WO2012117965A1

WO2012117965A1 - Pigment composition for color filter, colored composition, and color filter

Info

Publication number: WO2012117965A1
Application number: PCT/JP2012/054573
Authority: WO
Inventors: 裕介飯田; 太郎室星; 雅之藤木
Original assignee: 東洋インキＳｃホールディングス株式会社; トーヨーケム株式会社
Priority date: 2011-03-02
Filing date: 2012-02-24
Publication date: 2012-09-07
Also published as: TW201239038A; JP2012181378A

Abstract

A diketopyrrolopyrrole pigment composition for a color filter, comprising C.I. pigment red 254 and a diketopyrrolopyrrole pigment represented by formula (1) at a ratio of 97:3-85:15 by mass. (In formula (1), A and B independently represent a hydrogen atom or a substituent, wherein A and/or B represents -CON(R¹)R²; and R¹ and R² independently represent a hydrogen atom, an alkyl group having 1-20 carbon atoms, or a phenyl group which may have a substituent.)

Description

Color filter pigment composition, coloring composition, and color filter

The present invention relates to a color liquid crystal display device, a color filter pigment composition for use in the production of a color filter used in a color image pickup tube element, a color composition, and a color filter formed using the same. is there.

In the liquid crystal display device, a liquid crystal layer sandwiched between two polarizing plates controls the amount of light passing through the first polarizing plate by controlling the degree of polarization of light passing through the first polarizing plate. The type using twisted nematic (TN) type liquid crystal is the mainstream. By providing a color filter between the two polarizing plates, color display is possible, and in recent years it has come to be used in televisions, personal computer monitors, etc., so that the color filter has higher brightness, higher contrast ratio, The demand for high color reproducibility is increasing.

A color filter is a surface of a transparent substrate such as glass, in which two or more kinds of fine band (striped) filter segments of different hues are arranged in parallel or crossing each other, or fine filter segments are arranged vertically and horizontally. It is made up of those arranged in In general, it is often formed from filter segments of three colors of red, green, and blue. Each of these segments is as fine as several microns to several hundreds of microns, and is arranged in a predetermined arrangement for each hue. ing.

In general, in a color liquid crystal display device, a transparent electrode for driving liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for aligning liquid crystal in a certain direction is further formed thereon. Yes. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, a high temperature treatment of generally 200 ° C. or higher, preferably 230 ° C. or higher is required in the production process for forming the color filter. For this reason, at present, a method called a pigment dispersion method using a pigment having excellent light resistance and heat resistance as a colorant is mainly used as a method for producing a color filter.

In the pigment dispersion method, a pigment having excellent light resistance and heat resistance, such as a diketopyrrolopyrrole pigment, an anthraquinone pigment, a perylene pigment or a disazo pigment, may be used alone or in combination for the red filter segment. It is common.

Among the diketopyrrolopyrrole pigments, C.I. I. Pigment Red 254 is a pigment having particularly high brightness, and is therefore used as a color filter. In recent years, there has been a strong demand for a high contrast ratio for color filters. For this purpose, it is necessary to make the primary particle size of diketopyrrolopyrrole pigments as fine as possible. However, since the diketopyrrolopyrrole pigments that have been refined have the property of being easy to grow crystals due to their intermolecular hydrogen bonds, crystallization occurs in the heating process when forming the color filter, and foreign matter is generated. Is a problem.

Incidentally, the diketopyrrolopyrrole pigment can be obtained by the production method disclosed in Patent Document 1 and Patent Document 2 (hereinafter referred to as “succinic acid ester synthesis method”). Methods for obtaining a mixture of at least two structurally different diketopyrrolopyrrole pigments using a plurality of nitrile compounds as raw materials in the succinate synthesis method are disclosed in Patent Document 1, Patent Document 2, and Patent Document 3 Has been. However, these documents do not describe any suitability for color filter applications.

In Patent Document 4, a mixture of at least two structurally different diketopyrrolopyrrole pigments obtained by a succinate synthesis method using a nitrile compound having a plurality of specific structural formulas as a raw material is used for a color filter. However, there is no specific and sufficient description in the specification regarding the usefulness in color filter applications.

In Patent Documents 5 and 6, a diketopyrrolopyrrole pigment (mainly CI Pigment Red 254) and a diketopyrrolopyrrole compound having at least one specific structural formula are used in combination with a high contrast ratio. There has been proposed and disclosed a coloring composition for a color filter which is present and suppresses crystal precipitation due to a heating process. Patent Document 7 also describes a pigment dispersion composition for a color filter using a diketopyrrolopyrrole pigment.

JP 58-210084 A Japanese Patent Application Laid-Open No. 07-90189 JP-A-61-120861 Special table 2007-514798 gazette WO2009 / 081930 pamphlet JP 2009-149707 A WO2009 / 144115 pamphlet

However, the above-described prior art has a problem that the balanced performance required for color filter use cannot be obtained in terms of brightness, contrast ratio, and crystal precipitation suppression.
The present invention provides a pigment composition for a color filter, a coloring composition, and a color filter using the same, which have a high brightness and a high contrast ratio and do not cause crystal precipitation of a diketopyrrolopyrrole pigment even in a heating process. The task is to do.

The present inventors have described C.I. I. As a result of studying various combinations of CI Pigment Red 254 and other diketopyrrolopyrrole pigments, a specific diketopyrrolopyrrole pigment having a pigment structure in which a substituent is introduced asymmetrically is obtained. I. The present inventors have found that a pigment composition contained in a specific ratio with respect to CI Pigment Red 254 is very excellent in achieving the above-described problems, and have reached the present invention.

That is, the present invention relates to C.I. I. Pigment Red 254 and a diketopyrrolopyrrole pigment represented by the following formula (1), C.I. I. The present invention relates to a diketopyrrolopyrrole pigment composition for color filters, wherein the mass ratio of Pigment Red 254 to the diketopyrrolopyrrole pigment represented by the following formula (1) is 97: 3 to 85:15.

(In the formula (1), A and B are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a cyano group, —CF ₃ , or —CON (R ¹ ) R ² , and at least one of A and B is —CON (R ¹ ) R ^2. R ¹ and R ² are each independently hydrogen An atom, an alkyl group having 1 to 20 carbon atoms, or an optionally substituted phenyl group.)

Another aspect of the present invention is a color composition containing a colorant, a binder resin, and an organic solvent, wherein the colorant contains the diketopyrrolopyrrole pigment composition. Related to things.

Still another aspect of the invention relates to a color filter comprising a filter segment formed from the color filter coloring composition.

According to the present invention, a pigment composition for a color filter, a colored composition, and a color filter using the same, which have high brightness and high contrast ratio and do not cause crystal precipitation of a diketopyrrolopyrrole pigment even in a heating process. Can be provided.

Hereinafter, the present invention will be described in detail based on preferred embodiments.
The following “CI” means a color index (CI).
C. I. Pigment Red 254 is 3,6-bis (4-chlorophenyl) -2,5-dihydropyrrolo [3,4-c] pyrrole-1,4-dione.

1. Diketopyrrolopyrrole Pigment Composition The diketopyrrolopyrrole pigment composition for color filters according to the present invention (hereinafter, “diketopyrrolopyrrole” may be abbreviated as “DPP”) is C.I. I. Pigment Red 254 and a DPP pigment represented by the following formula (1) (hereinafter, referred to as “specific heterodiketopyrrolopyrrole pigment” and sometimes abbreviated as “specific hetero DPP pigment”) are 97 in mass ratio. : 3 to 85:15.
As the specific hetero DPP pigment, a plurality of types may be used in combination.

In formula (1), in A and B, the alkyl group having 1 to 4 carbon atoms may be linear or branched, and specifically includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, Examples thereof include isobutyl group, sec-butyl group, and tert-butyl group.

The alkoxyl group having 1 to 4 carbon atoms may be linear or branched, and specifically includes a methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert- A butoxy group is mentioned.

In R ¹ and R ² , the alkyl group having 1 to 20 carbon atoms may be linear or branched. Specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec -Butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, hexadecyl, octadecyl, icosyl, 1,5-dimethylhexyl, 1,6-dimethylheptyl Group, 2-ethylhexyl group and the like, but are not limited thereto.

Examples of the phenyl group which may have a substituent include a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a cyano group, a trifluoromethyl group, a nitro group, a carbamoyl group, and a sulfamoyl group. And a phenyl group having one or more substituents. The phenyl group may have two or more different types of substituents. More specifically, a phenyl group, p-methylphenyl group, 4-tert-butylphenyl group, p-nitrophenyl group, p-methoxyphenyl group, p-chlorophenyl group, 2-methyl-3-chlorophenyl group, 2 , 4-dichlorophenyl group, 3-carbamoylphenyl group, 2-chloro-4-carbamoylphenyl group, 2-methyl-4-carbamoylphenyl group, 2-methoxy-4-carbamoylphenyl group, 2-chloro-5-carbamoylphenyl Group, 2-methyl-5-carbamoylphenyl group and the like, but are not limited thereto.

In a preferred embodiment, the specific hetero DPP pigment includes at least one of a DPP pigment represented by the following formula (1-1) and a DPP pigment represented by the following formula (1-2).

(In Formula (1-1) and Formula (1-2), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an optionally substituted phenyl. Group.)

Specific examples of the specific heterodiketopyrrolopyrrole pigment will be given below, but the present invention is not limited thereto. The following exemplary compounds include compounds not included in the above formulas (1-1) and (1-2), which are shown as formulas (1-3a) to (1-3f).

In the specific hetero DPP pigment, the formula (1-1b), formula (1-1c), formula (1-1d), formula (1-1f), formula (1-1g), formula (1-1h), formula ( 1-2b), a carbamoyl group substituted with an alkyl group having 4 or more carbon atoms such as formula (1-2c), formula (1-2d), or formula (1-2e), or a carbamoyl group substituted with a phenyl group. It is preferable from the viewpoint of the contrast ratio and the effect of suppressing crystal precipitation. More preferably, ^one of R ¹ and R ² in the formula (1) is an alkyl group having 4 to 20 carbon atoms or a phenyl group, and the other is a hydrogen atom.

In the present invention, C.I. I. The ratio of Pigment Red 254 to the specific hetero DPP pigment is characterized by being in the range of 97: 3 to 85:15 by mass ratio. When the ratio of the specific hetero DPP pigment exceeds 15% by mass, an effect of suppressing crystallization is obtained. I. The excellent color tone of CI Pigment Red 254 is impaired. This is because the specific hetero DPP pigment is C.I. I. This is because the color tone is inferior to that of Pigment Red 254. On the other hand, when the ratio of the specific hetero DPP pigment is less than 3% by mass, the effect of increasing the contrast ratio and suppressing the crystal precipitation is not sufficient. When the crystal precipitation suppressing effect is not sufficient, light scattering occurs due to the crystalline foreign matter deposited on the surface of the coating film in the heating step, causing a decrease in brightness and contrast ratio. Therefore, by using a DPP pigment composition in which two specific pigments are mixed in the above mass ratio range, a high brightness and a high contrast ratio are achieved, and crystal precipitation of the DPP pigment is suppressed even in the heating step. Can do.

(Method for producing diketopyrrolopyrrole pigment composition)
C. I. Pigment Red 254 can be produced by a succinic diester synthesis method. That is, using 2 mol of 4-chlorobenzonitrile per 1 mol of succinic acid diester, in an inert organic solvent such as tert-amyl alcohol, in the presence of an alkali metal or an alkali metal alkoxide, a high temperature of 80 to 110 ° C. By carrying out a condensation reaction in order to produce an alkali metal salt of the DPP compound, and subsequently protonating the alkali metal salt of the DPP compound with water, alcohol, acid, or the like. I. Pigment Red 254 can be obtained. At this time, the size of the primary particle diameter obtained can be controlled by the temperature in protonation, the type, ratio and amount of water, alcohol or acid.
C. I. The manufacturing method of the pigment red 254 is not limited to this method. Commercially available C.I. I. Pigment Red 254 may be used.

Specific hetero DPP pigments are described in, for example, the document Synth. Commun. , 1988, 18, 1213 and Tetrahedron, 58 (2002) 5547-5565. The method for producing the specific hetero DPP pigment is not limited to this method.

C. I. Pigment Red 254 and the specific hetero DPP pigment can be simultaneously produced as a fine particle pigment composition. This can be achieved by using a method using at least two structurally different benzonitrile compounds (hereinafter referred to as “succinic acid diester co-synthesis method”) in the succinic acid diester synthesis method. Specifically, in the method described in Patent Document 5, a plurality of benzonitrile compounds to be used are selected from 4-chlorobenzonitrile and a benzonitrile compound represented by the following formula (2). . I. A DPP pigment composition containing CI Pigment Red 254 and a specific hetero DPP pigment can be produced.

(In the formula (2), A and B are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a cyano group, —CF ₃ , or —CON (R ¹ ) R ² , and at least one of A and B is —CON (R ¹ ) R ^2. R ¹ and R ² are each independently hydrogen An atom, an alkyl group having 1 to 20 carbon atoms, or an optionally substituted phenyl group.)

C. I. Pigment Red 254 and the specific hetero-DPP pigment may be produced separately, but it is desirable to produce a pigment composition by simultaneously synthesizing both by the succinic acid diester co-synthesis method for ease of production. . When using what was manufactured separately, you may mix simply before disperse | distributing 2 types of pigments, and you may grind and mix by a salt milling process.

Succinic acid diester co-synthesis method, C.I. I. When producing a pigment composition containing CI Pigment Red 254 and a specific hetero DPP pigment, 2 mol of a mixture of 4-chlorobenzonitrile and a benzonitrile compound of the formula (2) is reacted with 1 mol of succinic acid diester. Let At this time, the C.I. I. It is necessary to adjust the mixing ratio (molar ratio) of 4-chlorobenzonitrile and the benzonitrile compound of formula (2) so that the mass ratio of Pigment Red 254 and the specific hetero-DPP pigment is 97: 3 to 85:15. There is. Since the reactivity varies depending on the type of benzonitrile compound of formula (2), the mixing ratio (molar ratio) between 4-chlorobenzonitrile and the benzonitrile compound of formula (2) varies. In order to keep the mass ratio of the DPP pigment composition within a desired range, the mixing ratio (molar ratio) of 4-chlorobenzonitrile and the benzonitrile compound of the formula (2) is about 80:20 to 98: 2. Become a range. In the succinic acid diester co-synthesis method, a DPP pigment (that is, a diketopyrrolopyrrole pigment containing no p-chlorophenyl group) in which 2 moles of the benzonitrile compound of the formula (2) is reacted with 1 mole of the succinic acid diester is obtained. Although it may be produced, the mixing ratio in this range is very small, so there is almost no adverse effect.

In the succinic acid diester co-synthesis method, the reaction ratio of the succinic acid diester to the benzonitrile compound is basically 2 mol of the benzonitrile compound with respect to 1 mol of the succinic acid diester. Using an excess of about 25 mol% of the required molar amount relative to the nitrile compound is effective for improving the yield.

In the pigment composition produced by the co-synthesis method of succinic acid diester, C.I. I. The mass ratio between Pigment Red 254 and the specific hetero DPP pigment can be determined by analysis using TOF-MASS, FD-MASS, LC-MASS, or NMR. Alternatively, as disclosed in JP-A-08-199085, a DPP pigment composition is obtained by stirring at room temperature with di-tert-butyl dicarbonate and 4-dimethylaminopyridine in tetrahydrofuran. It may be determined by analysis using NMR, MASS, LC-MASS or the like after conversion to the DPP compound. Alternatively, the hydrogen of the NH group of the pyrrolopyrrole ring may be substituted with an alkyl group using an alkyl halide or the like and converted into soluble DPP, and then determined by the above analysis.

(Dye derivative)
In the DPP pigment composition, a pigment derivative can be used for the purpose of suppressing pigment crystal growth and improving pigment dispersibility. That is, in one embodiment, the DPP pigment composition further contains a dye derivative.
Examples of the dye derivative used include quinacridone derivatives, diketopyrrolopyrrole derivatives, benzoisoindole derivatives, anthraquinone derivatives, dianthraquinone derivatives, thiazine indigo derivatives, azo dye derivatives, and quinophthalone derivatives. Multiple types of dye derivatives may be used.

The structure of the pigment derivative can be represented by the following formula (3), but the pigment derivative is not limited to those represented by these formulas.

In formula (3), P is quinacridone residue, diketopyrrolopyrrole residue, benzoisoindole residue, anthraquinone residue, dianthraquinone residue, thiazineindigo residue, azo dye residue, or quinophthalone residue And
m is an integer of 1 to 4,
Each L is independently —OH; —SO ₃ H, —COOH, a monovalent to trivalent metal salt of these acidic groups, an alkylammonium salt; a phthalimidomethyl group which may have a substituent; or It is a group represented by any of the following formulas (a), (b), (c), (d), (e), and (f).

In the above formula _{(a) ~ (f),} 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,
R ³ and R ⁴ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted alkenyl group having 2 to 30 carbon atoms, or R ³ and R ⁴ together are a heterocyclic ring which may have a substituent, further containing a nitrogen, oxygen or sulfur atom,
R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an optionally substituted carbon. An alkenyl group having a number of 2 to 20,
R ¹⁰ is a substituent represented by the formula (a) or the formula (b),
R ¹¹ is a chlorine atom, —OH, an alkoxyl group, a substituent represented by the formula (a) or the formula (b),
Z is —CONH—, —NHCO—, —SO ₂ NH—, or —NHSO ₂ —;
R ¹² is a hydrogen atom, —NH ₂ , —NHCOCH ₃ , —NHR ¹³ _, or a substituent represented by the formula (c), wherein R ¹³ has 1 to carbon atoms that may have a substituent. An alkyl group having 20 or an alkenyl group having 2 to 20 carbon atoms which may have a substituent.

Examples of the monovalent to trivalent metal in L in the above formula (3) include sodium, potassium, magnesium, calcium, iron, and aluminum.
Alkyl ammonium salts include ammonium salts of long-chain monoalkylamines such as octylamine, laurylamine, or stearylamine, or quaternary compounds such as palmityltrimethylammonium salt, dilauryldimethylammonium salt, or distearyldimethylammonium salt. Examples include alkylammonium salts.
As the phthalimidomethyl group which may have a substituent, the alkyl group which may have a substituent, the alkenyl group which may have a substituent, or the heterocyclic substituent which may have a substituent, A halogen atom, a cyano group, a nitro group, a carbamoyl group, an N-substituted carbamoyl group, a sulfamoyl group, an N-substituted sulfamoyl group, an alkoxyl group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, and the like. However, it is not limited to these. The alkyl group and alkenyl group may be linear or branched.

The dye derivative is a sulfonation reaction by heating in sulfuric acid or fuming sulfuric acid, a phthalimide methylation reaction in which dehydration condensation is performed with N-hydroxymethylphthalimide in sulfuric acid, and chlorosulfonated using chlorosulfonic acid and thionyl chloride. It is synthesized by a known production method such as sulfonamidation reaction in which an amine component such as dimethylaminopropylamine is reacted.

Examples of the amine component used for forming 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 , N-sec-butylpropylamine, dibutylamine, di-sec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisoamylamine, dihexylamine, dicyclohexylamine, di (2-ethylhexyl) ) Amine, dioctylamine, N, -Methyloctadecylamine, didecylamine, diallylamine, N, N-ethyl-1,2-dimethylpropylamine, N, N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine, N, N -Dimethylaminoethylamine, N, N-dimethylaminoamylamine, N, N-dimethylaminobutylamine, N, N-diethylaminoethylamine, N, N-diethylaminopropylamine, N, N-diethylaminohexylamine, N, N-diethylamino Butylamine, N, N-diethylaminopentylamine, N, N-dipropylaminobutylamine, N, N-dibutylaminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-di Sobutylaminopentylamine, N, N-methyl-laurylaminopropylamine, N, N-ethyl-hexylaminoethylamine, N, N-distearylaminoethylamine, N, N-dioleylaminoethylamine, N, N-di Stearylaminobutylamine, piperidine, 2-pipecoline, 3-pipecoline, 4-pipecoline, 2,4-lupetidine, 2,6-lupetidine, 3,5-lupetidine, 3-piperidinemethanol, pipecolic acid, isonipecotic acid, isonipecotic acid Methyl, ethyl isonipecotate, 2-piperidineethanol, pyrrolidine, 3-hydroxypyrrolidine, N-aminoethylpiperidine, N-aminoethyl-4-pipecoline, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropi -2-pipecoline, N-aminopropyl-4-pipecoline, N-aminopropylmorpholine, N-methylpiperazine, N-butylpiperazine, N-methylhomopiperazine, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine, Examples thereof include, but are not limited to, 1-cyclopentylpiperazine and the like.

In the case of introducing a substituent into the azo dye, the azo dye derivative can also be produced by introducing the substituent into a diazo component or a coupling component in advance and then performing a coupling reaction.

The method of using the pigment derivative is to use the DPP pigment composition in a pigment carrier (also referred to as a pigment composition carrier), that is, in a binder resin (in the case of using a resin type dispersant, in a binder resin and a resin type dispersant). In addition to the method of mixing with the pigment composition at the time of dispersion, a method of mixing in water or an organic solvent at the time of pigment production, or a method of adding at the time of salt milling can be mentioned. The method of mixing the pigment derivative in water or an organic solvent at the time of pigment production or the method of adding it at the time of salt milling exhibits the effect of suppressing the crystal growth of the DPP pigment, but exhibits the effect of suppressing the crystal growth. In order to achieve this, it is required that the dye derivative is efficiently adsorbed on the surface of the DPP pigment and does not easily desorb. For this reason, a dye derivative partially having a chemical structure similar to that of the pigment to be used is often selected. For these reasons, dye derivatives having a quinacridone structure, a DPP structure, a thiazine indigo structure, or a benzoisoindole structure are generally effective for DPP pigments.

Furthermore, when a dye derivative is used, it is required that the color tone of the DPP pigment composition is not impaired as much as possible. From the viewpoint of hue, it is preferable to use a DPP derivative, benzoisoindole derivative, thiazineindigo derivative, azo dye derivative, or quinophthalone derivative that exhibits a yellow or orange color.

The compounding amount of the dye derivative is preferably 0.5 parts by mass or more, more preferably 3 parts by mass or more with respect to 100 parts by mass of the pigment in order to sufficiently exhibit the crystal growth inhibiting effect. . On the other hand, in order to maintain a good color tone of the DPP pigment, the amount of the dye derivative is preferably 40 parts by mass or less and more preferably 35 parts by mass or less with respect to 100 parts by mass of the pigment. That is, the blending amount of the dye derivative is preferably in the range of 0.5 to 40% by mass with respect to 100% by mass of the pigment, and more preferably in the range of 3 to 35% by mass with respect to 100% by mass of the pigment. is there.

Hereinafter, although the specific example of a pigment derivative is described, it is not limited to these.
(Specific examples of quinacridone derivatives)
As the quinacridone derivative, specifically, a compound represented by the following formula (4) can be used, but is not limited thereto.

(Specific examples of diketopyrrolopyrrole derivatives)
As the DPP derivative, specifically, a compound represented by the following formula (5) or formula (6) can be used, but is not limited thereto.

(Specific examples of benzoisoindole derivatives)
As the benzoisoindole derivative, specifically, a compound represented by the following formula (7) can be used, but is not limited thereto.

(Specific examples of anthraquinone derivatives)
Specifically as an anthraquinone derivative, the compound represented by following formula (8) can be used, However, It is not limited to these.

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

(Specific examples of thiazine indigo derivatives)
As the thiazineindigo derivative, specifically, a compound represented by the following formula (10) can be used, but is not limited thereto.

(Specific examples of azo dye derivatives)
As the azo dye derivative, specifically, a compound represented by the following formula (11), formula (12), or formula (13) can be used, but is not limited thereto.

(Specific examples of quinophthalone derivatives)
As the quinophthalone derivative, specifically, compounds represented by the following formulas (14-1) to (14-13) can be used, but are not limited thereto.

(Average primary particle diameter of pigment composition)
The DPP pigment composition according to the present invention preferably has a very fine primary particle diameter, a narrow distribution width, and a sharp particle size distribution. The average primary particle diameter (that is, the average primary particle diameter of each pigment particle (and dye derivative) constituting the pigment composition) obtained by TEM (transmission electron microscope) of the DPP pigment composition is calculated as follows. In order to ensure dispersibility, the thickness is preferably 5 nm or more, and in order to obtain a sufficient contrast ratio, it is preferably 70 nm or less. For these reasons, the more preferable average primary particle diameter is 10 nm or more and 40 nm or less. When the average primary particle diameter is in the above range at the stage when the DPP pigment composition is produced by the above synthesis method, it may be used as it is. Otherwise, the pigment is refined and adjusted by a salt milling process or the like. It is desirable to granulate.

(Miniaturization of pigment composition)
A salt milling process is preferable for refining the pigment composition.
Salt milling is a process in which a mixture of a pigment composition, a water-soluble inorganic salt, and a water-soluble organic solvent is heated using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, or sand mill. After mechanically kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt works as a crushing aid, and it is thought that the pigment is crushed using the high hardness of the inorganic salt during salt milling, thereby generating an active surface and causing crystal growth. Yes. Therefore, the crushing of the pigment and the crystal growth occur simultaneously during the kneading, and the primary particle diameter of the pigment obtained varies depending on the kneading conditions.

In order to promote crystal growth by heating, the heating temperature is preferably 35 to 150 ° C. in order to promote appropriate and sufficient crystal growth as a color filter colorant. When the heating temperature is less than 35 ° C., crystal growth does not occur sufficiently, and the shape of the pigment composition particles may become nearly amorphous. On the other hand, when the heating temperature exceeds 150 ° C., crystal growth proceeds. In this case, the primary particle size of the pigment composition becomes large, which is not preferable as a colorant for a color filter.
The kneading time for 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 at the time of subjecting the pigment composition to salt milling, a pigment composition having a sharp particle size distribution with a very fine primary particle diameter and a wide distribution range can be obtained.

As the water-soluble inorganic salt used for the salt milling treatment, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of price. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by mass, and most preferably 300 to 1200 parts by mass, based on the total amount of pigment (100 parts by mass), from the viewpoint of both processing efficiency and production efficiency.

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

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 weight, and most preferably 50 to 500 parts by weight, based on 100 parts by weight of the pigment composition.

When performing the salt milling treatment, a pigment derivative may be used in combination to improve kneading efficiency, which is very effective for making the pigment composition finer and sized. As this pigment derivative, the above-mentioned pigment derivatives are preferably used, but are not limited thereto. The amount of the dye derivative used is preferably such that it does not affect the color tone, that is, in the range of 0.5 to 40 parts by mass with respect to 100 parts by mass of the pigment composition.

Furthermore, when performing the salt milling treatment, a resin may be added as necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin is preferably solid at room temperature, insoluble in water, and more preferably partially soluble in the organic solvent. The amount of 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.

2. Coloring composition (including photosensitive coloring composition)
The DPP pigment composition according to the present invention can be used as a colored composition when used in combination with a binder resin and an organic solvent. This coloring composition is particularly preferably used for a color filter.
That is, this coloring composition contains a coloring agent, a binder resin, and an organic solvent, and this coloring agent contains the DPP pigment composition according to the present invention. As the colorant, a colorant other than the DPP pigment composition (other colorant) may be used in combination.

(Other colorants)
The other colorant is a pigment or dye other than the above DPP pigment composition, and is used in combination as necessary for the purpose of adjusting the chromaticity within the range not impairing the effects of the present invention. It may be a component. Multiple other colorants may be used.

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, 255, 264, 270, 272, 273, 274, 276, 277, 278, 279, Mention may be made of red pigments such as 280, 281, 282, 283, 284, 285, 286 or 287. Examples of red dyes include xanthene series, azo series (pyridone series, barbituric acid series, metal complex series, etc.), disazo series, and anthraquinone series. Specifically, C.I. I. Examples thereof include salt-forming compounds of xanthene acid dyes such as Acid Red 52, 87, 92, 289 and 338.

Also, C.I. I. Pigment orange 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, 82,185,187,188,193,194,198,199,213,214,218,219,220, or may be used in combination of a yellow pigment 221, and the like. Examples of the orange dye and / or yellow dye include quinoline series, azo series (pyridone series, barbituric acid series, metal complex series, etc.), disazo series, and methine series.

Preferred examples of the colorant used in combination include C.I. I. Pigment red 177, 242 and C.I. I. Pigment yellow 139, 150, 185.

In the color composition, when a colorant other than the DPP pigment composition is used in combination, the lightness and contrast ratio are excellent in the total amount of the colorant (total amount of the DPP pigment composition and other colorant) (100% by mass). The DPP pigment composition is preferably in the range of 40% by mass to 100% by mass, more preferably in the range of 60% by mass to 100% by mass, from the viewpoint of sufficiently exhibiting the above effects.

(Binder resin)
Examples of the binder resin contained in the coloring composition include conventionally known thermoplastic resins and thermosetting resins. A plurality of types of binder resins may be used.
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, polyurethane resin Polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resins, 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 developing type colored resist, it is preferable to use an alkali-soluble vinyl resin copolymerized with an acidic group-containing ethylenically unsaturated monomer. 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 resins having an acidic group such as a carboxyl group or a sulfone group. Specific examples of the alkali-soluble resin include 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 Examples include isobutylene / (anhydrous) maleic acid copolymer. Among these, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group, is preferably used because of its high heat resistance and transparency.
Here, “(meth) acrylic acid” refers to both acrylic acid and methacrylic acid, and its derivatives are used in the same meaning.

Energy ray curable resins having ethylenically unsaturated active double bonds include reactive substitution of isocyanate groups, aldehyde groups, epoxy groups, etc. on polymers having reactive substituents such as hydroxyl groups, carboxyl groups, amino groups, etc. A resin in which a photo-crosslinkable group such as a (meth) acryloyl group or a styryl group is introduced into the polymer by reacting a (meth) acrylic compound having a group or cinnamic acid is used. Further, a polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is half-treated with a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. An esterified product is also used.

A thermoplastic resin having both alkali-soluble performance and energy ray curing performance is also preferred as the color filter coloring composition.
The following are mentioned as a monomer which comprises the said thermoplastic resin. Of these, a plurality of types of monomers may be used.

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) Acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, or ethoxypoly Ji glycol (meth) acrylate of (meth) acrylates;
(Meth) acrylamides such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, or acryloylmorpholine ;
Styrenes such as styrene or α-methylstyrene;
Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether; or
And fatty acid vinyls such as vinyl acetate or vinyl propionate.

Alternatively, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane, 1,6-bismaleimidehexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3- Maleimidocoumarin, 4,4′-bismaleimidediphenylmethane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, N, N′-1,3-phenylenedimaleimide, N, N′-1,4 -Phenylenedimaleimide, N- (1-pyrenyl) maleimide, N- (2,4,6-trichlorophenyl) maleimide, N- (4-aminophenyl) maleimide, N- (4-nitrophenyl) maleimide, N- Benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N- Cuccinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimide propionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N- [4- (2-benzimidazolyl) phenyl N-substituted maleimides such as maleimide and 9-maleimide acridine.

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. Especially, an epoxy resin and a melamine resin are used more suitably from a viewpoint of heat resistance improvement.

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 disperse the colorant preferably. 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 obtained by connecting four separation columns in series in the gel permeation chromatography “HLC-8120GPC” manufactured by Tosoh Corporation. This is a polystyrene-equivalent molecular weight measured using “TSK-GEL SUPER H5000”, “H4000”, “H3000”, and “H2000” manufactured by the company and using tetrahydrofuran as the mobile phase.

When the coloring composition is used as a coloring composition for a color filter, in the binder resin, a carboxyl group that acts as a pigment adsorbing group and an alkali-soluble group during development, and an aliphatic group that acts as an affinity group for the pigment carrier and solvent And the balance of aromatic groups is important for pigment dispersibility, developability, and durability. In order to obtain appropriate developability for forming a fine pattern, 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 the developing solution is poor and fine pattern formation may be difficult, and if it exceeds 300 mgKOH / g, the fine pattern may not remain in development.

The amount of the binder resin is preferably 20 parts by mass or more in order to obtain film formability and various resistances based on the total mass of the colorant (that is, with respect to 100 parts by mass of the colorant). In order to ensure the density and color characteristics, the amount is preferably 500 parts by mass or less.

(Organic solvent)
For the coloring composition, the pigment composition is sufficiently dispersed in the pigment composition carrier, and is applied onto a substrate such as a glass substrate so as to have a dry film thickness of 0.2 to 5 μm to form a filter segment. In order to facilitate this, an organic solvent is included. The organic solvent is selected in consideration of good applicability of the coloring composition, solubility of each component of the coloring composition, and safety.

Examples of the organic solvent include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane. 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3- Methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N -Dimethylformamide, n-butyl alcohol, n-butylbenzene, n-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 monotertiary 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 dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether 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, Chill isobutyl ketone, methyl cyclohexanol, acetic acid n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.

Among them, since the solubility of each component of the coloring composition and the coating property of the coloring composition are good, aliphatic hydroxy acid esters such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol It is preferable to use glycol acetates such as monomethyl ether acetate and ethylene glycol monoethyl ether acetate, aromatic alcohols such as benzyl alcohol, and alicyclic ketones such as cyclohexanone.

These organic solvents can be used singly or in combination of two or more. The blending amount of the organic solvent is 500, based on the total mass of the colorant as a reference (100 parts by mass) from the viewpoint of adjusting the colored composition to an appropriate viscosity and forming a filter segment having a desired uniform film thickness. It is preferably used in an amount of ˜4000 parts by mass.

(Pigment dispersion)
The coloring composition is C.I. I. A DPP pigment composition containing Pigment Red 254 and a specific hetero DPP pigment in a specific ratio in a colorant carrier comprising the binder resin and an organic solvent, a kneader, a two-roll mill, a three-roll mill, a ball mill, It can be produced by finely dispersing using various dispersing means such as a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor. Here, the DPP pigment composition and other colorants may be simultaneously dispersed in the colorant carrier, or those separately dispersed in the colorant carrier may be mixed.

When dispersing the colorant in the colorant carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, and a surfactant may be appropriately contained. Since the dispersion aid has a great effect of preventing re-aggregation of the colorant after dispersion, the color composition obtained by dispersing the colorant in the colorant carrier using the dispersion aid has contrast and viscosity stability. Become good.

(Resin type dispersant and surfactant)
The resin-type dispersant has a pigment-affinity part having the property of adsorbing to the colorant and a part compatible with the colorant carrier, and adsorbs to the colorant to disperse the colorant to the colorant carrier. It works to stabilize. Specific examples of resin-type dispersants include 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. , Polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkyleneimines) and polyesters having free carboxyl groups, and their salts Oil-soluble dispersants such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Resin, water-soluble polymer, polyester, modified poly Acrylate-based, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more, not necessarily limited thereto.

As a commercially available resin-type dispersant,
Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, 171, 174, 180, 181 manufactured by Big Chemie Japan 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 Bykumen, etc .;
SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, manufactured by Nippon Lubrizol 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc .;
EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, manufactured by Ciba Japan 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc .;
Ajinomoto Fine Techno Co., Ltd. Ajisper PA111, PB711, PB821, PB822, PB824, etc. are mentioned.

As surfactant,
Sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, monoethanolamine lauryl sulfate Anionic surfactants such as triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, 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;
Chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts;
Examples thereof include amphoteric surfactants such as alkylbetaines such as alkyldimethylaminoacetic acid betaine and alkylimidazolines.
These can be used alone or in admixture of two or more, but are not necessarily limited thereto.

When a resin-type dispersant and / or a surfactant is added, the total amount of the colorant is used as a standard (100 parts by mass), and may be blended in an amount of 0.1 part by mass or more in order to obtain the blending effect. It is preferable to use it in an amount of 55 parts by mass or less in order to obtain appropriate dispersibility. That is, it is preferably 0.1 to 55 parts by mass, and more preferably 0.1 to 45 parts by mass.

The colored composition of the present invention further contains a photopolymerizable monomer and / or a photopolymerization initiator, and can be used as a photosensitive colored composition. In a preferred embodiment, the photosensitive coloring composition is a color filter coloring composition.

(Photopolymerizable monomer)
The photopolymerizable monomer used includes monomers or oligomers that are cured by ultraviolet rays or heat to produce a transparent resin, and these can be used alone or in combination of two or more. The amount of the monomer is preferably 5 to 400 parts by mass based on the total weight of the colorant (100 parts by mass), and more preferably 10 to 300 parts by mass 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, 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 (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, Pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) a Relate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, methylolated melamine (meta ) Various acrylic esters and methacrylic esters such as acrylic esters, epoxy (meth) acrylates, urethane acrylates;
(Meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile and the like. However, it is not necessarily limited to these.

(Photopolymerization initiator)
When a photosensitive coloring composition is cured by ultraviolet irradiation and a filter segment is formed by a photolithographic method, it can be adjusted in the form of a solvent development type or alkali development type colored resist material by adding a photopolymerization initiator. .

As a photopolymerization initiator,
4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2- Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4- Acetophenone compounds such as morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one;
Benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyldimethyl ketal;
Benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3 ', 4,4'-tetra (t-butyl Peroxycarbonyl) benzophenone compounds such as benzophenone;
Thioxanthone compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-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 (trichloro Methyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4 , 6-Bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- (4′-methoxystyryl)- Triazine compounds such as 6-triazine;
1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], or O- (acetyl) -N- (1-phenyl-2-oxo-2- (4 ′ Oxime ester compounds such as -methoxy-naphthyl) ethylidene) hydroxylamine;
Phosphine compounds such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide;
Quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone;
A borate compound; a carbazole compound; an imidazole compound; or a titanocene compound is used.

These photopolymerization initiators can be used alone or as a mixture of two or more at any ratio as required. These photopolymerization initiators are preferably 2 to 200 parts by mass based on the total amount of the colorant in the photosensitive coloring composition (100 parts by mass), and 3 to 3 in terms of photocurability and developability. More preferably, it is 150 parts by mass.

(Sensitizer)
The photosensitive coloring composition can further contain a sensitizer.
Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphyrin derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 ', or 4,4'-tetra (t-butylperoxycarbonyl) benzopheno And 4,4′-diethylaminobenzophenone.

More specifically, edited by Shin Okawara et al., “Dye Handbook” (1986, Kodansha), edited by Shin Okawara et al., “Chemistry of Functional Dye” (1981, CMC), edited by Tadasaburo Ikemori et al. Examples include, but are not limited to, sensitizers described in "Special Functional Materials" (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.

Two or more sensitizers may be used at an arbitrary ratio as necessary. The blending amount when using the sensitizer is preferably 3 to 60 parts by mass based on the total weight (100 parts by mass) of the photopolymerization initiator contained in the photosensitive coloring composition. From the viewpoints of colorability and developability, it is more preferably 5 to 50 parts by mass.

(Amine compounds)
The coloring composition or the photosensitive coloring composition can contain an amine compound that functions to reduce dissolved oxygen. A plurality of types of amine compounds may be used in combination.

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

(Leveling agent)
In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the coloring composition or the photosensitive coloring composition. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by BYK Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. It is also possible to use dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain.
In general, the leveling agent is preferably used in an amount of 0.003 to 0.5% by mass in the total weight (100% by mass) of the colored composition or the photosensitive colored composition.

Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, having a hydrophilic group but low solubility in water, and when added to a coloring composition, It has the feature of low surface tension lowering ability, and also has good wettability to the glass plate even though the surface tension lowering ability is low. In particular, those capable of suppressing the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

The bonding form of polyalkylene oxide units with dimethylpolysiloxane is as follows: pendant type in which polyalkylene oxide units are bonded in repeating units of dimethylpolysiloxane, terminal-modified type in which the end of dimethylpolysiloxane is bonded, and alternating with dimethylpolysiloxane. Any of a linear block copolymer type bonded repeatedly may be used. Dimethylpolysiloxanes having polyalkylene oxide units are 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 thereto.

An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.
Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.

Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts.
Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And ether type or ester type surfactants such as polyethylene glycol monolaurate.
Furthermore, amphoteric surfactants such as alkylbetaines such as alkyldimethylaminoacetic acid betaine and alkylimidazolines may be used, and fluorine or silicone surfactants may be used.

(Curing agent, curing accelerator)
The coloring composition or the photosensitive coloring composition may contain a curing agent and / or a curing accelerator as necessary in order to assist the curing of the thermosetting resin.
As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited to these, and thermosetting resins. Any curing agent may be used as long as it can react with the. Among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine curing agent are preferable. These may be used alone or in combination of two or more.
The curing agent is preferably contained in an amount of 1 to 100 parts by mass with respect to the total amount (100 parts by mass) of the thermosetting resin.

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 amidine compounds and salts thereof (eg Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2- Til-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), guanamine compounds (eg, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (eg, 2,4-diamino-6) -Methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6- And methacryloyloxyethyl-S-triazine / isocyanuric acid adduct). These may be used alone or in combination of two or more.
The content of the curing accelerator is preferably 0.01 to 15 parts by mass with respect to the total amount (100 parts by mass) of the thermosetting resin.

(Other additive components)
The coloring composition or the photosensitive coloring composition may contain a storage stabilizer in order to stabilize the viscosity with time. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.

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

As an adhesion improver,
Vinylsilanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, vinyltrimethoxysilane;
(meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane;
β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3, Epoxy silanes such as 4-epoxycyclohexyl) methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane;
N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-amino Aminosilanes such as propyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane;
Silane coupling agents such as thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane; The adhesion improver is 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on the total amount of the colorant in the coloring composition or photosensitive coloring composition (based on 100 parts by weight of the coloring agent). Can be used.

(Removal of coarse particles)
In the coloring composition and the photosensitive coloring composition, coarse particles having a primary particle size of 5 μm or more, preferably 1 μm or more, more preferably 0, by means of centrifugation, filtration with a sintered filter or a membrane filter, or the like. It is preferable to remove coarse particles of 5 μm or more and mixed dust. Thus, it is preferable that the coloring composition does not substantially contain particles of 0.5 μm or more, and more preferably does not contain particles larger than 0.3 μm (0.3 μm or less).

3. Color filter The color filter which concerns on this invention has a filter segment formed from the coloring composition containing the DPP type pigment composition which concerns on this invention, or a photosensitive coloring composition. That is, the color filter according to the present invention includes a red filter segment, a green filter segment, and a blue filter segment, and the red filter segment contains a DPP pigment composition according to the present invention or a photosensitive coloring. It is formed from a composition.

The green filter segment can be formed using an ordinary green coloring composition containing an arbitrary green pigment and an optional colorant carrier (binder resin and organic solvent, the same applies hereinafter). Examples of the green pigment include C.I. I. Pigment Green 7, 10, 36, 37, 58, etc. are used.

A yellow pigment can be used in combination with the green coloring composition. Examples of yellow pigments 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, 82,185,187,188,193,194,198,199,213,214,218,219,220, or it can be given a yellow pigment 221, and the like. A basic dye exhibiting a yellow color and a salt-forming compound of an acid dye may be used in combination.

The blue filter segment can be formed using a normal blue coloring composition containing an arbitrary blue pigment and an arbitrary colorant carrier. Examples of blue pigments include C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, etc. are used. A purple pigment can be used in combination with the blue coloring composition. Examples of purple pigments that can be used in combination include C.I. I. And violet pigments such as CI Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50. A basic dye exhibiting blue or purple or a salt-forming compound of an acid dye can also be used. When using a dye, a xanthene dye is preferable in terms of heat resistance and lightness.

(Color filter manufacturing method)
The color filter can be manufactured by a printing method or a photolithography method.
The formation of the filter segment by the printing method can be patterned simply by repeating the printing and drying of the coloring composition prepared as the printing ink. Therefore, the color filter manufacturing method is low in cost and excellent in mass productivity. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In order to perform printing, it is preferable that the ink is not dried and solidified on the printing plate or on the blanket. Control of ink fluidity on a printing press is also important, and ink viscosity can be adjusted with a dispersant or extender pigment.

When the filter segment is formed by photolithography, the colored composition prepared as a solvent developing type or alkali developing type colored resist material is applied on a transparent substrate by spray coating, spin coating, slit coating, roll coating or the like. By the method, it is applied so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, after immersing in a solvent or alkali developer or spraying the developer with a spray or the like to remove uncured parts to form a desired pattern, the same operation is repeated for other colors to produce a color filter. can do. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the above printing method can be manufactured.

In the development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution. In order to increase the sensitivity to UV exposure, after coating and drying the colored resist, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Then, ultraviolet exposure can 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 method, and the colored composition or the photosensitive colored composition according to the present invention can be used in any method. . The electrodeposition method is a method for producing a color filter by electrodepositing each color filter segment on a transparent conductive film by electrophoresis of colloidal particles using a transparent conductive film formed on a substrate. 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 this filter segment is transferred to a desired substrate.

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

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples and comparative examples, “part” means “part by mass”.
At the time of producing the pigment composition or the colored composition, as the dye derivative, a DPP derivative of the formula (6-3), a benzoisoindole derivative of the formula (7-1), an anthraquinone derivative of the formula (8-5), and a formula ( The quinophthalone derivative of 14-1) was used.

(Average primary particle diameter of pigment composition)
The average primary particle diameter of the produced pigment composition was measured (calculated) by the following method.
Propylene glycol monomethyl ether acetate was added to the powder of the pigment composition, a small amount of Disperbyk-161 was added as a resin-type dispersant, and the sample for measurement was prepared by treatment with ultrasonic waves for 1 minute. This sample was taken with a transmission (TEM) electron microscope and three photographs (for 3 fields of view) showing the primary particles of 100 or more pigments were taken, and the size of 100 primary particles was measured in order from the upper left. did. Specifically, the short axis diameter and the long axis diameter of the primary particles of each pigment are measured in nm units, the average is the primary particle diameter of the pigment particles, and a total of 300 distributions are created in increments of 5 nm. A median value in increments of 5 nm (for example, 8 nm in the case of 6 nm or more and 10 nm or less) was approximated as the particle diameter of those particles, and the number average particle diameter was calculated by calculating based on each particle diameter and the number thereof.

1. Production of specific heterodiketopyrrolopyrrole pigment (production of compound formula (15))
The compound of the following formula (15) was synthesized by the method described in Tetrahedron, 58 (2002) 5547-5565.

(Specific Heterodiketopyrrolopyrrole Pigment Formula (1-1a) Production)
While adding 220 parts of tert-amyl alcohol to the reaction vessel 1 and cooling with a water bath, 32 parts of 60% NaH was added and heated and stirred at 90 ° C. Next, 200 parts of tert-amyl alcohol, 93.0 parts of the compound of the above formula (15), and 54.8 parts of 4-carbamoylbenzonitrile are placed in the reaction vessel 2 and heated at 80 ° C. It was dripped over 2 hours. After reacting at 120 ° C. for 10 hours, cooling to 60 ° C., adding 400 parts of methanol and 50 parts of acetic acid, followed by filtration, washing with methanol and drying, the specificity represented by formula (1-1a) 58.3 parts of hetero-DPP pigment were obtained.
(Identification method of specific hetero DPP pigment)
The identification of the specific hetero-DPP pigment is performed by using the MALDI mass spectrometer autoflex II (hereinafter referred to as TOF-MS) manufactured by Bruker Daltonics, Inc., with the coincidence between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. Identified.
As a result of mass spectrometry by TOF-MS, the m / Z value was 365.09, and it was identified as a specific hetero DPP pigment represented by the formula (1-1a). The following specific hetero DPP compounds were similarly identified for the synthesized products.

(Production of Specific Heterodiketopyrrolopyrrole Pigment Formula (1-1b))
Except that 54.8 parts of 4-carbamoylbenzonitrile was changed to 75.8 parts of 4- (butylcarbamoyl) benzonitrile, the production was carried out in the same manner as in the production of the specific hetero DPP pigment of the formula (1-1a). -1b) to obtain 65.9 parts of the specific hetero DPP pigment.

(Production of Specific Heterodiketopyrrolopyrrole Pigment Formula (1-1c))
Under a nitrogen atmosphere, 200 parts of toluene was placed in a reaction vessel equipped with a reflux tube, 99.4 parts of 4-cyanobenzoyl chloride was added, and the mixture was heated and stirred at 90 ° C. Next, 79.5 parts of dibutylamine was added dropwise to the reaction vessel over 1 hour. After reacting at 100 ° C. for 4 hours, the mixture was cooled to room temperature, and extracted by adding 500 parts of ethyl acetate and 500 parts of 2N aqueous sodium hydroxide solution. Extraction was performed by adding 500 parts of saturated saline to the organic layer. Further, activated carbon and sodium sulfate were added to the obtained organic layer, and the mixture was filtered through Celite, and the solvent was removed to obtain 135.5 parts of a compound of the following formula (2-1c).

While adding 220 parts of tert-amyl alcohol to the reaction vessel 1 and cooling with a water bath, 32 parts of 60% NaH was added and heated and stirred at 90 ° C. Next, 200 parts of tert-amyl alcohol, 93.0 parts of the compound of the above formula (15), and 98.2 parts of the benzonitrile compound of the above formula (2-1c) are placed in the reaction vessel 2 and dissolved by heating. The reaction vessel 1 was added dropwise over 2 hours. After reacting at 120 ° C. for 10 hours, cooling to 60 ° C., adding 400 parts of methanol and 50 parts of acetic acid, followed by filtration, washing with methanol and drying, the specificity represented by formula (1-1c) 74.1 parts of hetero-DPP pigment were obtained.

(Production of specific heterodiketopyrrolopyrrole pigment formula (1-1d))
Under a nitrogen atmosphere, 200 parts of toluene was placed in a reaction vessel equipped with a reflux tube, 99.4 parts of 4-cyanobenzoyl chloride was added, and the mixture was heated and stirred at 90 ° C. Next, 79.5 parts of octylamine was added dropwise to the reaction vessel over 1 hour. After reacting at 100 ° C. for 4 hours, the mixture was cooled to room temperature, and extracted by adding 500 parts of ethyl acetate and 500 parts of 2N aqueous sodium hydroxide solution. Extraction was performed by adding 500 parts of saturated saline to the organic layer. Furthermore, activated carbon and sodium sulfate were added to the obtained organic layer, and the mixture was filtered through Celite, and the solvent was removed to obtain 127.9 parts of 4- (octylcarbamoyl) benzonitrile.

While adding 220 parts of tert-amyl alcohol to the reaction vessel 1 and cooling with a water bath, 32 parts of 60% NaH was added and heated and stirred at 90 ° C. Next, 200 parts of tert-amyl alcohol, 93.0 parts of the compound of the above formula (15), and 98.2 parts of 4- (octylcarbamoyl) benzonitrile are placed in a reaction vessel 2 and dissolved by heating. Over 2 hours. After reacting at 120 ° C. for 10 hours, cooling to 60 ° C., adding 400 parts of methanol and 50 parts of acetic acid, followed by filtration, washing with methanol and drying, the specificity represented by the formula (1-1d) 68.3 parts of hetero-DPP pigment were obtained.

(Production of specific heterodiketopyrrolopyrrole pigment formula (1-1 g))
Under a nitrogen atmosphere, 100 parts of toluene was placed in a reaction vessel equipped with a reflux tube, 33.1 parts of 4-cyanobenzoyl chloride was added, and the mixture was heated and stirred at 90 ° C. Subsequently, 56.6 parts of octadecylamine was dripped at reaction container over 1 hour. After reacting at 100 ° C. for 4 hours, the mixture was cooled to room temperature, and extracted by adding 400 parts of ethyl acetate and 400 parts of 2N aqueous sodium hydroxide solution. Extraction was performed by adding 400 parts of saturated saline to the organic layer. Furthermore, activated carbon and sodium sulfate were added to the obtained organic layer, and the mixture was filtered through Celite, and the solvent was removed to obtain 73.3 parts of 4- (octadecylcarbamoyl) benzonitrile.

Into the reaction vessel 1, 66.0 parts of tert-amyl alcohol was added and 10 parts of 60% NaH was added while cooling in a water bath, and the mixture was heated and stirred at 90 ° C. Next, 60 parts of tert-amyl alcohol, 27.9 parts of the compound of the above formula (15), and 45.7 parts of 4- (octadecylcarbamoyl) benzonitrile are placed in the reaction vessel 2 and dissolved by heating. Over 2 hours. After reacting at 120 ° C. for 10 hours, cooling to 60 ° C., adding 120 parts of methanol and 15 parts of acetic acid, followed by filtration, washing with methanol and drying, the specificity represented by the formula (1-1 g) 19.8 parts of hetero-DPP pigment were obtained.

(Production of Specific Heterodiketopyrrolopyrrole Pigment Formula (1-1h))
Except that 54.8 parts of 4-carbamoylbenzonitrile was changed to 82.2 parts of 4-cyano-N-phenylbenzamide, the production was carried out in the same manner as in the production of the specific hetero DPP pigment of the formula (1-1a). -1 h), 63.4 parts of a specific hetero-DPP pigment represented by formula (1) was obtained.

(Production of Specific Heterodiketopyrrolopyrrole Pigment Formula (1-2c))
Under a nitrogen atmosphere, 100 parts of toluene was placed in a reaction vessel equipped with a reflux tube, 49.7 parts of 3-cyanobenzoyl chloride was added, and the mixture was heated and stirred at 90 ° C. Subsequently, 39.8 parts of dibutylamine was dripped at reaction container over 1 hour. After reacting at 100 ° C. for 4 hours, the mixture was cooled to room temperature, and extracted by adding 500 parts of ethyl acetate and 500 parts of 2N aqueous sodium hydroxide solution. Extraction was performed by adding 500 parts of saturated saline to the organic layer. Further, activated carbon and sodium sulfate were added to the obtained organic layer, and the mixture was filtered through Celite, and the solvent was removed to obtain 67.8 parts of a compound of the following formula (2-2c).

While adding 110 parts of tert-amyl alcohol to the reaction vessel 1 and cooling in a water bath, 16 parts of 60% NaH was added, and the mixture was heated and stirred at 90 ° C. Next, 100 parts of tert-amyl alcohol, 46.5 parts of the compound of the above formula (15), and 49.1 parts of the benzonitrile compound of the above formula (2-2c) are placed in the reaction vessel 2 and dissolved by heating. The reaction vessel 1 was added dropwise over 2 hours. After reacting at 120 ° C. for 10 hours, the mixture is cooled to 60 ° C., 200 parts of methanol and 25 parts of acetic acid are added, and then filtered, washed with methanol and dried, and the specific formula represented by formula (1-2c) 26.1 parts of hetero-DPP pigment were obtained.

(Production of Specific Heterodiketopyrrolopyrrole Pigment Formula (1-2d))
Under a nitrogen atmosphere, 100 parts of toluene was placed in a reaction vessel equipped with a reflux tube, 49.7 parts of 3-cyanobenzoyl chloride was added, and the mixture was heated and stirred at 90 ° C. Next, 39.8 parts of octylamine was added dropwise to the reaction vessel over 1 hour. After reacting at 100 ° C. for 4 hours, the mixture was cooled to room temperature, and extracted by adding 500 parts of ethyl acetate and 500 parts of 2N aqueous sodium hydroxide solution. Extraction was performed by adding 500 parts of saturated saline to the organic layer. Further, activated carbon and sodium sulfate were added to the obtained organic layer and the mixture was filtered through Celite, and the solvent was removed to obtain 65.2 parts of 3- (octylcarbamoyl) benzonitrile.

While adding 110 parts of tert-amyl alcohol to the reaction vessel 1 and cooling in a water bath, 16 parts of 60% NaH was added, and the mixture was heated and stirred at 90 ° C. Next, 100 parts of tert-amyl alcohol, 46.5 parts of the compound of the above formula (15), and 49.1 parts of 3- (octylcarbamoyl) benzonitrile are placed in the reaction vessel 2 and dissolved by heating. Over 2 hours. After reacting at 120 ° C. for 10 hours, cooling to 60 ° C., adding 200 parts of methanol and 25 parts of acetic acid, followed by filtration, washing with methanol and drying, are performed as specified by the formula (1-2d) 27.4 parts of hetero DPP pigment were obtained.

(Production of specific heterodiketopyrrolopyrrole pigment formula (1-2e))
Except that 54.8 parts of 4-carbamoylbenzonitrile was changed to 82.2 parts of 3-cyano-N-phenylbenzamide, the production was carried out in the same manner as in the production of the specific hetero DPP pigment of the formula (1-1a). -2e) to obtain 57.3 parts of a specific hetero DPP pigment.

2. Production of diketopyrrolopyrrole pigment (production of diketopyrrolopyrrole pigment formula (16))
The same procedure as in the production of the specific hetero DPP pigment of the formula (1-1a) except that 54.8 parts of 4-carbamoylbenzonitrile was changed to 66.3 parts of 4-cyanobiphenyl was represented by the following formula (16). 65.9 parts of DPP pigment were obtained.

3. Production of diketopyrrolopyrrole pigment composition <Example 1>
(Production of Pigment Composition 1 (R-1))
C. I. 100 parts of a 95/5 (mass ratio) mixture of CI Pigment Red 254 and the specific hetero DPP pigment of the formula (1-1a), 1000 parts of sodium chloride, and 120 parts of diethylene glycol are made of 1 gallon kneader (manufactured by Inoue Seisakusho). It was charged in and kneaded at 60 ° C for 10 hours. Next, the kneaded mixture is poured into warm water, stirred for 1 hour while heating to about 80 ° C. to form a slurry, filtered and washed with water to remove salt and diethylene glycol, and then dried at 80 ° C. for 24 hours, and then pulverized. As a result, 97.1 parts of Pigment Composition 1 (R-1) was obtained. The average primary particle size was 29.5 nm.

<Example 2>
(Production of Pigment Composition 2 (R-2))
Pigment composition 2 was prepared in the same manner as in the production of pigment composition 1 (R-1) except that the specific hetero DPP pigment of formula (1-1a) was changed to the specific hetero DPP pigment of formula (1-1b). (R-2) 96.4 parts were obtained. The average primary particle size was 27.5 nm.

<Example 3>
(Production of Pigment Composition 3 (R-3))
C. I. Except that the mixing ratio of Pigment Red 254 and the specific hetero-DPP pigment of the formula (1-1c) was changed to 97/3 (mass ratio), it was carried out in the same manner as in the production of pigment composition 1 (R-1). 97.2 parts of pigment composition 3 (R-3) was obtained. The average primary particle size was 30.2 nm.

<Example 4>
(Production of Pigment Composition 4 (R-4))
Pigment composition 4 was prepared in the same manner as in the production of pigment composition 1 (R-1), except that the specific hetero DPP pigment of formula (1-1a) was changed to the specific hetero DPP pigment of formula (1-1c). 95.8 parts of (R-4) was obtained. The average primary particle size was 26.9 nm.

<Example 5>
(Production of Pigment Composition 5 (R-5))
C. I. Pigment Red 254 and the specific hetero DPP pigment of formula (1-1c) were used in the same manner as in the preparation of Pigment Composition 1 (R-1) except that 100 parts of a 90/10 (mass ratio) mixture was used. 95.2 parts of composition 5 (R-5) was obtained. The average primary particle size was 25.2 nm.

<Example 6>
(Production of Pigment Composition 6 (R-6))
C. I. Pigment Red 254 and the specific hetero DPP pigment of formula (1-1c) were used in the same manner as in the production of Pigment Composition 1 (R-1) except that 100 parts of a 85/15 (mass ratio) mixture was used. 96.2 parts of composition 6 (R-6) were obtained. The average primary particle size was 27.7 nm.

<Example 7>
(Production of Pigment Composition 7 (R-7))
Pigment composition 7 was prepared in the same manner as in the production of pigment composition 1 (R-1) except that the specific hetero DPP pigment of formula (1-1a) was changed to the specific hetero DPP pigment of formula (1-1d). 97.8 parts of (R-7) was obtained. The average primary particle size was 25.9 nm.

<Example 8>
(Production of Pigment Composition 8 (R-8))
Except that the specific hetero DPP pigment of the formula (1-1c) was changed to the specific hetero DPP pigment of the formula (1-1d), the same procedure as in the production of the pigment composition 6 (R-6) was carried out, and a pigment composition 8 95.7 parts of (R-8) was obtained. The average primary particle size was 28.9 nm.

<Example 9>
(Production of Pigment Composition 9 (R-9))
Pigment composition 9 was carried out in the same manner as in the production of pigment composition 1 (R-1) except that the specific hetero DPP pigment of formula (1-1a) was changed to the specific hetero DPP pigment of formula (1-1g). 96.4 parts of (R-9) was obtained. The average primary particle size was 32.5 nm.

<Example 10>
(Production of Pigment Composition 10 (R-10))
Pigment composition 10 was prepared in the same manner as in the production of pigment composition 1 (R-1) except that the specific hetero DPP pigment of formula (1-1a) was changed to the specific hetero DPP pigment of formula (1-1h). 97.2 parts of (R-10) were obtained. The average primary particle size was 28.5 nm.

<Example 11>
(Production of Pigment Composition 11 (R-11))
Pigment composition 11 was prepared in the same manner as in the production of pigment composition 6 (R-6) except that the specific hetero DPP pigment of formula (1-1c) was changed to the specific hetero DPP pigment of formula (1-1h). 96.5 parts of (R-11) was obtained. The average primary particle size was 26.9 nm.

<Example 12>
(Production of Pigment Composition 12 (R-12))
Except that the specific hetero DPP pigment of the formula (1-1a) was changed to the specific hetero DPP pigment of the formula (1-2c), the same procedure as in the production of the pigment composition 1 (R-1) was carried out. 95.9 parts of (R-12) was obtained. The average primary particle size was 31.2 nm.

<Example 13>
(Production of Pigment Composition 13 (R-13))
Except that the specific hetero DPP pigment of the formula (1-1a) was changed to the specific hetero DPP pigment of the formula (1-2d), the same procedure as in the production of the pigment composition 1 (R-1) was carried out, and the pigment composition 13 96.6 parts of (R-13) was obtained. The average primary particle size was 32.7 nm.

<Example 14>
(Production of Pigment Composition 14 (R-14))
Except that the specific hetero DPP pigment of the formula (1-1a) was changed to the specific hetero DPP pigment of the formula (1-2e), the same procedure as in the production of the pigment composition 1 (R-1) was carried out. 97.3 parts of (R-14) was obtained. The average primary particle size was 30.9 nm.

<Example 15>
(Production of Pigment Composition 15 (R-15))
C. I. 100 parts of a 95/5 (mass ratio) mixture of CI Pigment Red 254 and a specific hetero DPP pigment of formula (1-1c), 3.0 parts of a pigment derivative of a benzoisoindole derivative of formula (7-1), sodium chloride 1000 parts and 120 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 10 hours. Next, the kneaded mixture is poured into warm water, stirred for 1 hour while heating to about 80 ° C. to form a slurry, filtered and washed with water to remove salt and diethylene glycol, and then dried at 80 ° C. overnight for grinding. As a result, 99.8 parts of pigment composition 15 (R-15) was obtained. The average primary particle size was 24.1 nm.

<Example 16>
(Production of Pigment Composition 16 (R-16))
To a stainless steel reaction vessel equipped with a reflux tube, 200 parts of tert-amyl alcohol dehydrated with molecular sieves and 140 parts of sodium tert-amyl alkoxide are added in a nitrogen atmosphere, and heated to 100 ° C. with stirring to obtain an alcoholate solution. Prepared. Meanwhile, 88 parts of diisopropyl succinate, 110.1 parts of 4-chlorobenzonitrile and 11.2 parts of the benzonitrile compound of the formula (2-1c) are added to a glass flask and heated to 90 ° C. with stirring. Dissolved to prepare solutions of these mixtures. The heated solution of the mixture was slowly dropped into the alcoholate solution heated to 100 ° C. at a constant rate over 2 hours with vigorous stirring. After completion of the dropwise addition, heating and stirring were continued at 90 ° C. for 2 hours to obtain an alkali metal salt of a DPP compound. Further, 600 parts of methanol, 600 parts of water, and 304 parts of acetic acid were added to a glass jacketed reaction vessel, and cooled to −10 ° C. While rotating the shear disk having a diameter of 8 cm at 4000 rpm using a high-speed stirring disperser, the cooled mixture was cooled to 75 ° C., and the previously obtained alkali metal salt solution of the DPP compound was Small portions were added. At this time, the rate of addition of the alkali metal salt of the DPP compound at 75 ° C. is adjusted while cooling so that the temperature of the mixture of methanol, acetic acid and water is always kept at −5 ° C. or lower. While being added in small portions over approximately 120 minutes. After addition of the alkali metal salt, red crystals were precipitated to form a red suspension. Subsequently, the obtained red suspension was washed with an ultrafiltration device at 5 ° C. and then filtered to obtain a red paste. This paste was re-dispersed in 3500 parts of methanol cooled to 0 ° C. to make a suspension with a methanol concentration of about 90%, and stirred at 5 ° C. for 3 hours to perform particle sizing and washing with crystal transition. Subsequently, the resultant was separated by an ultrafiltration machine, and the obtained DPP compound aqueous paste was dried at 80 ° C. for 24 hours and pulverized to obtain 110.8 parts of a DPP pigment composition.

C. of the obtained DPP pigment composition I. As a result of quantitative analysis using HPLC for the content of Pigment Red 254 and the specific hetero DPP pigment represented by Formula (1-1c), C.I. I. The mass ratio of Pigment Red 254 to the specific hetero DPP pigment of the formula (1-1c) was 94.1 / 5.9.

Subsequently, 96.8 parts of pigment composition 16 (R-16) were obtained in the same manner as in the production of pigment composition 1 (R-1) except that 100.0 parts of the obtained DPP pigment composition was used. It was. The average primary particle size was 26.5 nm.

<Comparative Example 1>
(Production of Pigment Composition 17 (R-17))
Without using a specific hetero DPP pigment, I. Pigment composition 17 (R-17) 97.3 parts were obtained in the same manner as in the production of pigment composition 1 (R-1) except that 100.0 parts of Pigment Red 254 was used alone. The average primary particle size was 33.9 nm.

<Comparative Example 2>
(Production of Pigment Composition 18 (R-18))
C. I. The same procedure as in the preparation of Pigment Composition 1 (R-1) was conducted except that 100 parts of a 70/30 (mass ratio) mixture of CI Pigment Red 254 and the specific hetero DPP pigment of the formula (1-1c) was used. 95.1 parts of product 18 (R-18) was obtained. The average primary particle size was 29.9 nm.

<Comparative Example 3>
(Production of Pigment Composition 19 (R-19))
C. I. Pigment composition was prepared in the same manner as in Pigment Composition 1 (R-1) except that 100 parts of a 30/70 (mass ratio) mixture of CI Pigment Red 254 and the specific hetero DPP pigment of formula (1-1c) was used. 95.8 parts of product 19 (R-19) were obtained. The average primary particle size was 38.8 nm.

<Comparative example 4>
(Production of Pigment Composition 20 (R-20))
Except that the specific hetero DPP pigment of the formula (1-1c) was changed to the specific hetero DPP pigment of the formula (1-1d), the same procedure as in the production of the pigment composition 18 (R-18) was performed, and the pigment composition 20 96.3 parts of (R-20) was obtained. The average primary particle size was 34.8 nm.

<Comparative Example 5>
(Production of Pigment Composition 21 (R-21))
Except that the specific hetero DPP pigment of the formula (1-1c) was changed to the specific hetero DPP pigment of the formula (1-1h), the same procedure as in the production of the pigment composition 18 (R-18) was carried out, and a pigment composition 21 96.1 parts of (R-21) was obtained. The average primary particle size was 29.7 nm.

<Comparative Example 6>
(Production of Pigment Composition 22 (R-22))
Except that the specific hetero DPP pigment of the formula (1-1a) was changed to a DPP pigment of the formula (16), it was carried out in the same manner as in the production of the pigment composition 1 (R-1), and the pigment composition 22 (R-22). ) 95.9 parts were obtained. The average primary particle size was 29.4 nm.

<Comparative Example 7>
(Production of Pigment Composition 23 (R-23))
Except that the specific hetero DPP pigment of the formula (1-1c) was changed to the DPP pigment of the formula (16), the same procedure as in the production of the pigment composition 6 (R-6) was carried out, and the pigment composition 23 (R-23) ) 96.6 parts were obtained. The average primary particle size was 27.5 nm.

The contents of the produced DPP pigment compositions 1 to 23 (R-1 to 23) are shown in Table 1. “PR254” described in Table 1 is C.I. I. Pigment Red 254 is meant.

4). Manufacture of other pigments (Manufacture of dianthraquinone pigment 1 (PR177-1))
90 parts of a dianthraquinone pigment (CI Pigment Red 177), 900 parts of sodium chloride and 110 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 10 hours. Next, the kneaded mixture is poured into warm water, stirred for 1 hour while heating to about 80 ° C. to form a slurry, filtered and washed with water to remove salt and diethylene glycol, and then dried at 80 ° C. overnight for grinding. As a result, 85.0 parts of anthraquinone pigment 1 (PR177-1) were obtained. The average primary particle size was 38.2 nm.

5. Manufacture of binder resin solution (Preparation of acrylic resin solution 1)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirring device was charged with 196 parts of cyclohexanone, heated to 80 ° C., and purged with nitrogen in the reaction vessel. 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 Toagosei Co., Ltd.) 20.7 And a mixture of 1.1 parts of 2,2′-azobisisobutyronitrile were added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. The methoxypropyl acetate was added to the previously synthesized resin solution so that the non-volatile content was 20% by mass. Was added to prepare an acrylic resin solution 1. The weight average molecular weight (Mw) was 26000.

(Preparation of acrylic resin solution 2)
207 parts of cyclohexanone was charged into a reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer, and the temperature was raised to 80 ° C. From the tube, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei 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 dropping, the reaction was further continued for 3 hours to obtain a copolymer resin solution. Next, after the nitrogen gas was stopped and the mixture was stirred while injecting dry air for 1 hour with respect to the total amount of the copolymer solution obtained, the mixture was cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Karenz manufactured by Showa Denko KK). MOI) A mixture of 6.5 parts, 0.08 part dibutyltin laurate and 26 parts cyclohexanone was added dropwise at 70 ° C. over 3 hours. After completion of the dropwise addition, the reaction was further continued for 1 hour to obtain an acrylic resin solution. After cooling to room temperature, sample 2 parts of the resin solution, heat dry at 180 ° C. for 20 minutes, measure the nonvolatile content, and add cyclohexanone to the previously synthesized resin solution so that the nonvolatile content is 20% by mass. Thus, an acrylic resin solution 2 was prepared. The weight average molecular weight (Mw) was 18000.

(Weight average molecular weight of binder resin)
The weight average molecular weight of the acrylic resin is a polystyrene equivalent weight average molecular weight measured by GPC (gel permeation chromatography).

6). Preparation of coloring composition using diketopyrrolopyrrole pigment composition <Example 17>
(Preparation of colored composition 1 (RP-1))
A mixture having the following composition is uniformly stirred and mixed, dispersed with Picomill (manufactured by Asada Tekko Co., Ltd.) for 8 hours using zirconia beads having a diameter of 0.1 mm, filtered through a 5 μm filter, and colored composition 1 (RP-1) was produced.
DPP pigment composition 1 (R-1) 11.0 parts Dye derivative (14-1) 1.0 part Acrylic resin solution 1 40.0 parts Propylene glycol monomethyl ether acetate 48.0 parts

<Examples 18 to 32>
(Preparation of colored compositions 2 to 16 (RP-2 to 16))
Colored compositions 2 to 16 (RP-2 to 16) were the same as colored composition 1 (RP-1) except that pigment composition 1 (R-1) was changed to the pigment composition shown in Table 2. Was made.

<Example 33>
(Preparation of colored composition 17 (RP-17))
A colored composition 17 (RP-17) was produced in the same manner as the colored composition 1 (RP-1) except that a mixture having the following composition was used.
DPP pigment composition 4 (R-4) 11.0 parts DPP dye derivative of formula (6-3) 1.0 part Resin-type dispersant (BYK161, 30% solution manufactured by BYK Chemie) 6.0 parts Acrylic Resin solution 1 31.0 parts Propylene glycol monomethyl ether acetate 51.0 parts

<Comparative Examples 8-14>
(Preparation of colored compositions 18 to 24 (RP-18 to 24))
Colored compositions 18 to 24 (RP-18 to 24) were prepared in the same manner as colored composition 1 (RP-1), except that pigment composition 1 (R-1) was changed to the pigment composition shown in Table 2. Produced.

7. Preparation of other colored compositions (Preparation of colored composition 25 (RP-25))
A coloring composition 25 (RP-25) for toning was prepared in the same manner as the coloring composition 1 (RP-1) except that the mixture having the following composition was used.
Dianthraquinone pigment (PR177-1) 10.8 parts Anthraquinone dye derivative of formula (8-5) 1.2 parts Acrylic resin solution 1 40.0 parts Propylene glycol monomethyl ether acetate 48.0 parts

8). Preparation of photosensitive coloring composition <Example 34>
(Preparation of photosensitive coloring composition 1 (RR-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare photosensitive coloring composition 1 (RR-1).
Coloring composition 1 (RP-1) 38.1 parts Coloring composition 25 (RP-25) 3.9 parts Acrylic resin solution 2 13.2 parts Photopolymerizable monomer ("Aronix M400" manufactured by Toagosei Co., Ltd.) 2.8 parts Photopolymerization initiator (“Irgacure 907” manufactured by Ciba Japan) 2.0 parts Sensitizer (“EAB-F” manufactured by Hodogaya Chemical Co., Ltd.) 0.4 part Ethylene glycol monomethyl ether acetate 39. 6 copies

<Examples 35 to 50>
(Preparation of photosensitive coloring compositions 2 to 17 (RR-2 to 17))
Coloring composition 1 (RP-1) was changed to coloring compositions 2 to 17 (RP-2 to 17), and further, coloring compositions 2 to 17 (RP-2 to 17) and coloring composition 25 (RP-25) ) Was changed in the same manner as in Example 34 except that the ratio was changed within 42 parts of the total amount of the colored composition. Photosensitive colored compositions 2 to 17 (RP-2 to 17) were produced. As for the ratio change, coloring compositions 2 to 17 (RP-2 to 17) are colored so as to match the chromaticity of x = 0.640 and y = 0.336 with a C light source during coating film evaluation. The ratio of composition 25 (RP-25) was changed.

<Comparative Examples 15 to 21>
(Preparation of photosensitive coloring compositions 18 to 24 (RR-18 to 24))
The coloring composition 1 (RP-1) is changed to the coloring compositions 18 to 24 (RP-18 to 24), and further the coloring compositions 18 to 24 (RP-18 to 24) and the coloring composition 25 (RP-25). ) Was changed in the same manner as in Example 34 except that the ratio was changed within 42 parts of the total amount of the colored composition. Photosensitive colored compositions 18 to 24 (RR-18 to 24) were produced. As for the ratio change, coloring compositions 18 to 24 (RP-18 to 24) are colored so as to match the chromaticity of x = 0.640 and y = 0.336 with a C light source during coating film evaluation. The ratio of composition 25 (RP-25) was changed.

9. Preparation and evaluation of coating film using photosensitive coloring composition Evaluation of color characteristics, contrast ratio, and crystal precipitation due to heat of red coating film prepared using photosensitive coloring composition (RR-1 to 24) obtained. The following method was used. Table 3 shows the types and evaluation results of the coloring composition in the photosensitive coloring composition.

(Evaluation of color characteristics of coating film)
On a glass substrate of 100 mm × 100 mm and 0.7 mm thickness, a photosensitive coloring composition is applied to a film thickness such that x = 0.640 and y = 0.336 using a C light source, and after drying, ultrahigh pressure mercury An ultraviolet ray of 300 mJ / cm ² was irradiated using a lamp. Furthermore, the red coating film was obtained by heating at 230 degreeC for 60 minutes. Thereafter, the lightness (Y) of the obtained coating film was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.).

(Evaluation of contrast ratio of coating film)
A method for measuring the contrast ratio of the coating film will be described. The light emitted from the backlight unit for liquid crystal display is polarized through the polarizing plate, passes through the dried coating film of the colored composition applied on the glass substrate, and reaches the polarizing plate. If the polarizing planes of the polarizing plate and the polarizing plate are parallel, light is transmitted through the polarizing plate, but if the polarizing plane is perpendicular, the light is blocked by the polarizing plate. However, when the light polarized by the polarizing plate passes through the dried coating film of the colored composition, scattering by the pigment particles occurs, and when a part of the polarization plane is displaced, the polarized light is polarized when the polarizing plate is parallel. When the amount of light transmitted through the plate is reduced and the polarizing plate is perpendicular, a part of the light is transmitted through the polarizing plate. This transmitted light was measured as the luminance on the polarizing plate, and the ratio (contrast ratio) between the luminance when the polarizing plate was parallel and the luminance when it was orthogonal was calculated.
(Contrast ratio) = (Luminance when parallel) / (Luminance when direct)
Accordingly, when scattering occurs due to the pigment in the coating film, the brightness when parallel is reduced and the brightness when perpendicular is increased, 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. In the measurement, a black mask with a 1 cm square hole was applied to the measurement portion in order to block unnecessary light. For the contrast ratio measurement, a red coating film obtained by the same method as that used in the color characteristic evaluation was used.

(Evaluation of crystal precipitation on the coating surface)
A photosensitive coloring composition is applied to a glass substrate having a thickness of x = 0.640 using a C light source on a glass substrate having a size of 100 mm × 100 mm and 0.7 mm, dried, and then dried using an ultrahigh pressure mercury lamp. Irradiation with ultraviolet rays of cm 2 was performed. Subsequently, heat treatment was performed at 230 ° C. for 60 minutes, and then heat treatment at 240 ° C. for 60 minutes was repeated twice. The coating film surface of 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.
A: Heat treatment at 230 ° C. for 60 minutes, no crystal precipitation even after the first heat treatment at 240 ° C. for 60 minutes, and the second heat treatment at 240 ° C. for 60 minutes B: Heat treatment at 230 ° C. for 60 minutes and the first heat treatment at 240 ° C. No crystal precipitation even after 60 minutes of heat treatment (crystallized by second heat treatment at 240 ° C. for 60 minutes)
C: No crystal precipitation after heat treatment at 230 ° C. for 60 minutes, but there is crystal precipitation after the first heat treatment at 240 ° C. for 60 minutes D: Crystal precipitation after heat treatment at 230 ° C. for 60 minutes

From the results in Table 3, C.C. I. Examples using a DPP pigment composition containing Pigment Red 254 and a specific hetero DPP pigment in a specific ratio (mass ratio 97: 3 to 85:15) are particularly excellent in contrast ratio, It was found that high brightness can be maintained and crystal precipitation of the DPP pigment due to the heating process can be suppressed.

In the comparison of Example 34, Example 35, Example 37, Example 40, Example 42, and Example 43, it has a substituent that can be expected to have a steric hindrance effect such as an alkyl group having 4 or more carbon atoms or a phenyl group. This was found to be more effective in increasing the contrast ratio and suppressing crystal precipitation.

On the other hand, C.I. I. When the pigment combined with Pigment Red 254 is a DPP-containing pigment of the formula (16) and is not a specific hetero DPP pigment, as shown in Comparative Examples 20 and 21, the contrast ratio is inferior and crystal precipitation is suppressed. The effect also declined.
In the comparison of Examples 36 to 39 and Comparative Examples 15 to 17, the lightness decreases as the content ratio of the specific hetero DPP pigment of the formula (1-1c) increases, but the crystal precipitation suppressing effect tends to increase. It has been found that there is an optimum point for the contrast ratio, and that the brightness and contrast ratio can be balanced by controlling the content ratio of the specific hetero DPP pigment. Further, by comparing Example 37 and Example 48, it was found that the dye derivative treatment was effective in increasing the contrast ratio.

In the comparison between Example 37 and Example 49, a pigment composition produced by a succinic acid diester co-synthesis method and C.I. I. It was found that the same effect was obtained with a pigment composition prepared by separately synthesizing Pigment Red 254 and a specific hetero DPP pigment and mixing them during the salt milling treatment.

10. Preparation of color filter Green photosensitive coloring composition and blue photosensitive coloring composition used for preparation of a color filter were prepared. For red, the photosensitive coloring composition 4 (RR-4) was used.

(Preparation of green coloring composition 1 (GP-1))
The mixture having the composition shown below was uniformly stirred and mixed, dispersed with picomil for 8 hours using zirconia beads having a diameter of 0.1 mm, filtered through a 5 μm filter, and green colored composition 1 (GP-1) Was made.
Green pigment (CI Pigment Green 36) 6.8 parts Yellow pigment (CI Pigment Yellow 150) 5.2 parts Resin type dispersant ("EFKA4300" manufactured by Ciba Japan) 1.0 part Acrylic resin Solution 1 35.0 parts Propylene glycol monomethyl ether acetate 52.0 parts

(Preparation of green photosensitive coloring composition 1 (GR-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to produce 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 Toagosei Co., Ltd.) 2.8 parts Photopolymerization initiator (Ciba Japan) "Irgacure 907" manufactured by the company) 2.0 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts 39.6 parts ethylene glycol monomethyl ether acetate

(Preparation of blue coloring composition 1 (BP-1))
The mixture having the composition shown below was uniformly stirred and mixed, dispersed with picomil for 8 hours using zirconia beads having a diameter of 0.1 mm, filtered through a 5 μm filter, and blue colored composition 1 (BP-1) Was made.
Blue pigment (CI Pigment Blue 15: 6) 7.2 parts Purple Pigment (CI Pigment Violet 23) 4.8 parts Resin-type dispersant ("EFKA4300" manufactured by Ciba Japan) 1.0 part Acrylic resin solution 1 35.0 parts Propylene glycol monomethyl ether acetate 52.0 parts

(Preparation of blue photosensitive coloring composition 1 (BR-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare 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 Toagosei Co., Ltd.) 3.3 parts Photopolymerization initiator (Ciba Japan) "Irgacure 907" manufactured by the company) 2.0 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts 45.1 parts ethylene glycol monomethyl ether acetate

A black matrix is patterned on a glass substrate, and photosensitive coloring composition 4 (RR-4) is applied onto the substrate with a spin coater so that x = 0.640 and y = 0.336. Then, a colored film was formed. The coating was irradiated with 300 mJ / cm ² of ultraviolet rays through a photomask using an ultrahigh pressure mercury lamp. Next, spray development was performed with an alkaline developer composed of a 0.2% by weight aqueous sodium carbonate solution to remove unexposed portions, followed by washing with ion-exchanged water. The substrate was heated at 230 ° C. for 20 minutes to obtain a red filter segment. Formed.
By the same method, the green photosensitive coloring composition 1 (GR-1) was formed to a thickness such that x = 0.300 and y = 0.600, and the blue photosensitive coloring composition 1 (BR-1) was added. The film was applied in such a film thickness as x = 0.150 and y = 0.060 to form a green filter segment and a blue filter segment to obtain a color filter.

By using the photosensitive coloring composition 4 (RR-4), it was possible to produce a color filter having high brightness and high contrast ratio and no crystal precipitation in the heating process.

The disclosure of the present application is related to the subject matter described in Japanese Patent Application No. 2011-044576 filed on Mar. 2, 2011, the entire disclosure of which is incorporated herein by reference.
It should be noted that various modifications and changes may be made to the above-described embodiments without departing from the novel and advantageous features of the present invention other than those already described. Accordingly, all such modifications and changes are intended to be included within the scope of the appended claims.

Claims

C. I. Pigment red 254, and a diketopyrrolopyrrole pigment represented by the following formula (1):
C. above. I. A diketopyrrolopyrrole pigment composition for color filters, wherein the mass ratio of CI Pigment Red 254 and the diketopyrrolopyrrole pigment represented by the following formula (1) is 97: 3 to 85:15.

(In the formula (1), A and B are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a cyano group, —CF 3 , or —CON (R 1 ) R 2 , and at least one of A and B is —CON (R 1 ) R 2. R 1 and R 2 are each independently hydrogen An atom, an alkyl group having 1 to 20 carbon atoms, or an optionally substituted phenyl group.)
The diketopyrrolopyrrole pigment represented by the formula (1) includes a diketopyrrolopyrrole pigment represented by the following formula (1-1), and a diketopyrrolopyrrole represented by the following formula (1-2). The diketopyrrolopyrrole pigment composition for color filters according to claim 1, comprising at least one of the pigments.

(In Formula (1-1) and Formula (1-2), R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an optionally substituted phenyl. Group.)
The substituent of the phenyl group is selected from the group consisting of a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a cyano group, a trifluoromethyl group, a nitro group, a carbamoyl group, and a sulfamoyl group. The diketopyrrolopyrrole pigment composition for a color filter according to claim 1 or 2, which is one or more selected groups.
The diketopyrrolopyrrole pigment composition for color filters according to any one of claims 1 to 3, further comprising a dye derivative.
Contains a colorant, a binder resin, and an organic solvent,
A color composition for a color filter, wherein the colorant contains the diketopyrrolopyrrole pigment composition according to any one of claims 1 to 4.
The coloring composition for a color filter according to claim 5, further comprising a photopolymerizable monomer and / or a photopolymerization initiator.
A color filter comprising a filter segment formed from the coloring composition for a color filter according to claim 5 or 6.