JP6846739B2 - Diketopyrrolopyrrole pigment composition and coloring composition using the diketopyrrolopyrrole pigment composition - Google Patents

Description

The present invention relates to a diketopyrrolopyrrole pigment composition in which the hue can be arbitrarily controlled and a coloring composition using the diketopyrrolopyrrole pigment composition.

Since the pigment selectively absorbs or reflects light of a specific wavelength, it can be recognized as a color. Organic pigments are generally classified into azo pigments and polycyclic pigments based on their chemical structures. Azo pigments have an azo group as a chromophore, have a clear hue, have a large coloring power, and are relatively inexpensive. Therefore, printing inks, paints, plastics, stationery, etc. are mainly colored from yellow to red. Widely used in, but has difficulty in weather resistance. Weather resistance is improved by introducing a benzimidazolone skeleton into the pigment structure and forming hydrogen bonds between the molecules. (Patent Document 1, Non-Patent Document 1) However, when such a skeleton is introduced into a pigment, the pigment becomes economically expensive, and at the same time, the color characteristics change before and after the introduction of the skeleton, so that the weather resistance is improved. However, due to changes in color characteristics, the pigment cannot be used. Examples of pigments into which the benzimidazolone skeleton has been introduced include C.I. I. Pigment Yellow 120, 151, 154, 175, 180, 181, 194, C.I. I. Pigment Orange 36, 62, 64, 72, C.I. I. Pigment Red 171, 175, 176, 208, C.I. I. Pigment Violet 32 is mentioned, but it is expensive as compared with general azo pigments, and the colors that can be selected are also limited.

On the other hand, polycyclic pigments have higher weather resistance than azo pigments. A typical polycyclic pigment is a blue copper phthalocyanine pigment, which exhibits a clear blue color. Examples of pigments exhibiting yellow to red colors include isoindoline, anthraquinone, diketopyrrolopyrrole, perylene, and quinacridone pigments, but the types and variations of colors are smaller than those of azo pigments, and the means of selection is limited. ..

As a method of controlling the hue of an organic pigment, a method of controlling the crystal type such as copper phthalocyanine (for example, α type, β type, ε type) or a solid solution such as diketopyrrolopyrrole is prepared to control the hue. Examples thereof include a method (Patent Document 2), and the most effective method for controlling a dye is a method of introducing a substituent such as a halogen or an alkyl group into the pigment skeleton as an axochrome group. (Non-Patent Document 2) However, while this method complicates the reaction process, it also has a high economic cost, and when halogen is used, PCB or the like may be produced as an unintentional by-product. There is also. (Non-Patent Document 3) Therefore, the hue control method using halogen should not be used in consideration of future human health and the global environment.

Japanese Unexamined Patent Publication No. 56-38354 Japanese Unexamined Patent Publication No. 63-408279

Kentaro Shima, "Technology of Functional Pigments", Popular Edition, CMC Publishing, September 24, 2004, p. 80 Isao Hashimoto, "Handbook of Organic Pigments", First Edition, Color Office, May 2006, p. 26-35 Study Group on Industrial-Technically and Economically Reducible Levels of PCBs By-Production in Organic Pigments, "Report on Industrial-Technically and Economically Reducible Levels of PCBs By-Production in Organic Pigments", January 29, 2016, p. 8-15

The problem to be solved by the present invention is that a diketopyrrolopyrrole pigment having good weather resistance can be used to control the hue more economically and arbitrarily without introducing a new auxiliary color group into the substituent. It is an object of the present invention to provide a pyrolopyrrolop pigment composition and a coloring composition using the diketopyrrolopyrrole pigment composition.

As a result of diligent studies, the present inventors have found that the above problems can be solved by using a diketopyrrolopyrrole pigment and an aromatic compound having a highly resistant amide bond, and have reached the present invention.

［一般式（１）中、Ｒ₁〜Ｒ₁₀はそれぞれ独立して、水素原子、ハロゲン原子、シアノ基、ニトロ基、トリフルオロメチル基、アミノ基、炭素数１〜４のアルキル基、炭素数１〜４のアルケニル基、炭素数６〜１０のアリール基、−ＯＲ₁₁、−ＣＯＯＲ₁₂、−ＣＯＮＨＲ₁₃、−ＮＨＣＯＲ₁₄または−ＳＯ₂ＮＨＲ₁₅を表す。Ｒ₁₁〜Ｒ₁₅は、それぞれ独立して、水素原子または炭素数１〜４のアルキル基を表す。］

［一般式（２）中、Ｒ₁₆〜Ｒ₂₅はそれぞれ独立して、水素原子、ハロゲン原子、シアノ基、ニトロ基、トリフルオロメチル基、アミノ基、炭素数１〜４のアルキル基、炭素数１〜４のアルケニル基、炭素数６〜１０のアリール基、−ＯＲ₁₁、−ＣＯＯＲ₁₂、−ＣＯＮＨＲ₁₃、−ＮＨＣＯＲ₁₄または−ＳＯ₂ＮＨＲ₁₅を表す。Ｒ₁₁〜Ｒ₁₅は、それぞれ独立して、水素原子または炭素数１〜４のアルキル基を表す。Ｘ、Ｙはそれぞれ独立して、−ＣＯＮＨ−または−ＮＨＣＯ−を表す。］ That is, the present invention relates to a diketopyrrolopyrrole pigment composition, which comprises a diketopyrrolopyrrole pigment represented by the general formula (1) and an aromatic amide compound represented by the general formula (2).

[In the general formula (1), R _{1 to} R ₁₀ are independently hydrogen atom, halogen atom, cyano group, nitro group, trifluoromethyl group, amino group, alkyl group having 1 to 4 carbon atoms, and carbon number of carbon atoms. Represents an alkenyl group of 1-4, an aryl group of 6-10 carbon atoms, -OR ₁₁ , -COOR ₁₂ , -CONHR ₁₃ , -NHCOR ₁₄ or -SO ₂ NHR ₁₅ . R _{11 to} R ₁₅ independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

[In the general formula (2), R _{16 to} R ₂₅ are independently hydrogen atom, halogen atom, cyano group, nitro group, trifluoromethyl group, amino group, alkyl group having 1 to 4 carbon atoms, and carbon number of carbon atoms. Represents an alkenyl group of 1-4, an aryl group of 6-10 carbon atoms, -OR ₁₁ , -COOR ₁₂ , -CONHR ₁₃ , -NHCOR ₁₄ or -SO ₂ NHR ₁₅ . R _{11 to} R ₁₅ independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. X and Y independently represent -CONH- or -NHCO-. ]

［一般式（３）中、Ｒ₂₆およびＲ₂₇は、それぞれ独立して、水素原子、ハロゲン原子、シアノ基、トリフルオロメチル基、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基または炭素数６〜１０のアリール基を表す。］ The present invention also relates to the above-described diketopyrrolopyrrole pigment composition, wherein the diketopyrrolopyrrole pigment is represented by the general formula (3).

[In the general formula (3), R ₂₆ and R ₂₇ are independently hydrogen atom, halogen atom, cyano group, trifluoromethyl group, alkyl group having 1 to 4 carbon atoms, and alkoxy having 1 to 4 carbon atoms, respectively. Represents a group or an aryl group having 6 to 10 carbon atoms. ]

The present invention also relates to a coloring composition containing the above-mentioned diketopyrrolopyrrole pigment composition and a resin.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a diketopyrrolopyrrole pigment composition whose hue can be controlled more economically and arbitrarily, and a coloring composition using the diketopyrrolopyrrole pigment.

It is a reflection spectrum of the ink using the pigment red 255 series coloring composition. (Examples 15 and 17, Comparative Example 1) FIG. 3 is a reflection spectrum of an ink using a pigment red 254-based coloring composition. (Example 20, Comparative Example 2) FIG. 3 is a reflection spectrum of an ink using a pigment red 264-based coloring composition. (Example 23, Comparative Example 3) FIG. 3 is a reflection spectrum of an ink using a pigment red 272-based coloring composition. (Example 26, Comparative Example 4)

Hereinafter, the present invention will be described in detail.

Examples of the diketopyrrolopyrrole pigment used in the present invention include diketopyrrolopyrrole pigments represented by the following general formula (1).

[In the general formula (1), R _{1 to} R ₁₀ are independently hydrogen atom, halogen atom, cyano group, nitro group, trifluoromethyl group, amino group, alkyl group having 1 to 4 carbon atoms, and carbon number of carbon atoms. Represents an alkenyl group of 1-4, an aryl group of 6-10 carbon atoms, -OR ₁₁ , -COOR ₁₂ , -CONHR ₁₃ , -NHCOR ₁₄ or -SO ₂ NHR ₁₅ . R _{11 to} R ₁₅ independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

In the general formula (1), _{examples of the halogen atom in R 1 to} R ₁₀ include fluorine, chlorine, bromine and iodine.

The alkyl group having 1 to 4 carbon atoms in R _{1 to} R ₁₅ may be linear or branched, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and sec. -Butyl group, tert-butyl group and the like can be mentioned.

The alkenyl group having 1 to 4 carbon atoms in R _{1 to} R ₁₀ may be linear or branched, and specific examples thereof include a vinyl group, a 1-propenyl group, an aryl group, a 2-butenyl group and a 3-butenyl group. Groups, isopropenyl groups, isobutenyl groups, 1,3-butadienyl groups and the like can be mentioned, but are not limited thereto.

_{The aryl group having 6 to 10} carbon atoms in R _{1 to} R 10 is a substituted or unsubstituted monocyclic or condensed polycyclic aromatic group, for example, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, o. -Tolyl group, m-tolyl group, p-tolyl group and the like can be mentioned, but the present invention is not limited thereto.

Preferred diketopyrrolopyrrole pigments used in the present invention include diketopyrrolopyrrole pigments represented by the following general formula (3).

[In the general formula (3), R _{26 to} R ₂₇ are independently hydrogen atom, halogen atom, cyano group, trifluoromethyl group, alkyl group having 1 to 4 carbon atoms, and alkoxy group having 1 to 4 carbon atoms. Alternatively, it represents an aryl group having 6 to 10 carbon atoms. ]

The halogen atom of the general formula (3), the alkyl group having 1 to 4 carbon atoms, and the aryl group having 6 to 10 carbon atoms are synonymous with those of the general formula (1).

The alkoxy group having 1 to 4 carbon atoms in the general formula (3) may be linear or branched, and specific examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and an isobutoxy group. Examples thereof include a sec-butoxy group and a tert-butoxy group.

Specific examples of the diketopyrrolopyrrole pigment include, but are not limited to, the diketopyrrolopyrrole pigments shown below.

(Manufacturing method of diketopyrrolopyrrole pigment)
The diketopyrrolopyrrole pigment used in the present invention can be produced, for example, by reacting the corresponding aromatic nitrile with a succinic acid diester in an organic solvent as shown in JP-A-58-210084. The method for producing the diketopyrrolopyrrole pigment is not limited to this method.

Ｒは、アルキル基を表す。

R represents an alkyl group.

The diketopyrrolopyrrole pigment may be a pigment having any crystal form, or may be a mixed crystal of pigments having all crystal forms, so-called polymorphs. The crystal morphology of these pigments can be confirmed by powder X-ray diffraction measurement and X-ray crystal structure analysis.

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

The diketopyrrolopyrrole pigment composition of the present invention contains an aromatic amide compound represented by the general formula (2).

［一般式（２）中、Ｒ₁₆〜Ｒ₂₅はそれぞれ独立して、水素原子、ハロゲン原子、シアノ基、ニトロ基、トリフルオロメチル基、アミノ基、炭素数１〜４のアルキル基、炭素数１〜４のアルケニル基、炭素数６〜１０のアリール基、−ＯＲ₁₁、−ＣＯＯＲ₁₂、−ＣＯＮＨＲ₁₃、−ＮＨＣＯＲ₁₄または−ＳＯ₂ＮＨＲ₁₅を表す。Ｒ₁₁〜Ｒ₁₅は、それぞれ独立して、水素原子または炭素数１〜４のアルキル基を表す。Ｘ、Ｙはそれぞれ独立して、−ＣＯＮＨ−、または、−ＮＨＣＯ−を表す。］

[In the general formula (2), R _{16 to} R ₂₅ are independently hydrogen atom, halogen atom, cyano group, nitro group, trifluoromethyl group, amino group, alkyl group having 1 to 4 carbon atoms, and carbon number of carbon atoms. Represents an alkenyl group of 1-4, an aryl group of 6-10 carbon atoms, -OR ₁₁ , -COOR ₁₂ , -CONHR ₁₃ , -NHCOR ₁₄ or -SO ₂ NHR ₁₅ . R _{11 to} R ₁₅ independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. X and Y independently represent -CONH- or -NHCO-. ]

_{The halogen atoms of R 16 to} R ₂₅ of the general formula (2), the alkyl group having 1 to 4 carbon atoms, the alkenyl group having 1 to 4 carbon atoms, and the aryl group having 6 to 10 carbon atoms are those of the general formula (1). Synonymous.

Specific examples of the aromatic amide compound include, but are not limited to, the compounds shown below.

(Method for producing aromatic amide compound)
The aromatic amide compound used in the present invention can be produced by reacting the corresponding aromatic amine with oxalyl chloride in the presence of a base (for example, triethylamine or the like) in an organic solvent such as toluene. The method for producing the aromatic amide compound is not limited to this method.

(Method for Producing Diketopyrrolopyrrole Pigment Composition)
As a method for producing the diketopyrrolopyrrole pigment composition of the present invention, a method of mixing a diketopyrrolopyrrole pigment and an aromatic amide compound with a solvent, or a method of dissolving the diketopyrrolopyrrole pigment in a solvent and then mixing with another solvent to precipitate the diketopyrrolopyrrole pigment composition. A method of mixing the two using a salt milling treatment can be mentioned. Further, a method of mixing the aromatic amide compound of the present invention with the reaction solution immediately after the synthesis of diketopyrrolopyrrole and precipitating it can be mentioned, but the method for producing the diketopyrrolopyrrole pigment composition is limited to this method. is not it.

Examples of solvents for mixing or dissolving diketopyrrolopyrrole pigments and aromatic amide compounds include sulfuric acid, N, N-dimethylformamide, N-methylformamide, tetramethylurea, N, N-dimethylacetamide. , N-Methylpyrrolidone, dimethylsulfoxide, sulfolane, glacial acetic acid, ketones such as cyclohexanone, alcohols such as n-butanol, isopropyl alcohol, cyclohexanol or benzyl alcohol, as well as ethylene glycol, propylene glycol, ethers such as ethylene glycol dimethyl ether, Diphenyl ether, anisole, aromatic hydrocarbons such as nitrobenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, toluene, xylene, esters such as ethyl acetate and butyl acetate are included, but not limited to.

Furthermore, when the diketopyrrolopyrrole pigment is dissolved and mixed, it is preferable to use a base in the solvent in order to facilitate the dissolution. Examples of bases include alkali metal alcoholates such as sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium methoxide, potassium ethoxide, potassium tert-butoxide, sodium hydroxide and potassium hydroxide. , Not limited to these.

The solvent used for precipitating the diketopyrrolopyrrole pigment and the aromatic amide compound after dissolving them in the solvent may be a solvent that can be mixed with the above polar solvent and that precipitates the diketopyrrolopyrrole pigment composition of the present invention. Anything is fine.

More preferred solvents for dissolving diketopyrrolopyrrole pigments are sulfuric acid, N, N-dimethylformamide, N-methylformamide, tetramethylurea, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, alcohol. A more preferred solvent for precipitating the diketopyrrolopyrrole pigment composition of the present invention is water.

The mixing or dissolution temperature of the diketopyrrolopyrrole pigment and the aromatic amide compound depends on the boiling point of the solvent, but is 10 to 100 ° C, more preferably 20 to 60 ° C. The dissolution time is preferably 30 minutes to 24 hours. When the particles are mixed with another solvent and precipitated, a low temperature of -10 to 30 ° C. is preferable when the particles are to be made fine. Further, when the particles are largely controlled, the particles may be heated at 40 to 100 ° C. after mixing the precipitation solvent, and the heating time is preferably 30 minutes to 24 hours.

The amount of the aromatic amide compound to be mixed with the diketopyrrolopyrrole pigment is 0.01 to 60% by mass, more preferably 0.5 to 50% by mass.

When the diketopyrrolopyrrole pigment and the aromatic amide compound are mixed, two or more kinds of each may be used in combination.

The salt milling treatment involves using a mixture of a diketopyrrolopyrrole pigment, the aromatic amide compound of the present invention, a water-soluble inorganic salt and a water-soluble organic solvent as a kneader, a 2-roll mill, a 3-roll mill, a ball mill, an attritor, a sand mill, etc. This is a process of mechanically kneading while heating using the kneader of the above, and then removing the water-soluble inorganic salt and the water-soluble organic solvent by washing with water. The kneading temperature of the salt milling treatment is preferably 40 to 150 ° C., and the kneading time is preferably 1 to 24 hours. The amount of the aromatic amide compound of the present invention to be mixed with the diketopyrrolopyrrole pigment is 0.01 to 60% by mass, more preferably 0.5 to 50% by mass. When the diketopyrrolopyrrole pigment and the aromatic amide compound are mixed, two or more of each may be used in combination.

As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of price. From the viewpoint of both treatment efficiency and production efficiency, the water-soluble inorganic salt is preferably used in an amount of 50 to 2000% by mass, most preferably 300 to 1000% by mass, based on the total mass of the pigment (100% by mass).

The water-soluble organic solvent has a function of wetting the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent easily evaporates, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000% by mass, most preferably 50 to 500% by mass, based on the total mass of the pigment (100% by mass).

When the salt milling treatment is performed, a resin may be added if necessary. The type of resin used is not particularly limited, and a natural resin, a modified natural resin, a synthetic resin, a synthetic resin modified with a natural resin, or the like can be used. The resin used is preferably solid at room temperature, water-insoluble, and more preferably partially soluble in the organic solvent. The amount of the resin used is preferably in the range of 5 to 200% by mass based on the total weight of the pigment (100% by mass).

When the salt milling treatment is performed, a dye derivative may be added if necessary. The dye derivative is a compound in which a phthalimide methyl group or a basic substituent represented by the following general formulas (4) and (5) is introduced into the dye.

In the general formula (4)
W is a direct _{bond, -CH 2 NHCOCH 2 -, -} SO 2 NH -, - CONHOCH 2 NH-, or - represents a (CH _{2) q} NH-.
R ₂₈ and R ₂₉ each independently represent a saturated or unsaturated alkyl group which may be substituted, or R ₂₈ and R ₂₉ which may be substituted heterocycles containing nitrogen, oxygen or sulfur atoms. ..
However, n and q represent integers of 1 to 10.

In the general formula (5)
Z is a direct _{bond, -SO 2 -, - CO -} , - CH 2 NHCOCH 2 -, - (CH 2) q -, - SO 2 NH -, - CONH -, - CH 2 NHCOCH 2 NH-, or - (CH ₂ ) _q Represents NH-. However, q represents an integer of 1 to 10.
R ₃₀ , R ₃₁ , R ₃₂ , and R ₃₃ each independently represent a hydrogen atom, a saturated or unsaturated alkyl group that may be substituted, or an aryl group.
R ₃₄ represents a saturated or unsaturated alkyl or aryl group that may be substituted.

As the dye derivative, a diketopyrrolopyrrole derivative, a quinacridone derivative, and an azo dye derivative are preferable from the viewpoint of not polluting the hue of the dichlorodiketopyrrolopyrrole pigment.

The following compounds can be used as the diketopyrrolopyrrole derivative, but the diketopyrrolopyrrole derivative is not limited thereto.

Further, as the quinacridone derivative, the following compounds can be used, but the quinacridone derivative is not limited thereto.

Examples of the azo dye derivative include compounds represented by the following general formula (6).

In the general formula (6)
A and B represent a hydroxyl group or a basic substituent represented by the following general formulas (7) and (8).

In the general formulas (7) and (8),
R ₃₅ and R ₃₆ each independently represent a saturated or unsaturated alkyl group which may be substituted, or R ₃₅ and R ₃₆ which may be substituted heterocycles containing nitrogen, oxygen or sulfur atoms. .. However, n represents an integer of 1 to 10.

The following compounds can be used as the azo dye derivative, but the azo dye derivative is not limited thereto.

When the salt milling treatment is performed, a resin, a surfactant, and a higher fatty acid may be added in addition to the dye derivative, if necessary.
The resin that can be used is not particularly limited, but rosin, rosin derivative, rosin-modified maleic acid resin, rosin-modified phenol resin, rubber derivative, protein derivative, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, polyvinyl acetate, etc. Epoxy resin, acrylic resin, maleic acid resin, styrene resin, styrene-maleic acid copolymer resin, butyral resin, polyester resin, melamine resin, phenol resin, polyurethane resin, polyamide resin, polyimide resin, alkyd resin, rubber resin, cellulose Kind, benzoguanamine resin, urea resin can be mentioned. Further, the surfactant is not particularly limited, and any of anionic, neutral and cationic surfactants may be used.

Higher fatty acids are acids with a large number of carbon atoms that form fats and oils by reacting with glycerin, and are widely contained as components of animal fats and vegetable oils. , Stearic acid, linolenic acid, oleic acid and the like. As the higher fatty acid, a fatty acid having 10 or more carbon atoms is preferable, and an unsaturated higher fatty acid that is liquid at 20 to 30 ° C. is preferable. On the other hand, fatty acids having a small number of carbon atoms include acetic acid, valeric acid, and lacuic acid, which are in the state of free acids and are hydrophilic. Higher lipophilic fatty acids are suitable as fatty acids that moisten the pigment to increase the grinding effect and promote miniaturization. Further, the water-soluble inorganic salts and water-soluble organic solvents used in wet pulverization are separated from the fine pigments by washing with water, but hydrophilic fatty acids having a small number of carbon atoms are dissolved in water, and BOD and COD. It is not preferable because it causes an increase in the amount of water. If necessary, two or more kinds of higher fatty acids may be mixed and used.

The coloring composition of the present invention may be aqueous or non-aqueous. Water, an organic solvent, a polymerizable monomer, or the like can be used as a medium for dispersing the diketopyrrolopyrrole pigment composition in the coloring composition of the present invention. When the coloring composition of the present invention is an aqueous coloring composition, a mixture containing water as a main component and optionally added with a hydrophilic organic solvent can be used. Examples of the hydrophilic organic solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, isobutyl alcohol, 2-butanol, isobutanol, tert-butyl alcohol, pentanol, hexanol, cyclohexanol and benzyl alcohol. , Alcohols such as diacetone alcohol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol Polyhydric alcohols such as 1,5-pentanediol, glycerin, 1,2,6-hexanetriol, thiodiglycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monobutyl ether, triethylene glycol monomethyl ether, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate triethylene glycol mono Glycol derivatives such as ethyl ether, ethylene glycol monophenyl ether, ethylene oxide adduct of diglycerin, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenetriamine. , Triethylenetetramine, polyethyleneimine, tetramethylpropylenediamine and other amines, as well as formamide, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, thiodiethanol, thiodiglycerol, sulfolane, 2-pyrrolidone. , N-Methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, acetonitrile, acetone, methyl ethyl ketone, ethylene carbonate, propylene carbonate and other water-soluble solvents. Can be mentioned ..

Further, the water-based coloring composition of the present invention may contain an aqueous resin. Examples of the aqueous resin include water-soluble resins that are soluble in water, water-dispersible resins that are dispersed in water, colloidal dispersion resins, and mixtures thereof. Specific examples of the water-based resin include acrylic-based, styrene-acrylic-based, polyester-based, polyamide-based, polyurethane-based, and fluorine-based resins.

Further, in order to improve the dispersion of the diketopyrrolopyrrole pigment composition and the quality of the image quality using the coloring composition of the present invention, a surfactant and a dispersant may be used. Examples of the surfactant include anionic, nonionic, cationic and amphoteric surfactants, and any of the surfactants may be used, but anionic or nonionic surfactants may be used. It is preferable to use it. Examples of anionic surfactants include fatty acid salts, alkyl sulfates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, dialkyl sulfosuccinates, alkyldiarylether disulfonates, alkyl phosphates, and polyoxyethylene alkyls. Examples thereof include ether sulfate, polyoxyethylene alkylaryl ether sulfate, naphthalene sulfonate formalin condensate, polyoxyethylene alkyl phosphate ester salt, glycerol volate fatty acid ester, polyoxyethylene glycerol fatty acid ester and the like.

Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene oxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, and glycerin. Examples thereof include fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, fluorine-based, and silicon-based.

When the coloring composition of the present invention is a non-aqueous coloring composition, it is dispersed in a non-aqueous binder using the diketopyrrolopyrrole pigment composition as a medium. Resins used for non-aqueous binders include, for example, petroleum resins, casein, cellac, rosin-modified maleic acid resins, rosin-modified phenolic resins, nitrocellulose, cellulose acetate butyrate, cyclized rubber, rubber chloride, rubber oxide, and hydrochloric acid. Rubber, phenol resin, alkyd resin, polyester resin, unsaturated polyester resin, amino resin, epoxy resin, vinyl resin, vinyl chloride, vinyl chloride-vinyl acetate copolymer, acrylic resin, methacrylic resin, polyurethane resin, silicon resin, fluorine Examples thereof include resins, dry oils, synthetic dry oils, styrene / maleic acid resins, styrene / acrylic resins, polyamide resins, polyimide resins, benzoguanamine resins, melamine resins, urea resins, chlorinated polypropylene, butyral resins, vinylidene chloride resins and the like. A photocurable resin may be used as the non-aqueous binder.

Examples of the solvent used for the non-aqueous binder include aromatic solvents such as toluene, xylene and methoxybenzene, and acetate esters such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate. Solvents, propionate solvents such as ethoxyethyl propionate, alcohol solvents such as methanol and ethanol, ether solvents such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether and diethylene glycol dimethyl ether, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and the like. Ketone solvent, aliphatic hydrocarbon solvent such as hexane, nitrogen compound solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, γ-butyrolactam, N-methyl-2-pyrrolidone, aniline, pyridine, etc. , Lactone-based solvents such as γ-butyrolactone, carbamate esters such as a 48:52 mixture of methyl carbamate and ethyl carbamate, and the like.

(Photopolymerizable monomer)
A photopolymerizable monomer may be added to the coloring composition of the present invention, if necessary. The photopolymerizable monomer includes a monomer or an oligomer that is cured by ultraviolet rays, heat, or the like to form a transparent resin.

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

The blending amount of the photopolymerizable monomer is preferably 5 to 400 parts by mass with respect to 100 parts by mass of the colorant, and more preferably 10 to 300 parts by mass from the viewpoint of photocurability and developability. ..

(Photopolymerization initiator)
The colored composition of the present invention is subjected to solvent-developed or alkali-developed photosensitive by adding a photopolymerization initiator in order to cure the composition by ultraviolet irradiation and form a filter segment by a photolithography method, if necessary. It can be prepared in the form of a sex coloring composition.

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

The content of the photopolymerization initiator is preferably 2 to 200 parts by mass with respect to 100 parts by mass of the colorant, and more preferably 3 to 150 parts by mass from the viewpoint of photocurability and developability.

(Sensitizer)
Further, the coloring composition of the present invention may contain a sensitizer, if necessary.
Examples of the sensitizer include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, and anthraquinone derivatives. , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonoal derivatives and other polymethine dyes, acrydin derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indolin derivatives, Azulene derivative, azurenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine derivative , Naphthalocyanine derivative, Subphthalocyanine derivative, Pyrylium derivative, Thiopyrylium derivative, Tetraphyllin derivative, Anuren derivative, Spiropyran derivative, Spiroxazine derivative, Thiospiropirane derivative, Metal allene complex, Organic ruthenium complex, or Michler ketone derivative, α-Acyloxy ester , Acylphosphine oxide, methylphenylglycolate, benzyl, 9,10-phenanthrene quinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalofenone, 3,3', or 4,4' -Tetra (t-butylperoxycarbonyl) benzophenone, 4,4'-diethylaminobenzophenone and the like can be mentioned.
These sensitizers can be used alone or in admixture of two or more at any ratio as required.

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

The content of the sensitizer is preferably 3 to 60 parts by mass with respect to 100 parts by mass of the photopolymerization initiator contained in the coloring composition, and 5 to 50 parts by mass from the viewpoint of photocurability and developability. Is more preferable.

(Antioxidant)
The coloring composition of the present invention may contain an antioxidant, if necessary. Antioxidants are photopolymerization initiators and thermosetting compounds contained especially when used in color filter applications, which are oxidized and yellowed by the thermal process during thermosetting and ITO (indium tin oxide) annealing. In order to prevent this, the transmittance of the coating film can be increased. Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented, and a high transmittance of the coating film can be obtained.

The "antioxidant" in the present invention may be a compound having an ultraviolet absorbing function, a radical catching function, or a peroxide decomposition function. Specifically, the antioxidant is a hindered phenolic or hindered amine compound. , Phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, sulcylic acid ester-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, and the like can be used.

Among these antioxidants, from the viewpoint of achieving both the transmittance and the sensitivity of the coating film, the ones preferable are hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. Agents can be mentioned. Further, more preferably, it is a hindered phenol-based antioxidant, a hindered amine-based antioxidant, or a phosphorus-based antioxidant.

Examples of the hindered phenolic antioxidant include 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl), and the like. 1,3,5-Tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di) -T-butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,6-di-t-butyl-4- Nonylphenol, 2,2'-isobutylidene-bis- (4,6-dimethyl-phenol), 4,4'-butylidene-bis- (2-t-butyl-5-methylphenol), 2,2'-thio- Bis- (6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,2'thiodiethylbis- (3,5-di-t-butyl-4-hydroxyphenyl) )-Propionate, 1,1,3-tris- (2'-methyl-4'-hydroxy-5'-t-butylphenyl) -butane, 2,2'-methylene-bis- (6- (1-methyl) -Cyclohexyl) -p-cresol), 2,4-dimethyl-6- (1-methyl-cyclohexyl) -phenol, N, N-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydro) Shinnamamide) and the like. In addition, oligomer-type and polymer-type compounds having a hindered phenol structure can also be used.

Examples of hindered amine antioxidants include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate. N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine, 2-methyl-2- (2,2,6,6-tetramethyl-4) -Piperidyl) Amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) (1,2,3) 4-butanetetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl} {(2,2,6,6) -Tetramethyl-4-piperidyl) imino} Hexamethyl {(2,2,6,6-tetramethyl-4-piperidyl) imino}], poly [(6-morpholino-1,3,5-triazin-2,4) -Diyl) {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethine {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl succinate and 1- (2-Hydroxyethyl) -4-hydroxy-2,2,6,6-polycondensate with tetramethylpiperidine, N, N'-4,7-tetrakis [4,6-bis {N-butyl-N -(1,2,2,6,6-pentamethyl-4-piperidyl) amino} -1,3,5-triazine-2-yl] -4,7-diazadecan-1,10-diamine and the like. In addition, oligomer-type and polymer-type compounds having a hindered amine structure can also be used.

Phenyl antioxidants include tris (isodecyl) phosphite, tris (tridecyl) phosphite, phenylisooctylphosphite, phenylisodecylphosphite, phenyldi (tridecyl) phosphite, diphenylisooctylphosphite, diphenylisodecyl. Phosphite, Diphenyltridecylphosphite, Triphenylphosphite, Tris (nonylphenyl) phosphite, 4,4'isopropyridene diphenolalkylphosphite, trisnonylphenylphosphite, trisdinonylphenylphosphite, tris (2) , 4-di-t-butylphenyl) phosphite, tris (biphenyl) phosphite, distearyl pentaerythritol diphosphite, di (2,4-di-t-butylphenyl) pentaerythritol diphosphite, di (nonyl) Phenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidenebis (3-methyl-6-t-butylphenol) diphosphyte, hexatridecyl 1,1,3- Tris (2-methyl-4-hydroxy-5-t-butylphenyl) butanetriphosphite, 3,5-di-t-butyl-4-hydroxybenzylphosphite diethyl ester, sodium bis (4-t-butylphenyl) Phosphite, Sodium-2,2-Methylene-bis (4,6-di-t-butylphenyl) -Phosphite, 1,3-bis (diphenoxyphosphonyloxy) -benzene, ethylbis phosphite (2, 4-Ditert-butyl-6-methylphenyl) and the like. In addition, oligomer-type and polymer-type compounds having a phosphite structure can also be used.

Examples of sulfur-based antioxidants include 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and 2,4-bis [(octylthio) methyl]-. Examples thereof include o-cresol and 2,4-bis [(laurylthio) methyl] -o-cresol. In addition, oligomer-type and polymer-type compounds having a thioether structure can also be used.

As the benzotriazole-based antioxidant, oligomer-type and polymer-type compounds having a benzotriazole structure can be used.

Specifically, as a benzophenone-based antioxidant, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2- Hydroxy-4-octadeciloxybenzophenone, 2,2'dihydroxy-4-methoxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2- Examples thereof include hydroxy-4-methoxy-5 sulfobenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-chlorobenzophenone and the like. In addition, oligomer-type and polymer-type compounds having a benzophenone structure can also be used.

Examples of the triazine-based antioxidant include 2,4-bis (allyl) -6- (2-hydroxyphenyl) 1,3,5-triazine. In addition, oligomer-type and polymer-type compounds having a triazine structure can also be used.

Examples of the salicylic acid ester-based antioxidant include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butyl phenyl salicylate. In addition, oligomer-type and polymer-type compounds having a sulcylic acid ester structure can also be used.

These antioxidants can be used alone or in admixture of two or more at any ratio as required.

The content of the antioxidant is more preferably 0.5 to 5.0% by mass based on the solid content mass of the coloring composition in terms of hue.

(Amine compound)
Further, the coloring composition of the present invention may contain, if necessary, an amine compound having a function of reducing dissolved oxygen.

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

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

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

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

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

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

(Curing agent, curing accelerator)
Further, in order to assist the curing of the thermosetting resin, the coloring composition of the present invention may contain a curing agent, a curing accelerator, or the like, if necessary. Phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective as the curing agent, but the curing agent is not particularly limited to these, and is a thermosetting resin. Any curing agent may be used as long as it can react with. Further, among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine-based curing agent are preferably mentioned. Examples of the curing accelerator include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl). -N, N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (eg, triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (eg, dimethylamine, etc.), imidazole derivative bicyclic amidin compounds and salts thereof (eg, eg, dimethylamine). Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2- Ethyl-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), guanamine compounds (eg, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (eg, 2,4-diamino-6, etc.) -Methacryloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6- Methacryloyloxyethyl-S-triazine, isocyanuric acid adduct, etc.) and the like can be used. These may be used alone or in combination of two or more. The content of the curing accelerator is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the thermosetting resin.

(Other additive ingredients)
If necessary, the coloring composition of the present invention may contain a storage stabilizer to stabilize the viscosity over time. Further, an adhesion improver such as a silane coupling agent can be contained in order to improve the adhesion with the transparent substrate.

Examples of the storage stabilizer include quaternary ammonium chloride such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and phosphorous acid and their methyl ethers, t-butylpyrocatechol, tetraethylphosphine, tetraphenylphosphine and the like. Examples thereof include organic phosphine and phosphite. The storage stabilizer can be used in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the colorant.

Adhesion improvers include vinylsilanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylic silanes such as γ-methacryloxypropyltrimethoxysilane, and β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino) Ethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysisilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-amino Examples thereof include aminosilanes such as propyltrimethoxysilane and N-phenyl-γ-aminopropyltriethoxysilane, and silane coupling agents such as thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the colorant in the coloring composition.

The coloring composition of the present invention can be obtained by dispersing a diketopyrrolopyrrole pigment composition, a binder resin, and an aqueous or non-aqueous medium with a dispersing device. The method for dispersing the diketopyrrolopyrrole pigment composition is not particularly limited. A commonly used mixing and stirring device such as an anchor blade can be used for dispersion. Among the mixing and stirring devices, Ultra Disper [Asada Steel Co., Ltd., trade name], Ebara Milder [Ebara Seisakusho Co., Ltd., trade name], TK Homo Mixer, TK Pipeline Mixer, TK Homo Jetter, TK Homomic Line Flow, High-speed stirring and mixing devices such as Philmix [above, Special Machinery Industry Co., Ltd., trade name], Clearmix [M Technique Co., Ltd., trade name], and Kady Mill [Kinetic Dispersion Co., Ltd., trade name] are preferable. In addition, kneaders for roll mills, bead mills, kneaders, extruders, etc., high-pressure homogenizer [Izumi Food Machinery Co., Ltd., product name], minilab 8.3H type [Rannie, product name], homovalve type high-pressure homogenizer, micro Fluidizer [Microfluidics, product name], Nanomizer [Nanomizer Co., Ltd., product name], Ultimateer [Sugino Machine Limited, product name], Genus PY [Shiramizu Chemical Co., Ltd., product name], DeBEE2000 [Nippon BEE Co., Ltd.] , Trade name], etc., and a method of dispersing using a chamber-type high-pressure homogenizer or the like can be mentioned. Among these, a roll mill, a bead mill, a kneader and a high-pressure homogenizer are preferable from the viewpoint of reducing the particle size. A plurality of these devices can be combined.

When dispersing the diketopyrrolopyrrole pigment composition, a dye derivative may be added if necessary. Dye derivatives are synonymous with the compounds described during the salt milling process.

After obtaining the colored composition by such a method, a step of further centrifuging to separate the precipitate may be included in order to remove the precipitate and coarse particles. As a device used for centrifugation, generally, a centrifugal settler for centrifuging suspended substances by rotating a non-perforated rotating bowl at high speed, and a rotary basket having pores or slits on the side wall are used for centrifugal filtration.・ A dehydrator is known. In the present invention, among these, a centrifugal settler can be preferably used [for example, "Chemical Equipment Handbook" edited by the Society of Chemical Engineers of Japan, 2nd revised edition, 2nd edition, Maruzen Co., Ltd., April 5, 1996, See page 798]. Examples of the centrifugal settler include a centrifugal settler such as a centrifugal settling tube type, a cylindrical type, a separation plate type, a basket type, and a scride canter type.

The concentration of the diketopyrrolopyrrole pigment composition contained in the coloring composition of the present invention is preferably in the range of 1 to 35% by mass, more preferably in the range of 2 to 25% by mass.

Applications of the coloring composition of the present invention include image recording materials for forming images, particularly color images, and specifically, various printing inks and paints such as offset, gravure, flexo, screen, and inkjet. It can be applied to color filters used in displays such as LCDs, PDPs, organic electroluminescence and electronic paper, and imaging elements such as CCDs.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In addition, "part" in an Example represents "mass part".

Production of aromatic amide compound 1

120 parts of anhydrous toluene, 7.82 parts of aniline, and 7.98 parts of triethylamine were mixed, and 5.00 parts of oxalyl chloride was added dropwise thereto over 20 minutes. After the dropping, heating and stirring were performed at 70 ° C. for 3 hours. After air cooling, 80 parts of methanol and 50 parts of water were added to the reaction solution, and after stirring for 1 hour, the solid was collected by suction filtration. The obtained solid was washed with 100 parts of water and 80 parts of methanol. It was dried overnight in a vacuum dryer (40 ° C.) to obtain 8.30 parts of the desired product. The yield was 88.5%. Compounds were identified by a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was the target product at m / z = 241.31 (molecular weight 240.26).

Production of aromatic amide compound 2

The aromatic amide compound 2 was produced by using 8.75 parts of 3-fluoroaniline instead of aniline in the method for producing the aromatic amide compound 1, and 9.10 parts of the target product was obtained. The yield was 83.6%. Compounds were identified by a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was the target product at m / z = 277.32 (molecular weight 276.24).

Production of aromatic amide compound 3

The aromatic amide compound 3 was produced by using 8.75 parts of 4-fluoroaniline instead of aniline in the method for producing the aromatic amide compound 1, and 8.93 parts of the target product was obtained. The yield was 82.1%. Compounds were identified by a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was the target product at m / z = 277.43 (molecular weight 276.24).

Production of aromatic amide compound 4

The aromatic amide compound 4 was produced by using 9.56 parts of 2,6-dimethylaniline instead of aniline in the method for producing the aromatic amide compound 1, and 10.20 parts of the target product was obtained. The yield was 87.4%. Compounds were identified by a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was the target product at m / z = 297.45 (molecular weight 296.37).

Aromatic amide compound 5

Oxanilide (Tokyo Chemicals) was used.

<< Manufacturing method of diketopyrrolopyrrole pigment >>
C. I. Pigment Red 254

Under a nitrogen atmosphere, 40 parts of tert-amyl alcohol dehydrated by molecular sieve and 28 parts of sodium-tert-amyl alkoxide were mixed and heated to 100 ° C. with stirring to prepare an alcoholate solution. On the other hand, 24 parts of molecular sieve-dehydrated tert-amyl alcohol, 17.6 parts of diisopropyl succinate and 20 parts of 4-chlorobenzonitrile are mixed and heated to 90 ° C. with stirring to dissolve the mixture. It was adjusted. The heated solution of this mixture was slowly added dropwise at a constant rate over 2 hours with vigorous stirring in the previously prepared alcoholate solution. After completion of the dropping, the mixture was heated and stirred at 90 ° C. for 2 hours to obtain a reaction solution of dichlorodiketopyrrolopyrrole.
Next, 120 parts of methanol, 120 parts of water and 23.4 parts of acetic acid were mixed and cooled to 0 ° C. While vigorously stirring the cooled mixture, the previously obtained reaction solution of dichloromethane at 90 ° C. was added while cooling with a refrigerant so as to maintain a temperature of 5 ° C. or lower. This solution was stirred at 40 ° C. for 1 hour, and then the dichloromethane pyrrolol pigment was filtered off using Nutche. Then, 120 parts of methanol and 200 parts of water were sprinkled on the mixture for washing. The filtered pigment was dried at 80 ° C. for 24 hours to obtain 22.3 parts of the desired pigment.

C. I. Pigment Red 255

C. I. Pigment Red 255 was manufactured by C.I. I. 15 parts of benzonitrile was used instead of 4-chlorobenzonitrile in the method for producing Pigment Red 254. 17.1 parts of the desired pigment were obtained.

C. I. Pigment Red 264

C. I. Pigment Red 264 was manufactured by C.I. I. 26.1 parts of 4-cyanobiphenyl was used instead of 4-chlorobenzonitrile in the method for producing Pigment Red 254. 28.2 parts of the desired pigment was obtained.

C. I. Pigment Red 272

C. I. Pigment Red 272 was manufactured by C.I. I. 17 parts of 4-cyanotoluene was used instead of 4-chlorobenzonitrile in the method for producing Pigment Red 254. 19.5 parts of the desired pigment was obtained.

[Example 1]
(Diketopyrrolopyrrole Pigment Composition (P-1))
15 parts of sodium-tert-butoxide was dissolved in 1400 parts of anhydrous N, N-dimethylformamide, and C.I. I. 14.4 parts of Pigment Red 255 and 6.0 parts of the aromatic amide compound 1 were added to dissolve them, and the mixture was stirred at 30 ° C. for 3 hours. Then, 1500 parts of ice and 2500 parts of water were mixed, and a mixture dissolved in N, N-dimethylformamide was added to water cooled to 0 ° C. After stirring this solution at room temperature for 2 hours, the diketopyrrol pigment composition P-1 was filtered off using Nutche. Then, 2000 parts of water was sprinkled and washed. The filtered pigment was dried at 80 ° C. for 24 hours to obtain 15.8 parts of a pigment composition.

[Examples 2 to 13]
(Diketopyrrolopyrrole Pigment Composition (P-2 to 13))
Hereinafter, C.I. I. Pigment Red 255, aromatic amide compound 1, sodium-tert-butoxide are changed to the types and amounts of diketopyrrolopyrrole pigments and aromatic amide compounds shown in Table 3, except that the diketopyrrolopyrrole pigment composition P- Diketopyrrolopyrrole pigment compositions P-2 to 13 were prepared in the same manner as in 1.

[Example 14]
(Diketopyrrolopyrrole Pigment Composition (P-14))
C. I. 100 parts of Pigment Red 255, 20.5 parts of aromatic amide compound 1, 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 6 hours. Salt milling treatment was performed. The obtained kneaded product was put into 3000 parts of warm water, stirred for 1 hour while heating at 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours. , 104 parts of diketopyrrolopyrrole pigment composition P-14 was obtained.

[Example 15]
(Coloring composition (T-1))
0.5 g of the pigment composition (P-1) obtained in Example 1, 50 parts by mass of varnish (Tamanol 361 (manufactured by Arakawa Chemical Industry Co., Ltd .: rosin-modified phenolic resin)), 20 parts by mass of linseed oil, No. 5 Solvent (Nippon Petroleum Co., Ltd .: solvent for offset ink) was added by 30 parts by mass and melted by heating at 200 ° C. 2.5 g was loaded with 150 lb (= 667 N) in a Hoover Marler at a rotation speed of 100 rpm 4 The mixture was kneaded repeatedly to obtain a coloring composition T-1.

[Examples 16 to 28, Comparative Examples 1 to 4]
(Coloring composition (T-2 to 18))
Coloring compositions (T-2 to 18) were prepared in the same manner as the coloring composition (T-1) except that the pigment composition (P-1) was changed as shown in Table 4. In addition, a pigment was used in the comparative example.

[Evaluation of coloring composition]
0.5 g of the coloring compositions (T-1 to 18) obtained in Examples 15 to 28 and Comparative Examples 1 to 4 and white ink (50 parts of titanium oxide were dispersed in 50 parts of the offset ink varnish). ) 5.0 g was kneaded four times at a rotation speed of 25 rpm with a Hoover Marler loaded with a load of 50 lb (= 222 N) to obtain ink. The hue evaluation of this ink was performed using a spectrophotometer (V560 manufactured by JASCO Corporation). Table 5 shows the hue results (L ^* , a ^* , b ^* ), and FIGS. 1 to 4 show the reflection spectra of each. L ^* , a ^* , and b ^* are based on JIS Z 8781-4.

For example, when the hue is yellowed ( ^{increasing b *} ) based on the coloring composition of Comparative Example 1, the coloring compositions of Examples 15, 16, 17, 20, and 25 are used in Comparative Example 1. A coloring composition having a yellowish hue can be obtained from the coloring composition of. Further, when the coloring composition of Comparative Example 1 has a bluish hue (b ^* is reduced), a coloring composition having a more bluish hue can be obtained by using the coloring compositions of Examples 23 and 24. be able to. Further, when the hue is made reddish ( ^{increasing a *} ) based on the coloring composition of Comparative Example 1, the hue is made more reddish by using the coloring compositions of Examples 21, 22, 26, and 27. Coloring composition can be obtained.

By treating the diketopyrrolopyrrole pigment with a specific aromatic amide compound, reflection spectroscopy can be controlled. As a result, a diketopyrrolopyrrole pigment composition and a coloring composition whose hue can be arbitrarily controlled were obtained.

1 in FIG. 1 is reflection spectroscopy of an ink in which the coloring composition T-1 and white ink are mixed.
FIG. 1-2 is reflection spectroscopy of an ink in which the coloring composition T-3 and white ink are mixed.
FIG. 1-3 is reflection spectroscopy of an ink in which the coloring composition T-15 and white ink are mixed.

FIG. 2-4 is reflection spectroscopy of an ink in which the coloring composition T-6 and white ink are mixed.
FIG. 5 in FIG. 2 is reflection spectroscopy of an ink in which the coloring composition T-16 and white ink are mixed.

6 in FIG. 3 is the reflection spectroscopy of the ink in which the coloring composition T-9 and the white ink are mixed.
7 in FIG. 3 is the reflection spectroscopy of the ink in which the coloring composition T-17 and the white ink are mixed.

8 of FIG. 4 is a reflection spectrum of an ink in which the coloring composition T-12 and white ink are mixed.
FIG. 9 in FIG. 4 is reflection spectroscopy of an ink in which the coloring composition T-18 and white ink are mixed.

Claims (3)

A diketopyrrolopyrrole pigment composition containing a diketopyrrolopyrrole pigment represented by the general formula (1) and an aromatic amide compound represented by the general formula (2).

[In the general formula (1), R _{1 to} R ₁₀ are independently hydrogen atom, halogen atom, cyano group, nitro group, trifluoromethyl group, amino group, alkyl group having 1 to 4 carbon atoms, and carbon. It represents an alkenyl group of number 1 to 4, an aryl group of 6 to 10 carbon atoms, -OR ₁₁ , -COOR ₁₂ , -CONHR ₁₃ , -NHCOR ₁₄ or -SO ₂ NHR ₁₅ . R _{11 to} R ₁₅ independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

[In the general formula (2), R _{16 to} R ₂₅ are independently hydrogen atom, halogen atom, cyano group, nitro group, trifluoromethyl group, amino group, alkyl group having 1 to 4 carbon atoms, and carbon. It represents an alkenyl group of number 1 to 4, an aryl group of 6 to 10 carbon atoms, -OR ₁₁ , -COOR ₁₂ , -CONHR ₁₃ , -NHCOR ₁₄ or -SO ₂ NHR ₁₅ . R _{11 to} R ₁₅ independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. X and Y independently represent -CONH- or -NHCO-. ]
The diketopyrrolopyrrole pigment composition according to claim 1, wherein the diketopyrrolopyrrole pigment is represented by the general formula (3).

[In the general formula (3), R ₂₆ and R ₂₇ are independently hydrogen atom, halogen atom, cyano group, trifluoromethyl group, alkyl group having 1 to 4 carbon atoms, and alkoxy having 1 to 4 carbon atoms, respectively. Represents a group or an aryl group having 6 to 10 carbon atoms. ]
A coloring composition containing the diketopyrrolopyrrole pigment composition according to claim 1 or 2 and a resin.

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