to 2000% by mass, more preferably 300 to 1200% by mass, based on the total amount of the pigment composition (100% 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.

For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, 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 and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by mass, more preferably 50 to 500 parts by mass, based on 100 parts by mass of the pigment composition.

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 finer pigmentation 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 preferably in the range of 0.5 to 40% by mass based on the extent that it does not affect the color tone, that is, the total amount of the pigment composition (100% by mass).

Further, in the salt milling treatment, a resin may be added if necessary. The type of resin used is not particularly limited as in the case of dissolution and precipitation, and natural resin, modified natural resin, synthetic resin, synthetic resin modified with natural resin and the like can be used. The resin used is preferably solid at room temperature, water-insoluble, and more preferably partially soluble in the organic solvent. The amount of the resin used is preferably in the range of 5 to 200 parts by mass with respect to 100 parts by mass of the pigment composition.

Further, in the salt milling treatment, an additive such as a resin type dispersant and / or a surfactant may be contained if necessary. The type of additive is not particularly limited, but a resin-type dispersant and / or a surfactant, which will be described later, are preferably used. The amount used when adding the resin-type dispersant and the surfactant is 100 parts by mass, preferably 0.1 to 55 parts by mass, and more preferably 0.1 to 45 parts by mass.

The dissolution precipitation treatment is a treatment in which the pigment is once dissolved in a good solvent, diluted with a large amount of a poor solvent, reprecipitated, and then the solvent is separated or distilled off.

Here, the good solvent is not particularly limited as long as it can dissolve the diketopyrrolopyrrole pigment composition, but is an inorganic acid (sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, hydrochloric acid, phosphoric acid, etc.), an aqueous solution thereof, and an organic acid (sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, etc.), and an organic acid (sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, etc.). Dichloroacetic acid, methanesulfonic acid, etc.), inorganic bases (sodium hydroxide, potassium hydroxide, calcium hydroxide, etc.) and their aqueous solutions, organic bases (triethylamine, diazabicycloundecene, sodium methoxydo, etc.), alcohol solvents (sodium methoxydo, etc.) Methanol, n-propanol, tert-amyl alcohol, etc.), ketone solvents (methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), ether solvents (tetrahydrofuran, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.), sulfoxide solvents (tetraxide solvents, etc.) Dimethyl sulfoxide, hexamethylene sulfoxide, sulfolane, etc.), ester solvents (ethyl acetate, n-butyl acetate, ethyl lactate, etc.), amide solvents (N, N-dimethylformamide, 1-methyl-2-pyrrolidone, etc.), Aromatic hydrocarbon solvents (toluene, xylene, etc.), aliphatic hydrocarbon solvents (octane, etc.), nitrile solvents (acetriform, etc.), halogen-based solvents (carbon tetrachloride, dichloromethane, etc.), ionic liquids (1- Ethyl-3-methylimidazolium tetrafluoroborate, etc.), carbon disulfide solvent, or a mixture thereof. The amount of the good solvent used is not particularly limited as long as it can dissolve the diketopyrrolopyrrole pigment composition, but from the viewpoint of industrial economy, 100 is used based on the total amount of the pigment composition (100% by mass). It is preferably ~ 5000% by mass, and more preferably 500 to 3000% by mass.

The temperature at which the pigment composition is dissolved is preferably -10 to 200 ° C, more preferably -10 to 130 ° C, still more preferably -10 to 100 ° C.

The poor solvent is not particularly limited as long as it precipitates the diketopyrrolopyrrole pigment composition when mixed with a solution containing the diketopyrrolopyrrole pigment composition dissolved in a good solvent, but is not particularly limited. Water, hydrochloric acid, aqueous sodium hydroxide solution, etc.) are preferable. The amount of the poor solvent used is preferably 50 to 5000 parts by mass and 100 to 3000 parts by mass with respect to 100 parts by mass of the solution containing the diketopyrrolopyrrole pigment composition from the viewpoint of industrial economy. Is more preferable.

The temperature at the time of precipitation is preferably −10 to 150 ° C., more preferably −5 to 130 ° C., and even more preferably 0 to 100 ° C.

By optimizing the conditions for the dissolution and precipitation treatment of 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, when carrying out dissolution precipitation, a dye derivative may be used in combination as appropriate, which is effective for finer pigmentation (fine particle size) 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 preferably in the range of 0.5 to 40% by mass based on the extent that it does not affect the color tone, that is, the total amount of the pigment composition (100% by mass).

Further, when carrying out dissolution precipitation, a resin may be added if necessary. The type of resin used is not particularly limited, and a natural resin, a modified natural resin, a synthetic resin, a synthetic resin modified with a natural resin, or the like can be used. The resin used is preferably solid at room temperature, water-insoluble, and more preferably partially soluble in the organic solvent. The amount of the resin used is preferably in the range of 5 to 200 parts by mass with respect to 100 parts by mass of the pigment composition.

Further, when carrying out dissolution precipitation, an additive such as a resin-type dispersant and / or a surfactant may be contained, if necessary. The type of additive is not particularly limited, but a resin-type dispersant and / or a surfactant, which will be described later, are preferably used. The amount used when adding the resin-type dispersant and the surfactant is 100 parts by mass, preferably 0.1 to 55 parts by mass, and more preferably 0.1 to 45 parts by mass.

The diketopyrrolopyrrole pigment composition of the present invention can be used as a coloring composition by using it in combination with a binder resin and an organic solvent. Further, a colorant other than the diketopyrrolopyrrole pigment composition of the present invention may be used in combination.

<Other colorants>
The coloring composition of the present invention may be used in combination with other coloring agents such as pigments and dyes other than the diketopyrrolopyrrole pigment composition of the present invention in order to adjust the chromaticity. Specific examples of other colorants are shown below.

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, 210, 242, 246, 254, 255, 264, 270, 272, 273, 274, 276, 277, 278, Red pigments such as 279, 280, 281, 282, 283, 284, 285, 286, or 287 can be mentioned. Examples of the red dye include xanthene type, azo type (pyridone type, barbituric acid type, metal complex type, etc.), disazo type, anthraquinone type and the like. Specifically, C.I. I. Examples thereof include salt-forming compounds of xanthene-based acid dyes such as Acid Red 52, 87, 92, 289, and 338.

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, Yellow pigments such as 193, 194, 198, 199, 213, 214, 218, 219, 220, or 221 can be used in combination. Examples of orange dyes and / or yellow dyes include quinoline dyes, azo dyes (pyridone dyes, barbituric acid dyes, metal complex dyes, etc.), disazo dyes, methine dyes, and the like.

Preferred colorants to be used in combination are C.I. I. Pigment Red 177, 254, 242, C.I. I. Pigment Yellow 139, 150, 185.

When a colorant other than the diketopyrrolopyrrole pigment is used in combination, the diketopyrrolopyrrole pigment composition of the present invention is preferably in the range of 40% by mass to 100% by mass in the total amount of the colorant (100% by mass). .. More preferably, it is in the range of 60% by mass to 100% by mass.

<Binder resin>
Examples of the binder resin contained in the coloring composition of the present invention include conventionally known thermoplastic resins and thermosetting resins. Examples of the thermoplastic resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, and polyurethane resin. , Polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resin and the like.

When used as a coloring composition for a color filter, a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region is preferable. When used in the form of an alkali-developable colored resist, it is preferable to use an alkali-soluble vinyl-based resin in which an acidic group-containing ethylenically unsaturated monomer is copolymerized. Further, in order to further improve the photosensitivity, an energy ray-curable resin having an ethylenically unsaturated active double bond can also be used.

Examples of the alkali-soluble resin obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer include a resin having an acidic group such as a carboxyl group and a sulfone group. Specifically, as the alkali-soluble resin, 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 Isobutylene / (anhydrous) maleic acid copolymer and the like can be mentioned. Among them, an acrylic resin having an acidic group and at least one resin selected from a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group, are preferably used because of their high heat resistance and transparency.

As an energy ray-curable resin having an ethylenically unsaturated active double bond, a polymer having a reactive substituent such as a hydroxyl group, a carboxyl group or an amino group is substituted with a reactive substituent such as an isocyanate group, an aldehyde group or an epoxy group. A resin is used in which a (meth) acrylic compound having a group or silicic acid is reacted to introduce a photocrosslinkable group such as a (meth) acryloyl group or a styryl group into the polymer. Further, a polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is half-esterified with a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. Esterified ones are also used.

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 monomer constituting the thermoplastic resin include the following. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-Ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) (Meta) acrylates such as acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, or ethoxypolyethylene glycol (meth) acrylate, or (meth) acrylamide, N, N -Dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, or (meth) acrylamides such as acryloylmorpholin, styrene, or α-methylstyrene Examples thereof include styrenes such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, vinyl ethers such as isobutyl vinyl ether, and fatty acid vinyls such as vinyl acetate and vinyl propionate.

Alternatively, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane 1,6-bismaleimidehexane, 3-maleimide propionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide Kumarin, 4,4'-bismaleimidediphenylmethane, bis (3-ethyl-5-methyl-4-maleimidephenyl) methane, N, N'-1,3-phenylenedimaleimide, N, N'-1,4- Phenylened maleimide, N- (1-pyrenyl) maleimide, N- (2,4,6-trichlorophenyl) maleimide, N- (4-aminophenyl) maleimide, N- (4-nitrophenyl) maleimide, N-benzyl Maleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-3-maleimide propionate, N-succinimidyl-4-maleimidebutyrate, N-succinimidyl-6-maleimide Examples thereof include N-substituted maleimides such as hexanoate, N- [4- (2-benzoimidazolyl) phenyl] maleimide, and 9-maleimide acrydin.

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. Of these, epoxy resins and melamine resins are more preferably used from the viewpoint of improving heat resistance.

The weight average molecular weight (Mw) of the binder resin is preferably in the range of 5,000 to 80,000, more preferably in the range of 7,000 to 50,000 in order to preferably disperse the colorant. The number average molecular weight (Mn) is preferably in the range of 2,500 to 40,000, and the value of Mw / Mn is preferably 10 or less.

Here, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are determined by connecting four separation columns in series in gel permeation chromatography "HLC-8120GPC" manufactured by Tosoh Corporation, and using Tosoh stocks as fillers in order. It is a polystyrene-equivalent molecular weight measured using tetrahydrofuran as the mobile phase using "TSK-GEL SUPER H5000", "H4000", "H3000", and "H2000" manufactured by the company.

When the binder resin is used as a coloring composition for a color filter, a carboxyl group that acts as a pigment adsorbing group and an alkali-soluble group during development, and an aliphatic group and an aromatic group that act as an affinity group for a pigment carrier and a solvent. Balance is important for pigment dispersibility, developability, and durability, and it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g. If the acid value is less than 20 mgKOH / g, the solubility in a developing solution is poor and it is difficult to form a fine pattern. If it exceeds 300 mgKOH / g, no fine pattern remains in the development.

The binder resin can be used in an amount of 20 to 500% by mass based on the total mass of the colorant. If it is less than 20% by mass, the film forming property and various resistances are insufficient, and if it is more than 500% by mass, the pigment concentration is low and the color characteristics cannot be exhibited.

<Organic solvent>
In the coloring composition of the present invention, the pigment is sufficiently dispersed in the pigment carrier and applied onto a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm to form a filter segment. Contains an organic solvent for ease. The organic solvent is selected in consideration of the solubility of each component of the coloring composition and the safety in addition to the good coatability of the coloring composition.

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, and 1,4-dioxane. , 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-butanol, 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-propyl acetate, 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, diisobutyl ketone, 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 Diethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethylate Dipropylene 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 glycol phenyl 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, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid ester and the like can be mentioned.

Among them, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl have good solubility of each component of the coloring composition and good coatability of the coloring composition. It is preferable to use glycol acetates such as ether acetate, aromatic alcohols such as benzyl alcohol, and ketones such as cyclohexanone.

These organic solvents may be used alone or in admixture of two or more. Further, since the organic solvent can adjust the coloring composition to an appropriate viscosity and form a filter segment having a desired uniform film thickness, 500 to 4000 mass is based on the total mass of the colorant (100% by mass). It is preferable to use it in an amount of%.

<Pigment dispersion>
In the coloring composition of the present invention, the diketopyrrolopyrrole pigment composition of the present invention is placed in a colorant carrier composed of the binder resin and an organic solvent in a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, and the like. It can be manufactured by finely dispersing it using various dispersion means such as a vertical sand mill, an annual bead mill, or an attritor. Further, in the coloring composition of the present invention, the diketopyrrolopyrrole pigment composition of the present invention and other coloring agents and the like may be dispersed in the coloring agent carrier at the same time, or those dispersed separately in the coloring material carrier may be mixed. You may.

Further, when the colorant is dispersed in the colorant carrier, a dispersion aid such as the above-mentioned pigment 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 obtained by dispersing the colorant in the colorant carrier using the dispersion aid has high contrast and viscosity stability. Become good.

(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 adsorbs the colorant to disperse the colorant on the colorant carrier. It works to stabilize. Specifically, as the resin type dispersant, polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , Polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products of these, amides and salts thereof formed by the reaction of poly (lower alkyleneimine) with polyester having a free carboxyl group. Oil-based dispersants such as, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, water-soluble such as polyvinylpyrrolidone. Resins, water-soluble polymer compounds, polyester-based, modified polyacrylate-based, ethylene oxide / propylene oxide-added compounds, phosphoric acid ester-based, etc. are used, and these can be used alone or in admixture of two or more. It is not necessarily limited to these.

Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170 manufactured by Big Chemie Japan. , 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, manufactured by Japan Lubrizol. , 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., BASF EFKA-46, 47, 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 and 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc. And so on.

Examples of the surfactant include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalin sulfonate, sodium alkyldiphenyl ether disulfonate. , Monoethanolamine lauryl sulfate, Triethanolamine lauryl sulfate, Ammonium lauryl sulfate, Monoethanolamine stearate, Monoethanolamine styrene-acrylic acid copolymer, Anionic surfactants such as polyoxyethylene alkyl ether phosphate; Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; alkyl Chaotic surfactants such as quaternary ammonium salts and their ethylene oxide adducts; alkyl betaines such as alkyldimethylaminoacetic acid betaine and amphoteric surfactants such as alkylimidazoline, which may be used alone or in combination of two or more. They can be mixed and used, but are not necessarily limited to these.

When a resin-type dispersant or a surfactant is added, the total amount of the colorant is used as a reference (100% by mass), preferably 0.1 to 55% by mass, and more preferably 0.1 to 45% by mass. .. When the blending amount of the resin type dispersant and the surfactant is less than 0.1% by mass, it is difficult to obtain the effect of addition, and when the blending amount is more than 55% by mass, the dispersion is affected by the excess dispersant. May affect.

The coloring composition of the present invention can be used as a photosensitive coloring composition by further adding a photopolymerizable monomer and / or a photopolymerization initiator.

<Photopolymerizable monomer>
The photopolymerizable monomer that may be used in the photosensitive coloring composition contains a monomer or oligomer that is cured by ultraviolet rays or heat to produce a transparent resin, and these may be used alone or in combination of two or more. Can be used. The blending amount of the monomer is preferably 5 to 400% by weight based on the total weight of the colorant (100% by weight), and more preferably 10 to 300% by weight from the viewpoint of photocurability and developability. preferable.

Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di ( Meta) Acrylate, Trimethylol Propanetri (Meta) Acrylate, Pentaerythritol Tri (Meta) Acrylate, Pentaerythritol Tetra (Meta) Acrylate, 1,6-Hexanediol Diglycidyl Ether Di (Meta) Acrylate, Bisphenol A Diglycidyl Etherdi (Meta) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, methylolated melamine (Meta) acrylic acid ester, epoxy (meth) acrylate, various acrylic acid esters such as urethane acrylate and methacrylic acid ester, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol tri Examples thereof include, but are not limited to, vinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, and acrylonitrile.

<Photopolymerization initiator>
When the photosensitive coloring composition is cured by ultraviolet irradiation and a filter segment is formed by a photolithography method, a photopolymerization initiator is added to the photosensitive coloring composition in the form of a solvent-developed or alkali-developed colored resist material. Can be adjusted.

Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-. Hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 Acetphenone compounds such as − [4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one; benzoin, benzoin Benzoin compounds such as methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylicized benzophenone, 4-benzoyl-4' -Methyldiphenyl sulfide, or benzophenone compounds such as 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorthioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4 Thioxanthone compounds such as −diisopropylthioxanthone, or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2-( p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6- Bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho-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, or 2,4- Triazine compounds such as trichloromethyl- (4'-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyl) Oxime)], or oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4'-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6) -Trimethylbenzoyl) phenylphosphine oxide, or phosphine compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrene quinone, camphorquinone, ethylanthraquinone; borate compounds; A carbazole-based compound; an imidazole-based compound; or a titanosen-based compound or the like is used.

These photopolymerization initiators can be used alone or in admixture of two or more at any ratio, if necessary. These photopolymerization initiators are preferably 2 to 200% by mass based on the total amount of the colorants in the photosensitive coloring composition (100% by mass), and are 3 to 200% by mass from the viewpoint of photocurability and developability. More preferably, it is 150% by mass.

<Sensitizer>
Further, the photosensitive coloring composition may contain a sensitizer.
Examples of the sensitizer include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, and anthraquinone derivatives. , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonoal derivatives and other polymethine dyes, acrydin derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indolin derivatives, Azulene derivative, azurenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine derivative , Naphthalocyanine derivative, Subphthalocyanine derivative, Pyrylium derivative, Thiopyrylium derivative, Tetraphyllin derivative, Anuren derivative, Spiropyran derivative, Spiroxazine derivative, Thiospiropirane derivative, Metal allene complex, Organic ruthenium complex, or Michler ketone derivative, α-Acyloxy ester , Acylphosphine oxide, methylphenylglycolate, benzyl, 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.

More specifically, Ogawara Nobu et al., "Dye Handbook" (1986, Kodansha), Ogawara Nobu et al., "Functional Dye Chemistry" (1981, CMC), Ikemori Chuzaburo et al., And " The sensitizers described in "Special Functional Materials" (1986, CMC) can be mentioned, but are not limited thereto. In addition, a sensitizer that absorbs light from the ultraviolet to the near infrared region can also be contained.

Two or more sensitizers may be used in any ratio as required. When the sensitizer is used, the blending amount is preferably 3 to 60% by mass, based on the total weight of the photopolymerization initiator contained in the photosensitive coloring composition (100% by mass), and is photocured. From the viewpoint of property and developability, it is more preferably 5 to 50% by mass.

<Amine compounds>
Further, the coloring composition or the photosensitive coloring composition may contain an amine compound having a function of reducing dissolved oxygen.

Examples of such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylaminobenzoate. Examples thereof include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.

<Leveling agent>
It is preferable to add a leveling agent to the coloring composition or the photosensitive coloring composition in order to improve the leveling property of the composition on the transparent substrate. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of the dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning Co., Ltd. and BYK-333 manufactured by Big Chemie Co., Ltd. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by Big Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can also be used in combination. The content of the leveling agent is usually preferably 0.003 to 0.5% by mass based on the total weight of the coloring composition or the photosensitive coloring composition (100% by mass).

A particularly preferable leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, which has a hydrophilic group but has low solubility in water, and when added to a coloring composition, the same. It is useful to have a feature of low surface tension lowering ability and good wettability to the glass plate despite low surface tension lowering ability, and the amount of addition does not cause defects in the coating film due to foaming. Those capable of sufficiently suppressing chargeability can be preferably used. As a leveling agent having such preferable properties, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. The polyalkylene oxide unit includes a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the polyalkylene oxide unit is bonded to the terminal of dimethylpolysiloxane, and dimethylpolysiloxane. It may be any of the linear block copolymer types that are alternately and repeatedly bonded. Didimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. 2207, but is not limited to these.

Anionic, cationic, nonionic, or amphoteric surfactants can be added as an adjunct to the leveling agent. Two or more kinds of surfactants may be mixed and used.
Anionic surfactants to be added as an auxiliary to the leveling agent include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalin sulfonate, and alkyldiphenyl ether disulfonic acid. Sodium, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include ester.

Examples of the chaotic surfactant added as a supplement to the leveling agent include alkyl quaternary ammonium salts and ethylene oxide adducts thereof. Nonionic surfactants to be added as a supplement to the leveling agent include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, and polyoxyethylene sorbitan monostearate. , Polyethylene glycol monolaurate and the like; alkyl betaines such as alkyldimethylaminoacetic acid betaine, amphoteric surfactants such as alkylimidazoline, and fluorine-based and silicone-based surfactants.

<Curing agent, curing accelerator>
The coloring composition or the photosensitive coloring composition may contain a curing agent, a curing accelerator, or the like, if necessary, in order to assist the curing of the thermosetting resin. Phenol-based resins, amine-based compounds, acid anhydrides, active esters, carboxylic acid-based compounds, sulfonic acid-based compounds, and the like are effective as the curing agent, but the curing agent is not particularly limited to these, and is a thermosetting resin. Any curing agent may be used as long as it can react with. Further, among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine-based curing agent are preferably mentioned. Examples of the curing accelerator include amine compounds (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, dimethylamine). 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, etc.) -Methacryloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6- Methacryloyloxyethyl-S-triazine, isocyanuric acid adduct, etc.) and the like can be used. These may be used alone or in combination of two or more. The content of the curing accelerator is preferably 0.01 to 15% by mass with respect to the total amount of the thermosetting resin (100% by mass).

<Other additive ingredients>
The coloring composition or the photosensitive coloring composition may contain a storage stabilizer to stabilize the viscosity over time. Further, an adhesion improver such as a silane coupling agent can be contained in order to improve the adhesion with the transparent substrate.

Examples of the storage stabilizer include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, t-butylpyrocatechol, tetraethylphosphine, tetraphenylphosphine and the like. Examples include organic phosphine and phosphite. The storage stabilizer can be used in an amount of 0.1 to 10% by mass based on the total amount of the colorant (100% by mass).

Adhesion improvers include vinylsilanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylic silanes such as γ-methacryloxypropyltrimethoxysilane, and 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 (amino) Ethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysisilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-amino Examples thereof include aminosilanes such as propyltrimethoxysilane and N-phenyl-γ-aminopropyltriethoxysilane, and silane coupling agents such as thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver is used in an amount of 0.01 to 10% by mass, preferably 0.05 to 5% by mass, based on the total amount of the colorant in the coloring composition or the photosensitive coloring composition (100% by mass). be able to.

<Removal of coarse particles>
The coloring composition and the photosensitive coloring composition have coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, and more preferably 0.5 μm or more by means such as centrifugation, filtration by a sintering filter or a membrane filter. It is preferable to remove coarse particles and mixed dust. As described above, it is preferable that the coloring composition does not substantially contain particles having a size of 0.5 μm or more. More preferably, it is 0.3 μm or less.

<Color filter>
Next, the color filter of the present invention will be described. The color filter of the present invention comprises a red filter segment, a green filter segment, and a blue filter segment, in which the red filter segment contains the diketopyrrolopyrrole pigment composition of the present invention. Alternatively, it is formed from a photosensitive coloring composition.

The green filter segment can be formed using a conventional green coloring composition containing a green pigment and a colorant carrier. Examples of the green pigment include C.I. I. Pigment Green 7, 10, 36, 37, 58 and the like are used.

Further, a yellow pigment can be used in combination with the green coloring composition. Examples of the yellow pigment that can be used in combination include 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, Yellow pigments such as 193, 194, 198, 199, 213, 214, 218, 219, 220, or 221 can be mentioned. It is also possible to use a salt-forming compound of a basic dye or an acid dye that exhibits yellow color in combination.

The blue filter segment can be formed using a conventional blue coloring composition containing a blue pigment and a colorant carrier. Examples of the blue pigment include C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64 and the like are used. Further, a purple pigment can be used in combination with the blue coloring composition. Examples of the purple pigment that can be used in combination include C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50 and other purple pigments can be mentioned. Further, a salt-forming compound of a basic dye or an acid dye exhibiting blue or purple can also 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 of the present invention can be manufactured by a printing method or a photolithography method.
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, and therefore, as a manufacturing method of the color filter, it is excellent in mass productivity at low cost. Furthermore, with the development of printing technology, it is possible to print fine patterns having high dimensional accuracy and smoothness. In order to perform 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. It is also important to control the fluidity of the ink on the printing machine, and the viscosity of the ink can be adjusted with a dispersant or an extender pigment.

When the filter segment is formed by the photolithography method, the coloring composition prepared as the solvent-developing type or alkali-developing type colored resist material is applied onto a transparent substrate by spray coating, spin coating, slit coating, roll coating or the like. By the method, the coating is applied so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet rays 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 manufacture a color filter. be able to. Further, in order to promote the polymerization of the colored resist material, heating can be applied as needed. According to the photolithography method, a color filter having higher accuracy than the above printing method can be manufactured.

At the time of development, an aqueous solution of sodium carbonate, sodium hydroxide or the like is used as the alkaline developer, and an organic alkali such as dimethylbenzylamine or 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 of the present invention can be produced by an electrodeposition method, a transfer method, or the like in addition to the above methods, and the coloring composition or the photosensitive coloring composition can be used in any of the methods. 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 each color filter segment is formed 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. It is also possible to form a thin film transistor (TFT) on the transparent substrate or the reflective substrate in advance, 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.

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

<Mass ratio of diketopyrrolopyrrole pigment>
The diketopyrrolopyrrole pigment represented by the formula (1), the diketopyrrolopyrrole pigment represented by the formula (2) and the diketopyrrolopyrrole represented by the formula (3) in the diketopyrrolopyrrole pigment composition. The pigment content was quantified using HPLC. The measurement conditions are as follows.

Equipment: 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 solution: 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)

<X-ray diffraction of diketopyrrolopyrrole pigment>
The powder X-ray diffraction measurement of the diketopyrrolopyrrole pigment composition was measured in a diffraction angle (2θ) in the range of 3 ° to 35 ° according to Japanese Industrial Standard JIS K0131 (general rule of X-ray diffraction analysis). The measurement conditions are as follows.

Equipment: Rigaku RINT2100
Sampling width: 0.02 °
Scan speed: 2.0
Divergence slit: 1 °
Divergence vertical restriction slit: 10 mm
Scattering slit: 2 °
Light receiving slit: 0.3 mm
Tube: Cu
Tube voltage: 30kV
Tube current: 30mA

<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-8120 GPC) 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))
To a stainless steel reaction vessel equipped with a reflux tube, 200 parts of molecular sieve-dehydrated tert-amyl alcohol and 140 parts of sodium-tert-amyl alkoxide were added under a nitrogen atmosphere and 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 slowly added dropwise to the alcoholate solution heated to 100 ° C. at a constant rate over 2 hours 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 obtained. The solution was added in small portions. At this time, the rate at which the alkali metal salt of the diketopyrrolopyrrole compound is added 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 paste was stirred at 5 ° C. for 3 hours to perform particle sizing and washing with crystal transition. Subsequently, the water paste of the diketopyrrolopyrrole compound obtained by filtration through an ultrafilter is dried at 80 ° C. for 24 hours and pulverized to obtain the diketopyrrolop representative of the formula (1). 150.8 parts of pyrrolop pigment was obtained.

[Production Example 2] (Production of diketopyrrolopyrrole pigment represented by the formula (2))
Diketopyrrolopyrrole pigment 120.7 represented by the formula (2) was carried out in the same manner as in Production Example 1 except that 153.6 parts of 4-bromobenzonitrile was changed to 117.4 parts of 4-chlorobenzonitrile. I got a part.

[Production Example 3] (Production of diketopyrrolopyrrole pigment represented by the formula (3-2))
While 220 parts of tert-amyl alcohol was placed in the reaction vessel 1 and cooled in a water bath, 32 parts of 60% NaH was added, and the mixture was heated and stirred at 90 ° C. Next, 100 parts of tert-amyl alcohol, 85.0 parts of the compound of the following formula (17) synthesized by the method described in Example 1 of JP2015-168725A, and N-butyl-4-cyano are placed in the reaction vessel 2. 68.7 parts of benzamide was dissolved by heating, and this was added dropwise to the reaction vessel 1 over 2 hours. After reacting at 120 ° C. for 10 hours, the mixture was cooled to 60 ° C., 400 parts of methanol and 50 parts of acetic acid were added, and then filtration and washing with methanol were performed. 93.2 parts of pyrrolop pigment was obtained.

[Production Example 4] (Production of diketopyrrolopyrrole pigment represented by the formula (3-5))
It was carried out in the same manner as in Production Example 3 except that 68.7 parts of N-butyl-4-cyanobenzamide was changed to 75.5 parts of N-phenyl-4-cyanobenzamide, and represented by the formula (3-5). 97.6 parts of diketopyrrolopyrrole pigment was obtained.

[Production Example 5] (Production of diketopyrrolopyrrole pigment represented by the formula (3-6))
It was carried out in the same manner as in Production Example 3 except that 68.7 parts of N-butyl-4-cyanobenzamide was changed to 68.7 parts of N-butyl-3-cyanobenzamide, and represented by the formula (3-6). 93.2 parts of diketopyrrolopyrrole pigment was obtained.

[Production Example 6] (Production of diketopyrrolopyrrole pigment represented by the formula (3-17))
The procedure was carried out in the same manner as in Production Example 3 except that 68.7 parts of N-butyl-4-cyanobenzamide was changed to 87.8 parts of N, N-dibutyl-4-cyanobenzamide, and the formula (3-17) was used. 105.6 parts of the diketopyrrolopyrrole pigment to be prepared was obtained.

[Production Example 7] (Production of diketopyrrolopyrrole pigment represented by the following formula (18))
Diketopyrrolopyrrole pigment represented by the following formula (18) was carried out in the same manner as in Production Example 3 except that 68.7 parts of N-butyl-4-cyanobenzamide was changed to 60.9 parts of 4-cyanobiphenyl. 88.1 copies were obtained.

[Production Example 8] (Production of diketopyrrolopyrrole pigment represented by the following formula (19))
Diketopyrrolop represented by the formula (19) was carried out in the same manner as in Production Example 3 except that 68.7 parts of N-butyl-4-cyanobenzamide was changed to 84.1 parts of 4- (octylthio) benzonitrile. 103.2 parts of the pyrrolop pigment was obtained.

[Production Example 9] (Production of diketopyrrolopyrrole pigment represented by the formula (3-12))
While 220 parts of tert-amyl alcohol was placed in the reaction vessel 1 and cooled in a water bath, 32 parts of 60% NaH was added, and the mixture was heated and stirred at 90 ° C. Next, 100 parts of tert-amyl alcohol, 74.0 parts of the compound of the following formula (20) synthesized by the method described in Example 3 of JP2015-168725A, and N-butyl-4-cyano were placed in the reaction vessel 2. 68.7 parts of benzamide was dissolved by heating, and this was added dropwise to the reaction vessel 1 over 2 hours. After reacting at 120 ° C. for 10 hours, the mixture was cooled to 60 ° C., 400 parts of methanol and 50 parts of acetic acid were added, and then filtration and washing with methanol were performed. 85.6 parts of pyrrolop pigment was obtained.

[Production Example 10] (Production of diketopyrrolopyrrole pigment represented by the formula (3-8))
While 220 parts of tert-amyl alcohol was placed in the reaction vessel 1 and cooled in a water bath, 32 parts of 60% NaH was added, and the mixture was heated and stirred at 90 ° C. Next, 100 parts of tert-amyl alcohol, 99.2 parts of the compound of the following formula (21) synthesized by the method described in Example 2 of JP2015-168725A, and N-butyl-4-cyano were placed in the reaction vessel 2. 68.7 parts of benzamide was dissolved by heating, and this was added dropwise to the reaction vessel 1 over 2 hours. After reacting at 120 ° C. for 10 hours, the mixture was cooled to 60 ° C., 400 parts of methanol and 50 parts of acetic acid were added, and then filtration and washing with methanol were performed. 103.0 parts of pyrrolop pigment was obtained.

[Production Example 11] (Production of diketopyrrolopyrrole pigment represented by the formula (3-18))
The procedure was carried out in the same manner as in Production Example 10 except that 68.7 parts of N-butyl-4-cyanobenzamide was changed to 87.8 parts of N, N-dibutyl-4-cyanobenzamide, and the formula (3-18) was used. 115.4 parts of the diketopyrrolopyrrole pigment to be obtained was obtained.

[Production Example 12] (Production of diketopyrrolopyrrole pigment represented by the following formula (22))
Diketopyrrolopyrrole represented by the following formula (22) was carried out in the same manner as in Production Example 10 except that 68.7 parts of N-butyl-4-cyanobenzamide was changed to 46.8 parts of 4-chlorobenzonitrile. 115.4 parts of the pigment was obtained.

[Production Example 13] (Production of diketopyrrolopyrrole pigment represented by the formula (3-10))
While 220 parts of tert-amyl alcohol was placed in the reaction vessel 1 and cooled in a water bath, 32 parts of 60% NaH was added, and the mixture was heated and stirred at 90 ° C. Next, 100 parts of tert-amyl alcohol, 82.0 parts of the compound of the following formula (23) synthesized by the method described in Example 7 of JP2015-168725A, and N-butyl-4-cyano were added to the reaction vessel 2. 68.7 parts of benzamide was dissolved by heating, and this was added dropwise to the reaction vessel 1 over 2 hours. After reacting at 120 ° C. for 10 hours, the mixture was cooled to 60 ° C., 400 parts of methanol and 50 parts of acetic acid were added, and then filtration and washing with methanol were performed. 91.1 parts of pyrrolop pigment was obtained.

[Production Example 14] (Production of Diketopyrrolopyrrole Pigment Mixture (RC-1))
To a stainless steel reaction vessel equipped with a reflux tube, 200 parts of molecular sieve-dehydrated tert-amyl alcohol and 140 parts of sodium-tert-amyl alkoxide were added under a nitrogen atmosphere and heated to 100 ° C. with stirring to prepare an alcoholate solution. Prepared. On the other hand, 88 parts of diisopropyl succinate, 104.5 parts of 4-chlorobenzonitrile and 19.3 parts of N, N-dibutyl-4-cyanobenzamide were added to a glass flask and heated to 90 ° C. with stirring. It was dissolved and a solution of these mixtures was prepared. The heated solution of this mixture was slowly added dropwise to the alcoholate solution heated to 100 ° C. at a constant rate over 2 hours 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 obtained. The solution was added in small portions. At this time, the rate at which the alkali metal salt of the diketopyrrolopyrrole compound is added 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 paste was stirred at 5 ° C. for 3 hours to perform particle sizing and washing with crystal transition. Subsequently, the diketopyrrolopyrrole pigment mixture (RC-1) was obtained by filtering the diketopyrrolopyrrole compound by filtration through an ultrafilter, drying the water paste of the diketopyrrolopyrrole compound at 80 ° C. for 24 hours, and pulverizing the mixture. 143.6 copies were obtained. The content of the diketopyrrolopyrrole pigment represented by the formula (2) and the diketopyrrolopyrrole pigment represented by the formula (3-17) in the obtained diketopyrrolopyrrole pigment mixture is quantified using HPLC. As a result of analysis, the contents of the diketopyrrolopyrrole pigment represented by the formula (2) and the diketopyrrolopyrrole pigment represented by the formula (3-17) were 90.9% by mass and 9.1% by mass, respectively. Met.

[Production Example 15] (Production of Diketopyrrolopyrrole Pigment Mixture (RC-2))
The same procedure as in Production Example 14 was carried out except that 104.5 parts of 4-chlorobenzonitrile was changed to 180.0 parts of 4-bromobenzonitrile, and 176.6 parts of the diketopyrrolopyrrole pigment mixture (RC-2) was added. Obtained. The content of the diketopyrrolopyrrole pigment represented by the formula (1) and the diketopyrrolopyrrole pigment represented by the formula (3-18) in the obtained diketopyrrolopyrrole pigment mixture is quantified using HPLC. As a result of analysis, the contents of the diketopyrrolopyrrole pigment represented by the formula (1) and the diketopyrrolopyrrole pigment represented by the formula (3-18) were 91.1% by mass and 8.9% by mass, respectively. Met.

<Manufacturing method of binder resin solution>
[Production Example 16] (Preparation of Acrylic Resin Solution 1)
196 parts of cyclohexanone was charged into 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, paracumylphenol ethylene oxide-modified acrylate (“Aronix M110” manufactured by Toa Synthetic Co., Ltd.) 20.7 A mixture of 1.1 parts of 2,2'-azobisisobutyronitrile 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, about 2 parts of the resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and methoxypropyl acetate is added so that the non-volatile content is 20% by mass in the previously synthesized resin solution. Was added to prepare an acrylic resin solution 1. The weight average molecular weight (Mw) was 26000.

[Production Example 17] (Preparation of Acrylic Resin Solution 2)
207 parts of cyclohexanone was placed 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 (Karens manufactured by Showa Denko Co., Ltd.). A mixture of 6.5 parts of MOI), 0.08 parts 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, about 2 parts of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and cyclohexanone was added to the previously synthesized resin solution so that the non-volatile content was 20% by mass. The acrylic resin solution 2 was prepared. The weight average molecular weight (Mw) was 18,000.

<Manufacturing method of diketopyrrolopyrrole pigment composition>
[Example 1] (Production of diketopyrrolopyrrole pigment composition (R-1))
47.5 parts of diketopyrrolopyrrole pigment of formula (1), 47.5 parts of diketopyrrolopyrrole pigment of formula (2), 5.0 parts of diketopyrrolopyrrole pigment of formula (3-2), 1000 parts of sodium chloride Parts and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (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. for 24 hours, and pulverized. To obtain 97.0 parts of the diketopyrrolopyrrole pigment composition (R-1).

[Example 2] (Production of diketopyrrolopyrrole pigment composition (R-2))
Diketo was carried out in the same manner as in Example 1 except that 5.0 parts of the diketopyrrolopyrrole pigment of the formula (3-2) was changed to 5.0 parts of the diketopyrrolopyrrole pigment of the formula (3-5). 96.8 parts of the pyrolopyrrolop pigment composition (R-2) was obtained.

[Example 3] (Production of diketopyrrolopyrrole pigment composition (R-3))
Diketo was carried out in the same manner as in Example 1 except that 5.0 parts of the diketopyrrolopyrrole pigment of the formula (3-2) was changed to 5.0 parts of the diketopyrrolopyrrole pigment of the formula (3-6). 97.8 parts of the pyrolopyrrolop pigment composition (R-3) was obtained.

[Example 4] (Production of diketopyrrolopyrrole pigment composition (R-4))
Diketo was carried out in the same manner as in Example 1 except that 5.0 parts of the diketopyrrolopyrrole pigment of the formula (3-2) was changed to 5.0 parts of the diketopyrrolopyrrole pigment of the formula (3-17). 97.2 parts of the pyrolopyrrolop pigment composition (R-4) was obtained.

[Example 5] (Production of diketopyrrolopyrrole pigment composition (R-5))
Diketo was carried out in the same manner as in Example 1 except that 5.0 parts of the diketopyrrolopyrrole pigment of the formula (3-2) was changed to 5.0 parts of the diketopyrrolopyrrole pigment of the formula (3-12). 97.1 parts of the pyrolopyrrolop pigment composition (R-5) was obtained.

[Example 6] (Production of Diketopyrrolopyrrole Pigment Composition (R-6))
Diketo was carried out in the same manner as in Example 1 except that 5.0 parts of the diketopyrrolopyrrole pigment of the formula (3-2) was changed to 5.0 parts of the diketopyrrolopyrrole pigment of the formula (3-8). 96.2 parts of the pyrolopyrrolop pigment composition (R-6) was obtained.

[Example 7] (Production of diketopyrrolopyrrole pigment composition (R-7))
Diketo was carried out in the same manner as in Example 1 except that 5.0 parts of the diketopyrrolopyrrole pigment of the formula (3-2) was changed to 5.0 parts of the diketopyrrolopyrrole pigment of the formula (3-10). 96.9 parts of the pyrolopyrrolop pigment composition (R-7) was obtained.

[Example 8] (Production of diketopyrrolopyrrole pigment composition (R-8))
The diketopyrrolopyrrole pigment of the formula (1) is 47.5 parts, the diketopyrrolopyrrole pigment of the formula (2) is 47.5 parts, and the diketopyrrolopyrrole pigment of the formula (3-2) is 5.0 parts. Except for changing to 66.5 parts of the diketopyrrolopyrrole pigment of 1), 28.5 parts of the diketopyrrolopyrrole pigment of the formula (2), and 5.0 parts of the diketopyrrolopyrrole pigment of the formula (3-17). The same procedure as in Example 1 was carried out to obtain 98.2 parts of the diketopyrrolopyrrole pigment composition (R-8).

[Example 9] (Production of diketopyrrolopyrrole pigment composition (R-9))
The diketopyrrolopyrrole pigment of the formula (1) is 47.5 parts, the diketopyrrolopyrrole pigment of the formula (2) is 47.5 parts, and the diketopyrrolopyrrole pigment of the formula (3-2) is 5.0 parts. Except for changing to 28.5 parts of the diketopyrrolopyrrole pigment of 1), 66.5 parts of the diketopyrrolopyrrole pigment of the formula (2), and 5.0 parts of the diketopyrrolopyrrole pigment of the formula (3-17). The same procedure as in Example 1 was carried out to obtain 98.0 parts of the diketopyrrolopyrrole pigment composition (R-9).

[Example 10] (Production of diketopyrrolopyrrole pigment composition (R-10))
The diketopyrrolopyrrole pigment of the formula (1) is 47.5 parts, the diketopyrrolopyrrole pigment of the formula (2) is 47.5 parts, and the diketopyrrolopyrrole pigment of the formula (3-2) is 5.0 parts. Except for changing to 19.0 parts of the diketopyrrolopyrrole pigment of 1), 76.0 parts of the diketopyrrolopyrrole pigment of the formula (2), and 5.0 parts of the diketopyrrolopyrrole pigment of the formula (3-17). The same procedure as in Example 1 was carried out to obtain 97.8 parts of a diketopyrrolopyrrole pigment composition (R-10).

[Example 11] (Production of diketopyrrolopyrrole pigment composition (R-11))
The diketopyrrolopyrrole pigment of the formula (1) is 47.5 parts, the diketopyrrolopyrrole pigment of the formula (2) is 47.5 parts, and the diketopyrrolopyrrole pigment of the formula (3-2) is 5.0 parts. Except for changing to 49.5 parts of the diketopyrrolopyrrole pigment of 1), 49.5 parts of the diketopyrrolopyrrole pigment of the formula (2), and 1.0 part of the diketopyrrolopyrrole pigment of the formula (3-2). The same procedure as in Example 1 was carried out to obtain 97.5 parts of the diketopyrrolopyrrole pigment composition (R-11).

[Example 12] (Production of diketopyrrolopyrrole pigment composition (R-12))
The diketopyrrolopyrrole pigment of the formula (1) is 47.5 parts, the diketopyrrolopyrrole pigment of the formula (2) is 47.5 parts, and the diketopyrrolopyrrole pigment of the formula (3-2) is 5.0 parts. Except for changing to 45.0 parts of the diketopyrrolopyrrole pigment of 1), 45.0 parts of the diketopyrrolopyrrole pigment of the formula (2), and 10.0 parts of the diketopyrrolopyrrole pigment of the formula (3-2). The same procedure as in Example 1 was carried out to obtain 97.3 parts of the diketopyrrolopyrrole pigment composition (R-12).

[Example 13] (Production of diketopyrrolopyrrole pigment composition (R-13))
The diketopyrrolopyrrole pigment of the formula (1) is 47.5 parts, the diketopyrrolopyrrole pigment of the formula (2) is 47.5 parts, and the diketopyrrolopyrrole pigment of the formula (3-2) is 5.0 parts. Except for changing to 42.5 parts of the diketopyrrolopyrrole pigment of 1), 42.5 parts of the diketopyrrolopyrrole pigment of the formula (2), and 15.0 parts of the diketopyrrolopyrrole pigment of the formula (3-2). The same procedure as in Example 1 was carried out to obtain 98.1 parts of the diketopyrrolopyrrole pigment composition (R-13).

[Example 14] (Production of diketopyrrolopyrrole pigment composition (R-14))
The diketopyrrolopyrrole pigment of the formula (1) is 47.5 parts, the diketopyrrolopyrrole pigment of the formula (2) is 47.5 parts, and the diketopyrrolopyrrole pigment of the formula (3-2) is 5.0 parts. Except for changing to 40.0 parts of the diketopyrrolopyrrole pigment of 1), 40.0 parts of the diketopyrrolopyrrole pigment of the formula (2), and 20.0 parts of the diketopyrrolopyrrole pigment of the formula (3-2). The same procedure as in Example 1 was carried out to obtain 97.0 parts of the diketopyrrolopyrrole pigment composition (R-14).

[Example 15] (Production of diketopyrrolopyrrole pigment composition (R-15))
The diketopyrrolopyrrole pigment of the formula (1) is 47.5 parts, the diketopyrrolopyrrole pigment of the formula (2) is 47.5 parts, and the diketopyrrolopyrrole pigment of the formula (3-2) is 5.0 parts. Except for changing to 69.5 parts of the diketopyrrolopyrrole pigment of 1), 29.5 parts of the diketopyrrolopyrrole pigment of the formula (2), and 1.0 part of the diketopyrrolopyrrole pigment of the formula (3-2). The same procedure as in Example 1 was carried out to obtain 97.8 parts of a diketopyrrolopyrrole pigment composition (R-15).

[Example 16] (Production of Diketopyrrolopyrrole Pigment Composition (R-16))
The diketopyrrolopyrrole pigment of the formula (1) is 47.5 parts, the diketopyrrolopyrrole pigment of the formula (2) is 47.5 parts, and the diketopyrrolopyrrole pigment of the formula (3-2) is 5.0 parts. Except for changing to 59.5 parts of the diketopyrrolopyrrole pigment of 1), 25.5 parts of the diketopyrrolopyrrole pigment of the formula (2), and 15.0 parts of the diketopyrrolopyrrole pigment of the formula (3-2). The same procedure as in Example 1 was carried out to obtain 96.9 parts of the diketopyrrolopyrrole pigment composition (R-16).

[Example 17] (Production of diketopyrrolopyrrole pigment composition (R-17))
The diketopyrrolopyrrole pigment of the formula (1) is 47.5 parts, the diketopyrrolopyrrole pigment of the formula (2) is 47.5 parts, and the diketopyrrolopyrrole pigment of the formula (3-2) is 5.0 parts. Except for changing to 19.5 parts of the diketopyrrolopyrrole pigment of 1), 79.5 parts of the diketopyrrolopyrrole pigment of the formula (2), and 1.0 part of the diketopyrrolopyrrole pigment of the formula (3-2). The same procedure as in Example 1 was carried out to obtain 97.4 parts of the diketopyrrolopyrrole pigment composition (R-17).

[Example 18] (Production of diketopyrrolopyrrole pigment composition (R-18))
The diketopyrrolopyrrole pigment of the formula (1) is 47.5 parts, the diketopyrrolopyrrole pigment of the formula (2) is 47.5 parts, and the diketopyrrolopyrrole pigment of the formula (3-2) is 5.0 parts. Except for changing to 17.0 parts of the diketopyrrolopyrrole pigment of 1), 68.0 parts of the diketopyrrolopyrrole pigment of the formula (2), and 15.0 parts of the diketopyrrolopyrrole pigment of the formula (3-2). The same procedure as in Example 1 was carried out to obtain 96.4 parts of the diketopyrrolopyrrole pigment composition (R-18).

[Example 19] (Production of diketopyrrolopyrrole pigment composition (R-19))
42.7 parts of diketopyrrolopyrrole pigment of formula (1), 42.7 parts of diketopyrrolopyrrole pigment of formula (2), 4.5 parts of diketopyrrolopyrrole pigment of formula (3-2), formula (8) 10.0 parts of the benzoisoindole derivative of -1), 1000 parts of sodium chloride, and 120 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 10 hours. Next, the kneaded mixture was put into warm water and stirred for 1 hour while heating at about 80 ° C. to form a slurry, which was filtered and washed with water to remove salt and diethylene glycol, then dried at 80 ° C. for 24 hours and crushed. This gave 97.1 parts of a diketopyrrolopyrrole pigment composition (R-19).

[Example 20] (Production of Diketopyrrolopyrrole Pigment Composition (R-20))
Diketopyrrolopyrrole was carried out in the same manner as in Example 19 except that 10.0 parts of the benzoisoindole derivative of the formula (8-1) was changed to 10.0 parts of the thiazine indigo derivative of the formula (11-6). 97.7 parts of the pigment composition (R-20) was obtained.

[Example 21] (Production of diketopyrrolopyrrole pigment composition (R-21))
The same procedure as in Example 19 was carried out except that 10.0 parts of the benzoisoindole derivative of the formula (8-1) was changed to 10.0 parts of the diketopyrrolopyrrole derivative of the formula (7-6). 98.2 parts of the pyrrole pigment composition (R-21) was obtained.

[Example 22] (Production of diketopyrrolopyrrole pigment composition (R-22))
Diketopyrrolopyrrole pigment composition was carried out in the same manner as in Example 19 except that 10.0 parts of the benzoisoindole derivative of the formula (8-1) was changed to 10.0 parts of the quinophthalone derivative of the formula (15-1). 97.5 parts of the product (R-22) were obtained.

[Example 23] (Production of diketopyrrolopyrrole pigment composition (R-23))
47.5 parts of diketopyrrolopyrrole pigment of formula (1), 52.5 parts of diketopyrrolopyrrole pigment mixture (RC-1), 1000 parts of sodium chloride, and 120 parts of diethylene glycol are added to a stainless steel 1-gallon kneader (Inoue Seisakusho). It was charged in (manufactured) and kneaded at 60 ° C. for 10 hours. Next, the kneaded mixture was put into warm water and stirred for 1 hour while heating at about 80 ° C. to form a slurry, which was filtered and washed with water to remove salt and diethylene glycol, then dried at 80 ° C. for 24 hours and crushed. This gave 97.9 parts of a diketopyrrolopyrrole pigment composition (R-23).

[Example 24] (Production of Diketopyrrolopyrrole Pigment Composition (R-24))
47.5 parts of diketopyrrolopyrrole pigment of formula (1), 52.5 parts of diketopyrrolopyrrole pigment mixture (RC-1), 47.5 parts of diketopyrrolopyrrole pigment of formula (2), diketopyrrolop The same procedure as in Example 23 was carried out except that the amount was changed to 52.5 parts of the pyrrolop pigment mixture (RC-2) to obtain 97.0 parts of the diketopyrrolopyrrole pigment composition (R-24).

[Example 25] (Production of Diketopyrrolopyrrole Pigment Composition (R-25))
275.0 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 14 in a stainless steel container. 303.0 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 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. A small amount of the previously obtained alkali metal salt mixed solution of the diketopyrrolopyrrole compound was added to the cooled mixture while rotating a 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 at which the alkali metal salt of the diketopyrrolopyrrole compound is added 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 paste was stirred at 5 ° C. for 3 hours to perform particle sizing and washing with crystal transition. Subsequently, the diketopyrrolopyrrole pigment composition (R-25) was obtained by filtering the diketopyrrolopyrrole compound by filtration through an ultrafilter, drying the water paste of the diketopyrrolopyrrole compound at 80 ° C. for 24 hours, and pulverizing the mixture. ) 150.3 parts were obtained.

[Example 26] (Production of Diketopyrrolopyrrole Pigment Composition (R-26))
In a stainless steel container, 1000 parts of tert-amyl alcohol in which 150 parts of a methanol solution of 28% sodium methoxide was dissolved was charged, and 47.5 parts of the diketopyrrolopyrrole pigment of the formula (1) and the diketo of the formula (2) were charged. 47.5 parts of the pyrolopyrrolop pigment and 5.0 parts of the diketopyrrolopyrrole pigment of the formula (3-17) were added, and the mixture was stirred for 2 hours. Then, while stirring 10000 parts of water, a solution of the diketopyrrolopyrrole pigment composition was added little by little. The obtained suspension of the diketopyrrolopyrrole pigment composition was filtered, washed with water, dried at 80 ° C. for 24 hours and night, and pulverized to obtain 95.5 parts of the diketopyrrolopyrrole pigment composition (R-26). ..

[Comparative Example 1] (Production of Diketopyrrolopyrrole Pigment Composition (R-27))
The diketopyrrolopyrrole pigment of the formula (1) is 47.5 parts, the diketopyrrolopyrrole pigment of the formula (2) is 47.5 parts, and the diketopyrrolopyrrole pigment of the formula (3-2) is 5.0 parts. The same procedure as in Example 1 was carried out except that the diketopyrrolopyrrole pigment (1) was changed to 100.0 parts, and 98.4 parts of the diketopyrrolopyrrole pigment (R-27) was obtained.

[Comparative Example 2] (Production of Diketopyrrolopyrrole Pigment Composition (R-28))
The diketopyrrolopyrrole pigment of the formula (1) is 47.5 parts, the diketopyrrolopyrrole pigment of the formula (2) is 47.5 parts, and the diketopyrrolopyrrole pigment of the formula (3-2) is 5.0 parts. The same procedure as in Example 1 was carried out except that the diketopyrrolopyrrole pigment (2) was changed to 100.0 parts, and 98.6 parts of the diketopyrrolopyrrole pigment (R-28) was obtained.

[Comparative Example 3] (Production of Diketopyrrolopyrrole Pigment Composition (R-29))
The diketopyrrolopyrrole pigment of the formula (1) is 47.5 parts, the diketopyrrolopyrrole pigment of the formula (2) is 47.5 parts, and the diketopyrrolopyrrole pigment of the formula (3-2) is 5.0 parts. The diketopyrrolopyrrole pigment composition was carried out in the same manner as in Example 1 except that the diketopyrrolopyrrole pigment of 1) was changed to 95.0 parts and the diketopyrrolopyrrole pigment of the formula (3-2) was changed to 5.0 parts. (R-29) 97.8 parts were obtained.

[Comparative Example 4] (Production of Diketopyrrolopyrrole Pigment Composition (R-30))
The diketopyrrolopyrrole pigment of the formula (1) is 47.5 parts, the diketopyrrolopyrrole pigment of the formula (2) is 47.5 parts, and the diketopyrrolopyrrole pigment of the formula (3-2) is 5.0 parts. The diketopyrrolopyrrole pigment composition was carried out in the same manner as in Example 1 except that the diketopyrrolopyrrole pigment of 2) was changed to 95.0 parts and the diketopyrrolopyrrole pigment of the formula (3-2) was changed to 5.0 parts. (R-30) 98.1 parts were obtained.

[Comparative Example 5] (Production of Diketopyrrolopyrrole Pigment Composition (R-31))
The diketopyrrolopyrrole pigment of the formula (1) is 47.5 parts, the diketopyrrolopyrrole pigment of the formula (2) is 47.5 parts, and the diketopyrrolopyrrole pigment of the formula (3-2) is 5.0 parts. Examples except that the diketopyrrolopyrrole pigment of 1) was changed to 50.0 parts, the diketopyrrolopyrrole pigment of the formula (2) was changed to 45.0 parts, and the diketopyrrolopyrrole pigment of the formula (18) was changed to 5.0 parts. The same procedure as in No. 1 was carried out to obtain 97.3 parts of the diketopyrrolopyrrole pigment composition (R-31).

[Comparative Example 6] (Production of Diketopyrrolopyrrole Pigment Composition (R-32))
The diketopyrrolopyrrole pigment of the formula (1) is 47.5 parts, the diketopyrrolopyrrole pigment of the formula (2) is 47.5 parts, and the diketopyrrolopyrrole pigment of the formula (3-2) is 5.0 parts. Examples except that the diketopyrrolopyrrole pigment of 1) was changed to 50.0 parts, the diketopyrrolopyrrole pigment of the formula (2) was changed to 45.0 parts, and the diketopyrrolopyrrole pigment of the formula (19) was changed to 5.0 parts. The same procedure as in No. 1 was carried out to obtain 97.6 parts of the diketopyrrolopyrrole pigment composition (R-32).

[Comparative Example 7] (Production of Diketopyrrolopyrrole Pigment Composition (R-33))
Except for changing 47.5 parts of the diketopyrrolopyrrole pigment of the formula (1) and 47.5 parts of the diketopyrrolopyrrole pigment of the formula (2) to 95.0 parts of the diketopyrrolopyrrole pigment of the formula (22). , The same procedure as in Example 1 was carried out to obtain 95.9 parts of a diketopyrrolopyrrole pigment composition (R-33).

[Comparative Example 8] (Production of Diketopyrrolopyrrole Pigment Composition (R-34))
The diketopyrrolopyrrole pigment of the formula (1) is 47.5 parts, the diketopyrrolopyrrole pigment of the formula (2) is 47.5 parts, and the diketopyrrolopyrrole pigment of the formula (3-2) is 5.0 parts. Except for changing to 80.0 parts of the diketopyrrolopyrrole pigment of 1), 18.0 parts of the diketopyrrolopyrrole pigment of the formula (2), and 2.0 parts of the diketopyrrolopyrrole pigment of the formula (3-17). The same procedure as in Example 1 was carried out to obtain 97.2 parts of the diketopyrrolopyrrole pigment composition (R-34).

[Comparative Example 9] (Production of Diketopyrrolopyrrole Pigment Composition (R-35))
The diketopyrrolopyrrole pigment of the formula (1) is 47.5 parts, the diketopyrrolopyrrole pigment of the formula (2) is 47.5 parts, and the diketopyrrolopyrrole pigment of the formula (3-2) is 5.0 parts. Except for changing to 10.0 parts of the diketopyrrolopyrrole pigment of 1), 88.0 parts of the diketopyrrolopyrrole pigment of the formula (2), and 2.0 parts of the diketopyrrolopyrrole pigment of the formula (3-17). The same procedure as in Example 1 was carried out to obtain 97.9 parts of a diketopyrrolopyrrole pigment composition (R-35).

[Comparative Example 10] (Production of Diketopyrrolopyrrole Pigment Composition (R-36))
The diketopyrrolopyrrole pigment of the formula (1) is 47.5 parts, the diketopyrrolopyrrole pigment of the formula (2) is 47.5 parts, and the diketopyrrolopyrrole pigment of the formula (3-2) is 5.0 parts. The diketopyrrolopyrrole pigment composition (R) was carried out in the same manner as in Example 1 except that the diketopyrrolopyrrole pigment of 1) was changed to 50.0 parts and the diketopyrrolopyrrole pigment of the formula (2) was changed to 50.0 parts. -36) 98.8 copies were obtained.

[Comparative Example 11] (Production of Diketopyrrolopyrrole Pigment Composition (R-37))
High-speed stirring of 47.5 parts of the diketopyrrolopyrrole pigment of the formula (1), 47.5 parts of the diketopyrrolopyrrole pigment of the formula (2), and 5.0 parts of the diketopyrrolopyrrole pigment of the formula (3-2). By stirring and mixing with a disper, 99.9 parts of a diketopyrrolopyrrole pigment composition (R-37) was obtained.

Table 1 shows the contents of the produced diketopyrrolopyrrole pigment compositions 1-37.

<Manufacturing method of coloring composition for color filter>
[Example 27] (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 parts Acrylic resin solution 1 40.0 parts Propylene glycol monomethyl ether acetate 48.0 parts

[Examples 28 to 52] (Coloring compositions (RP-2 to 26))
The diketopyrrolopyrrole pigment composition (R-1) was changed to the diketopyrrolopyrrole pigment composition (R-2 to 26) shown in Table 2 in the same manner as in Example 27, and the coloring composition was changed. The thing (RP-2-26) was obtained.

[Comparative Examples 12 to 22] (Coloring Compositions (RP-27 to 37))
The diketopyrrolopyrrole pigment composition (R-1) was changed to the diketopyrrolopyrrole pigment composition (R-27 to 37) shown in Table 2 in the same manner as in Example 27, and the coloring composition was changed. The thing (RP-27-37) was obtained.

<Evaluation of coloring composition for color filter>
The obtained coloring compositions (RP-1 to 37) 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 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 coloring composition applied on a glass substrate, and reaches the polarizing plate. If the polarizing plate and the polarizing planes of the polarizing plate are parallel, light passes through the polarizing plate, but if the polarizing planes are 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 polarized 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 Δ: Initial viscosity is 50 or more and less than 150 mPa · s ×: Initial viscosity is 150 mPa · s or more

(Evaluation of stability over time)
For those that had been allowed to stand at 40 ° C. for 7 days counting from the day of adjustment of 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 over time was calculated from the following formula. rice field.
Viscosity over time = (viscosity over time) / (initial viscosity) x 100 (%)
Viscosity stability was evaluated based on the viscosity thickening rate over time. If the thickening rate over time is 80% or more and less than 120%, it can be practically tolerated. If the viscosity is reduced or thickened beyond this range, when the coloring composition is applied onto the glass substrate, it cannot be applied under the same coating conditions, which causes a problem in productivity. .. More preferably, it is in the range of 90% or more and less than 110%.
◯: Time-dependent thickening rate 90% or more and less than 110% Δ: Time-related thickening rate 80% or more and less than 90%, or 110% or more and less than 120% ×: Time-related thickening rate less than 80% or 120% or more

<Method of producing other coloring compositions>
(Preparation of coloring composition (RP-38))
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-38). bottom.
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 53] (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-38) 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 (Hodogaya Chemical Industry "EAB-F") 0.4 parts Ethylene glycol monomethyl ether acetate 39.6 parts

[Examples 54 to 78] (Preparation of photosensitive coloring compositions (RR-2 to 26))
The coloring composition (RP-1) is changed to the coloring composition (RP-2 to 26), and further, the coloring composition (RP-2 to 25) and the coloring composition so as to have the same chromaticity as in Example 53. Photosensitive coloring compositions (RR-2 to 26) were prepared in the same manner as in Example 53 except that the ratio of (RP-38) was adjusted.

[Comparative Examples 23 to 33] (Preparation of photosensitive coloring compositions (RR-27 to 37))
The coloring composition (RP-1) is changed to the coloring composition (RP-27 to 37), and further, the coloring composition (RP-27 to 37) and the coloring composition so as to have the same chromaticity as in Example 53. Photosensitive coloring compositions (RR-27 to 37) were prepared in the same manner as in Example 53 except that the ratio of (RP-38) was adjusted.

<Evaluation of photosensitive coloring composition>
The obtained photosensitive coloring composition (RR-1 to 37) was evaluated as follows. The evaluation results are shown in Table 3.

(Color characteristic evaluation)
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 ultra-high 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 ultra-high 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. No crystal precipitation, but crystal precipitation in the second heat treatment at 240 ° C. for 60 minutes Δ: No crystal precipitation in the heat treatment at 230 ° C. for 60 minutes, but crystal precipitation in the further heat treatment at 240 ° C. for 60 minutes ×: 230 ° C. 60 Crystal precipitation occurs after minute heat treatment

From the results of Table 3, in the formation of the color filter, the diketopyrrolopyrrole pigment represented by the formula (1) in the present invention, the diketopyrrolopyrrole pigment represented by the formula (2), and the general formula (3) are shown. In the diketopyrrolopyrrole pigment composition containing the diketopyrrolopyrrole pigment, the mass ratio of the diketopyrrolopyrrole pigment represented by the formula (1) to the diketopyrrolopyrrole pigment represented by the formula (2) is Diketopyrrolopyrrole pigment composition that is 70:30 to 20:80 and does not have a maximum peak within the range of diffraction angle (2θ) = 5 to 12 ° in powder X-ray diffraction measurement using CuKα rays. The examples using the above were excellent in brightness and contrast ratio, and it was possible to suppress the crystal precipitation of the pigment due to the heating step.

<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 Co., Ltd.) for 5 hours using zirconia beads having a diameter of 0.5 mm, and then a 5 μm filter. 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 Co., Ltd.) for 5 hours using zirconia beads having a diameter of 0.5 mm, and then a 5 μm filter. 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-8) of the present invention is coated on the substrate with a spin coater to a thickness such that x = 0.640 and y = 0.328. It was applied to form a colored film. The coating film was irradiated with ultraviolet rays of ^{300 mJ / cm 2} using an ultra-high 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 blue photosensitive coloring composition 1 (BR-1) is applied to a thickness such that the green photosensitive coloring composition 1 (GR-1) has a thickness of x = 0.300 and y = 0.600. 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.

By using the photosensitive coloring composition (RR-8) of the present invention, it was possible to produce a color filter having excellent brightness and contrast and having no pigment crystal precipitation in the heating step.

Claims (6)

Diketopyrrolopyrrole containing a diketopyrrolopyrrole pigment represented by the formula (1), a diketopyrrolopyrrole pigment represented by the formula (2), and a diketopyrrolopyrrole pigment represented by the general formula (3). In the pigment composition, the mass ratio of the diketopyrrolopyrrole pigment represented by the formula (1) to the diketopyrrolopyrrole pigment represented by the formula (2) is 70:30 to 20:80, and is generally used. The content of the diketopyrrolopyrrole pigment represented by the formula (3) is 1% by mass to 20% by mass with respect to the total amount of the diketopyrrolopyrrole pigment composition, and powder X-ray diffraction using CuKα rays. Diketopyrrolopyrrole pigment composition having no maximum peak in the range of diffraction angle (2θ) = 5 to 12 °.

[In the general formula (3), R ¹ is a hydrogen atom, a halogen atom or a cyano group, and R ² and R ³ are independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituent. It is a phenyl group which may have. ]
The diketopyrrolop according to claim 1, wherein the mass ratio of the diketopyrrolopyrrole pigment represented by the formula (1) to the diketopyrrolopyrrole pigment represented by the formula (2) is 50:50 to 20:80. Pyrrolop pigment composition. The diketopyrrolopyrrole pigment according to claim 1 or 2, wherein the content of the diketopyrrolopyrrole pigment represented by the general formula (3) is 1% by mass to 15% by mass with respect to the total amount of the diketopyrrolopyrrole pigment composition. Ketopyrrolopyrrole pigment composition. The coloring composition for a color filter containing the diketopyrrolopyrrole pigment composition, the binder resin and the organic solvent according to any one of claims 1 to 3. The coloring composition for a color filter according to claim 4, further comprising at least one selected from the group consisting of a photopolymerizable monomer and a photopolymerization initiator. A color filter comprising a filter segment formed from the coloring composition for a color filter according to claim 4 or 5.

Images