JP5659823B2 - Color filter pigment composition, coloring composition, and color filter - Google Patents

Description

  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 becomes possible, and since it has recently been used in televisions and personal computer monitors, it has higher brightness, higher contrast, The demand for 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 hundred microns, and is arranged in a predetermined arrangement for each hue. ing.

  Generally, in a color liquid crystal display device, a transparent electrode for driving a liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for aligning the 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. Therefore, 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 for color filters.

  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 that is particularly excellent in lightness, but further improvement in lightness is desired. In recent years, there has been a strong demand for high contrast for color filters. For this purpose, it is necessary to make the primary particle diameter 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.

  By the way, the diketopyrrolopyrrole pigment can be obtained by a production method disclosed in Patent Literature 1 and Patent Literature 2 (hereinafter referred to as “succinic acid ester synthesis method”). Patent Document 3 discloses a method of 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. However, this document does 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, the description does not fully describe the usefulness in color filter applications.

  In Patent Document 5 and Patent Document 6, a diketopyrrolopyrrole pigment (mainly CI Pigment Red 254), a diaryl diketopyrrolopyrrole compound having at least one specific structural formula, and a pigment derivative are combined. A coloring composition for a color filter, which is used and has high contrast and crystal precipitation caused by a heating process, is disclosed. However, although these methods have improved the contrast and heat resistance to some extent, further improvements have been desired regarding the brightness.

  Patent Document 7 discloses a coloring composition for a color filter using a brominated diketopyrrolopyrrole pigment, but does not describe any lightness improving effect of the brominated diketopyrrolopyrrole pigment. Patent Document 8 describes that a brominated diketopyrrolopyrrole pigment composition is used for a color filter. However, the description does not sufficiently describe the effect of the structure and composition ratio in the brominated diketopyrrolopyrrole pigment composition.

JP 58-210084 Japanese Patent Application Laid-Open No. 07-90189 JP-A-61-120861 Special table 2007-514798 gazette WO2009 / 081930 pamphlet JP 2009-149707 A JP 1999-231516 A WO2009 / 144115 pamphlet

  The problem to be solved by the present invention is a pigment composition for a color filter, a coloring composition, and a high lightness and high contrast, which do not cause crystal precipitation of a diketopyrrolopyrrole pigment even by a heating process, and use thereof It is to provide a color filter.

  As a result of intensive studies, the present inventors have found that C.I. I. It has been found that the brightness is improved by applying a brominated diketopyrrolopyrrole pigment to a color filter instead of Pigment Red 254 (chlorinated diketopyrrolopyrrole pigment). Further, a pigment composition containing the brominated diketopyrrolopyrrole pigment and a diketopyrrolopyrrole pigment having a substituent introduced asymmetrically (hereinafter referred to as “specific hetero diketopyrrolopyrrole pigment”) in a specific ratio. As a result, it was found that a color filter with high brightness, high contrast, and suppressed crystal precipitation due to a heating process was obtained, and the present invention was achieved.

  That is, the present invention relates to a diketopyrrolopyrrole pigment represented by the following formula (1) and a diketopyrrolopyrrole pigment composition for color filters containing the diketopyrrolopyrrole pigment represented by the formula (2). In which the mass ratio of the formula (1) to the formula (2) is 97: 3 to 85:15, which relates to a diketopyrrolopyrrole pigment composition for a color filter.

[In Formula (2),
A is a hydrogen atom . Of B, an alkyl group having 1 to 12 carbon atoms, which may have a substituent phenyl ^{_{group, -CF 3, -OR 1, -SR}} 2, -CONH 2, -CONHR 6 , or -CON, (R ⁷⁾ R ^8, is,
R ¹ , R ² , R ^{6 to} R ⁸ are each independently an alkyl group having 1 to 12 carbon atoms, a phenyl group which may have a substituent, or an aralkyl group which may have a substituent. It is . ]

  In the present invention, the above formula (2) is replaced by the following formula (2-1), formula (2-2), formula (2-3), formula (2-4), formula (2-5), formula The diketopyrrolopyrrole pigment composition for color filters, which is either (2-6) or formula (2-7).

[In Formula (2-4), Formula (2-6), and Formula (2-7),
R ^{12 to} R ¹⁵ are each independently an alkyl group having 1 to 12 carbon atoms or a phenyl group which may have a substituent. ]

The present invention further relates to the above-described diketopyrrolopyrrole pigment composition for color filters, which further contains a dye derivative.

  Further, 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. About.

  The present invention further relates to a color filter coloring composition characterized by further containing a photopolymerizable monomer and / or a photopolymerization initiator.

  Moreover, this invention relates to the color filter characterized by including the filter segment formed from the said coloring composition for color filters.

  According to the present invention, there is provided a color filter pigment composition, a color composition, and a color filter using the same, which have high brightness and high contrast 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.
Note that “CI” described below means a color index (CI).

(Diketopyrrolopyrrole pigment composition)
The present invention relates to a diketopyrrolopyrrole pigment composition for color filters containing a brominated diketopyrrolopyrrole pigment of the following formula (1) and a specific hetero diketopyrrolopyrrole pigment of the following formula (2): ) And the formula (2) are in the range of 97: 3 to 85:15 in the diketopyrrolopyrrole pigment composition for color filters.

[式（２）中、
Ａは、水素原子である。Ｂは、炭素数１〜１２のアルキル基、置換基を有してもよいフェニル基、−ＣＦ₃、−ＯＲ¹、−ＳＲ² 、−ＣＯＮＨ₂、−ＣＯＮＨＲ⁶、または−ＣＯＮ（Ｒ⁷）Ｒ⁸、であり、
Ｒ¹ 、Ｒ ² 、Ｒ ⁶ 〜Ｒ⁸は、それぞれ独立して、炭素数１〜１２のアルキル基、置換基を有してもよいフェニル基、または、置換基を有してもよいアラルキル基である。]

[In Formula (2),
A is a hydrogen atom . Of B, an alkyl group having 1 to 12 carbon atoms, which may have a substituent phenyl ^{_{group, -CF 3, -OR 1, -SR}} 2, -CONH 2, -CONHR 6 , or -CON, (R ⁷⁾ R ^8, is,
R ¹ , R ² , R ^{6 to} R ⁸ are each independently an alkyl group having 1 to 12 carbon atoms, a phenyl group which may have a substituent, or an aralkyl group which may have a substituent. It is . ]

  The alkyl group having 1 to 12 carbon atoms may be linear or branched. Specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl Group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, 1,5-dimethylhexyl group, 1,6-dimethylheptyl group, 2-ethylhexyl group, etc., but are not limited thereto. Absent.

  Examples of the phenyl group which may have a substituent include an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, a halogen atom, a nitro group, a cyano group, a carbamoyl group, a sulfamoyl group, and an alkoxyl having 1 to 4 carbon atoms. And a phenyl group having a substituent such as a group. More specifically, phenyl group, p-methylphenyl group, 4-tert-butylphenyl group, p-nitrophenyl group, p-methoxyphenyl group, p-chlorophenyl group, 2,4-dichlorophenyl group, 3-carbamoyl Examples thereof include, but are not limited to, a phenyl group.

  Specific examples of the aralkyl group that may have a substituent include a benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group, and 2,4- Examples include, but are not limited to, a dichlorobenzyl group.

  Specific examples of the specific heterodiketopyrrolopyrrole pigment of the formula (2) that can be used in the present invention are listed below, but are not limited thereto.

  In Formula (2) used for the pigment composition of the present invention, Formula (2-1), Formula (2-2), Formula (2-4a), Formula (2-6b), Formula (2-7), etc. Is preferable from the viewpoints of hue, contrast, and crystal precipitation suppression effect.

  The ratio of the formula (1) and the formula (2) in the pigment composition of the present invention is characterized by being in the range of 97: 3 to 85:15 by mass ratio. When the ratio of the formula (2) exceeds 15% by mass, the crystal precipitation suppressing effect can be obtained, but the excellent color tone of the formula (1) is impaired. This is due to the fact that the specific hetero diketopyrrolopyrrole pigment of the formula (2) is inferior in color tone to the brominated diketopyrrolopyrrole pigment of the formula (1). On the other hand, when the ratio of the formula (2) is less than 3% by mass, the effect of increasing the contrast 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 the diketopyrrolopyrrole pigment composition in the above mass ratio range, high brightness and high contrast can be achieved, and crystal precipitation of the diketopyrrolopyrrole pigment can be suppressed even by the heating step.

(Production method of diketopyrrolopyrrole pigment)
The brominated diketopyrrolopyrrole pigment of formula (1) can be produced by a succinic diester synthesis method. That is, 2 moles of 4-bromobenzonitrile per mole 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 at a high temperature of 80 to 110 ° C. Performing a condensation reaction to produce an alkali metal salt of a diketopyrrolopyrrole compound, and then protonating the alkali metal salt of the diketopyrrolopyrrole compound with water, alcohol, acid, etc. Brominated diketopyrrolopyrrole pigments 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. The production method of the brominated diketopyrrolopyrrole pigment is not limited to this method.

  Specific heterodiketopyrrolopyrrole pigments of formula (2) are described, for example, in the literature Synth. Commun. , 1988, 18, 1213 and Tetrahedron, 58 (2002) 5547-5565. The method for producing the specific heterodiketopyrrolopyrrole pigment is not limited to this method.

  Moreover, the brominated diketopyrrolopyrrole pigment of the formula (1) and the specific hetero diketopyrrolopyrrole pigment of the formula (2) can be simultaneously produced as a fine pigment composition. This can be achieved by using a method using at least two structurally different benzonitrile compounds in the succinic acid diester synthesis method (hereinafter referred to as “succinic acid diester co-synthesis method”). Specifically, in the method described in Patent Document 5, a plurality of benzonitrile compounds to be used are selected from 4-bromobenzonitrile and a benzonitrile compound represented by the following formula (3). The diketopyrrolopyrrole pigment composition of the invention can be produced.

[In Formula (3),
A is a hydrogen atom . Of B, an alkyl group having 1 to 12 carbon atoms, which may have a substituent phenyl ^{_{group, -CF 3, -OR 1, -SR}} 2, -CONH 2, -CONHR 6 , or -CON, (R ⁷⁾ R ^8, is,
R ¹ , R ² , R ^{6 to} R ⁸ are each independently an alkyl group having 1 to 12 carbon atoms, a phenyl group which may have a substituent, or an aralkyl group which may have a substituent. It is . ]

  Specific examples of the benzonitrile compound of the above formula (3) that can be used in the present invention are listed below, but are not limited thereto.

  The pigment composition of the present invention may be prepared by separately mixing a brominated diketopyrrolopyrrole pigment and a specific hetero diketopyrrolopyrrole pigment, but from the viewpoint of ease of production, a succinic acid diester cosynthesis method may be used. It is desirable to produce a pigment composition at the same time. 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.

  When a pigment composition of brominated diketopyrrolopyrrole of formula (1) and a specific hetero diketopyrrolopyrrole of formula (2) is produced by a succinic acid diester cosynthesis method, 4 moles per mole of succinic acid diester 2 mol of a mixture of bromobenzonitrile and a benzonitrile compound of the formula (3) is reacted. At this time, 4-bromobenzonitrile and formula (3) are used so that the mass ratio of formula (1) and formula (2) in the resulting diketopyrrolopyrrole pigment composition is 97: 3 to 85:15. It is necessary to adjust the mixing ratio (molar ratio) with the benzonitrile compound. Since the reactivity varies depending on the type of benzonitrile compound of formula (3), the mixing ratio (molar ratio) of 4-bromobenzonitrile and formula (3) varies. In order to keep the mass ratio of the diketopyrrolopyrrole pigment composition within a desired range, the mixing ratio (molar ratio) of 4-bromobenzonitrile and formula (3) is generally in the range of 80:20 to 98: 2. become. In the succinic acid diester co-synthesis method, a diketopyrrolopyrrole pigment obtained by reacting 2 moles of the benzonitrile compound of formula (3) with respect to 1 mole of the succinic acid diester (that is, a diketopyrrolopyrrole pigment not containing a bromine atom). May be produced, but since the amount is very small, there is almost no adverse effect.

  In the succinic acid diester co-synthesis method, the reaction ratio of the succinic acid diester and the benzonitrile compound is basically 2 mol of the benzonitrile compound with respect to 1 mol of the succinic acid diester. Use in excess is effective for improving the yield.

  In the pigment composition produced by the succinic acid diester co-synthesis method, the mass ratio of the brominated diketopyrrolopyrrole pigment to the specific hetero diketopyrrolopyrrole pigment uses TOF-MASS, FD-MASS, LC-MASS or NMR. Can be analyzed. Alternatively, as disclosed in JP-A-08-199085, a diketopyrrolopyrrole pigment composition is obtained by stirring at room temperature with di-tert-butyl dicarbonate and 4-dimethylaminopyridine in tetrahydrofuran. After conversion into a soluble diketopyrrolopyrrole compound, analysis using NMR, MASS, LC-MASS, or the like may be performed. Alternatively, the above analysis may be performed after the hydrogen of the NH group of the pyrrolopyrrole ring is substituted with an alkyl group using an alkyl halide or the like and converted to a soluble diketopyrrolopyrrole.

(Dye derivative)
In the diketopyrrolopyrrole pigment composition of the present invention, a dye derivative can be used for the purpose of suppressing pigment crystal growth and improving pigment dispersibility. Examples of the dye derivatives used in the present invention include diketopyrrolopyrrole derivatives, benzoisoindole derivatives, anthraquinone derivatives, dianthraquinone derivatives, thiazine indigo derivatives, azo dye derivatives, quinophthalone derivatives, and quinacridone derivatives. Examples of the structure of the dye derivative include, but are not limited to, the dye derivative represented by the following formula (4).

[In Formula (4),
P is a diketopyrrolopyrrole residue, a benzoisoindole residue, an anthraquinone residue, a dianthraquinone residue, a thiazine indigo residue, an azo dye residue, a quinophthalone residue, or a quinacridone residue;
m is an integer of 1 to 4,
L is independently —OH; —SO ₃ H, —COOH, a monovalent to trivalent metal salt or alkylammonium salt of these acidic groups; a phthalimidomethyl group which may have a substituent; A group represented by (a), (b), (c), (d), (e), or (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 ¹⁶ and R ¹⁷ 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 ¹⁶ and R ¹⁷ are a heterocyclic ring which may have a substituent, which further contains a nitrogen, oxygen or sulfur atom,
R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted carbon atom. An alkenyl group of 2 to 20,
R ²³ is a substituent represented by formula (a) or formula (b),
R ²⁴ is a substituent represented by a chlorine atom, —OH, an alkoxyl group, formula (a), or formula (b);
Z is —CONH—, —NHCO—, —SO ₂ NH—, or —NHSO ₂ —;
R ²⁵ is a hydrogen atom, —NH ₂ , —NHCOCH ₃ , —NHR ₂₆ , or a substituent represented by the formula (c), wherein R ₂₆ has 1 to 1 carbon atoms which may have a substituent. It is a C2-C20 alkenyl group which may have a 20 alkyl group and a substituent. ]

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

  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, , Halogen atoms, nitro groups, cyano groups, carbamoyl groups, N-substituted carbamoyl groups, sulfamoyl groups, N-substituted sulfamoyl groups, alkoxy groups having 1 to 20 carbon atoms, alkylthio groups having 1 to 20 carbon atoms, and the like. However, it is not limited to these.

  The dye derivative is a sulfonation reaction by heating in sulfuric acid or fuming sulfuric acid, a phthalimide methylation reaction in which dehydration condensation with N-hydroxymethylphthalimide is carried out 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 to form the substituent represented by the above formula (a), formula (b), and formula (c) include dimethylamine, diethylamine, methylethylamine, N, N-ethyl. Isopropylamine, N, N-ethylpropylamine, N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butylethylamine, N, N-tert-butylethylamine, diisopropylamine, dipropylamine, N , N-sec-butylpropylamine, dibutylamine, di-sec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisoamylamine, dihexylamine, dicyclohexylamine, di (2-ethylhexyl) ) Amine, dioctylamine, N, N Methyl octadecylamine, didecylamine, diallylamine, N, N-ethyl-1,2-dimethylpropylamine, N, N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine, N, N- Dimethylaminoethylamine, N, N-dimethylaminoamylamine, N, N-dimethylaminobutylamine, N, N-diethylaminoethylamine, N, N-diethylaminopropylamine, N, N-diethylaminohexylamine, N, N-diethylaminobutylamine N, N-diethylaminopentylamine, N, N-dipropylaminobutylamine, N, N-dibutylaminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-di Butylaminopentylamine, N, N-methyl-laurylaminopropylamine, N, N-ethyl-hexylaminoethylamine, N, N-distearylaminoethylamine, N, N-dioleylaminoethylamine, N, N-distearyl Aminobutylamine, piperidine, 2-pipecoline, 3-pipecoline, 4-pipecoline, 2,4-lupetidine, 2,6-lupetidine, 3,5-lupetidine, 3-piperidinemethanol, pipecolic acid, isonipecotic acid, methyl isonipecotate , Ethyl isonipecotate, 2-piperidineethanol, pyrrolidine, 3-hydroxypyrrolidine, N-aminoethylpiperidine, N-aminoethyl-4-pipecoline, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl 2-pipecoline, N-aminopropyl-4-pipecoline, N-aminopropylmorpholine, N-methylpiperazine, N-butylpiperazine, N-methylhomopiperazine, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine, 1 -Cyclopentyl piperazine etc. are mentioned, However, It is not limited to these.

  In addition, when a substituent is introduced into the azo dye, the azo dye derivative can be produced by introducing the substituent into a diazo component or a coupling component in advance and then performing a coupling reaction.

  In addition to the method of mixing the diketopyrrolopyrrole pigment composition with the pigment composition when it is dispersed in the pigment carrier, the method of using the pigment derivative is not limited to the method of mixing in water or an organic solvent during the production of the pigment or the salt. The method of adding at the time of a milling process is 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 diketopyrrolopyrrole pigment, but the effect of suppressing the crystal growth In order to exhibit the above, it is required that the dye derivative is efficiently adsorbed on the surface of the diketopyrrolopyrrole pigment and is not easily desorbed. For this reason, the structure of the pigment derivative is often considered to have a partial chemical structure similar to the pigment used. For these reasons, when producing a diketopyrrolopyrrole pigment, a dye derivative having a diketopyrrolopyrrole structure, a thiazineindigo structure, a benzoisoindole structure, or a quinacridone structure is generally effective. is there.

  Moreover, when using a pigment derivative, it is required not to impair the color tone of the diketopyrrolopyrrole pigment composition as much as possible. From the viewpoint of hue, it is preferable to use diketopyrrolopyrrole derivatives, benzoisoindole derivatives, thiazineindigo derivatives, azo dye derivatives, or quinophthalone derivatives that exhibit yellow and orange colors.

It is preferable that the compounding quantity of a pigment derivative is the range of 0.5-40 mass% with respect to 100 mass% of pigments. More preferably, it is the range of 3-35 mass% with respect to 100 mass% of pigments.
When the amount is 0.5% by mass or less, the crystal growth suppressing effect is not sufficient, and when it is 40% by mass or more, the good color tone of the diketopyrrolopyrrole pigment is impaired.

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

(Specific examples of diketopyrrolopyrrole derivatives)
As the diketopyrrolopyrrole 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.

(Specific examples of quinacridone derivatives)
As the quinacridone derivative, specifically, a compound represented by the following formula (15) can be used, but is not limited thereto.

(Average primary particle diameter of pigment)
The diketopyrrolopyrrole pigment composition of the present invention needs to have a very fine primary particle diameter, a narrow distribution width, and a sharp particle size distribution. The average primary particle diameter determined by TEM (transmission electron microscope) of the diketopyrrolopyrrole pigment composition of the present invention is preferably in the range of 5 to 70 nm. If it is smaller than 5 nm, dispersion in an organic solvent becomes difficult. On the other hand, if it exceeds 70 nm, a sufficient contrast ratio cannot be obtained. For these reasons, a more preferable range is 10 to 40 nm. When the average primary particle diameter is in the above range at the stage when the diketopyrrolopyrrole pigment composition is produced by the above synthesis method, it may be used as it is. It is desirable to perform sizing and sizing.

(Miniaturization of pigment)
A salt milling treatment is preferable for the refinement of the pigment composition of the present invention.

  Salt milling is a process in which a mixture of pigment, water-soluble inorganic salt and 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 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. When the heating temperature is less than 35 ° C., crystal growth does not occur sufficiently, and the shape of the pigment particles becomes undesirably close to amorphous. On the other hand, when the heating temperature exceeds 150 ° C., crystal growth proceeds excessively and the primary particle diameter of the pigment increases, which is not preferable as a color filter colorant. 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 for salt milling the pigment, it is possible to obtain a pigment having a sharp particle size distribution with a very fine primary particle diameter and a wide distribution range.

  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 cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000% by mass, and most preferably 300 to 1200% by mass, based on the total amount of pigment (100% by mass) in terms 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 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 mass, and most preferably 50 to 500 parts by mass with respect to 100 parts by mass of the pigment.

  In the salt milling treatment, a pigment derivative may be used in combination to improve the kneading efficiency, which is very effective for making the pigment finer and sized. In the refinement of the diketopyrrolopyrrole pigment composition used in the present invention, it is preferable to use the dye derivative, but the invention is not limited to these. The amount of the dye derivative used is preferably such that it does not affect the color tone, that is, a range of 0.5 to 40% by mass with respect to 100% by mass of the pigment.

  Moreover, when performing a salt milling process, you may add resin as needed. 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 used is solid at room temperature, preferably insoluble in water, and more preferably partially soluble in the organic solvent. It is preferable that the usage-amount of resin is the range of 5-200 mass parts with respect to 100 mass parts of pigments.

  The diketopyrrolopyrrole pigment composition of the present invention can be used as a colored composition when used in combination with a binder resin and an organic solvent. Moreover, you may use together coloring agents other than the diketopyrrolopyrrole pigment composition of this invention.

(Other colorants)
The coloring composition of the present invention may be used in combination with a pigment or dye other than the diketopyrrolopyrrole pigment composition as long as the effects of the present invention are not impaired in order to adjust the chromaticity.

  For example, C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 146, 168, 169, 176, 177, 178, 179, 184, 185, 187, 200, 202, 208, 210, 242, 246, 254, 255, 264, 270, 272, 273, 274, 276, 277, 278, Mention may be made of red pigments such as 279, 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. And salt forming compounds of xanthene acid dyes such as Acid Red 52, 87, 92, 289 and 338.

  In addition, 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, 181 182,185,187,188,193,194,198,199,213,214,218,219,220, or a yellow pigment 221 and the like can be used in combination. 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 colorants to be used in combination are C.I. I. Pigment red 177, 254, 242, C.I. I. Pigment yellow 139, 150, and 185.

  When a colorant other than the diketopyrrolopyrrole pigment composition is used in combination, the diketopyrrolopyrrole pigment composition of the present invention is in the range of 40% by mass to 100% by mass in the total amount of the colorant (100% by mass). It is preferable. More preferably, it is the range of 60 mass%-100 mass%. When the diketopyrrolopyrrole pigment composition of the present invention is 40% by mass or less, the effect of excellent brightness and contrast ratio cannot be sufficiently exhibited.

(Binder resin)
Examples of the binder resin contained in the colored composition of the present invention include conventionally known thermoplastic resins and thermosetting resins.

  Examples of the thermoplastic resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, and polyurethane resin. Polyester 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, the spectral transmittance is preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Moreover, when using with the form of an alkali image development type colored resist, it is preferable to use the alkali-soluble vinyl resin which copolymerized the 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.

  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. In addition, polymers containing acid anhydrides such as styrene-maleic anhydride copolymer and α-olefin-maleic anhydride copolymer are half-esterified with a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. A modified version is also used.

  A thermoplastic resin having both alkali-soluble performance and energy ray curing performance is also preferable as the photosensitive coloring composition for color filters.

The following are mentioned as a monomer which comprises the said thermoplastic resin. 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,
Alternatively, (meth) acrylamide (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, acryloylmorpholine, etc. Acrylamides, styrenes, styrenes such as α-methylstyrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, fatty acid vinyls such as vinyl acetate or vinyl propionate Kind.

  Alternatively, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimide ethane 1,6-bismaleimidehexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide Coumarin, 4,4′-bismaleimide diphenylmethane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, N, N′-1,3-phenylenedimaleimide, N, N′-1,4- Phenylene dimaleimide, N- (1-pyrenyl) maleimide, N- (2,4,6-trichlorophenyl) maleimide, N- (4-aminophenyl) maleimide, N- (4-nitrophenyl) maleimide, N-benzyl Maleimide, N-bromomethyl-2,3-dichloromaleimide, N-sc N-imidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, 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 resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins. 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 connected to 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 binder resin is used as a coloring composition for a color filter, an aliphatic group and an aromatic group which act as an affinity group for a pigment adsorbing group and an alkali-soluble group during development, a pigment carrier and a solvent. The balance is important for pigment dispersibility, developability, and durability, and it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g. When the acid value is less than 20 mgKOH / g, the solubility in the developing solution is poor and it is difficult to form a fine pattern. When it exceeds 300 mgKOH / g, a fine pattern does not remain by development.

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

(Organic solvent)
In the colored composition of the present invention, the pigment is sufficiently dispersed in a pigment carrier, and applied to a glass substrate or the like so as to have a dry film thickness of 0.2 to 5 μm to form a filter segment. In order to facilitate, 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, Louis Seo 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, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl It is preferable to use glycol acetates such as ether acetate, aromatic alcohols such as benzyl alcohol, and ketones such as cyclohexanone.

  These organic solvents can be used individually by 1 type or in mixture of 2 or more types. Moreover, since the organic solvent can adjust the coloring composition to an appropriate viscosity and can form a filter segment with a desired uniform film thickness, the total mass of the colorant is based on 100 mass%, and is 500 to 4000 mass. % Is preferably used.

(Pigment dispersion)
The coloring composition of the present invention comprises a diketopyrrolopyrrole pigment composition containing a brominated diketopyrrolopyrrole pigment and a specific hetero diketopyrrolopyrrole pigment in a specific ratio, the binder resin and an organic solvent. It can be produced by finely dispersing in a colorant carrier using various dispersing means such as a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor. . In addition, the coloring composition of the present invention may be obtained by simultaneously dispersing a diketopyrrolopyrrole pigment composition and other colorants in a colorant carrier, or separately mixing them in a colorant carrier. Also good.

  Further, 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 a 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. , Polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amides formed by reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, and salts thereof Oil-soluble dispersants such as, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid 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.

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, and 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155, or Anti-Terra-U, 203, 204, or BYK -SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 160 manufactured by Nippon Lubrizol Corporation, such as P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykumen, etc. 0, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc. -EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, manufactured by Japan 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7 54,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

  Surfactants include 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 Anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and these can be used alone or in admixture of two or more, but are not necessarily limited thereto.

  In the case of adding a resin-type dispersant and a surfactant, the total amount of the colorant is based on (100% by mass), preferably 0.1 to 55% by mass, more preferably 0.1 to 45% by mass. . When the blending amount of the resin-type dispersant and the surfactant is less than 0.1% by mass, it is difficult to obtain the added effect. When the blending amount is more than 55% by mass, the dispersion is affected by an excessive dispersant. May affect.

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

(Photopolymerizable monomer)
The photopolymerizable monomer used in the photosensitive coloring composition of the present invention includes a monomer or an oligomer that forms a transparent resin by being cured by ultraviolet rays or heat, and these are used alone or in combination of two or more. It can be used by mixing. The amount of the monomer is preferably 5 to 400% by weight based on the total weight of the colorant (100% by weight), and more preferably 10 to 300% by weight from the viewpoint of photocurability and developability. preferable.

  Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycy Ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodeca Nyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate ester, epoxy (meth) acrylate, urethane acrylate and other acrylic esters and methacrylate esters, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl Examples include, but are not necessarily limited to, til (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.

(Photopolymerization initiator)
In the photosensitive coloring composition of the present invention, when the composition is cured by ultraviolet irradiation and a filter segment is formed by a photolithography method, a photopolymerization initiator is added to add a photopolymerization initiator to a solvent developing type or alkali developing type coloring resist material. It can be adjusted in the form.

  Examples of the photopolymerization initiator include 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 Acetophenone compounds such as-[4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzoin, benzoin Methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or Benzoin compounds such as dimethyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3 ', 4 Benzophenone compounds such as 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone, etc. 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxy) Phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloro) Methyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(4-Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- Triazine compounds such as (4′-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime) )], Or oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6- Phosphine compounds such as trimethylbenzoyl) phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; carbazole A imidazole compound; a titanocene compound, or the like.

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

(Sensitizer)
Furthermore, the photosensitive coloring composition of the present invention can 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, tetraphylline 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) benzophen Enone, 4,4'-diethylaminobenzophenone, and the like.

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

(Amine compounds)
In addition, the colored composition or the photosensitive colored composition of the present invention can contain an amine compound that has a function of reducing dissolved oxygen.

  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 colored composition or the photosensitive colored composition of the present invention. 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 Big Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. The content of the leveling agent is usually preferably 0.003 to 0.5% by mass based on the total weight of the colored composition or the photosensitive colored composition (100% by mass).

  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 characteristics of low surface tension reduction ability, and it is useful to have good wettability to the glass plate despite its low surface tension reduction ability. Those that can sufficiently suppress 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.

  In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used. Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. -2207, but is not limited 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 amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

(Curing agent, curing accelerator)
Moreover, in order to assist hardening of a thermosetting resin, the coloring composition or photosensitive coloring composition of this invention may contain the hardening | curing agent, the hardening accelerator, etc. as needed. 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. 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 Methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.) can be used. These may be used alone or in combination of two or more. As content of the said hardening accelerator, 0.01-15 mass% is preferable with respect to thermosetting resin whole quantity (100 mass%).

(Other additive components)
The coloring composition or photosensitive coloring composition of the present invention 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 can be mentioned. The storage stabilizer can be used in an amount of 0.1 to 10% by mass based on the total amount of the colorant (100% by mass).

  Examples of the adhesion improver include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino Ethyl) γ-aminopropyltrie Xisilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Examples include silane coupling agents such as aminosilanes such as -γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver is used in an amount of 0.01 to 10% by mass, preferably 0.05 to 5% by mass, based on the total amount of the colorant in the colored composition or photosensitive coloring composition (100% by mass). be able to.

(Removal of coarse particles)
The colored composition and the photosensitive colored composition of the present invention are 5 μm or larger coarse particles, preferably 1 μm or larger coarse particles, more preferably 0.8 μm, by means such as centrifugation, filtration with a sintered filter or a membrane filter. It is preferable to remove coarse particles of 5 μm or more and mixed dust. Thus, it is preferable that a coloring composition does not contain a particle | grain of 0.5 micrometer or more substantially. More preferably, it is 0.3 μm or less.

(Color filter)
Next, the color filter of the present invention will be described. The color filter of the present invention comprises a red filter segment, a green filter segment, and a blue filter segment, and the red filter segment therein contains the diketopyrrolopyrrole pigment composition of the present invention. Or a photosensitive coloring composition.

  The green filter segment can be formed using a conventional green coloring composition comprising a green pigment and a colorant carrier. 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, Mention may be made of yellow pigments such as 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, or 221. Further, a basic dye exhibiting yellow and a salt-forming compound of an acid dye can be used in combination.

  The blue filter segment can be formed using a normal blue coloring composition containing a blue pigment and a 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. In addition, a basic dye or a salt-forming compound of an acid dye exhibiting blue or purple can 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 of the present invention can be produced 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 does not dry and solidify 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 a method, it applies so that a dry film thickness may be set to 0.2-5 micrometers. 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 by spraying or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. 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 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 UV exposure sensitivity, after coating and drying the colored resist, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Thereafter, ultraviolet exposure can also be performed.

  The color filter of the present invention can be produced by an electrodeposition method, a transfer method or the like in addition to the above method, but the colored composition or the photosensitive colored composition of the present invention can be used in any method. The electrodeposition method is a method for producing a color filter by using a transparent conductive film formed on a substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. . 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. In addition, an overcoat film, a transparent conductive film, or the like is formed on the color filter of the present invention 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”.

  In addition, the diketopyrrolopyrrole derivative of the formula (6-3), the benzoisoindole derivative of the formula (7-1), and the anthraquinone derivative of the formula (8-5) can be used as a pigment derivative when producing the pigment composition and the colored composition. And quinophthalone derivatives of formula (14-1) were used.

(Average primary particle diameter of pigment)
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 ultrasonic treatment 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 minor axis diameter and major 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 5 nm increments. The 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.

<Method for producing diketopyrrolopyrrole pigment composition>
[Example 1]
(Production of Pigment Composition 1 (R-1))
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. On the other hand, 88 parts of diisopropyl succinate and 153.6 parts of 4-bromobenzonitrile were added to a glass flask and dissolved by heating to 90 ° C. with stirring to prepare a solution 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 for 2 hours at 90 ° C. to obtain an alkali metal salt of a diketopyrrolopyrrole compound. Furthermore, 600 parts of methanol, 600 parts of water and 304 parts of acetic acid were added to a reaction vessel with a glass jacket, and cooled to -10 ° C. While cooling this mixture with a high-speed stirring disperser and rotating a shear disk having a diameter of 8 cm at 4000 rpm, the alkali metal salt of the diketopyrrolopyrrole compound obtained above was cooled to 75 ° C. The solution was added in small portions. At this time, the rate of addition of the alkali metal salt of the diketopyrrolopyrrole compound at 75 ° C. while cooling so that the temperature of the mixture consisting of methanol, acetic acid and water is always kept at −5 ° C. or lower. Was 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 diketopyrrolopyrrole compound aqueous paste obtained by filtering with an ultrafiltration machine was dried at 80 ° C. for 24 hours and pulverized to thereby bromine the diketopyrrolopyrrole of formula (1). 150.8 parts of pigment were obtained.

  Subsequently, 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, 100 parts of tert-amyl alcohol, 99.2 parts of the compound of the following formula (16) synthesized by the method of Tetrahedron, 58 (2002) 5547-5565, and the benzonitrile compound of the formula (3-1) were added to the reaction vessel 2 60.9 parts was dissolved by heating and added dropwise to the reaction vessel 1 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, filtering off and washing with methanol, the specific heterogeneity represented by formula (2-1) is performed. 87.8 parts of ketopyrrolopyrrole pigment were obtained.

  Furthermore, 97.0 parts of the obtained brominated diketopyrrolopyrrole pigment of the formula (1), 3.0 parts of the specific hetero diketopyrrolopyrrole pigment of the formula (2-1), 1000 parts of sodium chloride, and 120 parts of diethylene glycol Was placed in 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. for 24 hours, and then pulverized. As a result, 96.5 parts of pigment composition 1 (R-1) which is a diketopyrrolopyrrole pigment composition was obtained. The average primary particle size was 36.8 nm.

[Example 2]
(Production of Pigment Composition 2 (R-2))
95.0 parts of the brominated diketopyrrolopyrrole pigment of the formula (1) obtained at the production of the pigment composition 1, 5.0 parts of the specific hetero diketopyrrolopyrrole pigment of the formula (2-1), 1000 parts of sodium chloride , 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. for 24 hours, and then pulverized. As a result, 97.2 parts of pigment composition 2 (R-2), which is a diketopyrrolopyrrole pigment composition, was obtained. The average primary particle size was 30.5 nm.

[Example 3]
(Production of Pigment Composition 3 (R-3))
95.0 parts of the brominated diketopyrrolopyrrole pigment of the formula (1) and 5.0 parts of the specific hetero diketopyrrolopyrrole pigment of the formula (2-1) are mixed with the brominated diketopyrrolopyrrole pigment 90 of the formula (1). Diketopyrrolopyrrole pigments were produced in the same manner as in the production of pigment composition 2 (R-2) except that 0.0 parts and 10.0 parts of the specific hetero diketopyrrolopyrrole pigment of formula (2-1) were changed. 96.9 parts of pigment composition 3 (R-3) which is a composition were obtained. The average primary particle size was 26.5 nm.

[Example 4]
(Production of Pigment Composition 4 (R-4))
95.0 parts of the brominated diketopyrrolopyrrole pigment of the formula (1) and 5.0 parts of the specific hetero diketopyrrolopyrrole pigment of the formula (2-1) are added to the brominated diketopyrrolopyrrole pigment 85 of the formula (1). Diketopyrrolopyrrole pigments were produced in the same manner as in the production of pigment composition 2 (R-2) except that 0.0 parts and 15.0 parts of the specific hetero diketopyrrolopyrrole pigment of formula (2-1) were changed. 97.1 parts of pigment composition 4 (R-4) which is a composition were obtained. The average primary particle size was 28.5 nm.

[Example 5]
(Production of Pigment Composition 5 (R-5))
The identification carried out in Pigment Composition 1 (R-1) except that 60.2 parts of the benzonitrile compound of the formula (3-1) were changed to 54.2 parts of the benzonitrile compound of the formula (3-2) It carried out similarly to manufacture of a hetero diketo pyrrolo pyrrole pigment, and obtained 85.2 parts of specific hetero diketo pyrrolo pyrrole pigments represented by Formula (2-2).

  Subsequently, 95.0 parts of a brominated diketopyrrolopyrrole pigment of formula (1), 5.0 parts of a specific heterodiketopyrrolopyrrole pigment of formula (2-2), 1000 parts of sodium chloride, and 120 parts of diethylene glycol, It was charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 10 hours. Next, the kneaded mixture is put 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 ethylene glycol, and then dried at 80 ° C. overnight. By grinding, 96.2 parts of pigment composition 5 (R-5) which is a diketopyrrolopyrrole pigment composition was obtained. The average primary particle size was 31.6 nm.

[Example 6]
(Production of Pigment Composition 6 (R-6))
First, in Pigment Composition 1 (R-1), except that 60.2 parts of the benzonitrile compound of the formula (3-1) was changed to 58.2 parts of the benzonitrile compound of the formula (3-3). In the same manner as in the production of the specific hetero diketopyrrolopyrrole pigment, 82.2 parts of the specific hetero diketopyrrolopyrrole pigment represented by the formula (2-3) was obtained.

  Subsequently, 95.0 parts of a brominated diketopyrrolopyrrole pigment of formula (1), 5.0 parts of a specific hetero diketopyrrolopyrrole pigment of formula (2-3), 1000 parts of sodium chloride, and 120 parts of diethylene glycol, It was charged in 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. for 24 hours, and then pulverized. As a result, 95.9 parts of pigment composition 6 (R-6), which is a diketopyrrolopyrrole pigment composition, was obtained. The average primary particle size was 34.6 nm.

[Example 7]
(Production of Pigment Composition 7 (R-7))
Specific performed in Pigment Composition 1 (R-1), except that 60.2 parts of the benzonitrile compound of formula (3-1) was changed to 84.1 parts of the benzonitrile compound of formula (3-4a) It carried out similarly to manufacture of hetero diketo pyrrolo pyrrole pigment, and obtained 94.1 parts of specific hetero diketo pyrrolo pyrrole pigments represented by Formula (2-4a).

  Subsequently, 95.0 parts of the brominated diketopyrrolopyrrole pigment of formula (1), 5.0 parts of the specific hetero diketopyrrolopyrrole pigment of formula (2-4a), 1000 parts of sodium chloride, and 120 parts of diethylene glycol, It was charged in 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, 97.9 parts of pigment composition 7 (R-7) which is a diketopyrrolopyrrole pigment composition was obtained. The average primary particle size was 28.6 nm.

[Example 8]
(Production of Pigment Composition 8 (R-8))
95.0 parts of the brominated diketopyrrolopyrrole pigment of the formula (1) and 5.0 parts of the specific hetero diketopyrrolopyrrole pigment of the formula (2-4a) are mixed with the brominated diketopyrrolopyrrole pigment 85 of the formula (1). Diketopyrrolopyrrole pigment composition, except that 0.0 part and 15.0 parts of the specific hetero diketopyrrolopyrrole pigment of formula (2-4a) were changed to the production of pigment composition 7 (R-7) 96.1 parts of pigment composition 8 (R-8) which is a product was obtained. The average primary particle size was 25.5 nm.

[Example 9]
(Production of Pigment Composition 9 (R-9))
The identification carried out in Pigment Composition 1 (R-1) except that 60.2 parts of the benzonitrile compound of the formula (3-1) were changed to 71.8 parts of the benzonitrile compound of the formula (3-4b) It carried out similarly to manufacture of a hetero diketo pyrrolo pyrrole pigment, and obtained the specific hetero diketo pyrrolo pyrrole pigment 79.1 parts represented by Formula (2-4b).

  Subsequently, 95.0 parts of a brominated diketopyrrolopyrrole pigment of formula (1), 5.0 parts of a specific hetero diketopyrrolopyrrole pigment of formula (2-4b), 1000 parts of sodium chloride, and 120 parts of diethylene glycol, It was charged in 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. for 24 hours, and then pulverized. As a result, 96.5 parts of pigment composition 9 (R-9), which is a diketopyrrolopyrrole pigment composition, was obtained. The average primary particle size was 31.1 nm.

[Example 10]
(Production of Pigment Composition 10 (R-10))
The specific heterozygous carried out in the pigment composition 1 (R-1) except that 60.2 parts of the benzonitrile compound of the formula (3-1) was changed to 49.7 of the benzonitrile compound of the formula (3-5) It carried out similarly to manufacture of a diketopyrrolopyrrole pigment, and obtained 66.9 parts of specific hetero diketopyrrolopyrrole pigments represented by Formula (2-5).

  Subsequently, 95.0 parts of the brominated diketopyrrolopyrrole pigment of formula (1), 5.0 parts of the specific hetero diketopyrrolopyrrole pigment of formula (2-5), 1000 parts of sodium chloride, and 120 parts of diethylene glycol, It was charged in 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. for 24 hours, and then pulverized. As a result, 97.5 parts of pigment composition 10 (R-10), which is a diketopyrrolopyrrole pigment composition, was obtained. The average primary particle size was 33.1 nm.

[Example 11]
(Production of Pigment Composition 11 (R-11))
Specific performed in Pigment Composition 1 (R-1), except that 60.2 parts of the benzonitrile compound of formula (3-1) was changed to 106.9 parts of the benzonitrile compound of formula (3-6b) It carried out similarly to manufacture of a hetero diketo pyrrolo pyrrole pigment, and 90.7 parts of specific hetero diketo pyrrolo pyrrole pigments represented by Formula (2-6b) were obtained.

  Subsequently, 95.0 parts of a brominated diketopyrrolopyrrole pigment of formula (1), 5.0 parts of a specific hetero diketopyrrolopyrrole pigment of formula (2-6b), 1000 parts of sodium chloride, and 120 parts of diethylene glycol, It was charged in 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. for 24 hours, and then pulverized. As a result, 98.1 parts of pigment composition 11 (R-11), which is a diketopyrrolopyrrole pigment composition, was obtained. The average primary particle size was 28.9 nm.

[Example 12]
(Production of Pigment Composition 12 (R-12))
The identification carried out in Pigment Composition 1 (R-1) except that 60.2 parts of the benzonitrile compound of the formula (3-1) were changed to 75.6 parts of the benzonitrile compound of the formula (3-6c) It carried out similarly to manufacture of a hetero diketo pyrrolo pyrrole pigment, and obtained 100.8 parts of specific hetero diketo pyrrolo pyrrole pigments represented by Formula (2-6c).

  Subsequently, 95.0 parts of a brominated diketopyrrolopyrrole pigment of formula (1), 5.0 parts of a specific hetero diketopyrrolopyrrole pigment of formula (2-6c), 1000 parts of sodium chloride, and 120 parts of diethylene glycol, It was charged in 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. for 24 hours, and then pulverized. As a result, 97.4 parts of pigment composition 12 (R-12) which is a diketopyrrolopyrrole pigment composition was obtained. The average primary particle size was 29.8 nm.

[Example 13]
(Production of Pigment Composition 13 (R-13))
The identification carried out in Pigment Composition 1 (R-1) except that 60.2 parts of the benzonitrile compound of the formula (3-1) were changed to 87.8 parts of the benzonitrile compound of the formula (3-7) It carried out similarly to manufacture of a hetero diketo pyrrolo pyrrole pigment, and obtained 85.2 parts of the specific hetero diketo pyrrolo pyrrole pigment represented by Formula (2-7).

  Subsequently, 95.0 parts of a brominated diketopyrrolopyrrole pigment of formula (1), 5.0 parts of a specific hetero diketopyrrolopyrrole pigment of formula (2-7), 1000 parts of sodium chloride, and 120 parts of diethylene glycol, It was charged in 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. for 24 hours, and then pulverized. As a result, 96.3 parts of pigment composition 13 (R-13), which is a diketopyrrolopyrrole pigment composition, was obtained. The average primary particle size was 28.2 nm.

[Example 14]
(Production of Pigment Composition 14 (R-14))
95.0 parts of the brominated diketopyrrolopyrrole pigment of the formula (1) and 5.0 parts of the specific hetero diketopyrrolopyrrole pigment of the formula (2-7) are added to the brominated diketopyrrolopyrrole pigment 85 of the formula (1). Diketopyrrolopyrrole pigment composition, except that 0.0 part and 15.0 parts of the specific hetero diketopyrrolopyrrole pigment of the formula (2-7) were changed to the production of pigment composition 13 (R-13) 95.1 parts of pigment composition 14 (R-14) as a product was obtained. The average primary particle size was 26.5 nm.

[Example 15]
(Production of Pigment Composition 15 (R-15))
The identification carried out in Pigment Composition 1 (R-1) except that 60.2 parts of the benzonitrile compound of the formula (3-1) were changed to 50.0 parts of the benzonitrile compound of the formula (3-8) It carried out similarly to manufacture of a hetero diketo pyrrolo pyrrole pigment, and obtained 64.5 parts of specific hetero diketo pyrrolo pyrrole pigments represented by Formula (2-8).

  Subsequently, 95.0 parts of the brominated diketopyrrolopyrrole pigment of the formula (1), 5.0 parts of the specific hetero diketopyrrolopyrrole of the formula (2-8), 1000 parts of sodium chloride, and 120 parts of diethylene glycol were mixed with stainless steel. It was charged in 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. for 24 hours, and then pulverized. As a result, 97.3 parts of pigment composition 15 (R-15) which is a diketopyrrolopyrrole pigment composition was obtained. The average primary particle size was 34.2 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, 146.0 parts of 4-bromobenzonitrile and 7.6 parts of the benzonitrile compound of the formula (3-1) 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 for 2 hours at 90 ° C. to obtain an alkali metal salt of a diketopyrrolopyrrole compound. Further, 600 parts of methanol, 600 parts of water, and 304 parts of acetic acid were added to a glass jacketed reaction vessel and cooled to -10 ° C. While cooling this mixture with a high-speed stirring disperser and rotating a shear disk having a diameter of 8 cm at 4000 rpm, the alkali metal salt of the diketopyrrolopyrrole compound obtained above was cooled to 75 ° C. The solution was added in small portions. At this time, the rate of addition of the alkali metal salt of the diketopyrrolopyrrole compound at 75 ° C. while cooling so that the temperature of the mixture consisting of methanol, acetic acid and water is always kept at −5 ° C. or lower. Was 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 diketopyrrolopyrrole compound aqueous paste obtained by filtering off with an ultrafiltration machine was dried at 80 ° C. for 24 hours and pulverized to obtain a diketopyrrolopyrrole pigment composition 145.8. Got a part.

  Regarding the content of the brominated diketopyrrolopyrrole pigment represented by the formula (1) and the specific hetero diketopyrrolopyrrole pigment represented by the formula (2-1) in the obtained diketopyrrolopyrrole pigment composition, When quantitative analysis was performed using HPLC, the mass ratio of the brominated diketopyrrolopyrrole pigment represented by the formula (1) and the specific hetero diketopyrrolopyrrole pigment represented by the formula (2-1) was 94.3: It was 5.7. The HPLC measurement conditions and retention time are as follows. In addition, the calibration curve necessary for the determination is a brominated diketopyrrolopyrrole pigment of the formula (1) synthesized by the production of the pigment composition 1 (R-1) and a specific hetero diketopyrrolo of the formula (2-1). Made with pyrrole pigment.

Apparatus: Gulliver series detector manufactured by JASCO Corporation; UV-970 detector column manufactured by JASCO Corporation; Symmetry C18 manufactured by Waters Corporation (5 μm, 2.1 mmφ × 150 mm)
Mobile phase A solution: dimethylformamide / water (1: 1)
Liquid B; dimethylformamide / water (97.5: 2.5)
Gladiendo (Liquid B);
47% → (15min) → 47% → (5min) → 100% → (25min) → 100%
Wavelength: 510nm
Column temperature: 35 ° C
Flow rate: 0.3 mL / min
Sample injection volume: 5 μL (dissolved in N-methylpyrrolidone / 28% CH ₃ ONa methanol solution)
The above formula (1) retention time; 11.9 to 12.9
Formula (2-1) retention time; 13.2-14.1

  Subsequently, 100.0 parts of the obtained diketopyrrolopyrrole pigment composition, 1000 parts of sodium chloride, 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. did. 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, 97.6 parts of pigment composition 16 (R-16), which is a diketopyrrolopyrrole pigment composition, was obtained. The average primary particle size was 32.2 nm.

[Example 17]
(Production of Pigment Composition 17 (R-17))
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, 146.0 parts of 4-bromobenzonitrile and 7.6 parts of the benzonitrile compound of the formula (3-1) 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 for 2 hours at 90 ° C. to obtain an alkali metal salt of a diketopyrrolopyrrole compound. Further, 600 parts of methanol, 600 parts of water, and 304 parts of acetic acid were added to a glass jacketed reaction vessel and cooled to -10 ° C. While cooling this mixture with a high-speed stirring disperser and rotating a shear disk having a diameter of 8 cm at 4000 rpm, the alkali metal salt of the diketopyrrolopyrrole compound obtained above was cooled to 75 ° C. The solution was added in small portions. At this time, the rate of addition of the alkali metal salt of the diketopyrrolopyrrole compound at 75 ° C. while cooling so that the temperature of the mixture consisting of methanol, acetic acid and water is always kept at −5 ° C. or lower. Was 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 mixture was filtered with an ultrafilter to obtain a red paste of a diketopyrrolopyrrole compound. Further, after redispersing the obtained red paste in 3000 ml of water, a pigment derivative slurry in which 5.5 parts of a pigment derivative of a benzoisoindole derivative represented by the formula (7-1) was added to 100 parts of water under stirring. The mixture was added and stirred at 10 ° C. or lower for 1 hour, and then washed by filtration to obtain a diketopyrrolopyrrole compound aqueous paste. This water paste was dried at 80 ° C. for 24 hours and pulverized to obtain 154.8 parts of a diketopyrrolopyrrole pigment composition.

  In the same manner as in the production of the pigment composition 16 (R-16), the brominated diketopyrrolopyrrole pigment represented by the formula (1) in the diketopyrrolopyrrole pigment composition and the formula (2-1) The content of the specific hetero diketopyrrolopyrrole pigment to be analyzed was quantitatively analyzed using HPLC, and the brominated diketopyrrolopyrrole pigment represented by the formula (1) and the specific formula represented by the formula (2-1) The mass ratio of the heterodiketopyrrolopyrrole pigment was 94.8: 5.2.

  Subsequently, 100.0 parts of the obtained diketopyrrolopyrrole pigment composition, 1000 parts of sodium chloride, 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. did. 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, 96.6 parts of pigment composition 17 (R-17) which is a diketopyrrolopyrrole pigment composition was obtained. The average primary particle size was 27.2 nm.

[Example 18]
(Production of Pigment Composition 18 (R-18))
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, 146.0 parts of 4-bromobenzonitrile and 7.6 parts of the benzonitrile compound of the formula (3-1) 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 for 2 hours at 90 ° C. to obtain an alkali metal salt of a diketopyrrolopyrrole compound. Further, 600 parts of methanol, 600 parts of water, and 304 parts of acetic acid were added to a glass jacketed reaction vessel and cooled to -10 ° C. While cooling this mixture with a high-speed stirring disperser and rotating a shear disk having a diameter of 8 cm at 4000 rpm, the alkali metal salt of the diketopyrrolopyrrole compound obtained above was cooled to 75 ° C. The solution was added in small portions. At this time, the rate of addition of the alkali metal salt of the diketopyrrolopyrrole compound at 75 ° C. while cooling so that the temperature of the mixture consisting of methanol, acetic acid and water is always kept at −5 ° C. or lower. Was 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 diketopyrrolopyrrole compound aqueous paste obtained by filtering off with an ultrafiltration machine was dried at 80 ° C. for 24 hours and pulverized to obtain a diketopyrrolopyrrole pigment composition 145.8. Got a part.

  In the same manner as in the production of the pigment composition 16 (R-16), the brominated diketopyrrolopyrrole pigment represented by the formula (1) in the diketopyrrolopyrrole pigment composition and the formula (2-1) The content of the specific hetero diketopyrrolopyrrole pigment to be analyzed was quantitatively analyzed using HPLC, and the brominated diketopyrrolopyrrole pigment represented by the formula (1) and the specific formula represented by the formula (2-1) The mass ratio of the heterodiketopyrrolopyrrole pigment was 94.5: 5.5.

  Subsequently, 85.5 parts of the obtained diketopyrrolopyrrole pigment composition, 4.5 parts of a pigment derivative of a benzoisoindole derivative of the formula (7-1), 1000 parts of sodium chloride, and 120 parts of diethylene glycol were added to stainless steel. It was charged in 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. for 24 hours, and then pulverized. As a result, 95.6 parts of pigment composition 18 (R-18), which is a diketopyrrolopyrrole pigment composition, was obtained. The average primary particle size was 26.2 nm.

[Example 19]
(Production of Pigment Composition 19 (R-19))
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. On the other hand, 88 parts of diisopropyl succinate, 138.3 parts of 4-bromobenzonitrile and 15.1 parts of benzonitrile compound of formula (3-1) 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 for 2 hours at 90 ° C. to obtain an alkali metal salt of a diketopyrrolopyrrole compound. Further, 600 parts of methanol, 600 parts of water, and 304 parts of acetic acid were added to a glass jacketed reaction vessel and cooled to -10 ° C. While cooling this mixture with a high-speed stirring disperser and rotating a shear disk having a diameter of 8 cm at 4000 rpm, the alkali metal salt of the diketopyrrolopyrrole compound obtained above was cooled to 75 ° C. The solution was added in small portions. At this time, the rate of addition of the alkali metal salt of the diketopyrrolopyrrole compound at 75 ° C. while cooling so that the temperature of the mixture consisting of methanol, acetic acid and water is always kept at −5 ° C. or lower. Was 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 diketopyrrolopyrrole compound aqueous paste obtained by filtering off with an ultrafiltration machine was dried at 80 ° C. for 24 hours and pulverized to obtain a diketopyrrolopyrrole pigment composition 145.8. Got a part.
In the same manner as in the production of the pigment composition 16 (R-16), the brominated diketopyrrolopyrrole pigment represented by the formula (1) in the diketopyrrolopyrrole pigment composition and the formula (2-1) The content of the specific hetero diketopyrrolopyrrole pigment to be analyzed was quantitatively analyzed using HPLC, and the brominated diketopyrrolopyrrole pigment represented by the formula (1) and the specific formula represented by the formula (2-1) The mass ratio of the heterodiketopyrrolopyrrole pigment was 88.9: 11.1.

  Subsequently, 100.0 parts of the obtained diketopyrrolopyrrole pigment composition, 1000 parts of sodium chloride, 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. did. 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, 98.1 parts of pigment composition 19 (R-19), which is a diketopyrrolopyrrole pigment composition, was obtained. The average primary particle size was 28.8 nm.

[Comparative Example 1]
(Production of Pigment Composition 20 (R-20))
Brominated diketopyrrolopyrrole pigment of the formula (1) 100.0 parts, 1000 parts of sodium chloride, and 120 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. for 24 hours, and then pulverized. As a result, 96.6 parts of pigment composition 20 (R-20), which is a diketopyrrolopyrrole pigment composition, was obtained. The average primary particle size was 38.9 nm.

[Comparative Example 2]
(Production of Pigment Composition 21 (R-21))
10.0 parts of brominated diketopyrrolopyrrole pigment of formula (1), 30.0 parts of specific hetero diketopyrrolopyrrole pigment of formula (2-1), 1000 parts of sodium chloride and 120 parts of diethylene glycol The mixture was placed in a 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. for 24 hours, and then pulverized. As a result, 95.8 parts of pigment composition 21 (R-21), which is a diketopyrrolopyrrole pigment composition, was obtained. The average primary particle size was 28.4 nm.

[Comparative Example 3]
(Production of Pigment Composition 22 (R-22))
10.0 parts of brominated diketopyrrolopyrrole pigment of formula (1), 50.0 parts of specific hetero diketopyrrolopyrrole pigment of formula (2-1), 1000 parts of sodium chloride and 120 parts of diethylene glycol The mixture was placed in a 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. for 24 hours, and then pulverized. As a result, 94.8 parts of pigment composition 22 (R-22), which is a diketopyrrolopyrrole pigment composition, was obtained. The average primary particle size was 35.4 nm.

[Comparative Example 4]
(Production of Pigment Composition 23 (R-23))
80.0 parts of the specific heterodiketopyrrolopyrrole pigment of the formula (2-1), 1000 parts of sodium chloride, and 110 parts of diethylene glycol are charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 10 hours. did. 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, 76.8 parts of pigment composition 23 (R-23) which is a diketopyrrolopyrrole pigment composition was obtained. The average primary particle size was 39.4 nm.

[Comparative Example 5]
(Production of Pigment Composition 24 (R-24))
10.0 parts of brominated diketopyrrolopyrrole pigment of formula (1), 30.0 parts of specific hetero diketopyrrolopyrrole pigment of formula (2-4a), 1000 parts of sodium chloride and 120 parts of diethylene glycol The mixture was placed in a 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. for 24 hours, and then pulverized. As a result, 95.8 parts of pigment composition 24 (R-24), which is a diketopyrrolopyrrole pigment composition, was obtained. The average primary particle size was 27.3 nm.

[Comparative Example 6]
(Production of Pigment Composition 25 (R-25))
Commercially available C.I. I. Pigment Red 254 ("Irgafore Red B-CF" manufactured by Ciba Specialty Chemicals), 100.0 parts, 1000 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) at 60 ° C. And kneading 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, 97.8 parts of pigment composition 25 (R-25), which is a diketopyrrolopyrrole pigment composition, was obtained. The average primary particle size was 36.3 nm.

[Comparative Example 7]
(Production of Pigment Composition 26 (R-26))
Commercially available C.I. I. Pigment Red 254 (“Irgafoa Red B-CF” manufactured by Ciba Specialty Chemicals) 90.0 parts, 10.0 parts of a specific heterodiketopyrrolopyrrole pigment of the formula (2-1), 1000 parts of sodium chloride, and diethylene glycol 120 The parts were placed in a stainless 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. for 24 hours, and then pulverized. As a result, 95.8 parts of pigment composition 26 (R-26), which is a diketopyrrolopyrrole pigment composition, was obtained. The average primary particle size was 31.4 nm.

  The contents of the produced pigment compositions 1 to 26 (R-1 to 26) are shown in Table 1. “PR254” described in Table 1 is C.I. I. Pigment red 254.

<Method for producing other pigments>
(Production 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 in a stainless 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. for 24 hours, and then pulverized. As a result, 85.0 parts of anthraquinone pigment 1 (PR177-1) were obtained. The average primary particle size was 38.2 nm.
(Production of azo pigment 1 (PY150-1))
90 parts of an azo pigment (CI Pigment Yellow 150), 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. for 24 hours, and then pulverized. As a result, 85.0 parts of azo pigment 1 (PY150-1) was obtained. The average primary particle size was 26.2 nm.

<Method for producing 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 A mixture of 1.1 parts of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for another 3 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes, and the nonvolatile content was measured. The methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile 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 the dropwise addition, the reaction was further continued for 3 hours to obtain a copolymer resin solution. Next, after the nitrogen gas was stopped and 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).

<Method for producing colored composition using diketopyrrolopyrrole pigment composition>
[Example 20]
(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.
Diketopyrrolopyrrole 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 21 to 38]
(Preparation of colored compositions 2-19 (RP-2-19))
Colored compositions 2 to 19 (RP-2 to 19) were treated 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.

[Example 39]
(Preparation of colored composition 20 (RP-20))
The mixture having the composition shown below is stirred and mixed uniformly, dispersed with picomil for 8 hours using zirconia beads having a diameter of 0.1 mm, filtered through a 5 μm filter, and colored composition 20 (RP-20) is obtained. Produced.
Diketopyrrolopyrrole pigment composition 19 (R-19) 11.0 parts Dye derivative (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

[Example 40]
(Preparation of colored composition 21 (RP-21))
The mixture having the composition shown below was stirred and mixed uniformly, dispersed with picomil for 8 hours using zirconia beads having a diameter of 0.1 mm, filtered through a 5 μm filter, and coloring composition 21 (RP-21) was obtained. Produced.
Diketopyrrolopyrrole pigment composition 19 (R-19) 12.0 parts Resin-type dispersant (“Ajisper PB821” manufactured by Ajinomoto Fine Techno Co.) 3.6 parts Acrylic resin solution 1 23.0 parts Propylene glycol monomethyl ether acetate 61.4 parts

[Comparative Examples 8-14]
(Preparation of colored compositions 22 to 28 (RP-22 to 28))
The colored compositions 22 to 28 (RP-22 to 28) were changed in the same manner as the colored composition 1 (RP-1) except that the pigment composition 1 (R-1) was changed to the pigment composition described in Table 2. Produced.

<Method for producing other colored composition>
(Preparation of colored composition 29 (RP-29))
A mixture of the following composition is 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 colored composition 29 (RP-29) is obtained. Produced.
Dianthraquinone pigment (PR177-1) 10.8 parts Dye derivative (8-5) 1.2 parts Acrylic resin solution 1 40.0 parts Propylene glycol monomethyl ether acetate 48.0 parts

(Preparation of colored composition 30 (YP-30))
A mixture having the following composition is 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 colored composition 30 (YP-30) is obtained. Produced.
Azo pigment (PY150-1) 12.0 parts Resin-type dispersant ("BYK6919" (50% solution) manufactured by Big Chemie) 6.0 parts Acrylic resin solution 1 25.0 parts Propylene glycol monomethyl ether acetate 57.0 parts

<Production method of photosensitive coloring composition>
[Example 41]
(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) 38.2 parts Coloring composition 29 (RP-29) 3.8 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 parts Ethylene glycol monomethyl ether acetate 39.6 Part

[Examples 42 to 61]
(Preparation of photosensitive coloring compositions 2 to 21 (RR-2 to 21))
The coloring composition 1 (RP-1) is changed to the coloring compositions 2 to 21 (RP-2 to 21), and further the coloring compositions 2 to 21 (RP-2 to 21) and the coloring composition 29 (RP-29). ) Was changed in the same manner as in Example 41 except that the ratio was changed (within 42 parts of the total amount of the colored composition), to produce photosensitive colored compositions 2 to 21 (RP-2 to 21). In addition, about ratio change, it colors with coloring composition 2-21 (RP-2-21) so that it may suit chromaticity of x = 0.640, y = 0.328 with a C light source in the case of coating-film evaluation. The ratio of composition 29 (RP-29) was changed.

[Comparative Examples 15-18, 20, 21]
(Preparation of photosensitive coloring compositions 22-25, 27, 28 (RR-22-25, 27, 28))
Coloring composition 1 (RP-1) is changed into coloring compositions 22-25, 27, 28 (RP-22-25, 27, 28), and further coloring compositions 22-25, 27, 28 (RP-22) To 25, 27, 28) and the colored composition 29 (RP-29), except that the ratio of the colored composition 29 is changed within 42 parts of the colored composition. -25, 27, 28 (RR-22-25, 27, 28) were produced. Regarding the ratio change, the colored compositions 22 to 25, 27 and 28 (RP-22 to RP-22) are adjusted so that the chromaticity of x = 0.640 and y = 0.328 is obtained with the C light source at the time of coating film evaluation. 25, 27, 28) and the ratio of the colored composition 29 (RP-29) were changed.

[Comparative Example 19]
(Preparation of photosensitive coloring composition 26 (RR-26))
The colored composition 1 (RP-1) is changed to the colored composition 26 (RP-26), the colored composition 29 (RP-29) is changed to the colored composition 30 (YP-30), and the colored composition 26 ( RP-26) and the coloring composition 30 (YP-30) The photosensitive coloring composition 26 (RR-) was changed in the same manner as in Example 41 except that the ratio was changed (the ratio was changed within 42 parts of the total amount of the coloring composition). 26) was produced. Regarding the ratio change, the coloring composition 26 (RP-26) and the coloring composition 30 (in order to match the chromaticity of x = 0.640 and y = 0.328 with a C light source during coating film evaluation. The ratio of YP-30) was changed.

<Preparation and evaluation of coating film using photosensitive coloring composition>
The color characteristics, contrast ratio, and crystal precipitation due to heat of the red coating film produced using the obtained photosensitive coloring composition (RR-1 to 28) were evaluated by the following methods. 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 = 0.328 with 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. Then, the brightness (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 passes through the polarizing plate, is polarized, 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, resulting in deviation in a part of the polarization plane. 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. In contrast ratio measurement, a red coating film obtained by the same method as that used for color characteristic evaluation was used.

(Evaluation of crystal precipitation on the coating film 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.

◎ ... After heat treatment at 230 ° C for 60 minutes, after further heat treatment at 240 ° C for 60 minutes,
No crystal precipitation even after further heat treatment at 240 ° C. for 60 minutes ○ No crystal precipitation after heat treatment at 230 ° C. for 60 minutes and further heat treatment at 240 ° C. for 60 minutes (there is crystal precipitation at the second heat treatment at 240 ° C. for 60 minutes) )
Δ: Crystal precipitation does not occur after heat treatment at 230 ° C. for 60 minutes, but crystal deposition occurs after further heat treatment at 240 ° C. for 60 minutes.

  From the results of Table 3, in the color filter formation, the diketopyrrolo containing the brominated diketopyrrolopyrrole pigment and the specific hetero diketopyrrolopyrrole pigment in the present invention at a specific ratio (mass ratio 97: 3-85: 15). It was found that the examples using the pyrrole pigment composition were particularly excellent in lightness, had a high contrast, and could suppress crystal precipitation of the diketopyrrolopyrrole pigment due to the heating process.

  In comparison between Example 43 and Comparative Example 21, a photosensitive coloring composition using a diketopyrrolopyrrole pigment composition containing a brominated diketopyrrolopyrrole pigment and a specific hetero diketopyrrolopyrrole pigment is conventionally used. C. I. The result was higher brightness and higher contrast than the photosensitive coloring composition containing CI Pigment Red 254, and no problem with crystal precipitation. Moreover, although the brominated diketopyrrolopyrrole pigment which does not contain the specific hetero diketopyrrolopyrrole pigment of the comparative example 15 was excellent in the brightness, it turned out that it is low contrast and crystal | crystallization precipitation cannot be suppressed. Furthermore, from the results of Example 42, Examples 45 to 47, and Examples 49 to 53, it was also confirmed that there was selectivity for the specific heterodiketopyrrolopyrrole pigment.

In Examples 41 to 44 and Comparative Examples 15 to 18, the brightness decreases as the content ratio of the specific heterodiketopyrrole pigment of formula (2-1) increases, but the crystal precipitation suppression effect tends to increase. all right. Further, it has been found that there is an optimum point with respect to contrast, and it is possible to balance lightness and contrast by controlling the content ratio of the specific heterodiketopyrrole pigment.

  In Example 42 and Example 56, the pigment composition produced by the succinic acid diester co-synthesis method, the brominated diketopyrrolopyrrole pigment and the specific hetero diketopyrrolopyrrole pigment were separately synthesized and mixed during the salt milling process. It was found that the same effect can be obtained with the pigment composition produced in this manner. The same effect could be confirmed in the comparison between Example 43 and Example 59.

  In Examples 56 to 58, it was found that the dye derivative treatment was effective in increasing contrast and suppressing crystal precipitation.

<Production of color filter>
The green photosensitive coloring composition and the blue photosensitive coloring composition used for preparation of a color filter were produced. In addition, the photosensitive coloring composition 16 (RR-16) of this invention was used about red.

(Preparation of green coloring composition 1 (GP-1))
The mixture having the composition shown below was stirred and mixed uniformly, 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 prepare 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 stirred and mixed uniformly, 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 a blue photosensitive coloring composition 1 (BR-1).
Blue coloring composition 1 (BP-1) 34.0 parts Acrylic resin solution 2 15.2 parts Photopolymerizable monomer (“Aronix M400” manufactured by 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 the photosensitive coloring composition 16 (RR-16) of the present invention is formed on the substrate with a spin coater so that x = 0.640 and y = 0.328. To form a colored film. 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. In the same manner, 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 to a thickness of x = 0.150 and y = 0.060, respectively, to form a green filter segment and a blue filter segment to obtain a color filter.

  By using the photosensitive coloring composition 16 (RR-16) of the present invention, it was possible to produce a color filter having high brightness and high contrast and no crystal precipitation in the heating process.

Claims (6)

In the diketopyrrolopyrrole pigment composition for color filters containing the diketopyrrolopyrrole pigment represented by the following formula (1) and the diketopyrrolopyrrole pigment represented by the formula (2), the formula (1) The diketopyrrolopyrrole pigment composition for color filters, wherein the mass ratio of the formula (2) is 97: 3 to 85:15.

[In Formula (2),
A is a hydrogen atom . Of B, an alkyl group having 1 to 12 carbon atoms, which may have a substituent phenyl ^{_{group, -CF 3, -OR 1, -SR}} 2, -CONH 2, -CONHR 6 , or -CON, (R ⁷⁾ R ^8, is,
R ¹ , R ² , R ^{6 to} R ⁸ are each independently an alkyl group having 1 to 12 carbon atoms, a phenyl group which may have a substituent, or an aralkyl group which may have a substituent. It is . ] The above formula (2) is converted into the following formula (2-1), formula (2-2), formula (2-3), formula (2-4), formula (2-5), formula (2-6), Or a diketopyrrolopyrrole pigment composition for a color filter according to claim 1, which is any one of formula (2-7).

[In Formula (2-4), Formula (2-6), and Formula (2-7),
R ^{12 to} R ¹⁵ are each independently an alkyl group having 1 to 12 carbon atoms or a phenyl group which may have a substituent. ]  The diketopyrrolopyrrole pigment composition for color filters according to claim 1 or 2, further comprising a dye derivative.   A coloring composition containing a coloring agent, a binder resin, and an organic solvent, wherein the coloring agent contains the diketopyrrolopyrrole pigment composition according to any one of claims 1 to 3. Composition.   Furthermore, the coloring composition for color filters of Claim 4 containing a photopolymerizable monomer and / or a photoinitiator.   A color filter comprising a filter segment formed from the colored composition for a color filter according to claim 4.